WO2016161927A1 - 光学玻璃 - Google Patents

光学玻璃 Download PDF

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Publication number
WO2016161927A1
WO2016161927A1 PCT/CN2016/078511 CN2016078511W WO2016161927A1 WO 2016161927 A1 WO2016161927 A1 WO 2016161927A1 CN 2016078511 W CN2016078511 W CN 2016078511W WO 2016161927 A1 WO2016161927 A1 WO 2016161927A1
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Prior art keywords
glass
total amount
less
refractive index
optical
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PCT/CN2016/078511
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English (en)
French (fr)
Inventor
孙伟
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成都光明光电股份有限公司
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Application filed by 成都光明光电股份有限公司 filed Critical 成都光明光电股份有限公司
Priority to US15/546,244 priority Critical patent/US10287205B2/en
Priority to JP2017545639A priority patent/JP6934420B2/ja
Publication of WO2016161927A1 publication Critical patent/WO2016161927A1/zh

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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
    • C03C3/062—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
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0087—Simple or compound lenses with index gradient
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3411—Yttrium
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3417—Lanthanum
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3452—Gadolinium
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3488—Ytterbium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0025—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration
    • G02B27/005—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration for correction of secondary colour or higher-order chromatic aberrations
    • G02B27/0062—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration for correction of secondary colour or higher-order chromatic aberrations by controlling the dispersion of a lens material, e.g. adapting the relative partial dispersion

Definitions

  • the present invention relates to an optical glass having high refractive index and low dispersion characteristics, and a glass preform for press molding and an optical element formed of the above glass.
  • the high refractive index low dispersion optical glass is capable of correcting chromatic aberration and miniaturizing the optical system, and thus has been rapidly developed in recent years.
  • high refractive index low dispersion optical glass having a refractive index nd of 1.78 to 1.95 and an Abbe number ⁇ d of 32 to 50 is increasingly required in the market.
  • the formulation system usually adopted for such optical glass is a bismuth borate glass system, but if the content of B 2 O 3 and SiO 2 as a network former is high, the refractive index nd of the optical glass may be lowered; When the amount of the component which imparts a high refractive index to the glass is relatively large, the stability of the glass is likely to be lowered, and the problem of devitrification during the production process is caused. At the same time, the cost reduction of glass is the direction of glass improvement in recent years, and expensive raw material GeO 2 is often introduced in the conventional manufacturing, and the cost is high.
  • the technical problem to be solved by the present invention is to provide an optical glass having a high refractive index and a low dispersion property having a refractive index nd of 1.78 to 1.95 and an Abbe number ⁇ d of 32 to 50, and the glass composition does not contain GeO 2 and is not easily devitrified.
  • the present invention also provides a glass preform and an optical element formed from the above optical glass.
  • optical glass expressed by cationic %, including:
  • the total amount of Si 4+ and B 3+ is 30 to 70%
  • the total amount of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 20 to 55%;
  • Nb 5+ 0 to 20%
  • the total amount of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ is 0-20%;
  • the total amount of Li + , Na + and K + is less than 10%
  • the total amount of and/or Ba 2+ , Mg 2+ , Ca 2+ and Sr 2+ is less than 10%.
  • the total amount of Li + , Na + and K + is less than 5%;
  • the total amount of and/or Ba 2+ , Mg 2+ , Ca 2+ and Sr 2+ is less than 5%.
  • the refractive index nd of the glass is 1.85 to 1.95
  • the Abbe number ⁇ d is 32 to 40
  • the wavelength corresponding to the glass transmittance of 70% is 420 nm or less.
  • the total amount of 4+ and B 3+ is 40 to 65%; and/or the total amount of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 25 to 50%; and/or (Si 4+ + B 3+ )/(La 3+ +Y 3+ +Gd 3+ +Yb 3+ ) is greater
  • Zn 2+ 1.1 to 3%; and/or Gd 3+ : 0 to 2.5% (excluding 2.5%); and/or Ti 4+ : 0 to 3% (excluding 3%).
  • the refractive index nd of the glass is 1.78 to 1.85
  • the Abbe number ⁇ d is 40 to 50
  • the wavelength corresponding to 80% of the glass transmittance is 420 nm or less.
  • composition does not contain Ta 5+ .
  • the refractive index nd of the glass is 1.78 to 1.95
  • the Abbe number ⁇ d is 32 to 50
  • the glass density is 5 g/m 3 or less
  • the glass crystallization upper limit temperature is 1250 ° C or lower.
  • the glass preform is formed of the above optical glass.
  • the optical element is formed of the above optical glass.
  • an optical glass having a refractive index nd of 1.78 to 1.95, an Abbe number ⁇ d of 32 to 50, and excellent transmittance is provided, and a glass preform formed of the optical glass is provided.
  • optical components According to the above optical glass and an optical element such as a lens manufactured from the above-described glass preform or optical element blank, it can be used for an optical system.
  • the inventors have conducted repeated studies and found that an optical glass having a specific glass composition can attain the object of the present invention.
  • composition range of the present invention The reason for limiting the composition range of the present invention will be described below.
  • content and total amount of each component are represented by cationic %.
  • the content and total amount are both molar contents.
  • Si 4+ is a network of glass forming cations, and has the effects of maintaining glass stability, maintaining viscosity suitable for molding of molten glass, and improving chemical durability. However, if the content of Si 4+ is less than 1%, the above effects are not obtained; If the content exceeds 20%, it is difficult to achieve a desired refractive index and Abbe number, and the glass is refractory and devitrification is intensified. Therefore, the content of Si 4+ is limited to 1 to 20%. Further, a lower limit of the content of Si 4+ is preferably 2%, a more preferred lower limit is 5%; a preferred upper limit is 15%, a more preferred upper limit is 13%, and a still more preferred upper limit is 12%.
  • B 3+ is also a cation of the network of glass, and is an essential component for the glass to be low-dispersion and to maintain meltability, lower the liquidus temperature, and improve the stability of the glass. If the content thereof is less than 25%, the stability of the glass is lowered, and the above effects are not obtained; if the content thereof exceeds 60%, it is difficult to satisfy the desired refractive index, and the chemical durability is deteriorated. Therefore, the content of B 3+ of the present invention is 25 to 60%. Further, the lower limit of the content of B 3+ is preferably 30%, the more preferred lower limit is 32%; the upper limit of the content of B 3+ is preferably 55%, and the more preferred upper limit is 48%.
  • the chemical stability and heat resistance of the glass can be improved, and more
  • the glass has a refractive index nd of 1.85 to 1.95, an Abbe number ⁇ d of 32 to 40, and a B 3+ content of 45 to 60%. Further, when the B 3+ content is 45 to 55%, it is more advantageous for the glass.
  • the refractive index nd is 1.78 to 1.85, and the Abbe number ⁇ d is 40 to 50.
  • both B 3+ and Si 4+ are network forming components, and the total content of B 3+ and Si 4+ is 30% or more from the viewpoint of achieving a desired refractive index and maintaining glassiness ;
  • the total amount of B 3+ and Si 4+ is limited to 30 to 70%, preferably 40 to 65%.
  • the glass when the total amount of B 3+ and Si 4+ is 30 to 60%, further, when the total amount of B 3+ and Si 4+ is 40 to 55%, it is more advantageous for the glass to obtain the refractive index nd. 1.85 to 1.95, Abbe number ⁇ d is 32 to 40 and improve the chemical stability and heat resistance of the glass; when the total amount of B 3+ and Si 4+ is 40 to 65%, further, B 3+ and Si When the total amount of 4+ is 50 to 65%, it is more advantageous for the glass to have a refractive index nd of 1.78 to 1.85 and an Abbe number ⁇ d of 40 to 50.
  • La 3+ is an essential component for achieving high refractive index and low dispersion characteristics. If the amount is less than 10%, it is difficult to obtain a desired refractive index; if the content exceeds 40%, the crystallization upper limit temperature rises and the devitrification resistance deteriorates. Therefore, the content of La 3+ is 10 to 40%. Further, the upper limit of the content of La 3+ is preferably 35%, and the more preferable upper limit is 30%; the lower limit of the content of La 3+ is preferably 15%, and the more preferred lower limit is 20%.
  • the present invention preferably introduces two or more rare earth oxides simultaneously.
  • the present inventors have found that the coexistence of two or more kinds of rare earth cations increases the total rare earth cations in the glass composition, and by introducing these similar components, the optical properties of high refraction and low dispersion are achieved, and at the same time, Good control of glass crystallization.
  • Y 3+ and La 3+ have an effect of lowering the crystallization maximum temperature and greatly improving the devitrification resistance, and at the same time, the Y 3+ glass transmittance is more excellent with respect to Gd 3+ and Ta 3+ .
  • the content of Y 3+ exceeds 15%, the crystallization maximum temperature rises and the devitrification resistance deteriorates. Therefore, the content of Y 3+ is 0 to 15%. Further, the content of Y 3+ is preferably in the range of 0 to 13%, and more preferably in the range of 0 to 10%.
  • Gd 3+ and Yb 3+ may also coexist with La 3+ and have a function of lowering the liquidus temperature, greatly improving the resistance to devitrification, and improving chemical durability.
  • the present inventors have found that La 3+ , Y 3+ , Gd 3+ , and Yb 3+ have a total measurement range of 20 to 55% from the viewpoint of maintaining low dispersion and improving refractive index and improving resistance to devitrification. It is 25 to 45%.
  • the content of Gd 3+ is in the range of 0 to 10%, preferably in the range of 0 to 8%, and more preferably not added.
  • the content of Yb 3+ ranges from 0 to 10%, preferably from 0 to 5%, more preferably not added.
  • the glass when the total amount of La 3+ , Y 3+ , Gd 3+ , and Yb 3+ is 25 to 50%, further, when the total of La 3+ , Y 3+ , Gd 3+ , and Yb 3+ When the amount is 30 to 50%, it is more advantageous for the glass to have a refractive index nd of 1.85 to 1.95, an Abbe number ⁇ d of 32 to 40, and a glass transmittance of 70% or less corresponding to a wavelength of 420 nm or less.
  • the content of Gd 3+ is from 1 to 8%, further, when the content of Gd 3+ is from 2.5 to 8%, the liquidus temperature of the glass can be lowered, and the moldability of the glass melt can be improved;
  • the content of 3+ is from 0 to 8%, further, when the content of Gd 3+ is from 0 to 2.5% (excluding 2.5%), the devitrification resistance of the glass is further excellent.
  • (Si 4+ + B 3+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ ) is less than 1, the glass forming property of the glass is lowered; but if it exceeds 2.5, It is difficult to maintain the required optical characteristics, so (Si 4+ + B 3+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ ) is greater than 1 but less than 2.5, preferably greater than 1 but less than 2.2, More preferably, it is more than 1 but less than 2.
  • the corresponding wavelength is 420 nm or less; when (Si 4+ + B 3+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ ) is greater than or equal to 1.5 but less than At 2.5 o'clock, further, when (Si 4+ + B 3+ ) / (La 3 + + Y 3 + + Gd 3 + + Yb 3 + ) is 1.7 to 2.3, it is more advantageous for the glass to obtain a refractive index nd of 1.78. ⁇ 1.85, the Abbe number ⁇ d is 40 to 50, and the corresponding wavelength is 420 nm or less when the glass transmittance reaches 80%, and the crystallization property of the glass can be effectively improved.
  • the present invention introduces a rare earth component such as La 3+ as a glass component.
  • a rare earth component such as La 3+
  • the thermal stability of the glass is significantly lowered, and components such as Nb 5+ , Ti 4+ , Ta 5+ , W 6+ , Zr 4+ , and Bi 4+ have It has an effect of increasing the refractive index and has an effect of improving dispersibility, and thus it is necessary to contain at least one of Nb 5+ , Ta 5+ , Ti 4+ , W 6+ , Zr 4+ , and Bi 4+ and one or more groups. Minute.
  • Nb 5+ has an effect of increasing the refractive index, lowering the upper limit temperature of the glass crystallization, and improving the resistance to devitrification, while improving the thermal stability of the glass by coexistence with La 3+ as a glass component.
  • the content of Nb 5+ exceeds 20%, the glass crystallization upper limit temperature rises, the devitrification resistance deteriorates, and it is difficult to achieve a desired Abbe number, and the coloration of the glass is also enhanced. Therefore, the content of Nb 5+ is in the range of 0 to 20%, preferably 0 to 15%, more preferably 0.5 to 10%.
  • Ti 4+ also has an effect of increasing the refractive index, improving chemical durability, and resistance to devitrification. If the content of Ti 4+ exceeds 15%, the glass transition temperature or the crystallization upper limit temperature rises, the press molding property deteriorates, and the tendency of the glass to be colored tends to be exhibited. Therefore, the content of Ti 4+ ranges from 0 to 15%, preferably from 0 to 8%.
  • the content of Ti 4+ is preferably from 1 to 8%, more preferably from 3 to 8%, still more preferably from 3 to 7%; and when the refractive index nd is less than 1.85, the content of Ti 4+ is preferably It is 0 to 8%, more preferably 0 to 5%, further preferably 0 to 3% (excluding 3%), and still more preferably not added.
  • Ta 5+ has the effect of achieving high refractive index and low dispersion and improving glass stability.
  • Ta 5+ is an expensive component, and if the content exceeds 10%, the crystallization upper limit temperature rises and the devitrification resistance decreases. Therefore, the content of Ta 5+ is in the range of 0 to 10%, preferably 0 to 7%, and more preferably not added.
  • W 6+ can increase the refractive index and lower the crystallization maximum temperature. However, if the content of W 6+ exceeds 5%, the mold formability is lowered and the glass tends to be colored. Therefore, the content of W 6+ ranges from 0 to 5%.
  • Nb 5+ does not easily cause redox reaction with the press molding die, and it is difficult to bring the glass. Defects such as sintering of the molding die, atomization and damage of the glass surface.
  • the total amount of Nb 5+ , Ti 4+ , Ta 5+ , and W 6+ exceeds 20%, it is difficult to maintain desired optical characteristics and glass forming properties. Therefore, the total amount of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ is 0 to 20%, preferably 0 to 15%, and further preferably only Nb 5+ is introduced.
  • the glass transmittance reaches 70%, the corresponding wavelength is 420 nm or less; when the total amount of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ is 0 to 8%, it is more favorable for the glass to obtain the refractive index nd. It is 1.78 to 1.85, and the Abbe number ⁇ d is 40 to 50.
  • the corresponding wavelength is 420 nm or less, and the crystallization maximum temperature of the glass can be effectively lowered.
  • Control (Nb 5+ +Ti 4+ )/(Nb 5+ +Ti 4+ +Ta 5+ +W 6+ ) is 0.7 to 1, which can realize optical characteristics and thermal stability of glass, and is not easily caused by compression molding. Redox reaction of the mold. More preferably, (Nb 5+ +Ti 4+ )/(Nb 5+ +Ti 4+ +Ta 5+ +W 6+ ) is 0.8 to 1, further preferably (Nb 5+ +Ti 4+ )/(Nb 5+ +Ti 4+ +Ta 5+ +W 6+ ) is 0.9 to 1.
  • control (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ ) / (Si 4 + + B 3+ ) is 0.01 to 0.5, preferably 0.02 to 0.4, more preferably 0.03 to 0.35;
  • control (Nb 5+ +Ti 4+ +Ta 5+ +W 6+ )/(La 3+ +Y 3+ +Gd 3+ +Yb 3+ ) is 0.02 ⁇ 0.6, preferably 0.03 to 0.5, more preferably 0.04 to 0.4.
  • Zr 4+ is also a component having an effect of increasing the refractive index.
  • the content of Zr 4+ exceeds 15%, the glass is refractory, the glassability is deteriorated, and the crystallization maximum temperature tends to increase. Therefore, the content range of Zr 4+ is limited to 0 to 15%, preferably 0 to 10%.
  • Zn 2+ has a function of lowering the glass melting temperature or the transition temperature.
  • the content of Zn 2+ is in the range of 0 to 10%, preferably 0 to 5%, more preferably Contains no Zn 2+ .
  • the content of Bi 3+ ranges from 0 to 10%, preferably from 0 to 6%, and more preferably does not contain Bi 3+ .
  • Li + , Na + and K + are optional components which improve the glass meltability and lower the glass transition temperature. If the total content of Li + , Na + and K + exceeds 10%, it is difficult to achieve a desired refractive index, and glass stability and chemical durability are also lowered, and therefore, the total amount of Li + , Na + and K + is smaller than 10%, preferably less than 5%, more preferably not contained.
  • Ba 2+ , Mg 2+ , Ca 2+ , and Sr 2+ have an effect of improving the meltability of the glass and lowering the glass transition temperature.
  • the total amount of Ba 2+ , Mg 2+ , Ca 2+ , and Sr 2+ exceeds 10%, the devitrification resistance of the glass is deteriorated, the refractive index is lowered, and the chemical durability is also deteriorated. Therefore, the total amount of Ba 2+ , Mg 2+ , Ca 2+ and Sr 2+ is less than 10%, preferably less than 5%, and more preferably is not contained.
  • the optical glass of the present invention is an oxide glass, and actually the anion component is composed of O 2- .
  • the anion component is composed of O 2- .
  • a small amount of Cl - , F - may be added as a clarifying agent, but the content of O 2- is preferably greater than or equal to 98 anionic %, more preferably greater than or equal to 99 anionic %, further preferably greater than or equal to 99.5 anionic %, Most preferably 100 anionic %.
  • the optical glass of the present invention has a refractive index nd ranging from 1.78 to 1.95.
  • the preferred range is that the lower limit of the refractive index nd is 1.80; and from the viewpoint of maintaining glass stability, the upper limit of the refractive index is preferably 1.92.
  • the optical glass of the present invention has an Abbe number ⁇ d of 32 to 50.
  • the Abbe number ⁇ d is larger.
  • the lower limit of the preferred Abbe number ⁇ d is 35.
  • the upper limit of the relaxation of the Abbe number ⁇ d exerts an advantageous effect in maintaining and improving the stability of the glass. From such a viewpoint, the upper limit of the Abbe number ⁇ d is preferably 48.
  • the corresponding wavelength ( ⁇ 70 ) is less than or equal to 420 nm when the glass transmittance reaches 70%; and the glass transmittance is 80% when the glass nd is less than 1.85.
  • the corresponding wavelength ( ⁇ 80 ) is less than or equal to 420 nm.
  • ⁇ 70 is preferably less than or equal to 410 nm, still more preferably less than or equal to 400 nm, and still more preferably less than or equal to 390 nm.
  • ⁇ 80 is preferably less than or equal to 410 nm, still more preferably less than or equal to 400 nm, and still more preferably less than or equal to 390 nm.
  • the above ⁇ 70 or ⁇ 80 is a wavelength at which the light transmittance is 70% or 80% in the wavelength range of 280 to 700 nm.
  • the light transmittance is a spectral transmittance obtained from incident light having a direction perpendicular to the polished surface of a glass sample having surfaces parallel to each other having a thickness of 10.0 ⁇ 0.1 mm.
  • the spectral transmittance also includes the loss of reflection of light on the surface of the sample.
  • the above-described polishing means that the surface roughness and the surface roughness are smoothed to a sufficiently small state with respect to the measurement wavelength range.
  • the crystallization upper limit temperature of the optical glass of the present invention preferably ranges from less than or equal to 1250 ° C, more preferably ranges from less than or equal to 1200 ° C, further preferably ranges from less than or equal to 1150 ° C, and most preferably ranges from less than or equal to 1100 ° C.
  • the density ⁇ of the optical glass of the present invention preferably ranges from less than or equal to 5 g/m 3 , more preferably in the range of less than or equal to 4.95 g/m 3 , further preferably in the range of less than or equal to 4.8 g/m 3 , and still more preferably in the range of less than or equal to 4.8 g/m 3 Or equal to 4.5 g/m 3 , and most preferably in the range of less than or equal to 4.3 g/m 3 .
  • the powdery compound raw material or the cullet raw material is weighed in accordance with the glass composition of the target, and is conditioned. After being supplied to a molten container made of a platinum alloy, it is heated and melted. After the raw material is completely melted and vitrified, the temperature of the molten glass is raised and clarified. The clarified molten glass is homogenized by stirring by a stirrer, continuously supplied to the glass outflow pipe, and discharged, and quenched and solidified to obtain a glass molded body.
  • the melting temperature of the optical glass is preferably in the range of 1300 to 1450 °C.
  • the glass preform and optical element of the present invention are formed from the optical glass of the present invention.
  • the glass preform and the optical element of the present invention have high refractive index and low dispersion characteristics, and do not contain expensive components such as Ge. Therefore, optical elements such as various lenses and prisms having high optical value can be provided at low cost.
  • optical glass of the present invention can be obtained by referring to the following examples and applying the adjustment method of the content of each of the above glass components.
  • an oxide glass having the compositions (indicated by cation %) shown in Tables 1 to 9 a raw material such as a nitrate, a carbonate, a sulfate, a hydroxide, an oxide, or a boric acid is used, and each of the materials is weighed.
  • the raw material powder is thoroughly mixed to form a blended raw material, and the blended raw material is placed in a platinum crucible, heated, melted, clarified, and stirred at 1300 to 1450 ° C to obtain a uniform molten glass.
  • This molten glass was poured into a preheated mold, quenched, and held at a temperature near the glass transition temperature for two hours, and then slowly cooled to obtain the respective optical glasses of Examples 1 to 16.
  • the refractive index and Abbe number are in accordance with the GB/T 7962.1-1987 colorless optical glass test method Rate and dispersion coefficient test.
  • the optical fiber short-wave transmission spectral characteristics are expressed by the degree of coloration.
  • the glass is made into a sample having a thickness of 10 mm ⁇ 0.1 mm, and when the glass nd is greater than or equal to 1.85, the corresponding wavelength ( ⁇ 70 ) when the glass transmittance reaches 70% is tested; when the glass nd is less than 1.85, the glass transmittance is tested.
  • the density ( ⁇ ) was tested in accordance with the "GB/T 7962.20-1987 Colorless Optical Glass Test Method Density Test Method".
  • the crystallization performance of the glass was measured by the ladder furnace method.
  • the glass was made into a sample of 180*10*10 mm, polished on the side, placed in a furnace with a temperature gradient for 4 hours, and taken out, and the crystallized condition was observed under a microscope.
  • the highest temperature corresponding to the appearance of the glass is the upper limit temperature of the crystallization of the glass.
  • ⁇ Ln 3+ refers to the total amount of La 3+ , Y 3+ , Gd 3+ and Yb 3+ ;
  • ⁇ HR means the total amount of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ ;
  • ⁇ R + means the total amount of Li + , Na + and K + ;
  • ⁇ R 2+ refers to the total amount of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • the present invention is an optical glass which can be stably supplied and which has high refractive index and low dispersibility, and is suitable for use in a glass preform for molding and an optical element.

Abstract

一种折射率为1.78～1.95、阿贝数为32～50的高折射低分散特性的光学玻璃，由该光学玻璃形成的玻璃预制体和光学元件。该玻璃组成中不含GeO 2，不易失透。该光学玻璃，以阳离子％表示，包括：Si 4+：1～20％；B 3+：25～60％；La 3+：10～40％；Y 3+：0～15％；Nb 5+：0～20％；Ti 4+：0～15％；Ta 5+：0～10％；W 6+：0～5％；Zr 4+：0～15％；Zn 2+：0～10％；Bi 3+：0～10％。

Description

光学玻璃 技术领域
本发明涉及一种具有高折射率低色散特性的光学玻璃，以及由上述玻璃形成的压制成型用玻璃预制件和光学元件。
背景技术
高折射率低色散光学玻璃能够修正色差，使光学系统小型化，因此近年来得到快速发展。特别是折射率nd为1.78～1.95、阿贝数νd为32～50的高折射率低色散光学玻璃，市场需求日益增大。
这类光学玻璃通常采用的配方体系是镧硼酸盐玻璃体系，但如果作为网络形成体的B2O3和SiO2的含量较高，可能导致光学玻璃的折射率nd下降；但若配方体系中赋予玻璃高折射率的成分相对较多的话，又容易导致玻璃稳定性下降、在制造过程中失透等问题。同时，玻璃的低成本化是近年来玻璃改良的方向，以往制造中常常引入昂贵的原料GeO2，成本较高。
发明内容
本发明所要解决的技术问题是提供一种折射率nd为1.78～1.95、阿贝数νd为32～50的高折射低分散特性的光学玻璃，且玻璃组成中不含GeO2，不易失透。
本发明还要提供一种由上述光学玻璃形成的玻璃预制件和光学元件。
本发明解决技术问题所采用的技术方案是：光学玻璃，以阳离子％表示，包括：
Si4+：1～20％；
B3+：25～60％；
并且，Si4+、B3+的合计量为30～70％；
La3+：10～40％；
Y3+：0～15％；
La3+、Y3+、Gd3+和Yb3+的合计量为20～55％；
(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.5；
Nb5+：0～20％；
Ti4+：0～15％；
Ta5+：0～10％；
W6+：0～5％；
Nb5+、Ti4+、Ta5+和W6+的合计量为0～20％；
(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.7～1；
(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.01～0.5；
(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.02～0.6；
Zr4+：0～15％；
Zn2+：0～10％；
Bi3+：0～10％。
进一步的，还包括：
Li+、Na+和K+的合计量小于10％；
和/或Ba2+、Mg2+、Ca2+和Sr2+的合计量小于10％。
进一步的，还包括，
Li+、Na+和K+的合计量小于5％；
和/或Ba2+、Mg2+、Ca2+和Sr2+的合计量小于5％。
进一步的，其中，Si4+：2～15％；和/或B3+：25～45％(不含45％)；和/或La3+：15～35％；和/或Y3+：0～13％；和/或Gd3+：0～10％；和/或Yb3+：0～10％；和/或Nb5+：0～15％；和/或Ti4+：1～8％；和/或Ta5+：0～7％；和/或Zr4+：0～10％；和/或Zn2+：0～5％；和/或Bi3+：0～6％；和/或Si4+、B3+的合计量为30～60％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.2；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～15％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.8～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.02～0.4；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.03～0.5。
进一步的，其中，Si4+：5～13％；和/或B3+：30～45％(不含45％)；和/或La3+：20～35％；和/或Y3+：0～10％；和/或Gd3+：1～8％；和/或Yb3+：0～5％；和/或Nb5+：0.5～10％；和/或Ti4+：3～8％；和/或Zn2+：0～1.1％(不含1.1％)；和/或Si4+、B3+的合计量为40～55％；和/或La3+、Y3+、Gd3+ 和Yb3+的合计量为30～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为3～15％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.9～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.03～0.35；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.04～0.4。
进一步的，其中，Gd3+：2.5～8％；和/或Ti4+：3～7％。
进一步的，上述玻璃折射率nd为1.85～1.95，阿贝数νd为32～40；其玻璃透射比达到70％时对应的波长为420nm以下。
进一步的，其中，Si4+：2～15％；和/或B3+：45～60％；和/或La3+：15～35％；和/或Y3+：0～13％；和/或Gd3+：0～10％；和/或Yb3+：0～10％；和/或Nb5+：0～15％；和/或Ti4+：0～8％；和/或Ta5+：0～7％；和/或Zr4+：0～10％；和/或Zn2+：0～5％；和/或Bi3+：0～6％；和/或Si4+、B3+的合计量为40～65％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于或等于1.5但小于2.5；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～15％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.8～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.02～0.4；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.03～0.5。
进一步的，其中，Si4+：5～13％；和/或B3+：45～55％；和/或La3+：20～35％；和/或Y3+：0～10％；和/或Gd3+：0～8％；和/或Yb3+：0～5％；和/或Nb5+：0.5～10％；和/或Ti4+：0～5％；和/或Zn2+：0.5～5％；和/或Si4+、B3+的合计量为50～65％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～45％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为1.7～2.3；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～8％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.9～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.03～0.35；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.04～0.4。
进一步的，其中，Zn2+：1.1～3％；和/或Gd3+：0～2.5％(不含2.5％)；和/或Ti4+：0～3％(不含3％)。
进一步的，上述玻璃折射率nd为1.78～1.85，阿贝数νd为40～50；其玻璃透射比达到80％时对应的波长为420nm以下。
进一步的，其中，组成中不含Ta5+。
进一步的，上述玻璃折射率nd为1.78～1.95，阿贝数νd为32～50，玻璃密度为5g/m3以下，玻璃析晶上限温度为1250℃以下。
玻璃预制件，由上述的光学玻璃形成。
光学元件，由上述的光学玻璃形成。
发明的有益效果是：本发明提供一种折射率nd为1.78～1.95、阿贝数νd为32～50且透过率优良的光学玻璃，并且提供一种由所述光学玻璃形成的玻璃预制体和光学元件。根据上述光学玻璃以及由上述玻璃预制件或光学元件坯料制造的光学元件例如透镜等，能够用于光学系统。
具体实施方式
为了达到本发明的目的，本发明人经过反复研究，发现具有特定的玻璃组成的光学玻璃能够达到本发明的目的。
下面对本发明组成范围的限定理由进行说明，如果没有特殊说明，各成分的含量和合计量以阳离子％表示。所述含量和合计量均为摩尔含量。
Si4+是玻璃的网络形成阳离子，具有维持玻璃稳定性、维持适于熔融玻璃成形的粘性、改善化学耐久性等效果，但若Si4+的含量低于1％，得不到上述效果；如果其含量超过20％，则难以实现期望的折射率和阿贝数，且玻璃难熔，失透加剧。因此，将Si4+的含量限定为1～20％。进一步的，Si4+的含量优选的下限为2％，更优选的下限为5％；优选的上限为15％，更优选的上限为13％，更进一步优选的上限为12％。
B3+也是玻璃的网络形成阳离子，是玻璃低色散化且维持熔融性、降低液相温度以及提高玻璃稳定性的必需成分。如果其含量小于25％，则玻璃稳定性下降，并且无法得到上述效果；如果其含量超过60％，则难以满足期望的折射率，并且化学耐久性会恶化。因此，本发明的B3+的含量为25～60％。进一步的，B3+的含量优选的下限为30％，更优选的下限为32％；B3+的含量优选的上限为55％，更优选的上限为48％。
特别的，当B3+含量为25～45％时，进一步的，B3+含量为30～45％(不含45％)时，能提高玻璃的化学稳定性和耐热性，且更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40；当B3+含量为45～60％时， 进一步的，B3+含量为45～55％时，更有利于玻璃得到折射率nd为1.78～1.85，阿贝数νd为40～50。
另外，B3+和Si4+均是网络形成组分，从达到期望的折射率以及维持成玻璃性等方面出发，要使B3+和Si4+的总含量达到30％以上；但如果B3+和Si4+的总含量超过70％，则难以得到需要的光学特性，因此将B3+和Si4+的合计量限定为30～70％，优选范围为40～65％。
特别的，当B3+和Si4+的合计量为30～60％时，进一步的，B3+和Si4+的合计量为40～55％时，更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40并提高玻璃的化学稳定性和耐热性；当B3+和Si4+的合计量为40～65％时，进一步的，B3+和Si4+的合计量为50～65％时，更有利于玻璃得到折射率nd为1.78～1.85，阿贝数νd为40～50。
La3+是实现高折射率低分散特性的必需成分。如果其量小于10％，则难以得到期望的折射率；如果含量超过40％，则析晶上限温度上升，耐失透性恶化。因此，La3+的含量为10～40％。进一步的，La3+的含量优选的上限为35％，更优选的上限为30％；La3+的含量优选的下限为15％，更优选的下限为20％。
本发明优选同时引入两种或两种以上稀土氧化物。本发明人发现，两种或两种以上稀土类阳离子共存，使玻璃组成中整体的稀土类阳离子增加，通过引入这些作用相类似的组份，实现高折射低色散的光学性能，同时还能更好地控制玻璃析晶。
Y3+与La3+共存具有降低析晶上限温度、大幅度地改善耐失透性的作用，同时相对Gd3+与Ta3+而言，引入Y3+玻璃透过率更优异。但如果Y3+的含量超过15％，则析晶上限温度上升，耐失透性恶化。因此，Y3+的含量为0～15％。进一步的，Y3+的含量优选范围为0～13％，更优选的范围为0～10％。
Gd3+、Yb3+也可以与La3+共存而具有降低液相温度、大幅度地改善耐失透性、改善化学耐久性的作用。本发明人发现，从维持低色散性并且提高折射率以及改善耐失透性等方面出发，La3+、Y3+、Gd3+以及Yb3+合计量范围为20～55％，优选范围为25～45％。其中，Gd3+的含量范围为0～10％，优选范围为0～8％，更优选不加入。Yb3+的含量范围为0～10％，优选0～5％， 更优选不加入。
特别的，当La3+、Y3+、Gd3+和Yb3+的合计量为25～50％时，进一步的，当La3+、Y3+、Gd3+和Yb3+的合计量为30～50％时，更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40，其玻璃透射比达到70％时对应的波长为420nm以下。
特别的，当Gd3+的含量为1～8％时，进一步的，当Gd3+的含量为2.5～8％时，能降低玻璃的液相温度、提高玻璃融液的成型性；当Gd3+的含量为0～8％时，进一步的，当Gd3+的含量为0～2.5％(不含2.5％)时，玻璃的耐失透性能更优异。
另外，如果(Si4++B3+)/(La3++Y3++Gd3++Yb3+)不足1时，则玻璃的成玻璃性就会下降；但如果超过2.5，则难以维持需要的光学特性，因此(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.5，优选为大于1但小于2.2，更优选为大于1但小于2。
特别的，当(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.2时，进一步的，当(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2时，更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40，其玻璃透射比达到70％时对应的波长为420nm以下；当(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于或等于1.5但小于2.5时，进一步的，当(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为1.7～2.3时，更有利于玻璃得到折射率nd为1.78～1.85，阿贝数νd为40～50，其玻璃透射比达到80％时对应的波长为420nm以下，并能有效改善玻璃的析晶性能。
本发明为了在维持低色散性的同时提高玻璃的折射率，导入La3+等稀土类组分作为玻璃组分。但是，如果仅通过稀土类组分提高折射率，则玻璃的热稳定性会显著下降，Nb5+、Ti4+、Ta5+、W6+、Zr4+和Bi4+等组分具有提高折射率的作用，并且具有提高分散性的作用，因而需要含有Nb5+、Ta5+、Ti4+、W6+、Zr4+和Bi4+中至少一种及一种以上的组分。
Nb5+具有提高折射率、降低玻璃析晶上限温度、改善耐失透性的作用，同时通过与作为玻璃组分的La3+共存来改善玻璃的热稳定性。如果Nb5+的含量超过20％，则玻璃析晶上限温度会上升，耐失透性会恶化，难以实现 期望的阿贝数，此外玻璃的着色也会增强。因此，Nb5+的含量范围为0～20％，优选为0～15％，更优选为0.5～10％。
Ti4+也具有提高折射率、改善化学耐久性和耐失透性的作用。如果Ti4+的含量超过15％，则玻璃转变温度或析晶上限温度会上升，模压成型性能变差，同时显示出玻璃着色的倾向。因此，Ti4+的含量范围为0～15％，优选为0～8％。
尤其是，当折射率nd大于1.85时，Ti4+的含量优选1～8％，更优选3～8％，进一步优选3～7％；当折射率nd小于1.85时，Ti4+的含量优选为0～8％，更优选0～5％，进一步优选0-3％(不含3％)，更进一步优选为不加入。
Ta5+具有实现高折射率低色散、提高玻璃稳定性的作用。但是，Ta5+是昂贵的成分，并且如果其含量超过10％，则析晶上限温度会上升，耐失透性会下降。因此，Ta5+的含量范围为0～10％，优选为0～7％，更优选不加入。
W6+可提高折射率，降低析晶上限温度，但如果W6+的含量超过5％，则会显示出模压成形性下降并且玻璃着色的倾向。因此，W6+的含量范围为0～5％。
并且，在Nb5+、Ti4+、Ta5+、W6+等提高玻璃折射率的组分中，相对来说，Nb5+不易引起与模压成形模具的氧化还原反应，不易带来玻璃与模压成形模具的熔结、玻璃表面的雾化和损坏等缺陷。另外，如果Nb5+、Ti4+、Ta5+以及W6+的合计量超过20％，则难以维持需要的光学特性和和成玻璃性。因此Nb5+、Ti4+、Ta5+和W6+的合计量为0～20％，优选为0～15％，进一步优选仅引入Nb5+。
特别的，当Nb5+、Ti4+、Ta5+以及W6+的合计量为3～15％时，更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40，其玻璃透射比达到70％时对应的波长为420nm以下；当Nb5+、Ti4+、Ta5+以及W6+的合计量为0～8％时，更有利于玻璃得到折射率nd为1.78～1.85，阿贝数νd为40～50，其玻璃透射比达到80％时对应的波长为420nm以下，同时能有效降低玻璃的析晶上限温度。
控制(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.7～1，可实现光学特性和玻璃的热稳定性，以及不易引起与模压成形模具的氧化还原反应。更优选(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.8～1，进一步优选(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.9～1。
另外，为了在维持成玻璃性的同时实现需要的光学特性，控制(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.01～0.5，优选为0.02～0.4，更优选为0.03～0.35；控制(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.02～0.6，优选0.03～0.5，更优选为0.04～0.4。
Zr4+也是具有提高折射率的作用的组分。如果Zr4+的含量超过15％，则会显示出玻璃难熔，成玻璃性变差，析晶上限温度上升的倾向。因此，将Zr4+的含量范围限定为0～15％，优选为0～10％。
Zn2+具有使玻璃熔融温度或转变温度降低的作用。但在本发明中，如果其含量超过10％，则折射率会降低，玻璃的化学耐久性会降低，因而，Zn2+的含量范围为0～10％，优选为0～5％，更优选不含Zn2+。
特别的，当Zn2+的含量为0～1.1％(不含1.1％)时，更有利于玻璃得到折射率nd为1.85～1.95，阿贝数νd为32～40；当Zn2+的含量为0.5～5％时，进一步的，当Zn2+的含量为1.1～3％时，更有利于玻璃得到折射率nd为1.78～1.85，阿贝数νd为40～50，并且有利于降低玻璃的高温粘度和膨胀系数。Bi3+具有提高折射率和玻璃稳定性的作用，但其色散高，如果其含量超过10％，则实现不了所述的阿贝数，可见区域中的光线透射率会下降。因此，Bi3+的含量范围为0～10％，优选范围为0～6％，更优选为不含Bi3+。
Li+、Na+和K+是改善玻璃熔融性、降低玻璃转变温度的任意成分。如果Li+、Na+和K+的总含量超过10％，则难以实现期望的折射率，并且玻璃稳定性和化学耐久性也会下降，因此，Li+、Na+和K+的合计量小于10％，优选小于5％，更优选不含有。
Ba2+、Mg2+、Ca2+和Sr2+具有改善玻璃的熔融性、降低玻璃转变温度的作用。但是，如果Ba2+、Mg2+、Ca2+和Sr2+的合计量超过10％，则玻璃耐失透性恶化，折射率下降，化学耐久性也会恶化。因此，Ba2+、Mg2+、Ca2+和Sr2+ 的合计量小于10％，优选小于5％，更优选不含有。
本发明的光学玻璃是氧化物玻璃，实际上阴离子成分由O2-构成。如上所述，作为澄清剂也可以添加少量的Cl-、F-，但是O2-的含量优选大于或等于98阴离子％，更优选大于或等于99阴离子％，进一步优选大于或等于99.5阴离子％，最优选为100阴离子％。
本发明的光学玻璃的折射率nd范围为1.78～1.95。当高折射率化优先时，优选范围为折射率nd的下限为1.80；当从维持玻璃稳定性出发，优选范围为折射率的上限为1.92。
本发明的光学玻璃的阿贝数νd为32～50。当与高分散玻璃制成的透镜组合来修正色差时，阿贝数νd大些是有利的。从这样的观点出发，阿贝数νd优选的下限为35，另一方面，缓和阿贝数νd的上限在维持和提高玻璃稳定性方面会发挥有利作用。从这样的观点出发，阿贝数νd优选的上限为48。
下面，对本发明的光学玻璃的光线透射性进行说明。
在本发明的光学玻璃中，玻璃nd大于或等于1.85时，其玻璃透射比达到70％时对应的波长(λ70)小于或等于420nm；当玻璃nd小于1.85时，其玻璃透射比达到80％时对应的波长(λ80)小于或等于420nm。
在本发明中，λ70优选小于或等于410nm，再优选为小于或等于400nm，更优选为小于或等于390nm。
在本发明中，λ80优选小于或等于410nm，再优选为小于或等于400nm，更优选为小于或等于390nm。
上述λ70或λ80是在280～700nm的波长范围内光线透射率为70％或80％的波长。这里，光线透射率是使用具有研磨成10.0±0.1mm的厚度的彼此平行的面的玻璃样品，从与所述研磨的面垂直方向的入射光而得到的分光透射率。分光透射率也包含样品表面上的光的反射损失。另外，上述研磨意味着相对于测定波长域的波长、表面粗度被平滑化为足够小的状态。
本发明光学玻璃的析晶上限温度优选范围为小于或等于1250℃，更优选范围为小于或等于1200℃，进一步优选范围为小于或等于1150℃，最优选范围为小于或等于1100℃.
本发明光学玻璃的密度ρ优选范围为小于或等于5g/m3，更优选范围为小于或等于4.95g/m3，进一步优选范围为小于或等于4.8g/m3，更进一步优选范围为小于或等于4.5g/m3，最优选范围为小于或等于4.3g/m3。
下面，对本发明的光学玻璃的制造方法进行说明。
与目标的玻璃组成相对应地称量粉体状的化合物原料或碎玻璃原料，进行调和，在供应至铂合金制的熔融容器内之后，对其进行加热、熔融。在完全熔融上述原料并进行玻璃化之后，使该熔融玻璃的温度上升并进行澄清。通过搅拌器的搅拌使澄清后的熔融玻璃进行均匀化，并连续供应给玻璃流出管道而流出，进行急冷、固化，得到玻璃成形体。
另外，从得到均匀、低着色并且包含光学特性在内的诸特性稳定的玻璃方面出发，优选光学玻璃的熔融温度为1300～1450℃的范围。
本发明的玻璃预制件、光学元件由本发明的光学玻璃形成。本发明的玻璃预制件、光学元件具有高折射率低分散特性，不含Ge等昂贵的成分，因此能够以低成本提供光学价值高的各种透镜、棱镜等光学元件。
实施例
下面通过实施例来进一步详细说明本发明的技术方案，但是本发明不被这些实施例所限定。通过参考以下实施例并应用上述各玻璃成分的含量的调整法，而能够得到本发明的光学玻璃。
首先，为了得到具有表1～9所示的组成(以阳离子％来表示)的氧化物玻璃，使用硝酸盐、碳酸盐、硫酸盐、氢氧化物、氧化物、硼酸等原料，称量各原料粉末，进行充分混合，成为调合原料，将该调合原料放入到铂制坩埚中，以1300-1450℃进行加热、熔融、澄清、搅拌，而成为均匀的熔融玻璃。将该熔融玻璃流入到预热过的铸模中，进行急冷，在玻璃转变温度附近的温度下保持两个小时之后，进行缓冷，从而得到实施例1～16的各光学玻璃。
另外，实施例1～72的阴离子成分全部是O2-。各玻璃的特性通过以下所示的方法进行测定。
(1)折射率nd和阿贝数νd
折射率与阿贝数按照《GB/T 7962.1—1987无色光学玻璃测试方法折 射率和色散系数》测试。
(2)玻璃着色度(λ70、λ80)
光学玻璃短波透射光谱特性用着色度表示。将玻璃制作成10mm±0.1mm厚度的样品，当玻璃nd大于或等于1.85时，测试其玻璃透射比达到70％时对应的波长(λ70)；当玻璃nd小于1.85时，测试其玻璃透射比达到80％时对应的波长(λ80)。
(3)玻璃密度(ρ)
密度(ρ)按照按《GB/T 7962.20-1987无色光学玻璃测试方法密度测试方法》测试。
(4)玻璃析晶上限温度
采用梯温炉法测定玻璃的析晶性能，将玻璃制成180*10*10mm的样品，侧面抛光，放入带有温度梯度的炉内保温4小时后取出，在显微镜下观察析晶情况，玻璃出现晶体对应的最高温度即为玻璃的析晶上限温度。
表1
Figure PCTCN2016078511-appb-000001
Figure PCTCN2016078511-appb-000002
表2
Figure PCTCN2016078511-appb-000003
Figure PCTCN2016078511-appb-000004
表3
Figure PCTCN2016078511-appb-000005
Figure PCTCN2016078511-appb-000006
表4
Figure PCTCN2016078511-appb-000007
Figure PCTCN2016078511-appb-000008
表5
Figure PCTCN2016078511-appb-000009
Figure PCTCN2016078511-appb-000010
表6
Figure PCTCN2016078511-appb-000011
Figure PCTCN2016078511-appb-000012
表7
Figure PCTCN2016078511-appb-000013
Figure PCTCN2016078511-appb-000014
表8
Figure PCTCN2016078511-appb-000015
Figure PCTCN2016078511-appb-000016
表9
Figure PCTCN2016078511-appb-000017
Figure PCTCN2016078511-appb-000018
上述表1-9中：
∑Ln3+是指La3+、Y3+、Gd3+及Yb3+的合计量；
∑HR是指Nb5+、Ti4+、Ta5+及W6+的合计量；
∑R+是指Li+、Na+及K+的合计量；
∑R2+是指Mg2+、Ca2+、Sr2+及Ba2+的合计量。
本发明是能够稳定供应的且具备高折射率低分散性的光学玻璃，适用于成形用玻璃预制件以及光学元件。

Claims (15)

  1. 光学玻璃，其特征在于，以阳离子％表示，包括：
    Si4+：1～20％；
    B3+：25～60％；
    并且，Si4+、B3+的合计量为30～70％；
    La3+：10～40％；
    Y3+：0～15％；
    La3+、Y3+、Gd3+和Yb3+的合计量为20～55％；
    (Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.5；
    Nb5+：0～20％；
    Ti4+：0～15％；
    Ta5+：0～10％；
    W6+：0～5％；
    Nb5+、Ti4+、Ta5+和W6+的合计量为0～20％；
    (Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.7～1；
    (Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.01～0.5；
    (Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.02～0.6；
    Zr4+：0～15％；
    Zn2+：0～10％；
    Bi3+：0～10％。
  2. 如权利要求1所述的光学玻璃，其特征在于，还包括：
    Li+、Na+和K+的合计量小于10％；
    和/或Ba2+、Mg2+、Ca2+和Sr2+的合计量小于10％。
  3. 如权利要求1所述的光学玻璃，其特征在于，还包括，
    Li+、Na+和K+的合计量小于5％；
    和/或Ba2+、Mg2+、Ca2+和Sr2+的合计量小于5％。
  4. 如权利要求1所述的光学玻璃，其特征在于，其中，Si4+：2～15％；和/或B3+：25～45％(不含45％)；和/或La3+：15～35％；和/或Y3+：0～13％； 和/或Gd3+：0～10％；和/或Yb3+：0～10％；和/或Nb5+：0～15％；和/或Ti4+：1～8％；和/或Ta5+：0～7％；和/或Zr4+：0～10％；和/或Zn2+：0～5％；和/或Bi3+：0～6％；和/或Si4+、B3+的合计量为30～60％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2.2；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～15％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.8～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.02～0.4；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.03～0.5。
  5. 如权利要求1所述的光学玻璃，其特征在于，其中，Si4+：5～13％；和/或B3+：30～45％(不含45％)；和/或La3+：20～35％；和/或Y3+：0～10％；和/或Gd3+：1～8％；和/或Yb3+：0～5％；和/或Nb5+：0.5～10％；和/或Ti4+：3～8％；和/或Zn2+：0～1.1％(不含1.1％)；和/或Si4+、B3+的合计量为40～55％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为30～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于1但小于2；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为3～15％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.9～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.03～0.35；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.04～0.4。
  6. 如权利要求1所述的光学玻璃，其特征在于，其中，Gd3+：2.5～8％；和/或Ti4+：3～7％。
  7. 如权利要求1-6任一权利要求所述的光学玻璃，其特征在于，玻璃折射率nd为1.85～1.95，阿贝数νd为32～40；其玻璃透射比达到70％时对应的波长为420nm以下。
  8. 如权利要求1所述的光学玻璃，其特征在于，其中，Si4+：2～15％；和/或B3+：45～60％；和/或La3+：15～35％；和/或Y3+：0～13％；和/或Gd3+：0～10％；和/或Yb3+：0～10％；和/或Nb5+：0～15％；和/或Ti4+：0～8％；和/或Ta5+：0～7％；和/或Zr4+：0～10％；和/或Zn2+：0～5％；和/或Bi3+：0～6％；和/或Si4+、B3+的合计量为40～65％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～50％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为大于或等于1.5但小于2.5；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～15％； 和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.8～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.02～0.4；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.03～0.5。
  9. 如权利要求1所述的光学玻璃，其特征在于，其中，Si4+：5～13％；和/或B3+：45～55％；和/或La3+：20～35％；和/或Y3+：0～10％；和/或Gd3+：0～8％；和/或Yb3+：0～5％；和/或Nb5+：0.5～10％；和/或Ti4+：0～5％；和/或Zn2+：0.5～5％；和/或Si4+、B3+的合计量为50～65％；和/或La3+、Y3+、Gd3+和Yb3+的合计量为25～45％；和/或(Si4++B3+)/(La3++Y3++Gd3++Yb3+)为1.7～2.3；和/或Nb5+、Ti4+、Ta5+和W6+的合计量为0～8％；和/或(Nb5++Ti4+)/(Nb5++Ti4++Ta5++W6+)为0.9～1；和/或(Nb5++Ti4++Ta5++W6+)/(Si4++B3+)为0.03～0.35；和/或(Nb5++Ti4++Ta5++W6+)/(La3++Y3++Gd3++Yb3+)为0.04～0.4。
  10. 如权利要求1所述的光学玻璃，其特征在于，其中，Zn2+：1.1～3％；和/或Gd3+：0～2.5％(不含2.5％)；和/或Ti4+：0～3％(不含3％)。
  11. 如权利要求1-3、8-10任一权利要求所述的光学玻璃，其特征在于，玻璃折射率nd为1.78～1.85，阿贝数νd为40～50；其玻璃透射比达到80％时对应的波长为420nm以下。
  12. 如权利要求1所述的光学玻璃，其特征在于，其中，组成中不含Ta5+。
  13. 如权利要求1所述的光学玻璃，其特征在于，玻璃折射率nd为1.78～1.95，阿贝数νd为32～50，玻璃密度为5g/m3以下，玻璃析晶上限温度为1250℃以下。
  14. 玻璃预制件，其特征在于，由所述权利要求1-13项中任一权利要求所述的光学玻璃形成。
  15. 光学元件，其特征在于，由所述权利要求1-13项中任一权利要求所述的光学玻璃形成。
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