CN110316962B - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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Publication number
CN110316962B
CN110316962B CN201910660519.5A CN201910660519A CN110316962B CN 110316962 B CN110316962 B CN 110316962B CN 201910660519 A CN201910660519 A CN 201910660519A CN 110316962 B CN110316962 B CN 110316962B
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optical glass
glass
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tio
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CN110316962A (en
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孙伟
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CDGM Glass Co Ltd
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CDGM Glass 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
    • C03C3/076—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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Abstract

The invention provides an optical glass, which comprises the following components in percentage by weight: SiO 22：35～50％；TiO2：21～38％；Na2O：5～22％；K2O：1～12％；BaO：1～15％；Nb2O5: 0 to 10% of (Nb)2O5+K2O)/SiO20.02 to 0.45. Through reasonable component design, the optical glass has the advantages of 1.65-1.73 refractive index and 25-35 Abbe number, and has excellent chemical stability.

Description

Optical glass and optical element
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.65-1.73 and an Abbe number of 25-35.
Background
With the development of the photoelectric industry, the requirements of miniaturization, light weight and high performance are put forward for optical elements, so that the demand of optical glass with the refractive index of 1.65-1.73 and the Abbe number of 25-35 is more and more increased.
The optical glass can be corroded by the environment and various liquids (such as acid, alkali, water and the like) in the using process, so the resistance of the optical glass to the corrosion, namely the chemical stability of the optical glass is important for the use precision and the service life of instruments. CN101215086A discloses an optical glass having a refractive index of 1.65 to 1.85 and an Abbe number of 20 to 35, which contains a large amount of P2O5And Nb2O3The chemical stability is difficult to meet the requirements of modern optics on optical materials.
Disclosure of Invention
For the reasons, the technical problem to be solved by the invention is to provide the optical glass with excellent chemical stability, the refractive index of the optical glass is 1.65-1.73, and the Abbe number of the optical glass is 25-35.
The technical scheme adopted by the invention for solving the technical problem is as follows: the optical glass comprises the following components in percentage by weight: SiO 22：35～50％；TiO2：21～38％；Na2O：5～22％；K2O：1～12％；BaO：1～15％；Nb2O5: 0 to 10% of (Nb)2O5+K2O)/SiO20.02 to 0.45.
Further, the optical glass comprises the following components in percentage by weight: b is2O3: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/orCaO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or Ln2O3: 0 to 5 percent; and/or ZrO2: 0 to 5 percent; and/or Li2O: 0-8%; and/or Al2O3: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Sb2O3: 0 to 1%, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
Optical glass, the composition of which is expressed in weight percentage by SiO2：35～50％；TiO2：21～38％；Na2O：5～22％；K2O：1～12％；BaO：1～15％；Nb2O5：0～10％；B2O3：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～10％；Ln2O3：0～5％；ZrO2：0～5％；Li2O：0～8％；Al2O3：0～5％；ZnO：0～5％；Sb2O3: 0 to 1% of a composition of (Nb)2O5+K2O)/SiO20.02 to 0.45, the Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
Further, the optical glass comprises the following components in percentage by weight: TiO 22/SiO20.45 to 1.0; and/or B2O3/SiO2Is 0.2 or less; and/or (ZrO)2+K2O)/Na2O is 0.05 to 1.0; and/or TiO2/(BaO+Nb2O5) 1.5 to 10.0; and/or Nb2O5/TiO2Is 0.3 or less; and/or (CaO + MgO + ZnO)/BaO is 0.6 or less.
Further, the optical glass comprises the following components in percentage by weight: SiO 22: 37-47%; and/or TiO2: 25-35%; and/or Na2O: 8-18%; and/or BaO: 2-10%; and/or Nb2O5: 0 to 7 percent; and/or K2O: 3-10%; and/or B2O3: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or Ln2O3: 0 to 3 percent; and/or ZrO2: 0 to 3 percent; and/or Li2O: 0 to 4 percent; and/or Al2O3: 0 to 3 percent; and/or ZnO: 0 to 3 percent; and/or Sb2O3: 0 to 0.5%, wherein Ln is2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
Further, the optical glass comprises the following components in percentage by weight: TiO 22/SiO20.5 to 0.9; and/or B2O3/SiO2Is less than 0.15; and/or (ZrO)2+K2O)/Na2O is 0.1 to 0.8; and/or (Nb)2O5+K2O)/SiO20.05 to 0.35; and/or Nb2O5/TiO2Is 0.2 or less; and/or (CaO + MgO + ZnO)/BaO is 0.4 or less; and/or TiO2/(BaO+Nb2O5) Is 2.0 to 8.0.
Further, the optical glass comprises the following components in percentage by weight: SiO 22: 40-45%; and/or TiO2: 26-32%; and/or Na2O: 10-16%; and/or BaO: 3-9%; and/or Nb2O5: 0 to 3 percent; and/or K2O: 4-9%; and/or B2O3: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or Ln2O3: 0 to 1 percent; and/or ZrO2: 0-2%; and/or Li2O: 0 to 3 percent; and/or Al2O3: 0 to 1 percent; and/or ZnO: 0 to 1%, wherein Ln is2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
Further, in the above-mentioned case,the optical glass comprises the following components in percentage by weight, and the content of each component satisfies more than one of the following cases of 7: TiO 22/SiO20.55 to 0.8; and/or B2O3/SiO2Is 0.1 or less; and/or (ZrO)2+K2O)/Na2O is 0.2 to 0.6; and/or (Nb)2O5+K2O)/SiO20.08 to 0.25; and/or Nb2O5/TiO2Is 0.1 or less; and/or (CaO + MgO + ZnO)/BaO is 0.2 or less; and/or TiO2/(BaO+Nb2O5) 2.5 to 6.0.
Further, the above optical glass has a composition in weight percent of TiO2、SiO2、Na2O、K2The total content of O and BaO is 96% or more, and TiO is more preferable2、SiO2、Na2O、K2The total content of O and BaO is 97% or more, and TiO is more preferable2、SiO2、Na2O、K2The total content of O and BaO is 98% or more.
Furthermore, the refractive index nd of the optical glass is 1.65-1.73, preferably 1.66-1.72, and more preferably 1.67-1.71; abbe number vd25 to 35, preferably 28 to 33, and more preferably 29 to 32.
Further, the stability of the acid resistance of the above optical glass DAIs 2 or more, preferably 1; and/or stability against water action DWIs 2 or more, preferably 1; and/or a density rho of 3.2g/cm3Hereinafter, it is preferably 3.1g/cm3Hereinafter, more preferably 3.0g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 98 x 10-7Preferably 96X 10 or less,/K-7A value of less than or equal to K, more preferably 93X 10-7below/K; and/or transition temperature Tg600 ℃ or lower, preferably 590 ℃ or lower, more preferably 580 ℃ or lower; and/or degree of wear FAIs 150 to 200, preferably 160 to 190, and more preferably 170 to 185.
The glass preform is made of the optical glass.
And the optical element is made of the optical glass or the glass prefabricated member.
The optical instrument is made of the optical glass or the optical element.
The invention has the beneficial effects that: through reasonable component design, the optical glass has the advantages of 1.65-1.73 refractive index and 25-35 Abbe number, and has excellent chemical stability.
Detailed Description
The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the invention is not limited to this. The optical glass of the present invention may be simply referred to as glass in the following.
[ optical glass ]
The ranges of the respective components of the optical glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
SiO2Is a skeleton of an optical glass, and has a function of maintaining the chemical stability of the glass as a glass network forming bodyAnd the function of improving the devitrification resistance of the glass. When SiO is present2When the content is less than 35%, the above-mentioned effects are hardly obtained, and therefore SiO2The lower limit of the content of (b) is 35%, preferably the lower limit is 37%, more preferably the lower limit is 40%; when SiO is present2When the content of (3) is more than 50%, the glass-melting property is lowered and the transition temperature is raised, so that SiO2The upper limit of the content of (B) is 50%, preferably 47%, more preferably 45%.
TiO2Has the functions of improving the refractive index and dispersion of the glass, can participate in the formation of a glass network, can make the glass more stable and reduce the viscosity of the glass by introducing a proper amount of TiO more than 21 percent2To obtain the above effects, TiO is preferable2The lower limit of the content of (b) is 25%, more preferably the lower limit is 26%; but with a large introduction of TiO2Since the transmittance of the glass in the short wavelength region in the visible light region is lowered and the tendency of the glass to devitrify increases, TiO in the present invention2The upper limit of the content of (B) is 38%, preferably 35%, more preferably 32%.
In some embodiments of the invention, when TiO is used2/SiO2When the amount is less than 0.45, the meltability of the glass is lowered, the striae are deteriorated, and when TiO is used2/SiO2When the amount exceeds 1.0, the chemical stability and optical transmittance of the glass decrease and the density increases, so that TiO in the present invention2/SiO20.45 to 1.0, preferably TiO2/SiO20.5 to 0.9, more preferably TiO2/SiO20.55 to 0.8.
Na2O has the function of improving the meltability of the glass, has obvious effect of improving the melting effect and can also reduce the transformation temperature of the glass, and more than 5 percent of Na is introduced into the invention2O to obtain the above effect, preferably Na2The lower limit of the content of O is 8%, more preferably 10%; when Na is present2The O content exceeds 22%, the chemical stability and weather resistance of the glass are lowered, and therefore Na2The upper limit of the content of O is 22%, preferably 18%, more preferably 16%.
K2O has the function of improving the thermal stability and the melting property of the glass, and the glassIn the invention, more than 1 percent of K is introduced2O to obtain the above effect, preferably K2The lower limit of the content of O is 3%, and K is more preferable2The lower limit of the content of O is 4%; but when K2When the content of O exceeds 12%, the glass is deteriorated in devitrification resistance, so that K is2The upper limit of the content of O is 12%, preferably 10%, more preferably 9%.
Li2O can lower the glass transition temperature, but its content is high, which is disadvantageous in acid resistance stability and thermal expansion coefficient of the glass, and in corrosion of a melting vessel (e.g., platinum crucible), therefore, Li2The content of O is preferably 8% or less, more preferably 4% or less, and further preferably 3% or less. In some embodiments, even small amounts of Li are present2O, which also causes the thermal expansion coefficient of the glass to exceed the design requirements and the devitrification resistance to deteriorate, is more preferably not containing Li2O。
MgO can reduce the refractive index and melting temperature of the glass, but when the MgO is added excessively, the refractive index of the glass cannot meet the design requirement, the devitrification resistance and stability of the glass are reduced, and the cost of the glass is increased. Therefore, the MgO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.
CaO is useful for adjusting the optical constants of the glass and improving the processability of the glass, but when added in an excessive amount, the optical data of the glass is not satisfactory and the devitrification resistance is deteriorated. Therefore, the content of CaO is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 3%, and further preferably no CaO is introduced.
The addition of SrO to glass makes it possible to adjust the refractive index and abbe number of the glass, but if the addition amount is too large, the chemical stability of the glass decreases and the cost of the glass rapidly increases. Therefore, the SrO content is limited to 0 to 10%, preferably 0 to 5%, and more preferably 0 to 3%.
BaO is an essential component for adjusting the refractive index of the glass, improving the transmittance and strength of the glass in the present invention, and the effect is not significant when the content thereof is less than 1%, preferably the lower limit of the content of BaO is 2%, more preferably the lower limit of the content of BaO is 3%; however, if the content exceeds 15%, the devitrification resistance and chemical stability of the glass are deteriorated. Therefore, the upper limit of the BaO content is 15%, preferably 10%, more preferably 9%.
Nb2O5Is a high-refraction high-dispersion component, is an optional component in the invention, and controls Nb2O5The content of (A) is 10% or less, and deterioration of devitrification resistance and thermal stability of the glass can be suppressed. Therefore, Nb in the optical glass of the present invention2O5The content of (b) is 10% or less, preferably 7% or less, more preferably 3% or less.
In the present invention, (Nb) is2O5+K2O)/SiO2Below 0.02, the glass-melting properties deteriorate and the transition temperature rises, if (Nb)2O5+K2O)/SiO2If the amount exceeds 0.45, the thermal expansion coefficient of the glass increases and the chemical stability decreases. Thus, (Nb)2O5+K2O)/SiO2Is in the range of 0.02 to 0.45, preferably (Nb)2O5+K2O)/SiO2Is in the range of 0.05 to 0.35, more preferably (Nb)2O5+K2O)/SiO2The range of (A) is 0.08 to 0.25.
In some embodiments of the invention, if TiO2/(BaO+Nb2O5) Below 1.5, the degree of abrasion of the glass is not satisfactory, the thermal stability and devitrification resistance are reduced, and if TiO is used2/(BaO+Nb2O5) When the amount exceeds 10.0, the thermal expansion coefficient of the glass increases and the optical transmittance decreases. Thus, TiO2/(BaO+Nb2O5) In the range of 1.5 to 10.0, preferably TiO2/(BaO+Nb2O5) In the range of 2.0 to 8.0, more preferably TiO2/(BaO+Nb2O5) The range of (A) is 2.5 to 6.0.
In some embodiments of the invention, the Nb is modified by2O5/TiO2The content of the glass is controlled to be less than 0.3, so that the optical transmittance and the glass forming stability of the glass can be improved, and the chemical stability of the glass can be optimized, preferably
Nb2O5/TiO2Less than 0.2, the glass is easy to obtainMore preferably Nb, to obtain a suitable degree of abrasion2O5/TiO2Is 0.1 or less.
Al2O3The chemical stability of the glass can be improved to some extent, but the content thereof is too large, and the resistance to devitrification and melting of the glass are lowered, so that the content thereof is 5% or less, preferably 3% or less, and more preferably 1% or less.
B2O3Has an effect of improving the meltability of the glass, but when the content thereof is more than 10%, the chemical stability and devitrification resistance of the glass are lowered. Thus, in the present invention B2O3The upper limit of the content of (B) is 10%, preferably 5%, more preferably 3%. In some embodiments, by not introducing B2O3The desired chemical stability can be obtained.
In some embodiments of the invention, if B2O3/SiO2If it exceeds 0.2, the chemical stability and devitrification resistance of the glass are lowered and the optical transmittance is deteriorated, so that B2O3/SiO2Is 0.2 or less, preferably 0.15 or less, and more preferably 0.1 or less.
Ln2O3Is a component for increasing the refractive index of the glass and increasing the chemical stability of the glass, is an optional component in the optical glass of the present invention, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a). By mixing Ln2O3The content of (b) is controlled to 5% or less, whereby the devitrification resistance of the glass can be improved and a desired refractive index and Abbe number can be obtained. Thus, in the optical glass of the present invention, Ln2O3The upper limit of the content range is 5%, preferably 3%, more preferably 1%.
ZnO is added into the glass of the system of the invention, the refractive index and dispersion of the glass can be adjusted, the transition temperature of the glass is reduced, but when the content of ZnO exceeds 5 percent, the devitrification resistance of the glass is reduced, meanwhile, the high-temperature viscosity is smaller, the forming is difficult, and the thermal expansion coefficient and the refractive index temperature coefficient of the glass are increased. Therefore, in the present invention, the ZnO content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably not contained.
In some embodiments of the present invention, the appropriate abrasion and hardness of the glass can be obtained and the stability against water effect of the glass can be improved by setting (CaO + MgO + ZnO)/BaO to 0.6 or less, preferably 0.4 or less, more preferably 0.2 or less.
ZrO2Is a component having an effect of increasing the refractive index, and when the content thereof is large, the devitrification resistance of the glass is lowered, and ZrO in the present invention2The content of (b) is 5% or less, preferably 3% or less, more preferably 2% or less, and further preferably not incorporated.
In some embodiments of the invention, the (ZrO) is controlled2+K2O)/Na2O is in the range of 0.05-1.0, the melting property and viscosity of the glass can be adjusted, the forming property of the glass is improved, the forming stripes of the glass are reduced, the devitrification resistance of the glass is improved, and (ZrO) is preferred2+K2O)/Na2O is 0.1 to 0.8, more preferably (ZrO)2+K2O)/Na2O is 0.2 to 0.6.
By adding 0-1% of Sb2O3、SnO2SnO and CeO2One or more components in the glass can be used as a clarifying agent to improve the clarifying effect of the glass, and 0-0.5% of the clarifying agent is preferably added. But when Sb is2O3When the content exceeds 1%, the glass tends to have a reduced fining property and the deterioration of the forming mold is promoted by the strong oxidation thereof, so that Sb in the present invention is2O3The amount of (B) is 1% or less, preferably 0.5% or less. SnO2SnO may be added as a fining agent, but when the content exceeds 1%, the glass is colored, or when the glass is heated, softened and press-molded again, Sn tends to become a starting point of nucleation and devitrification occurs, so that the SnO of the present invention2And SnO are contained in an amount of 1% or less, preferably 0.5% or less, and more preferably not contained. CeO (CeO)2Action and addition amount ratio of (B) and SnO2The content is 1% or less, preferably 0.5% or lessIt is more preferable that no component is contained.
In order that the glass of the present invention is excellent in chemical stability and abrasion resistance and low in transition temperature and thermal expansion coefficient while attaining a desired refractive index and Abbe number, TiO is preferable2、SiO2、Na2O、K2The total content of O and BaO is 96% or more, and TiO is more preferable2、SiO2、Na2O、K2The total content of O and BaO is 97% or more, and TiO is more preferable2、SiO2、Na2O、K2The total content of O and BaO is 98% or more.
Other components not mentioned above, such as P, can be added as necessary within the range not impairing the characteristics of the glass of the present invention2O5、GeO2、TeO2、Bi2O3、Ta2O5And Ga2O3The upper limit of the content of the above components, which are contained singly or in combination, is preferably 5%, more preferably 3%, still more preferably 1%, and yet still more preferably not contained. In some embodiments of the invention, WO3Since the incorporation of (A) causes deterioration in devitrification resistance and coloring degree of the glass, WO is preferably not contained3。
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As2O3And PbO. Although As2O3Has the effects of eliminating bubbles and better preventing the glass from coloring, but As2O3The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace.
The term "not introduced", "not containing" or "0%" as used herein means that the compound, molecule or element is not intentionally added as a raw material to the optical glass of the present invention; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (nd) and Abbe number (. nu.) of optical glassd) The test was carried out according to the method specified in GB/T7962.1-2010.
The refractive index (nd) of the optical glass is 1.65-1.73, preferably 1.66-1.72, more preferably 1.67-1.71; abbe number (v)d) 25 to 35, preferably 28 to 33, and more preferably 29 to 32.
< stability against acid Effect >
Stability of acid resistance of optical glasses (D)A) (powder method) the test was carried out according to the method prescribed in GB/T17129.
Stability of acid resistance of the optical glass of the present invention (D)A) Is 2 or more, preferably 1.
< stability against Water action >
Water-resistant stabilization of optical glassesSex (D)W) (powder method) the test was carried out according to the method prescribed in GB/T17129.
Stability to Water action of the optical glass of the invention (D)W) Is 2 or more, preferably 1.
< Density >
The density (. rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
The optical glass of the present invention has a density (. rho.) of 3.2g/cm3Hereinafter, it is preferably 3.1g/cm3Hereinafter, more preferably 3.0g/cm3The following.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass-30/70℃) And testing data at-30-70 ℃ according to a method specified in GB/T7962.16-2010.
The coefficient of thermal expansion (. alpha.) of the optical glass of the present invention-30/70℃) Is 98 x 10-7Preferably 96X 10 or less,/K-7A value of less than or equal to K, more preferably 93X 10-7and/K is less than or equal to.
< transition temperature >
Transition temperature (T) of optical glassg) The test was carried out according to the method specified in GB/T7962.16-2010.
Transition temperature (T) of the optical glass of the present inventiong) Is 600 ℃ or lower, preferably 590 ℃ or lower, and more preferably 580 ℃ or lower.
< degree of abrasion >
Degree of abrasion (F) of optical glassA) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:
FA＝V/V0×100＝(W/ρ)/(W0/ρ0)×100
in the formula: v is the volume abrasion amount of the sample to be measured;
V0-the amount of wear of the standard sample volume;
w is the abrasion loss of the quality of the sample to be measured;
W0-abrasion loss of standard sample mass;
rho is the density of the sample to be measured;
ρ0-standard sample density.
Degree of abrasion (F) of optical glass of the present inventionA) Is 150 to 200, preferably 160 to 190, and more preferably 170 to 185.
< degree of bubbling >
The bubble degree of the optical glass is tested according to the method specified in GB/T7962.8-2010.
The optical glass of the present invention has a bubble degree of B class or more, preferably A class or more, more preferably A class0More than grade.
[ production method ]
The method for manufacturing the optical glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1100-1350 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Glass preform and optical element
The glass preform can be produced from the optical glass produced by, for example, grinding or press molding such as reheat press molding or precision press molding. That is, the glass preform may be produced by machining the optical glass by grinding, polishing, or the like, or by producing a preform for press molding from the optical glass, subjecting the preform to reheat press molding, and then polishing, or by precision press molding the preform obtained by polishing.
It should be noted that the means for producing the glass preform is not limited to the above means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, display equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 1 to 2 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.
TABLE 1
Figure BDA0002138393670000121
Figure BDA0002138393670000131
TABLE 2
Figure BDA0002138393670000132
Figure BDA0002138393670000141
< glass preform example >
Various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens and a plano-concave lens, and preforms such as prisms were produced from the glasses obtained in examples 1 to 20 of optical glass by means of polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
The preforms obtained in the above examples of glass preforms were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to desired values.
Next, each preform is ground and polished to produce various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, and prisms. The surface of the resulting optical element may be coated with an antireflection film.
< optical Instrument example >
The optical element obtained by the above-described optical element embodiment is used for, for example, imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automobile field, photolithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or for image pickup devices and apparatuses in the vehicle-mounted field, by forming an optical component or an optical assembly by using one or more optical elements through optical design.

Claims (20)

1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 22：35～50％；TiO2：21～38％；Na2O：5～22％；K2O：1～12％；BaO：1～15％；Nb2O5: 0 to 10% of (Nb)2O5+K2O)/SiO20.02 to 0.45 of TiO2/(BaO+Nb2O5) 1.5 to 6.815, TiO2/SiO20.45 to 0.935, and (CaO + MgO + ZnO)/BaO is 0.245 or less.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: b is2O3: 0 to 10 percent; and/or SrO: 0 to 10 percent; and/or CaO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or Ln2O3: 0 to 5 percent; and/or ZrO2: 0 to 5 percent; and/or Li2O: 0-8%; and/or Al2O3: 0 to 5 percent; and/or ZnO: 0 to 5 percent; and/or Sb2O3: 0 to 1%, wherein Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
3. Optical glass, characterized in that its composition, expressed in weight percentage, is represented by SiO2：35～50％；TiO2：21～38％；Na2O：5～22％；K2O：1～12％；BaO：1～15％；Nb2O5：0～10％；B2O3：0～10％；SrO：0～10％；CaO：0～10％；MgO：0～10％；Ln2O3：0～5％；ZrO2：0～5％；Li2O：0～8％；Al2O3：0～5％；ZnO：0～5％；Sb2O3: 0 to 1% of a composition of (Nb)2O5+K2O)/SiO20.02 to 0.45 of TiO2/(BaO+Nb2O5) 1.5 to 6.815, TiO2/SiO20.45 to 0.935, (CaO + MgO + ZnO)/BaO of 0.245 or less, the Ln2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
4. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: b is2O3/SiO2Is 0.2 or less; and/or (ZrO)2+K2O)/Na2O is 0.05 to 1.0; and/or Nb2O5/TiO2Is 0.3 or less.
5. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 22: 37-47%; and/or TiO2: 25-35%; and/or Na2O: 8-18%; and/or BaO: 2-10%; and/or Nb2O5: 0 to 7 percent; and/or K2O: 3-10%; and/or B2O3: 0 to 5 percent; and/or SrO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or MgO: 0 to 5 percent; and/or Ln2O3: 0 to 3 percent; and/or ZrO2: 0 to 3 percent; and/or Li2O: 0 to 4 percent; and/or Al2O3: 0 to 3 percent; and/or ZnO: 0 to 3 percent; and/or Sb2O3: 0 to 0.5%, wherein Ln is2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
6. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: TiO 22/SiO20.5 to 0.9; and/or B2O3/SiO2Is less than 0.15; and/or (ZrO)2+K2O)/Na2O is 0.1 to 0.8; and/or (Nb)2O5+K2O)/SiO20.05 to 0.35; and/or Nb2O5/TiO2Is 0.2 or less; and/or TiO2/(BaO+Nb2O5) Is 2.0 to 6.815.
7. An optical glass according to any one of claims 1 to 3, wherein the composition is expressed in weight percent, wherein: SiO 22: 40-45%; and/or TiO2: 26-32%; and/or Na2O: 10-16%; and/or BaO: 3-9%; and/or Nb2O5: 0 to 3 percent; and/or K2O: 4-9%; and/or B2O3: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or Ln2O3: 0 to 1 percent; and/or ZrO2: 0-2%; and/or Li2O: 0 to 3 percent; and/or Al2O3: 0 to 1 percent; and/or ZnO: 0 to 1%, wherein Ln is2O3Is La2O3、Gd2O3、Y2O3、Yb2O3One or more of (a).
8. An optical glass according to any one of claims 1 to 3, wherein the components are present in an amount, expressed as a percentage by weight, that satisfies one or more of the following 7 conditions: TiO 22/SiO20.55 to 0.8; and/or B2O3/SiO2Is 0.1 or less; and/or (ZrO)2+K2O)/Na2O is 0.2 to 0.6; and/or (Nb)2O5+K2O)/SiO20.08 to 0.25; and/or Nb2O5/TiO2Is 0.1 or less; and/or (CaO + MgO + ZnO)/BaO is 0.2 or less; and/or TiO2/(BaO+Nb2O5) 2.5 to 6.0.
9. An optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, is TiO2、SiO2、Na2O、K2The total content of O and BaO is 96% or more.
10. An optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, is TiO2、SiO2、Na2O、K2The total content of O and BaO is 97% or more.
11. An optical glass according to any one of claims 1 to 3, characterised in that its composition, expressed in weight percentage, is TiO2、SiO2、Na2O、K2The total content of O and BaO is 98% or more.
12. An optical glass according to any one of claims 1 to 3, wherein the refractive index nd of the optical glass is 1.65 to 1.73; abbe number vdIs 25 to 35.
13. An optical glass according to any one of claims 1 to 3, wherein the refractive index nd of the optical glass is 1.66 to 1.72; abbe number vd28 to 33.
14. An optical glass according to any one of claims 1 to 3, wherein the refractive index nd of the optical glass is 1.67 to 1.71; abbe number vdIs 29 to 32.
15. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a stability to acid effects DAIs more than 2 types; and/or stability against water action DWIs more than 2 types; and/or a density rho of 3.2g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 98 x 10-7below/K; and/or transition temperature TgBelow 600 ℃; and/or degree of wear FAIs 150 to 200.
16. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a stability to acid effects DAIs of type 1; and/or stability against water action DWIs of type 1; and/or a density rho of 3.1g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 96 multiplied by 10-7below/K; and/or transition temperature TgBelow 590 ℃; and/or degree of wear FAIs 160 to 190.
17. An optical glass according to any one of claims 1 to 3, wherein the optical glass has a density p of 3.0g/cm3The following; and/or coefficient of thermal expansion alpha-30/70℃Is 93 x 10-7below/K; and/or transition temperature TgBelow 580 ℃; and/or degree of wear FA170 to 185.
18. A glass preform made of the optical glass according to any one of claims 1 to 17.
19. An optical element produced from the optical glass according to any one of claims 1 to 17 or the glass preform according to claim 18.
20. An optical device produced by using the optical glass according to any one of claims 1 to 17 or the optical element according to claim 19.
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