CN107879620B - Optical glass, glass preform and optical element - Google Patents

Optical glass, glass preform and optical element Download PDF

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CN107879620B
CN107879620B CN201610861598.2A CN201610861598A CN107879620B CN 107879620 B CN107879620 B CN 107879620B CN 201610861598 A CN201610861598 A CN 201610861598A CN 107879620 B CN107879620 B CN 107879620B
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optical glass
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CN107879620A (en
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匡波
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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
    • C03C3/062—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
    • G02B3/00—Simple or compound lenses

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a high-refraction low-dispersion optical glass with low cost, a refractive index of 1.77-1.85 and an Abbe number of 40-48. The optical glass has a refractive index of 1.77-1.85 and an Abbe number of 40-48, and comprises the following components in percentage by weight: SiO 22+B2O3：15‑40％；La2O3+Gd2O3+Y2O3：35‑70％；WO3+Nb2O5+ZrO2+TiO2：1‑30％；ZnO：11‑30％；Nb2O5/Gd2O3Is 0.01-0.45. The invention reduces Ta2O5The raw material cost is optimized; the optical glass of the present invention facilitates precision press-molding while achieving desired optical constants by reasonable composition design, and has excellent chemical stability, and a glass preform and an optical element formed from the optical glass.

Description

Optical glass, glass preform and optical element
Technical Field
The invention relates to high-refraction low-dispersion optical glass, in particular to low-cost high-refraction low-dispersion optical glass and an optical element.
Background
In recent years, with the rapid progress of digitization and high precision of optical systems, there has been an increasing demand for reducing the number of optical elements such as lenses and prisms used in the optical systems and reducing the weight and size of the entire optical systems in photographic equipment such as digital cameras and video cameras, and optical equipment such as image reproducing (projection) equipment such as projectors and projection televisions. In designing an optical system, a glass having a high refractive index or an aspherical lens is widely used to achieve miniaturization, ultra-thinning, and wide-angle, and the optical system is made lightweight and high-performance and the chromatic aberration is more easily corrected.
The early-stage manufactured high-refraction low-dispersion glass contains a large amount of Ta2O5An optical glass having a refractive index of 1.75 to 1.85 and an Abbe number of 34 to 44 as disclosed in CN1876589A, which contains more than 15% but less than 35% of Ta2O5. Tantalum being a rare metal, Ta2O5The use of (2) is extremely disadvantageous in terms of product cost control, and thus the use of Ta is reduced or eliminated in high refractive low dispersion glass compositions2O5The method becomes a research and development target of optical glass research and development workers.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the high-refraction low-dispersion optical glass with low cost, the refractive index of 1.77-1.85 and the Abbe number of 40-48.
The present invention also provides a glass preform and an optical element formed of the above optical glass.
The technical scheme adopted by the invention for solving the technical problem is as follows: an optical glass having a refractive index (nd) of 1.77 to 1.85 and an Abbe number (vd) of 40 to 48, and having a composition comprising, in weight percent: SiO 22+B2O3：15-40％；La2O3+Gd2O3+Y2O3：35-70％；WO3+Nb2O5+ZrO2+TiO2：1-30％；ZnO：11-30％；Nb2O5/Gd2O3Is 0.01-0.45.
Further, the composition of the material also comprises the following components in percentage by weight: al (Al)2O3：0-10％；Ta2O5：0-8％；Rn2O: 0-10% of (wherein Rn)2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-10%, wherein RO is one or more of MgO, CaO, SrO or BaO.
Further, SiO2+B2O3: 18 to 38 percent; and/or La2O3+Gd2O3+Y2O3: 35 to 65 percent; and/or WO3+Nb2O5+ZrO2+TiO2：2-20％；Rn2O: 0-5%, wherein Rn2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-5%, wherein RO is one or more of MgO, CaO, SrO or BaO.
Further, SiO2+B2O3: 20 to 35 percent; and/or La2O3+Gd2O3+Y2O3: 38 to 60 percent; and/or WO3+Nb2O5+ZrO2+TiO2：4-15％；Rn2O: 0-2% of (wherein Rn)2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-1%, wherein RO is one or more of MgO, CaO, SrO or BaO.
Further, the content of each component meets one or more than one of the following 9 conditions:
1)Ta2O5/Nb2O5: less than 1;
2)ZnO/(SiO2+B2O3) 0.3 to 2;
3)Gd2O3/(La2O3+Gd2O3+Y2O3) 0.2-0.55;
4)SiO2/(SiO2+B2O3) 0.2-0.6;
5)Nb2O5/Gd2O30.01-0.4;
6)(WO3+Ta2O5+Nb2O5)/(ZrO2+TiO2) 0.1 to 5;
7)Nb2O50.01-0.5 of/ZnO;
8)TiO2/(TiO2+Nb2O5) 0.01-0.8;
9)ZnO/(WO3+Ta2O5+Nb2O5+TiO2) Is 1.8 or more.
Further, wherein: nb2O5+ZrO2+TiO2：1-25％。
Further, wherein: nb2O5: greater than 0 but less than or equal to 8%; ZrO (ZrO)2: greater than 0 but less than or equal to 15%; TiO 22：0-8％；WO3：0-15％。
Further, wherein: la2O3：20-40％；Gd2O3：11-30％；Y2O3：0-15％。
Further, wherein: SiO 22：4-20％；B2O3：8-24％；Li2O：0-2％；Na2O：0-10％；K2O：0-10％。
Further, wherein: SiO 22: 5 to 18 percent; and/or B2O3: 10 to 23 percent; and/or La2O3: 20 to 35 percent; and/or Gd2O3: 11 to 25 percent; and/or Y2O3: 0 to 10 percent; and/or WO3: 0 to 10 percent; and/or Ta2O5: 0 to 5 percent; and/or Nb2O5: 0.1-6%; and/or ZrO2: 1 to 10 percent; and/or ZnO: 15 to 30 percent; and/or TiO2: 0 to 5; and/or Al2O3: 0 to 5 percent; and/or Li2O: 0 to 1 percent; and/or Na2O: 0 to 5 percent; and/or K2O: 0 to 5 percent; and/or Sb2O3: 0 to 0.5 percent; and/or RO: 0-5%, wherein RO is one or more of MgO, CaO, SrO or BaO.
Further, wherein: SiO 22: 6 to 15 percent; and/or B2O3: 12 to 20 percent; and/or La2O3: 22 to 32 percent; and/or Gd2O3: 12 to 22 percent; and/or Y2O3: 0 to 8 percent; and/or WO3: 0 to 7 percent; and/or ZrO2: 2 to 8 percent; and/or ZnO: 15 to 25 percent; and/or TiO2：0-2％。
Further, wherein: ta2O5/Nb2O5: less than 0.8; and/or ZnO/(SiO)2+B2O3) 0.5 to 1.8; and/or Gd2O3/(La2O3+Gd2O3+Y2O3) 0.25 to 0.5; and/or SiO2/(SiO2+B2O3) 0.23 to 0.5; and/or Nb2O5/Gd2O30.02-0.35; and/or (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) 0.1 to 3; and/or Nb2O5The content of/ZnO is 0.02-0.35; and/or TiO2/(TiO2+Nb2O5) 0.05-0.7; and/or ZnO/(WO)3+Ta2O5+Nb2O5+TiO2) Is 3-15.
Further, wherein: ta2O5/Nb2O5: less than 0.5; ZnO/(SiO)2+B2O3) 0.5-1.45; and/or Gd2O3/(La2O3+Gd2O3+Y2O3) 0.25-0.45; and/or SiO2/(SiO2+B2O3) 0.25-0.45; and/or Nb2O5/Gd2O30.05-0.25; and/or (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) 0.1 to 1; and/or Nb2O50.03-0.25 of/ZnO; and/or TiO2/(TiO2+Nb2O5) 0.1-0.6; and/or ZnO/(WO)3+Ta2O5+Nb2O5+TiO2) Is 4-12.
Further, wherein: nb2O5+ZrO2+TiO2：2-20％；La2O3+Gd2O3+Y2O3：40-55％。
Further, wherein: nb2O5+ZrO2+TiO2：4-15％。
Further, wherein: SiO 22、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、WO3、ZrO2And ZnO in a total content of 95% or more, and does not contain Ta2O5。
Further, wherein: SiO 22、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、ZrO2And ZnO in a total amount of 99% or more.
Further, the composition comprises the following components in percentage by weight:
Yb2O3：0-10％；
P2O5：0-10％；
Bi2O3：0-10％；
TeO2：0-10％；
Ga2O3:0-10％；
Lu2O3:0-10％；
GeO2：0-8％；
CeO2：0-1％；
SnO2：0-1％；
Sb2O3：0-1％；
F：0-10％。
further, the composition comprises the following components in percentage by weight:
Yb2O3：0-5％；
P2O5：0-5％；
Bi2O3：0-5％；
TeO2：0-5％；
Ga2O3:0-5％；
Lu2O3:0-5％；
GeO2：0-5％；
CeO2：0-0.5％；
SnO2：0-0.5％；
Sb2O3：0-1％；
F：0-5％。
further, the wavelength λ corresponding to the transmittance of the glass of 80%80Is below 410nm, and the corresponding wavelength lambda is when the transmittance reaches 5%5Is 350nm or less; the upper limit temperature of crystallization is below 1160 ℃; a glass transition temperature (Tg) of 630 ℃ or lower; the density (. rho.) of the glass was 5.00g/cm3The following.
Further, the wavelength λ corresponding to the transmittance of the glass of 80%80A wavelength lambda corresponding to a transmittance of 5% below 400nm5Is below 340 nm; the upper limit temperature of crystallization is below 1150 ℃; a glass transition temperature (Tg) of 620 ℃ or lower; the density (. rho.) of the glass was 4.90g/cm3The following
The glass preform is made of the optical glass.
The optical element is made of the optical glass.
The invention has the beneficial effects that: by lowering Ta2O5The raw material cost is optimized; the optical glass of the present invention facilitates precision press-molding while achieving desired optical constants by reasonable composition design, and has excellent chemical stability, and a glass preform and an optical element formed from the optical glass.
Detailed Description
I, optical glass
The optical glass of the invention reduces or even does not contain expensive Ta based on the consideration of reducing the cost of raw materials2O5And (3) obtaining the high-refractive-index low-dispersion optical glass with the refractive index of 1.77-1.85 and the Abbe number of 40-48.
The composition of the optical glass of the present invention will be described in detail below, and the content and total content of each glass component are expressed by weight percent unless otherwise specified. In the following description, when a value equal to or less than a predetermined value or a value equal to or greater than the predetermined value is mentioned, the predetermined value is also included.
B2O3Is a glass network forming component, has the functions of improving glass meltability and devitrification resistance and reducing glass transition temperature and density, and in order to achieve the above-mentioned effects, the invention introduces more than 8% of B2O3Preferably, more than 10% of B is introduced2O3More preferably, 12% or more of B is introduced2O3(ii) a However, when the amount of incorporation exceeds 24%, the glass stability is lowered and the refractive index is lowered, so that the high refractive index of the present invention cannot be obtained, and therefore, B of the present invention2O3The upper limit of the content of (b) is 24%, preferably 23%, more preferably 20%.
SiO2Also a glass former, with B2O3The loose chain-like layered networks formed are different, SiO2The three-dimensional network of silicon-oxygen tetrahedrons is formed in the glass, and is very compact and firm. Such networks are incorporated into glass for loose boroxine [ BO ]3]The network is reinforced to be compact, so that the high-temperature viscosity of the glass is improved, meanwhile, the addition of the silicon-oxygen tetrahedral three-dimensional network enhances the capability of the glass network for isolating crystallization cations such as La, Nb and Li, the crystallization threshold is increased, so that the crystallization resistance of the glass is improved, and SiO in the glass provided by the invention2The lower limit of the content is 4%, preferably 5%, more preferably 6%; if SiO2Since an excessively large content of (b) increases the glass transition temperature and lowers the glass meltability, the upper limit of the content is 20%, preferably 18%, and more preferably 15%.
B2O3And SiO2Are all glass network forming components, and when the total content of the glass network forming components is less than 15%, the crystallization tendency is increased, and stable glass cannot be obtained; when the total content thereof exceeds 40%, the optical constants of the glass may be lower than the designed values. Thus, B2O3And SiO2Total content of (B)2O3+SiO2) 15-40%, preferably 18-38%, more preferably 20-35%. In addition, the invention controls SiO2Content of (D) and SiO2And B2O3Ratio of the total content of (A) SiO2/(SiO2+B2O3) Within 0.2-0.6, the meltability of the glass can be ensured, and the stability and high-temperature viscosity of the glass can be effectively increased, especially when the SiO is2/(SiO2+B2O3) When the value is 0.23 to 0.5, the devitrification resistance of the glass can be effectively improved while maintaining the high-refractive low-dispersion optical characteristics and the low-transition temperature characteristics of the glass, and more preferably 0.25 to 0.45.
In the present invention, La2O3、Gd2O3、Y2O3Can increase the refractive index of the glass, and when the total content is less than 35%, the desired optical constants cannot be obtained, and when the total content exceeds 70%, the stability and devitrification resistance of the glass are lowered, and thus La2O3、Gd2O3、Y2O3Total content of (La)2O3+Gd2O3+Y2O3) 35 to 70%, preferably 35 to 65%, more preferably 38 to 60%, and still more preferably 40 to 55%.
La2O3Is an essential component for obtaining the desired optical properties of the present invention, in the formulation system of the present invention, B2O3And La2O3The glass can effectively improve the devitrification resistance of the glass and improve the chemical stability of the glass. When La2O3When the content of (b) is less than 20%, it is difficult to realize desired optical characteristics; however, when the content exceeds 40%, both devitrification resistance and melting property of the glass deteriorate. Thus, the La of the present invention2O3The content of (B) is 20 to 40%, preferably in the range of 20 to 35%, more preferably in the range of 22 to 32%.
Gd2O3Can increase the refractive index of the glass without significantly improving the dispersion of the glass, and in the present invention, 11% or more of Gd is introduced2O3And La2O3Coexisting, the stability of the formed glass can be improved, the chemical stability of the glass is obviously enhanced, and the excessive increase of the Abbe number is controlled while the refractive index is maintained; if the content exceeds 30%, the devitrification resistance of the glass decreases and the density of the glass tends to increase. Thus, Gd of the present invention2O3The content of (B) is 11 to 30%, preferably in the range of 11 to 25%, more preferably in the range of 12 to 22%.
The component with high refraction and low dispersion of the invention is preferably also introduced into Y2O3While the glass material cost is suppressed from increasing while maintaining a high refractive index and a high abbe number, the glass melting property and devitrification resistance are improved, and the glass crystallization upper limit temperature and specific gravity are lowered, if the content exceeds 15%, the glass stability and devitrification resistance are lowered. Thus, Y2O3The content is in the range of 0 to 15%, preferably in the range of 0 to 10%, more preferably in the range of 0 to 8%.
In the present invention La2O3And Gd2O3Coexistence; or preferably La2O3、Gd2O3And Y2O3Coexistence; more preferably Gd2O3/(La2O3+Gd2O3+Y2O3) In the range of 0.2 to 0.55, Gd is more preferable2O3/(La2O3+Gd2O3+Y2O3) In the range of 0.25 to 0.5, Gd is more preferable2O3/(La2O3+Gd2O3+Y2O3) The range of 0.25-0.45 can maximally overcome the defect of reducing or not using Ta2O5The adverse effect of lowering the glass stability is that a glass having a high refractive index and low dispersion and excellent glass stability is obtained and the glass is not easily colored.
Yb2O3And is a component imparting high-refractivity, low-dispersion properties, and when it is incorporated in an amount exceeding 10%, the devitrification resistance of the glass is lowered, so that the content thereof is limited to 0 to 10%, preferably 0 to 5%.
In the glass of the present invention, Nb2O5When the content exceeds 0, the glass composition has an excellent effect of lowering the liquidus temperature, and also has the effect of improving the refractive index, crystallization resistance and chemical durability of the glass without deteriorating the transmittance, and a suitable amount of Nb2O5The anti-devitrification performance of the glass can be effectively improved in the precise mould pressing process; if the content exceeds 8%, the glass dispersion increases and the optical characteristics of the glass of the present invention cannot be achieved. Thus, Nb2O5The content of (B) is in the range of more than 0 but 8% or less, preferably in the range of 0.1 to 6%. The research of the inventor finds that the Nb in the glass of the invention2O5Content and Gd2O3Ratio of contents Nb2O5/Gd2O3When it is 0.01 to 0.45, the chemical durability and devitrification resistance of the glass can be remarkably improved, particularly when Nb is added2O5/Gd2O3The effect is particularly remarkable when the amount is 0.01 to 0.4, more preferably 0.02 to 0.35, and still more preferably 0.05 to 0.25.
Ta2O5The refractive index, resistance to devitrification and viscosity of the molten glass can be increased, but they are expensive and do not contribute to the deterioration of the glassThe content is limited to 8% or less, preferably 5% or less, more preferably 1% or less, and further preferably not added, because this contributes to the reduction of the cost of raw materials.
Control of Ta in the optical glass of the invention2O5/Nb2O5A value of less than 1 is preferable for improving the devitrification resistance of the glass while effectively adjusting the refractive index and dispersion, and for containing an easily coloring component in the glass2O5/Nb2O5A value of less than 0.8 is effective for improving the coloring property of the glass, and Ta is more preferable2O5/Nb2O5A value of less than 0.5, more preferably Ta2O5/Nb2O5Is less than 0.3.
ZnO is added into the glass of the system, so that the refractive index and dispersion of the glass can be adjusted, the devitrification resistance of the glass is improved, the transition temperature of the glass is reduced, and the stability of the glass is improved. ZnO can also reduce the high-temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, and the transmittance of the glass can be improved. Particularly, when the glass of the present invention contains a small amount of tantalum oxide or even does not contain tantalum oxide, the decrease in optical constant can be compensated to some extent by introducing ZnO of 11% or more. However, if the amount of ZnO added is too large, the devitrification resistance of the glass is lowered, and the high-temperature viscosity is small, which makes molding difficult. In the glass system of the invention, if the content of ZnO is lower than 11 percent, the Tg temperature can not meet the design requirement; if the content is more than 30%, the devitrification resistance of the glass is reduced, and the high-temperature viscosity cannot meet the design requirement. Therefore, the lower limit of the content of ZnO is defined to be 11%, and the preferable lower limit is 15%; the upper limit of the content of ZnO is limited to 30%, and the preferred upper limit is 25%.
In order to obtain glass with low Tg temperature, good stability and easy melting, the inventor finds that when ZnO/(B)2O3+SiO2) In the range of 0.3 to 2, preferably ZnO/(B)2O3+SiO2) The ratio of (A) to (B) is in the range of 0.5 to 1.8, and ZnO/(B) is more preferable2O3+SiO2) In the range of 0.5 to 1.45, glass stability and Tg temperatureThe best balance can be achieved, and products with better quality can be obtained.
Meanwhile, in order to make the glass have excellent anti-devitrification performance under the condition of having a proper Tg temperature, Nb is preferably controlled2O5The value of/ZnO is in the range of 0.01 to 0.5, more preferably 0.02 to 0.35, still more preferably 0.03 to 0.25.
ZrO2The oxide is a high-refraction low-dispersion oxide, and can improve the refractive index of the glass and adjust the dispersion when added into the glass. At the same time, an appropriate amount of ZrO2When the glass is added, the devitrification resistance and the glass forming stability of the glass can be improved. In the present invention, if the content is more than 15%, the glass becomes hard to melt, the melting temperature increases, and inclusions in the glass and the transmittance thereof tend to decrease. Therefore, the content thereof is set to be more than 0 but 15% or less, preferably 1 to 10%, and more preferably 2 to 8%.
TiO2The glass is a high-refraction high-dispersion oxide, and the refractive index and the dispersion of the glass can be obviously improved by adding the oxide into the glass. The inventor finds that proper amount of TiO is added2In the glass of the present invention, the glass stability, especially the devitrification resistance, can be increased. But if too much TiO2When added to glass, the objective of low dispersion development is difficult to achieve, and the glass has a significantly reduced transmittance and deteriorated stability. Thus TiO2The content of (B) is 0 to 8%, preferably 0 to 5%, and more preferably 0 to 2%. In the present invention, TiO is preferably used2/(TiO2+Nb2O5) The value of (A) is controlled to be 0.01 to 0.8, the devitrification performance and chemical durability of the glass can be effectively adjusted, and TiO is more preferable2/(TiO2+Nb2O5) 0.05 to 0.7, and TiO is more preferable2/(TiO2+Nb2O5) Is 0.1-0.6.
WO3The main role of glass is to maintain optical constants and improve glass devitrification, but too high a content thereof lowers glass transmittance, increases coloring degree, and deteriorates devitrification performance. Therefore, WO3The content of (b) is preferably 0 to 15%, more preferably 0 to 10%, and still more preferably 0 to 7%.
WO3、Nb2O5、ZrO2、TiO2It is advantageous for maintaining the optical constants of the glass when the total content thereof is (WO)3+Nb2O5+ZrO2+TiO2) When the content is 1-30%, the devitrification resistance of the glass can be obviously improved, preferably 2-20%, and more preferably 4-15%; especially when Nb2O5、ZrO2、TiO2Total amount (Nb)2O5+ZrO2+TiO2) In the range of 1 to 25%, the chemical durability and glass forming property of the glass can be further optimized, and the total amount is preferably 2 to 20%, more preferably 4 to 15%.
WO3And TiO2The excessive introduction of the (D) can reduce the transmittance of the glass, but the two have better effects on the devitrification resistance of the glass, and the inventor finds that (WO) is the best for the optical glass of the system3+Ta2O5+Nb2O5)/(ZrO2+TiO2) When the concentration is controlled within the range of 0.1 to 5, the balance between the transmittance and the crystallization performance can be well satisfied, and the chemical stability of the glass can be further optimized, preferably (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) A value of (B) is 0.1 to 3, more preferably (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) Has a value of 0.1 to 1. Particularly, the inventor discovers that ZnO/(WO) is controlled by a large amount of experimental researches to ensure that glass has good transmittance and low cost while having excellent anti-devitrification performance and optical characteristics of high refraction and low dispersion3+Ta2O5+Nb2O5+TiO2) The above object can be achieved at 1.8 or more, preferably 3 to 15, and more preferably 4 to 12.
Introducing small amount of Al2O3The Al of the present invention can improve the stability and chemical stability of the formed glass, but when the content exceeds 10%, the glass tends to be deteriorated in melting property and to be reduced in devitrification resistance, so that the Al of the present invention2O3The content of (B) is 0 to 10%, preferably 0 to 5%, more preferably 0 to 1%, further preferably not incorporated.
Rn2O is selected from Li2O、Na2O、K2O, which can improve the melting properties of the glass and lower the Tg temperature of the glass. When Rn in glass2When the O content is 10% or less, Rn is stable in devitrification resistance because the glass refractive index is not easily lowered2The O content is limited to 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%.
Li2O is added to the glass component and is effective to lower the Tg of the glass. However, low softening point optical glasses are typically melted using platinum or platinum alloy vessels, and during the high temperature melting process, Li in the glass composition+The platinum or platinum alloy vessel is easy to corrode, and the finished glass generates more platinum-containing foreign matters, thereby causing the quality of the glass to be reduced. In the present invention, more than 2% of Li is contained2Since O drastically lowers the devitrification property of the glass, the content thereof is limited to 0 to 2%, preferably 0 to 1%.
Na2O and K2O is an optional component effective for lowering Tg, and if the content is too large, devitrification temperature is likely to rise and vitrification is difficult, so the content is limited to 0 to 10%, more preferably 0 to 5%, and still more preferably 0 to 1%, respectively.
RO (RO is one or more of MgO, CaO, SrO and BaO) improves the meltability of the glass and adjusts the glass gloss, but when the content thereof exceeds 10%, the devitrification resistance of the glass is lowered, so that in the present invention, the RO content is 0 to 10%, more preferably in the range of 0 to 5%, further preferably 0 to 1%, and further preferably not incorporated.
P2O5Is an optional component which can improve the devitrification resistance of the glass, particularly by reacting P2O5The content of (A) is 10% or less, and the reduction of the chemical durability, particularly the water resistance, of the glass can be suppressed. Therefore, the content is limited to 10% or less, preferably 5% or less, more preferably 3% or less, and further preferably not incorporated, based on the total mass of the glass in terms of oxide.
Bi2O3The content is limited to 10% or less, preferably 5% or less, more preferably 1% or less, and even more preferably not incorporated, because the devitrification resistance of the glass is lowered when the content exceeds 10%.
GeO2The component having the effect of increasing the refractive index of the glass and increasing the devitrification resistance is an optional component of the optical glass of the present invention, but the cost is high, and the incorporation of the component too much does not achieve the object of reducing the production cost of the present invention, and therefore the content is limited to 8% or less, preferably 5% or less, further 2% or less, and further, the incorporation is not selected.
In the present invention, if less than 10% of Lu is introduced2O3The glass may be used in combination with other rare earth components to further improve the stability of the glass, but the glass is expensive and the incorporation thereof into the glass is disadvantageous for the reduction of the production cost, so that the content thereof is limited to 10% or less, preferably 5% or less, more preferably 3% or less, and still more preferably not incorporated.
As an optional component of the present invention, by controlling Ga2O3At 10% or less, the devitrification resistance of the glass can be improved and the degree of abrasion of the glass can be increased, so that the content thereof is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and further preferably not incorporated.
TeO2Is an optional component for improving the refractive index of the glass and reducing the transition temperature of the glass, and when the content of the optional component is excessive, the optional component is easy to react with a platinum crucible, which is not favorable for the service life of equipment. Thus TeO2The content is limited to 10% or less, preferably 5% or less, and more preferably not incorporated.
By adding small amounts of Sb2O3、SnO2、CeO2The component can improve the fining effect of the glass, but when Sb is used2O3When the content exceeds 1%, the glass tends to be deteriorated in fining property, and the strong oxidation promotes the corrosion of platinum or platinum alloy vessel for melting glass and the deterioration of forming mold, so that the present inventionBright preference for Sb2O3The amount of (B) is 0 to 1%, more preferably 0 to 0.5%, further preferably not added. SnO2However, when the content exceeds 1%, the glass is colored, or when the glass is heated, softened, press-molded or the like and then re-molded, Sn becomes a starting point of crystal nucleus generation, and thus, devitrification tends to occur. Thus the SnO of the invention2The content of (b) is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably not added. CeO (CeO)2Action and addition amount ratio of (B) and SnO2The content is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no addition.
F is a component effective for lowering the glass transition temperature by lowering the dispersion, but when it is contained excessively, the refractive index of the glass is significantly lowered, the volatility of the glass melt is increased, and the texture is generated during the molding of the glass melt, or the refractive index variation due to volatilization tends to be increased. YF can be used as F as a raw material3、LaF3、GdF3、ZrF4、ZnF2Alkali metal fluoride or alkaline earth metal fluoride. In the present invention, it is preferable that the content of F is 0 to 10%, more preferably 0 to 5%, further preferably not incorporated, based on the total content of the optical glass.
In order to better achieve the object of the invention, the glass preferably comprises the components in percent by weight, preferably SiO2、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、WO3、ZrO2And ZnO in a total content of 95% or more, and does not contain Ta2O5(ii) a More preferably SiO2、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、WO3、ZrO2And ZnO in a total amount of 99% or more; further preferred is SiO2、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、ZrO2And ZnO in a total amount of 99% or more.
[ regarding components that should not be contained ]
If necessary, other components not mentioned above can be added within a range not impairing the characteristics of the glass of the present invention. However, since the glass is colored and absorbs at a specific wavelength in the visible light region even when a small amount of a transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained alone or in combination, thereby reducing the property of the present invention to improve the effect of the visible light transmittance, it is preferable that the optical glass, which requires transmittance at a wavelength in the visible light region, is not substantially contained.
In recent years, cations of Pb, 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.
The properties of the optical glass of the present invention will be described below.
[ optical constants of optical glass ]
The optical glass is high-refractivity low-dispersion glass, and a lens made of the high-refractivity low-dispersion glass is combined with a lens made of the high-refractivity high-dispersion glass in many cases and is used for chromatic aberration correction. The optical glass of the present invention has a glass refractive index (nd) in the range of 1.77 to 1.85, preferably in the range of 1.78 to 1.84, more preferably in the range of 1.785 to 1.84; abbe number (v) of the glass of the inventiond) In the range of 40 to 48, preferably in the range of 41 to 47.
[ transition temperature of optical glass ]
The optical glass gradually changes from a solid state to a plastic state in a certain temperature interval. The transition temperature is a temperature corresponding to an intersection point where extensions of straight line portions of a low temperature region and a high temperature region of a glass sample, which is heated from room temperature to a sag temperature, intersect.
The glass of the present invention has a transition temperature (Tg) of 630 ℃ or lower, preferably 620 ℃ or lower, more preferably 615 ℃ or lower, and still more preferably 610 ℃ or lower.
[ coloring of optical glass ]
Coloring degree (. lamda.) for short-wave transmission spectral characteristics of the glass of the present invention80/λ5) And (4) showing. Lambda [ alpha ]80Refers to the wavelength, lambda, corresponding to a glass having a transmittance of 80%5The wavelength corresponding to the glass transmittance of 5% is referred to. Wherein λ is80Was measured using a glass having a thickness of 10. + -. 0.1nm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280nm to 700nm and showing a wavelength of transmittance of 80%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glassinLight transmitted through the glass and having an intensity I emitted from a planeoutIn the case of light of (1) through (I)out/IinThe quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glasses, λ80A small value of (a) means that the glass itself is colored very little.
Optical glass lambda of the present invention80Less than or equal to 410nm, preferably lambda80In the range of 405nm or less, more preferably lambda80In the range of 400nm or less, more preferably λ80In the range of 395nm or less, still more preferably lambda80Is less than or equal to 390 nm. Lambda [ alpha ]5Less than or equal to 350nm, preferably lambda5In the range of 345nm or less, more preferably λ5Is less than or equal to 340nm, further preferred is λ5Is less than or equal to 335 nm.
[ Density of optical glass ]
The density of the optical glass is a unit volume at a temperature of 20 DEG CMass of (2) in g/cm3And (4) showing.
The density (. rho.) of the glass of the present invention is 5.00g/cm3Hereinafter, it is preferably 4.90g/cm3The following.
[ upper limit temperature of crystallization ]
Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient, keeping the temperature for 4 hours, taking out the sample, observing the crystallization condition of the glass under a microscope, and determining the highest temperature corresponding to the occurrence of crystals of the glass as the crystallization upper limit temperature of the glass. The lower the crystallization upper limit temperature of the glass is, the stronger the stability of the glass at high temperature is, and the better the production process performance is.
The glass of the present invention has a crystallization temperature of 1160 ℃ or lower, preferably 1155 ℃ or lower, more preferably 1150 ℃ or lower, and still more preferably 1140 ℃ or lower.
II, glass preform and optical element
Next, the optical preform and the optical element of the present invention are described.
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 prefabricated member has the characteristics of high refractive index and low dispersion; the optical element of the present invention has high refractive index and low dispersion characteristics, and can provide optical elements such as various lenses and prisms having high optical values at low cost.
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.
The lens can correct chromatic aberration by combining with a lens made of high-refractivity high-dispersion glass, and is suitable as a lens for chromatic aberration correction. Further, the lens is also effective for the compactness of an optical system.
Since the prism has a high refractive index, when the prism is incorporated in an imaging optical system, the optical path is bent to a desired direction, whereby a compact and wide-angle optical system can be realized.
Examples
The present invention is explained by the following examples, but the present invention should not be limited to these examples.
The melting and shaping methods for producing the optical glass may employ techniques well known to those skilled in the art. The preparation method comprises the steps of weighing and mixing glass raw materials (carbonate, nitrate, sulfate, hydroxide, oxide, boric acid and the like) according to the proportion of glass oxide, putting the mixture into a smelting device (such as a platinum crucible), then carrying out appropriate stirring, clarification and homogenization at 1150-1400 ℃, cooling to below 1250 ℃, pouring or leaking into a forming die, and finally carrying out post-treatment such as annealing and processing or directly carrying out compression forming by a precise compression technology.
[ optical glass examples ]
The characteristics of each glass of the present invention were defined by the following methods, and the measurement results are shown in tables 1 to 6, in which A1 represents SiO2+B2O3A2 represents La2O3+Gd2O3+Y2O3A3 denotes WO3+Nb2O5+ZrO2+TiO2K1 denotes Ta2O5/Nb2O5Value of (A), K2 represents SiO2/(SiO2+B2O3) K3 represents Nb2O5/Gd2O3K4 represents Gd2O3/(La2O3+Gd2O3+Y2O3) Value of (A), K5 (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) K6 denotes ZnO/(SiO)2+B2O3) K7 denotes Nb2O5The value of/ZnO, K8 represents TiO2/(TiO2+Nb2O5) K9 denotes ZnO/(WO)3+Ta2O5+Nb2O5+TiO2)。
(1) Refractive index nd and Abbe number vd
The refractive index and Abbe number were measured according to the method specified in GB/T7962.1-2010.
(2) Degree of glass coloration (. lamda.)80/λ5)
The spectral transmittance was measured using a glass sample having a thickness of 10. + -. 0.1mm with two optically polished planes opposed to each other, and calculated from the result thereof.
(3) Glass transition temperature (Tg)
The measurement was carried out according to the method specified in GB/T7962.16-2010.
(4) Density of glass (p)
The measurement was carried out according to the method specified in GB/T7962.20-2010.
(5) Upper limit temperature of crystallization
Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a sample of 180 x 10mm, polishing the side surface, putting the sample into a furnace with a temperature gradient, keeping the temperature for 4 hours, taking out the sample, observing the crystallization condition of the glass under a microscope, and determining the highest temperature corresponding to the occurrence of crystals of the glass as the crystallization upper limit temperature of the glass.
(6) Devitrification in glass production molding
After melting, clarifying and homogenizing, the glass flows out of a platinum or platinum alloy discharge pipe to a forming die to be formed into lump materials or section materials, the interior and the surface of the glass are observed after the glass is cooled, and the crystallization performance of the glass is insufficient when crystals appear in the interior or the surface of the glass. The absence of devitrification in the glass interior and on the surface is indicated by "A", and the presence of devitrification in the glass interior or on the surface is indicated by "O".
TABLE 1
Figure BDA0001123460060000141
TABLE 2
Figure BDA0001123460060000142
Figure BDA0001123460060000151
Figure BDA0001123460060000161
TABLE 3
Figure BDA0001123460060000162
Figure BDA0001123460060000171
TABLE 4
Figure BDA0001123460060000172
Figure BDA0001123460060000181
TABLE 5
Figure BDA0001123460060000182
Figure BDA0001123460060000191
TABLE 6
Figure BDA0001123460060000192
Figure BDA0001123460060000201
[ glass preform examples ]
The optical glasses obtained in examples 1 to 10 in table 1 were cut into a predetermined size, and then a release agent was uniformly applied to the surface of the optical glass, followed by heating, softening, and press-molding to prepare preforms of various lenses and prisms 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.
[ optical element examples ]
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 optical element may be coated with an antireflection film.
The invention is the optical glass with low cost, excellent chemical stability, high refraction and low dispersion, the refractive index is 1.77-1.85, the Abbe number is 40-48, and the optical element formed by the glass can meet the requirements of modern novel photoelectric products.

Claims (23)

1. Optical glass, characterized in that it has a refractive index of 1.77-1.85, an Abbe number of 40-48, and its composition, expressed in weight percent, comprises: SiO 22+B2O3：15-40％；La2O3+Gd2O3+Y2O3：35-70％；WO3+Nb2O5+ZrO2+TiO2：1-30％；ZnO：11-30％；Nb2O5/Gd2O30.01-0.45; nb2O50.01-0.5 of/ZnO; SiO 22/(SiO2+B2O3) 0.2-0.6; TiO 22/(TiO2+Nb2O5) 0.01-0.8; ZnO/(WO)3+Ta2O5+Nb2O5+TiO2) Is 1.8 or more.
2. The optical glass according to claim 1, wherein the composition is in weight percentThe ratio also indicates that: al (Al)2O3：0-10％；Ta2O5：0-8％；Rn2O: 0-10% of (wherein Rn)2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-10%, wherein RO is one or more of MgO, CaO, SrO or BaO.
3. The optical glass according to claim 1 or 2, wherein: SiO 22+B2O3: 18 to 38 percent; and/or La2O3+Gd2O3+Y2O3: 35 to 65 percent; and/or WO3+Nb2O5+ZrO2+TiO2：2-20％；Rn2O: 0-5%, wherein Rn2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-5%, wherein RO is one or more of MgO, CaO, SrO or BaO.
4. The optical glass according to claim 1 or 2, wherein: SiO 22+B2O3: 20 to 35 percent; and/or La2O3+Gd2O3+Y2O3: 38 to 60 percent; and/or WO3+Nb2O5+ZrO2+TiO2：4-15％；Rn2O: 0-2% of (wherein Rn)2O is Li2O、Na2O、K2One or more of O; and (3) RO: 0-1%, wherein RO is one or more of MgO, CaO, SrO or BaO.
5. The optical glass according to claim 1 or 2, wherein: the content of each component meets more than one of the following 6 conditions:
1)Ta2O5/Nb2O5: less than 1;
2)ZnO/(SiO2+B2O3) 0.3 to 2;
3)Gd2O3/(La2O3+Gd2O3+Y2O3) 0.2-0.55;
4)Nb2O5/Gd2O30.01-0.4;
5)(WO3+Ta2O5+Nb2O5)/(ZrO2+TiO2) Is 0.1-5.
6. The optical glass of claim 1 or 2, wherein: nb2O5+ZrO2+TiO2：1-25％。
7. The optical glass of claim 1 or 2, wherein: nb2O5: greater than 0 but less than or equal to 8%; ZrO (ZrO)2: greater than 0 but less than or equal to 15%; TiO 22：0-8％；WO3：0-15％。
8. The optical glass of claim 1 or 2, wherein: la2O3：20-40％；Gd2O3：11-30％；Y2O3：0-15％。
9. The optical glass of claim 1 or 2, wherein: SiO 22：4-20％；B2O3：8-24％；Li2O：0-2％；Na2O：0-10％；K2O：0-10％。
10. The optical glass of claim 1 or 2, wherein: SiO 22: 5 to 18 percent; and/or B2O3: 10 to 23 percent; and/or La2O3: 20 to 35 percent; and/or Gd2O3: 11 to 25 percent; and/or Y2O3: 0 to 10 percent; and/or WO3: 0 to 10 percent; and/or Ta2O5: 0 to 5 percent; and/or Nb2O5: 0.1-6%; and/or ZrO2: 1 to 10 percent; and/or ZnO: 15 to 30 percent; and/or TiO2: 0 to 5; and/or Al2O3: 0 to 5 percent; and/or Li2O: 0 to 1 percent; and/or Na2O: 0 to 5 percent; and/or K2O: 0 to 5 percent; and/or Sb2O3: 0 to 0.5 percent; and/or RO: 0-5%, wherein RO is one or more of MgO, CaO, SrO or BaO.
11. The optical glass of claim 1 or 2, wherein: SiO 22: 6 to 15 percent; and/or B2O3: 12 to 20 percent; and/or La2O3: 22 to 32 percent; and/or Gd2O3: 12 to 22 percent; and/or Y2O3: 0 to 8 percent; and/or WO3: 0 to 7 percent; and/or ZrO2: 2 to 8 percent; and/or ZnO: 15 to 25 percent; and/or TiO2：0-2％。
12. The optical glass of claim 1 or 2, wherein: ta2O5/Nb2O5: less than 0.8; and/or ZnO/(SiO)2+B2O3) 0.5 to 1.8; and/or Gd2O3/(La2O3+Gd2O3+Y2O3) 0.25 to 0.5; and/or SiO2/(SiO2+B2O3) 0.23 to 0.5; and/or Nb2O5/Gd2O30.02-0.35; and/or (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) 0.1 to 3; and/or Nb2O5The content of/ZnO is 0.02-0.35; and/or TiO2/(TiO2+Nb2O5) 0.05-0.7; and/or ZnO/(WO)3+Ta2O5+Nb2O5+TiO2) Is 3-15.
13. The optical glass of claim 1 or 2, wherein: ta2O5/Nb2O5: less than 0.5; ZnO/(SiO)2+B2O3) 0.5-1.45; and/or Gd2O3/(La2O3+Gd2O3+Y2O3) 0.25-0.45; and/or SiO2/(SiO2+B2O3) 0.25-0.45; and/or Nb2O5/Gd2O30.05-0.25; and/or (WO)3+Ta2O5+Nb2O5)/(ZrO2+TiO2) 0.1 to 1; and/or Nb2O50.03-0.25 of/ZnO; and/or TiO2/(TiO2+Nb2O5) 0.1-0.6; and/or ZnO/(WO)3+Ta2O5+Nb2O5+TiO2) Is 4-12.
14. The optical glass of claim 1 or 2, wherein: nb2O5+ZrO2+TiO2：2-20％；La2O3+Gd2O3+Y2O3：40-55％。
15. The optical glass of claim 1 or 2, wherein: nb2O5+ZrO2+TiO2：4-15％。
16. The optical glass of claim 1 or 2, wherein: SiO 22、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、WO3、ZrO2And ZnO in a total content of 95% or more, and does not contain Ta2O5。
17. The optical glass of claim 1 or 2, wherein: SiO 22、B2O3、La2O3、Gd2O3、Y2O3、TiO2、Nb2O5、ZrO2And ZnO in a total amount of 99% or more.
18. An optical glass according to claim 1 or 2, characterised in that its composition, expressed in weight percent, comprises:
Yb2O3：0-10％；
P2O5：0-10％；
Bi2O3：0-10％；
TeO2：0-10％；
Ga2O3:0-10％；
Lu2O3:0-10％；
GeO2：0-8％；
CeO2：0-1％；
SnO2：0-1％；
Sb2O3：0-1％；
F：0-10％。
19. an optical glass according to claim 1 or 2, characterised in that its composition, expressed in weight percent, comprises:
Yb2O3：0-5％；
P2O5：0-5％；
Bi2O3：0-5％；
TeO2：0-5％；
Ga2O3:0-5％；
Lu2O3:0-5％；
GeO2：0-5％；
CeO2：0-0.5％；
SnO2：0-0.5％；
Sb2O3：0-1％；
F：0-5％。
20. an optical glass according to claim 1 or 2, characterised in that the glass has a transmittance of 80% at the corresponding wavelength λ80Is below 410nmWavelength lambda corresponding to a transmittance of 5%5Is 350nm or less; the upper limit temperature of crystallization is below 1160 ℃; a glass transition temperature of 630 ℃ or lower; the density of the glass is 5.00g/cm3The following.
21. An optical glass according to claim 1 or 2, characterised in that the glass has a transmittance of 80% at the corresponding wavelength λ80A wavelength lambda corresponding to a transmittance of 5% below 400nm5Is below 340 nm; the upper limit temperature of crystallization is below 1150 ℃; the glass transition temperature is below 620 ℃; the density of the glass is 4.90g/cm3The following.
22. A glass preform made of the optical glass as claimed in any one of claims 1 to 21.
23. An optical element made of the optical glass according to any one of claims 1 to 21.
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