CN110835231B - Optical glass, glass preform or optical element prepared from optical glass, and optical instrument - Google Patents

Optical glass, glass preform or optical element prepared from optical glass, and optical instrument Download PDF

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CN110835231B
CN110835231B CN201810943241.8A CN201810943241A CN110835231B CN 110835231 B CN110835231 B CN 110835231B CN 201810943241 A CN201810943241 A CN 201810943241A CN 110835231 B CN110835231 B CN 110835231B
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optical glass
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CN110835231A (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
    • C03C3/062—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

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Abstract

The invention discloses optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument. Wherein the optical glass comprises, in mass percent, with respect to the total mass of the glass of the composition in terms of oxides: b 2 O 3 ：5～25％，La 2 O 3 ：25～45％，Gd 2 O 3 ：15～35％，Yb 2 O 3 ：0～10％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0.5～10％，Y 2 O 3 :0 to 10% and WO 3 :0 to 10% and does not contain Ta 2 O 5 ，Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 0.75 to 2. The invention strictly controls the components and content of the optical glass and the dosage proportion among specific components, so that the optical glass does not use Ta 2 O 5 Still has excellent performance under the condition of (2).

Description

Optical glass, glass preform or optical element prepared from optical glass, and optical instrument
Technical Field
The invention relates to the technical field of optical glass, in particular to optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument.
Background
At present, the development of digital photographing apparatuses, image pickup apparatuses, projection apparatuses, and the like has required higher optical elements, which requires the development and production of optical glasses with higher performance. Among them, a combination of a lens formed of a high-refractive-index low-dispersion optical glass and a lens formed of a high-refractive-index high-dispersion optical glass enables correction of chromatic aberration and miniaturization of an optical system, and particularly, a market demand for a high-refractive-index low-dispersion optical glass having a refractive index nd of more than 1.87 and an abbe number vd of more than 38.0 is increasing.
The basic system of the formula for meeting the optical index is that B-La-Zr-Ta is good, glass is easy to form, and production is facilitated, but Ta is expensive and is not beneficial to control of production cost. In addition, in general, more rare earth oxides are required to be introduced into a high-refraction low-dispersion glass formula system to improve the refractive index of the glass, but in different formula systems, more lanthanide oxides are introduced to influence the glass forming property, if the content is more, the glass is easy to crystallize, the crystallization upper limit temperature is higher, and the difficulty is brought to mass production process manufacturing.
Disclosure of Invention
The invention aims to provide optical glass, a glass prefabricated member or an optical element prepared from the optical glass and an optical instrument, and aims to solve the technical problems that high-refraction low-dispersion optical glass in the prior art is difficult to produce and high in cost.
In order to achieve the above object, according to one aspect of the present invention, there is provided an optical glass. The optical glass comprises the following components in percentage by mass relative to the total mass of the glass with the composition converted by oxides: b is 2 O 3 ：5～25％，La 2 O 3 ：25～45％，Gd 2 O 3 ：15～35％，Yb 2 O 3 ：0～10％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0.5～10％，Y 2 O 3 :0 to 10% and WO 3 :0 to 10% and does not contain Ta 2 O 5 ，Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 Is 0.75 to 2.
Further, the optical glass further comprises a glass selected from the group consisting of ZnO, baO, caO, srO, mgO, and Sb 2 O 3 、Li 2 O、Na 2 O and K 2 O, and the content is as follows: znO:0 to 15%, baO:0 to 10%, caO:0 to 10%, srO:0 to 10%, mgO:0 to 10% of Sb 2 O 3 ：0-1％，Li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10 percent.
Further, the optical glass is composed of B in mass percentage with respect to the total mass of the glass of the composition in terms of oxides 2 O 3 ：5～25％，La 2 O 3 ：30～43％，Gd 2 O 3 ：18～32％，Y 2 O 3 ：0～8％；Yb 2 O 3 ：0～8％；Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0.5～7％，WO 3 ：0～6％，ZnO：0～15％，BaO：0～10％，CaO：0～10％，SrO：0～10％，MgO：0～10％，Sb 2 O 3 :0 to 1 percent of Li and the total amount of Li is 0 to 10 percent 2 O、Na 2 O and K 2 O, composition, and Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 Is 0.75 to 2.
Further, the optical glass includes, in terms of mass percentage content with respect to the total mass of the glass of the composition in terms of oxides: b is 2 O 3 ：8～22％，La 2 O 3 ：20～40％，Gd 2 O 3 ：15～35％，Y 2 O 3 ：0～10％，Yb 2 O 3 :0～10％，Nb 2 O 5 ：5.6～10％，SiO 2 ：3～10％，ZrO 2 ：3～12％，TiO 2 :0.5 to 7% and/or WO 3 ：0～10％。
Further, Y 2 O 3 The content of (b) is 0.
Further, the optical glass does not contain WO 3 。
Further, nb 2 O 5 /SiO 2 0.8 to 1.5.
Further, nb 2 O 5 /SiO 2 Is 1 to 1.5.
Further, la 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total amount of (A) is 50 to 75%.
Further, la 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 Is 1.28 to 1.625.
Further, la 2 O 3 /Gd 2 O 3 Is 1.3 to 1.6.
Further, the upper limit temperature of devitrification of the optical glass is less than 1350 ℃, preferably less than 1300 ℃.
Further, the refractive index nd > 1.87, preferably nd > 1.88; the Abbe number vd is > 38.0, preferably vd > 39.0.
Further, the water-resistant stability Dw of the optical glass is above grade 3, preferably above grade 2, more preferably 1; stability against acid action D A At least 3 stages, preferably at least 2 stages, more preferably at least 1 stage.
Further, the stripes of the optical glass are of class C or more, preferably class B or more, more preferably class a; the degree of bubbling is class A or more, preferably class A 0 More than class A, more preferably A 00 And (4) stages.
According to another aspect of the present invention, there is provided a glass preform or an optical element. The glass preform or the optical element is produced from any of the above optical glasses.
According to a further aspect of the present invention, there is provided an optical instrument including an optical element, the optical element being any one of the optical elements described above.
By applying the technical scheme of the invention, the components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass does not use Ta 2 O 5 In the case of (2), the coating composition has devitrification resistance and excellent performance, and is easy to mass-produce and low in production cost.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In the present specification, unless otherwise specified, the contents of the respective components are all expressed in mass% with respect to the total mass of the glass in terms of oxides. The "composition in terms of oxides" refers to the composition of each component contained in the glass, which is expressed by assuming that all of the raw materials and the like as the glass components of the present invention are decomposed and converted into oxides during melting, and the total mass of the generated oxides is 100 mass%.
The basic role of each component in the optical glass will be described below, but the synergistic effect or unexpected effect of the components due to the specific content ratio is not unduly limited.
B 2 O 3 The glass is a skeleton component of the glass, and has the effects of improving the meltability of the glass, resisting devitrification and reducing the dispersion of the glass. However, when the amount of incorporation exceeds 25%, the glass stability is lowered and the refractive index is lowered, and when the amount of incorporation is less than 5%, the glass meltability is lowered and the optical constants required in the present invention are not obtained. Thus, B of the present invention 2 O 3 In an amount of 5 to 25%, preferably B 2 O 3 The content is 8-22%.
Nb 2 O 5 The glass also has the effect of improving the crystallization resistance and chemical durability of the glass in order to improve the refractive index and dispersion. When Nb 2 O 5 When the content is less than 2%, the above effects cannot be achieved; if the content exceeds 15%, the glass dispersion is improved, the coloring tendency is increased, the optical characteristics of the glass of the present invention cannot be achieved, and the devitrification resistance of the glass is deteriorated. Nb in the invention 2 O 5 The content is 2 to 15%, preferably Nb 2 O 5 The content is 5.6-10%.
SiO 2 The component constituting the glass skeleton has the effects of improving resistance to devitrification and increasing the operating temperature range, and also has the effects of improving chemical stability of glass, improving thermal stability of glass, and the like. If the content exceeds 15%, the glass has lowered meltability and the refractive index required in the present invention cannot be obtained. SiO in the invention 2 The content is 0.5 to 15%, preferably SiO 2 The content is 3-10%.
ZrO 2 A component for improving refractive index and stability. Glass is formed as an intermediate oxide, and therefore, it also has an effect of improving resistance to devitrification and chemical durability. ZrO (zirconium oxide) 2 When the content of (A) is less than 1%, the above-mentioned intended effect cannot be obtained, and when ZrO is contained in the composition 2 When the content of (b) exceeds 15%, devitrification tends to be strong and vitrification tends to be difficult. ZrO in the invention 2 The content is preferably 1 to 15%, preferably ZrO 2 The content is 3-12%.
TiO 2 Also has the function of improving the refractive index of the glass and can participate in the glassThe glass network is formed, and the glass is more stable by introducing the glass in a proper amount. However, if the amount is excessively contained, the glass dispersion is remarkably increased, and the transmittance of the glass in a short wavelength portion of the visible light region is lowered, so that the glass tends to be colored. In the present invention, tiO 2 The content is 0.5 to 10%, preferably 0.5 to 7%.
La 2 O 3 Are essential components for obtaining the desired optical properties of the present invention. When La 2 O 3 When the content of (b) is less than 25%, it is difficult to realize desired optical characteristics; however, when the content exceeds 45%, both the devitrification resistance and the melting property of the glass are deteriorated. Thus, la of the present invention 2 O 3 The content of (A) is 25-45%, la 2 O 3 The preferable range of the content is 30 to 43%.
In the present invention, gd is used 2 O 3 And La 2 O 3 Coexisting, the glass forming stability can be improved, but when Gd is present 2 O 3 When the content is less than 15%, the above effects are not obvious; if the content exceeds 35%, the devitrification resistance of the glass is lowered and the stability of the formed glass is deteriorated. Thus, gd of the present invention 2 O 3 The content of (B) is 15 to 35%, preferably in the range of 18 to 32%.
Y 2 O 3 The melting property and devitrification resistance of the glass can be improved and the upper limit temperature of devitrification of the glass can be lowered, but if the content exceeds 10%, the stability and devitrification resistance of the glass are lowered. Thus Y is 2 O 3 The content is in the range of 0 to 10%, preferably in the range of 0 to 8%.
Yb 2 O 3 Also, the high-refractivity low-dispersion component in the glass of the present invention is preferably Yb because the stability and devitrification resistance of the glass are lowered when the content exceeds 10% 2 O 3 The content is in the range of 0 to 10%, preferably in the range of 0 to 8%.
La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 Are the main components for increasing the refractive index of the glass, and can increase the refractive index without significantly increasing the dispersion. The addition of a certain amount of the rare earth oxide can reduce the crystallizationLimiting temperature, improving the devitrification resistance of the glass, improving chemical stability, not easily generating glass bubbles in the melting process and the like, so that the La in the high-refraction low-dispersion glass formula system of the invention 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content is not less than 50 percent to ensure that the technical effects are realized and the aim of the invention is achieved, preferably, the La is adopted in the invention 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total amount of (A) is 50 to 75%.
However, WO has an effect of improving the devitrification resistance because it is a glass formed as an intermediate oxide 3 When the content exceeds a certain amount, the devitrification tendency tends to be increased and vitrification becomes difficult, and the ultraviolet region transmittance tends to be decreased, or the affinity with a press mold increases and the mold tends to be easily thermally bonded in the case of press molding. Therefore, according to an exemplary embodiment of the present invention, the optical glass preferably does not contain Y 2 O 3 And/or WO 3 。
While ZnO can adjust the refractive index and dispersion of the glass, and a suitable amount of ZnO can improve the stability or melting property of the glass and press formability, when the content is too high, the refractive index decreases, which does not meet the requirements of the present invention, and the devitrification resistance of the glass decreases and the upper limit temperature of devitrification increases. The ZnO content of the present invention is 0 to 15%, preferably 0 to 10%, more preferably 0 to 5%.
Alkaline earth metal oxides such as BaO, caO, srO and MgO can lower the chemical stability of the glass and raise the crystallization upper limit temperature, but if the respective contents exceed 10%, the glass is lowered in devitrification resistance, so that BaO in the present invention is 0 to 10%; the CaO content is 0 to 10 percent; the SrO content is 0-10%, and the MgO content is 0-10%.
Li 2 O、Na 2 O and K 2 O is a component for suppressing phase separation and improving the stability of the glass. When the content thereof exceeds 10%, there is a tendency that chemical stability is significantly lowered or refractive index is lowered.
According to an exemplary embodiment of the present invention, an optical glass is provided. The optical glass comprises the following components in percentage by mass relative to the total mass of the glass with the composition converted by oxides: b 2 O 3 ：5～25％，La 2 O 3 ：25～45％，Gd 2 O 3 ：15～35％，Yb 2 O 3 ：0～10％，Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0.5～10％，Y 2 O 3 :0 to 10% and WO 3 :0 to 10% and does not contain Ta 2 O 5 ，Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 Is 0.75 to 2.
In the present invention by controlling Nb 2 O 5 With SiO 2 Ratio of contents of Nb 2 O 5 /SiO 2 Within 0.75-2, the glass has the advantages of increased melting property, effectively increased glass stability, less striae, good glass uniformity, improved refractive index, crystallization resistance and chemical durability, especially Nb 2 O 5 /SiO 2 The effect is especially obvious when the ratio is 1-1.5.
Generally, the more lanthanide oxides are introduced, the vitrification can be influenced, if the content is high, the glass is easy to crystallize, the crystallization upper limit temperature is high, and difficulty is brought to mass production process manufacturing; therefore, the content of lanthanide oxide with high-refraction low-dispersion performance can be generally below 60 percent to ensure that the glass is not easy to crystallize, and La oxide is controlled in the high-refraction low-dispersion glass of the invention 2 O 3 With Gd 2 O 3 La by weight of 2 O 3 /Gd 2 O 3 1.28 to 1.625, so that the upper crystallization temperature of the glass is not increased when the content of the lanthanide oxide is below 60% and exceeds 60%, and is below 1350 ℃, preferably below 1300 ℃, more preferably below 1280 ℃, and the components are ensuredHas better glass forming property, is not easy to generate glass bubbles in the melting process, also ensures good optical property, forming property and the like, preferably La 2 O 3 /Gd 2 O 3 1.3 to 1.6; more preferably, la 2 O 3 /Gd 2 O 3 Is 1.4 to 1.5.
By applying the technical scheme of the invention, the components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass does not use Ta 2 O 5 In the case of (2), the optical film has excellent devitrification resistance and optical properties, is easy to mass-produce, and is low in production cost.
In the present invention, Y 2 O 3 The melting property and devitrification resistance of the glass can be improved and the upper limit temperature of devitrification of the glass can be lowered, but if the content exceeds a certain amount, the stability and devitrification resistance of the glass are lowered. WO 3 Acting to increase the refractive index, but when WO 3 When the content exceeds 10%, the devitrification tendency tends to be strong, vitrification tends to be difficult, the dispersion is remarkably improved, and the transmittance on the short wavelength side of the visible light region of the glass is lowered and the coloring tendency tends to be increased, so that WO is preferable in the present invention 3 The content of (A) is 0-10%. According to a typical embodiment of the invention, the optical glass does not contain Y and/or W.
According to an exemplary embodiment of the present invention, the optical glass further comprises a material selected from the group consisting of ZnO, baO, caO, srO, sb 2 O 3 、Li 2 O、Na 2 O and K 2 O, and the content is as follows: znO:0 to 15%, baO:0 to 10%, caO:0 to 10%, srO:0 to 10% of Sb 2 O 3 ：0-1％，Li 2 O、Na 2 O and K 2 The total amount of O is 0 to 10 percent.
Preferably, according to an exemplary embodiment of the present invention, the optical glass consists of B in mass percent relative to the total mass of the glass of the composition in terms of oxides 2 O 3 ：5～25％，La 2 O 3 ：30～43％，Gd 2 O 3 ：18～32％，Y 2 O 3 ：0～8％；Yb 2 O 3 ：0～8％；Nb 2 O 5 ：2～15％，SiO 2 ：0.5～15％，ZrO 2 ：1～15％，TiO 2 ：0.5～7％，WO 3 ：0～6％，ZnO：0～15％，BaO：0～10％，CaO：0～10％，SrO：0～10％，MgO：0～10％，Sb 2 O 3 :0 to 1 percent of Li and the total amount of Li is 0 to 10 percent 2 O、Na 2 O and K 2 O, composition, and Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 /SiO 2 0.75 to 2. The components and the content of the optical glass and the dosage proportion among the specific components are strictly controlled, so that the optical glass has better devitrification resistance and excellent optical performance under the condition of not using Ta, is easy to produce in mass and has low production cost.
By adding small amounts of Sb 2 O 3 、SnO 2 、CeO 2 The component can improve the fining effect of the glass, but when Sb is used 2 O 3 When the content exceeds 1%, the glass tends to have a reduced fining ability and the deterioration of a forming mold is promoted by its strong oxidizing action, so Sb is preferable in the present invention 2 O 3 The amount of (B) is 0 to 1%, more preferably 0 to 0.5%. SnO 2 However, 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 invention 2 The content of (b) is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no addition. CeO (CeO) 2 Action and addition amount ratio of (2) to SnO 2 The content is preferably 0 to 1%, more preferably 0 to 0.5%, and further preferably no addition.
A certain amount of P can be properly introduced without affecting the performance of the optical glass of the present invention 2 O 5 、Al 2 O 3 、Bi 2 O 3 、GeO 2 、Lu 2 O 3 And F and the like.
The optical glass of the present invention is a high refractive index low dispersion glass, and a lens made of the high refractive index low dispersion glass is often combined with a lens made of the high refractive index high dispersion glass for chromatic aberration correction, and when the optical glass is used as a lens, the lens can be thinned as the refractive index is increased, which is advantageous for miniaturization of optical equipment, and the refractive index nd of the optical glass of the present invention is > 1.87, preferably nd > 1.88; the Abbe number vd is > 38.0, preferably vd > 39.0.
The ability of the polished surface of the optical glass element to resist the action of various erosion media such as water, acid and the like during the manufacturing and use process is called the chemical stability of the optical glass, which is mainly determined by the chemical components of the glass, and the stability Dw (powder method) of the optical glass of the present invention to resist water is above grade 3, preferably above grade 2, and more preferably above grade 1; stability against acid action D A The (powder method) is grade 3 or more, preferably grade 2 or more, and more preferably grade 1.
Measuring the crystallization performance of the glass by adopting a temperature gradient 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 (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is 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. According to an exemplary embodiment of the present invention, the upper crystallization temperature of the optical glass is preferably below 1350 ℃, preferably below 1300 ℃, more preferably below 1280 ℃.
The degree of streaking is a ratio of 4, i.e., A, B, C, and D, in comparison with a standard sample, in a direction in which streaks are most easily seen, using a streaking instrument composed of a point light source and a lens, wherein A is a ratio in which no streaks are visible to the naked eye under a predetermined detection condition, B is a ratio in which fine and scattered streaks are present under a predetermined detection condition, C is a ratio in which no parallel streaks are present slightly under a predetermined detection condition, and D is a ratio in which coarse streaks are present under a predetermined detection condition. Since the prior art does not use noble oxides such as Ta 2 O 5 Under the condition of (2), the crystallization resistance is poor, and the product with the thickness of more than 20mm is produced and is easy to generate crystallizationCrystal stripes. The thick-gauge product is the necessary gauge for manufacturing large-caliber (more than 60 mm) lenses. At present, due to the development of optical technology, more and more large-aperture lenses are needed, and manufacturers are further required to provide blank products with the thickness of more than 20 mm.
The bubble quality of the optical glass is measured according to the test method specified in GB/T7962.8-2010. The bubble degree is the grade of the allowable bubble content in the glass, the bubbles not only influence the appearance quality of a glass product, but also influence the optical performance, transparency, mechanical strength and the like of the glass, and cause a plurality of adverse effects on the glass, so the control of the bubble degree of the glass is very important, and the invention controls the bubble degree of the rare earth oxide La by controlling 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total content of (A) can further achieve a glass bubble degree of class A or more, preferably class A 0 More than class A, more preferably A 00 And (4) stages.
The optical glass of the present invention is a high refractive index low dispersion glass, and a lens made of the high refractive index low dispersion glass is often used for chromatic aberration correction in combination with a lens made of the high refractive index high dispersion glass, and when the optical glass is used as a lens, the lens can be thinned as the refractive index is increased, and it is advantageous for miniaturization of an optical device that the refractive index nd of the optical glass of the present invention is > 1.87, preferably nd > 1.88, and the Abbe number vd > 38.0, preferably vd > 39.0.
According to another aspect of the present invention, there is provided a glass preform or an optical element. The glass preform or the optical element is produced from any of the above optical glasses. The optical prefabricated member of the invention has the characteristics of high refractive index and low dispersion; the optical element of the present invention has a high refractive index and low dispersion characteristics, and can provide optical elements such as various lenses and prisms having excellent optical performance 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. Further, since the prism has a high refractive index, by combining the prism with an imaging optical system and bending the optical path to direct the prism in a desired direction, a compact and wide-angle optical system can be realized.
According to a further aspect of the present invention, there is provided an optical instrument including an optical element, the optical element being any one of the optical elements described above. The optical instrument of the present invention may be a digital camera, a video camera, or the like.
The advantageous effects of the present invention will be further described with reference to examples.
Examples
Examples of optical glasses
In order to obtain glasses having compositions shown in tables 1 to 6, carbonates, nitrates, hydroxides, oxides, boric acid, and the like were used as raw materials, raw materials corresponding to the components of the optical glass were weighed in proportion, and mixed sufficiently to obtain a blended raw material, the blended raw material was put into a platinum crucible, heated to 1200 to 1450 ℃, melted, stirred, and clarified to form a uniform molten glass, and the molten glass was appropriately cooled, poured into a preheated mold, kept at 650 to 700 ℃ for 2 to 4 hours, and then slowly cooled to obtain the optical glass. The characteristics of each glass were measured by the following methods, and the measurement results are shown in tables 1 to 6.
(1) Upper limit temperature of crystallization
Measuring the crystallization performance of the glass by adopting a gradient temperature furnace method, manufacturing the glass into a 180 x 10mm sample, polishing the side surface, putting the sample into a furnace with a temperature gradient (5 ℃/cm), heating to 1400 ℃, keeping the temperature for 4 hours, taking out the sample, naturally cooling to room temperature, observing the crystallization condition of the glass under a microscope, wherein the highest temperature corresponding to the occurrence of crystals of the glass is the crystallization upper limit temperature of the glass.
(2) Refractive index nd and Abbe number vd
The refractive index and the Abbe number were measured according to the method specified in GB/T7962.1-2010.
(3) Chemical stability
Test method according to GB/T17129Testing of stability to Water action Dw and to acid action D A 。
(4) Degree of striae
The measurement was carried out in accordance with the method defined in MLL-G-174B.
(5) Degree of bubbling
The bubble quality of the optical glass is measured according to the test method specified in GB/T7962.8-2010.
TABLE 1
Figure BDA0001769584260000071
Figure BDA0001769584260000081
TABLE 2
Figure BDA0001769584260000082
Figure BDA0001769584260000091
TABLE 3
Figure BDA0001769584260000092
Figure BDA0001769584260000101
TABLE 4
Figure BDA0001769584260000102
Figure BDA0001769584260000111
TABLE 5
Figure BDA0001769584260000112
Figure BDA0001769584260000121
TABLE 6
Figure BDA0001769584260000122
Figure BDA0001769584260000131
Optical preform embodiments
The optical glass obtained in example 1 in table 1 was cut into a predetermined size, and a mold release agent made of boron nitride powder was uniformly applied to the surface of the optical glass, and then heated, softened, and pressure-molded to produce 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 embodiments
The preforms obtained from the above optical preform examples were annealed to reduce the deformation in the glass and to fine-tune the optical properties such as refractive index to the 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 further coated with an antireflection film.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (19)

1. An optical glass comprising, in mass percent, with respect to the total mass of the glass of a composition converted to oxides: B2O3:5 to 25%, la2O3:25 to 45%, gd2O3:15 to 35%, yb2O3:0 to 10%, nb2O5:2 to 15%, siO2:0.5 to 15%, zrO2:1 to 15%, tiO2:0.5 to 10%, Y2O3:0 to 10% and WO3:0 to 10 percent and does not contain Ta2O5, and the weight ratio Nb2O5/SiO2 of Nb2O5 to SiO2 is 0.75 to 1; the weight ratio of La2O 3/Gd 2O3 of La2O3 to Gd2O3 is 1.28 to 1.625, and the crystallization upper limit temperature of the optical glass is lower than 1350 ℃; the refractive index nd of the optical glass is more than 1.87; the Abbe number vd is more than 38.0.
2. An optical glass according to claim 1, wherein the optical glass further comprises one or more selected from the group consisting of ZnO, baO, caO, srO, mgO, sb2O3, li2O, na2O and K2O in the following amounts: znO:0 to 15%, baO:0 to 10%, caO:0 to 10%, srO:0 to 10%, mgO:0 to 10%, sb2O3:0-1% and the total amount of Li2O, na2O and K2O is 0-10%.
3. The optical glass according to claim 1, wherein the optical glass consists of B in percentage by mass with respect to the total mass of the glass of the composition as converted to oxides 2 O 3 ：5~25%，La 2 O 3 ：30~43%，Gd 2 O 3 ：18~32%，Y 2 O 3 ：0~8%；Yb 2 O 3 ：0~8%; Nb 2 O 5 ：2~15%，SiO 2 ：0.5~15%，ZrO 2 ：1~15%，TiO 2 ：0.5~7%，WO 3 ：0~6%，ZnO：0~15%，BaO：0~10%，CaO：0~10%，SrO：0~10%，MgO：0~10%，Sb 2 O 3 :0 to 1 percent of Li, and the total amount is 0 to 10 percent 2 O、Na 2 O and K 2 O is composed of and Nb 2 O 5 With SiO 2 In a weight ratio of Nb 2 O 5 / SiO 2 0.75 to 1.
4. The optical glass according to claim 1 or 2, wherein the optical glass comprises, in terms of mass percentage content with respect to the total mass of the glass of the composition as converted to oxides: b is 2 O 3 ：8~22%，La 2 O 3 ：30~40%，Gd 2 O 3 ：15~35%，Y 2 O 3 ：0~10%， Yb 2 O 3 :0~10%，Nb 2 O 5 ：5.6~10%，SiO 2 ：3~10%，ZrO 2 ：3~12%，TiO 2 :0.5 to 7 percent and/or WO 3 ：0~10%。
5. The optical glass according to any one of claims 1 to 3, wherein Y is 2 O 3 The content of (B) is 0.
6. The optical glass according to any one of claims 1 to 3, wherein the optical glass does not contain WO 3 。
7. The optical glass according to any one of claims 1 to 3, the Nb 2 O 5 /SiO 2 0.75 to 0.95.
8. The optical glass according to any one of claims 1 to 3, wherein La 2 O 3 、Gd 2 O 3 、Y 2 O 3 And Yb 2 O 3 The total amount of (a) is 50 to 75%.
9. The optical glass according to any one of claims 1 to 3, wherein La 2 O 3 With Gd 2 O 3 In a weight ratio of La 2 O 3 /Gd 2 O 3 1.3 to 1.6.
10. The optical glass according to any one of claims 1 to 3, wherein the optical glass has an upper devitrification temperature lower than 1300 ℃.
11. The optical glass according to claim 1, wherein the optical glass has a refractive index nd > 1.88; the Abbe number vd is more than 39.0.
12. The optical glass according to any one of claims 1 to 3, wherein the stability Dw against water effect of the optical glass is of grade 3 or more; stability against acid action D A Above level 3.
13. The optical glass according to claim 12, wherein the stability Dw against water effect of the optical glass is above grade 2; stability against acid action D A Above level 2.
14. The optical glass according to claim 13, wherein the stability to water action Dw of the optical glass is of the order of 1; stability against acid action D A At level 1.
15. The optical glass according to any one of claims 1 to 3, wherein the optical glass has a striae of C-grade or higher; the bubble degree is above A level.
16. The optical glass according to claim 15, wherein the optical glass has a streak of class B or more; degree of bubbling of A 0 More than grade.
17. The optical glass according to claim 16, wherein the striae of the optical glass are class a; degree of bubbling of A 00 And (4) stages.
18. A glass preform or optical element produced from the optical glass of any one of claims 1 to 17.
19. An optical instrument comprising an optical element, wherein the optical element is according to claim 18.
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