CN115072993A - Optical glass, glass preform, optical element and optical instrument - Google Patents
Optical glass, glass preform, optical element and optical instrument Download PDFInfo
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- CN115072993A CN115072993A CN202210862912.4A CN202210862912A CN115072993A CN 115072993 A CN115072993 A CN 115072993A CN 202210862912 A CN202210862912 A CN 202210862912A CN 115072993 A CN115072993 A CN 115072993A
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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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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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
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- 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 provides an optical glass, which comprises the following components in percentage by weight: SiO 2 2 ：32～49％；B 2 O 3 ：2～12％；La 2 O 3 ：2～12％；Nb 2 O 5 ：20～28％；ZrO 2 ：1～8％；BaO：0.5～7％；Li 2 O：0.5～8％；Na 2 O: 5 to 20% of SiO 2 /B 2 O 3 2.0 to 9.0; SiO 2 2 /La 2 O 3 4.0 to 12.0; b is 2 O 3 /La 2 O 3 0.5 to 2.0; (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.0 to 3.0; nb 2 O 5 /SiO 2 0.3 to 1.5. Through reasonable component distribution ratio, the invention obtainsThe optical glass has negative anomalous dispersion and excellent devitrification resistance.
Description
The present application is a divisional application of the invention patent application entitled "optical glass, glass preform, optical element and optical instrument" with application number 201910566986.1, application date 2019, 06, 27.
Technical Field
The invention relates to optical glass, in particular to optical glass with a refractive index of 1.62-1.72 and an Abbe number of 35-42.
Background
Optical glass is an indispensable important component in optical instruments and optoelectronic products, and with the widespread popularity of optoelectronic products such as smart phones and single-lens reflex cameras in recent years, higher requirements are put on the performance of optical glass, for example, the optical glass is required to have the performance of eliminating or possibly eliminating residual chromatic aberration of a secondary spectrum, and the optical glass is required to have negative anomalous dispersion performance.
The requirement on the devitrification resistance of the optical glass is high in the production or secondary compression process of the optical glass. If the optical glass has poor devitrification resistance, the problems of devitrification and the like are easily generated in the production process, the glass is devitrified, the glass is discarded, particularly, the devitrification in the secondary pressing process can cause that an optical element formed by pressing cannot be used, and the cost and the energy are wasted. Therefore, the optimization of the devitrification resistance of the optical glass becomes a problem to be solved urgently in the research and development of the optical glass.
Disclosure of Invention
The technical problem solved by the invention is to provide an optical glass with excellent devitrification resistance. 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 2 2 ：32～49％；B 2 O 3 ：2～12％；La 2 O 3 ：2～12％；Nb 2 O 5 ：20～28％；ZrO 2 ：1～8％；BaO：0.5～7％；Li 2 O：0.5～8％；Na 2 O: 5 to 20% of SiO 2 /B 2 O 3 Is 9.0 or less; SiO 2 2 /La 2 O 3 4.0 to 12.0; b is 2 O 3 /La 2 O 3 0.5 to 2.0; (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.0 to 3.0; nb 2 O 5 /SiO 2 0.3 to 1.5.
Furthermore, the optical glass comprises the following components in percentage by weight: ZnO: 0 to 5 percent; and/or K 2 O: 0-6%; and/or MgO: 0-6%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or Al 2 O 3 : 0 to 5 percent; and/or P 2 O 5 : 0 to 5 percent; and/or Sb 2 O 3 ：0～1％。
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 : 36-45%; and/or B 2 O 3 : 3-10%; and/or La 2 O 3 : 3-10%; and/or Nb 2 O 5 : 22-28%; and/or ZrO 2 : 2-7%; and/or BaO: greater than 1% but less than or equal to 6%; and/or Li 2 O: 1-6%; and/or Na 2 O: 10-16%; and/or ZnO: 0 to 3 percent; and/or K 2 O: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or Al 2 O 3 : 0 to 3 percent; and/or P 2 O 5 : 0 to 3 percent; and/or Sb 2 O 3 ：0～0.5％。
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 : 36-42%; and/or B 2 O 3 : greater than 5% but less than or equal to 10%; and/or La 2 O 3 ：4～9％。
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 /B 2 O 3 2.0 to 9.0; and/or SiO 2 /La 2 O 3 4.5 to 10.0; and/or B 2 O 3 /La 2 O 3 0.6 to 1.5; and/or (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.2 to 2.5; and/or Nb 2 O 5 /SiO 2 0.4 to 1.2; and/or SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.0 to 8.0; and/or (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 2.0 to 10.0; and/or (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.0 to 5.0.
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 /B 2 O 3 4.0 to 9.0; and/or SiO 2 /La 2 O 3 5.0 to 9.0; and/or B 2 O 3 /La 2 O 3 0.7 to 1.2; and/or (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.2; and/or Nb 2 O 5 /SiO 2 0.5 to 1.0; and/or SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 7.0; and/or (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 3.0 to 8.0; and/or (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.3 to 3.0.
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 /B 2 O 3 5.0 to 8.5; and/or SiO 2 /La 2 O 3 6.0 to 8.3;and/or B 2 O 3 /La 2 O 3 Greater than or equal to 0.8 but less than 1.0; and/or (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.0; and/or Nb 2 O 5 /SiO 2 0.5 to 0.8; and/or SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 6.0; and/or (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 3.5 to 7.0; and/or (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.5.
Further, the optical glass comprises the following components in percentage by weight: SiO 2 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 5.5; and/or (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) Greater than 4.0 but less than or equal to 6.0; and/or (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.0.
Further, the above-mentioned optical glass has a Δ P g,F ≦ 0.001, preferably Δ P g,F ≦ 0.002, more preferably Δ P g,F ≦ 0.003, more preferably Δ P g,F ≤-0.004。
Further, the refractive index n of the above optical glass d 1.62 to 1.72, preferably 1.63 to 1.70, and more preferably 1.64 to 1.69; abbe number v d 35 to 42, preferably 36 to 41, and more preferably 37 to 40.
Further, the optical glass satisfies the following relation: delta P g,F +0.1×n d /v d ≧ 0.003, preferably satisfying the relationship: delta P g,F +0.1×n d /v d ≧ 0.001, more preferably the relationship: delta P g,F +0.1×n d /v d 0 or more, further preferably satisfies the relation: delta P g,F +0.1×n d /v d ≥0.0001。
Further, the transition temperature T of the above optical glass g Is 550 ℃ or lower, preferably 540 ℃ or lower, more preferably 530 ℃ or lower; andor a degree of bubbling of at least class A, preferably A 0 More preferably A or more 00 A stage; and/or acid stability RA is 2 or more, preferably 1; and/or the moisture resistance stability RC is of 3 or more, preferably 2 or more.
The glass preform is made of the optical glass.
And the optical element is made of the optical glass or the glass prefabricated member.
An optical device comprising the above optical glass or the above optical element.
The invention has the beneficial effects that: through reasonable component proportion, the optical glass obtained by the invention has negative anomalous dispersion and excellent devitrification resistance.
Detailed Description
The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications 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.
SiO 2 Is a skeleton of optical glass, and can be used as glass network forming body for maintaining chemical stability of glass and improving devitrification resistance of glass 2 When the content is less than 32%, the above effects are difficult to achieve; but when SiO 2 At contents higher than 49%, the glass becomes refractory and it is difficult to obtain the refractive index required for the present invention. Thus, SiO 2 The content of (B) is 32 to 49%, preferably 36 to 45%, more preferably 36 to 42%.
B 2 O 3 The glass of the present invention may also be used as a glass network forming body. In the invention, more than 2 percent of B is introduced 2 O 3 To prevent the devitrification resistance of the glass from lowering, when B 2 O 3 When the content is more than 12%, the chemical stability of the glass is deteriorated, and at the same time, the viscosity of the glass is decreased, and the volatilization is increased, which is disadvantageous for the stable control of the refractive index and dispersion. Thus, B 2 O 3 The content is limited to 2 to 12%, preferably 3 to 10%. In some embodiments of the invention, B is prepared by reacting 2 O 3 The content exceeding 5% is advantageous for elimination of bubbles, so B is more preferable 2 O 3 The content is more than 5% but less than or equal to 10%.
The invention has found through a great deal of research that SiO 2 /B 2 O 3 When the content of (b) is less than 9.0, the glass can have reasonable melting property and high-temperature viscosity, and is favorable for discharging bubbles in the production process, thereby improving the bubble degree of the glass, preventing the residual of glass raw materials, and simultaneously, the devitrification resistance of the glass can be excellent. In some embodiments, if SiO 2 /B 2 O 3 A value of less than 2.0, the chemical stability and transmittance of the glass are reduced. Thus, in the present invention, SiO 2 /B 2 O 3 Has a value of 9.0 or less, preferably SiO 2 /B 2 O 3 2.0 to 9.0, more preferably SiO 2 /B 2 O 3 4.0 to 9.0, and further preferably SiO 2 /B 2 O 3 5.0 to 8.5.
La 2 O 3 Can improve the refractive index of the glass, keep low dispersity and enhance the mechanical strength of the glass, and more than 2 percent of La is introduced into the invention 2 O 3 In order to achieve the above-mentioned effects and achieve the abnormal dispersibility, if the content thereof exceeds 12%, the melting temperature of the glass rises and the chemical stability is lowered. Thus, the La of the present invention 2 O 3 The content of (b) is 2 to 12%, preferably 3 to 10%, more preferably 4 to 9%.
In the present invention, if SiO 2 /La 2 O 3 Below 4.0, the devitrification resistance of the glass deteriorates, if SiO 2 /La 2 O 3 Above 12.0, the chemical stability, especially the acid resistance stability, of the glass is lowered, and therefore, SiO 2 /La 2 O 3 In the range of 4.0 to 12.0, preferably SiO 2 /La 2 O 3 4.5 to 10.0, more preferably SiO 2 /La 2 O 3 5.0 to 9.0, and further preferably SiO 2 /La 2 O 3 6.0 to 8.3.
In the present invention, if B 2 O 3 /La 2 O 3 Below 0.5, the melting properties of the glass become poor and the density increases, if B 2 O 3 /La 2 O 3 Above 2.0, the refractive index and the anomalous dispersion of the glass do not meet the design requirements, so B 2 O 3 /La 2 O 3 In the range of 0.5 to 2.0, preferably B 2 O 3 /La 2 O 3 0.6 to 1.5, and more preferably B 2 O 3 /La 2 O 3 0.7 to 1.2, and preferably B 2 O 3 /La 2 O 3 Is greater than or equal to 0.8 but less than 1.0.
In some embodiments of the invention, the SiO is provided by 2 /(La 2 O 3 +B 2 O 3 ) In the range of 3.0-8.0, the glass can obtain proper forming viscosity and improve the striae degree of the glass while ensuring good meltability, and SiO is preferred 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 7.0, more preferably SiO 2 /(La 2 O 3 +B 2 O 3 ) Is 3.5 to 6.0. In some embodiments, the SiO 2 /(La 2 O 3 +B 2 O 3 ) In the range of 3.5 to 5.5, the bubble degree of the glass can be further optimized, and SiO is more preferable 2 /(La 2 O 3 +B 2 O 3 ) Is 3.5 to 5.5.
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 6%, preferably 0 to 3%, and it is more preferable that no MgO is introduced.
CaO helps to adjust the optical constants of the glass, and increases the mechanical strength and hardness of the glass. However, when the amount of CaO added is too large, the optical data of the glass is not satisfactory, and the devitrification resistance is deteriorated. Therefore, the CaO content is limited to 0 to 6%, preferably 0 to 3%.
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 6%, preferably 0 to 3%, and more preferably SrO is not introduced.
BaO is an essential component for adjusting the refractive index of the glass and improving the transmittance and the strength of the glass in the invention, and the effect is not obvious when the content of BaO is less than 0.5 percent; however, when the content exceeds 7%, the devitrification resistance and chemical stability of the glass are deteriorated. Therefore, the BaO content is limited to 0.5 to 7%, preferably more than 1% but 6% or less.
In some embodiments of the invention, the composition is prepared by reacting (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) In the range of 2.0-10.0, the glass has excellent processing performance under the condition of obtaining excellent chemical stability, is beneficial to mechanical processing (cutting, grinding, polishing and the like) of the glass, and preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 3.0 to 8.0, more preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) Is 3.5 to 7.0, and more preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) Greater than 4.0 but less than or equal to 6.0.
Li 2 O has a strong effect of lowering the glass transition temperature, and in the present invention, 0.5% or more of Li is introduced 2 O to obtain the above effects, Li is preferable 2 The content of O is more than 1 percent; when Li 2 When the O content is large, the machinability tends to decrease, so Li 2 O content is 8% or less, and Li is preferable 2 The O content is below 6 percent.
Na 2 O has the function of improving the meltability of the glass and has obvious function of improving the melting effect, and more than 5 percent of Na is introduced into the invention 2 O to obtain the above effects, preferably Na 2 The content of O is more than 10 percent; when Na is present 2 The content of O exceeds 20%, and the glass tends to be lowered in chemical stability and weather resistance, so Na 2 The O content is 20% or less, preferably 16% or less.
K 2 O has a fluxing action, and when it exceeds 6%, the devitrification resistance of the glass is reduced, so that K 2 The upper limit of the O content is 6%, preferably 3%, and more preferably no introduction of K 2 O。
In the present invention, if (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) Below 1.0, the high-temperature viscosity of the glass is reduced, the striae degree is deteriorated, and the devitrification resistance is deteriorated; if (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) Above 3.0, the transition temperature and density of the glass increase. Thus, (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) Is in the range of 1.0 to 3.0, preferably (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.2 to 2.5, more preferably (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.2, and more preferably (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.0.
ZrO 2 Is a component having an increased refractive index, by containing, in an appropriate amount, ZrO 2 Also, the glass is less likely to be broken by machining. In order to obtain these effects well, ZrO in the glass of the present invention 2 The content of (b) is 1% or more, preferably 2% or more. On the other hand, from the viewpoint of improving the thermal stability of the glass, ZrO 2 The content of (b) is 8% or less, preferably 7% or less. By improving the thermal stability, it is possible to suppress the occurrence of devitrification during glass production and the occurrence of a melting residue during glass melting.
Nb 2 O 5 Is a component for improving the devitrification resistance, refractive index and dispersion of the glass to obtain an abnormal dispersion, and Nb is used in the invention 2 O 5 In an amount of 20% or more to achieve the above properties, preferably Nb 2 O 5 The content of (A) is more than 22%. When the content exceeds 28%, the thermal stability and optical transmittance of the glass decrease and the liquidus temperature tends to increase, so that Nb in the present invention 2 O 5 The content of (B) is 28% or less.
In the present invention, by controlling Nb 2 O 5 /SiO 2 In the range of 0.3 to 1.5, the glass can obtain excellent devitrification resistance under the condition that the optical transmittance of the glass is ensured, and Nb is preferred 2 O 5 /SiO 2 0.4 to 1.2, more preferably Nb 2 O 5 /SiO 2 0.5 to 1.0, and further preferably Nb 2 O 5 /SiO 2 0.5 to 0.8.
In some embodiments of the present invention, (Nb) is 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) less than 1.0, the desired refractive index and abnormal dispersibility are difficult to obtain for the glass, the chemical stability is reduced; if (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) exceeds 5.0, the optical transmittance of the glass decreases, and the transition temperature and the tendency to devitrify increase. Thus, (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is in the range of 1.0 to 5.0, preferably (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.3 to 3.0,more preferably (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.5, and (Nb) is more preferable 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.0.
ZnO can lower the glass transition temperature and improve the melting property of the glass, and when the content of ZnO exceeds 5 percent, the transmittance and the chemical stability of the glass tend to be reduced. Therefore, the content of ZnO is 0 to 5%, preferably 0 to 3%, and more preferably not introduced.
Al 2 O 3 The chemical stability of the glass can be improved, but when the content exceeds 5%, the dispersion of the glass increases and the meltability deteriorates. Thus, Al of the invention 2 O 3 The content of (B) is 0 to 5%, preferably 0 to 3%.
P 2 O 5 Is an optional component which can improve the devitrification resistance of the glass, particularly by reacting P 2 O 5 The content of (A) is 5% or less, and the decrease of the chemical stability, especially the moisture resistance stability of the glass can be suppressed. Thus, P 2 O 5 The content is limited to 5% or less, more preferably 3% or less, and further preferably not incorporated.
By adding small amounts of Sb 2 O 3 The refining effect of the glass can be improved, but when Sb is used 2 O 3 When 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 2 O 3 The amount of (B) is 1% or less, preferably 0.5% or less.
In the glass of the present invention, even when the glass contains a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo 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 effect of the present invention to improve the 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 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.
To achieve environmental friendliness, the glasses according to the invention do not contain As 2 O 3 And PbO. Although As 2 O 3 Has the effects of eliminating bubbles and better preventing the glass from being colored, but is As 2 O 3 The 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. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As 2 O 3 All cause environmental pollution.
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 also 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 glass, and may be present in small or trace amounts in the final glass.
The performance of the optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) of glass d ) And Abbe number (v) d ) The test was carried out according to the method specified in GB/T7962.1-2010.
Refractive index (n) of glass of the invention d ) 1.62 to 1.72, preferably 1.63 to 1.70, more preferably 1.64 to 1.69, and further preferably 1.65 to 1.69; abbe number (. nu.) d ) 35 to 42, preferably 36 to 41, and more preferably 37 to 40.
< negative anomalous dispersion >
By the following formulaIllustrating relative partial dispersion (P) g,F ) And negative anomalous dispersion (Δ P) g,F ) The origin of (1).
The relative partial dispersion for wavelengths x and y is represented by the following formula (1):
P x,y ＝(n x -n y )/(n F -n C ) (1)
the following formula (2) holds for most of the so-called "normal glasses" according to the Abbe number formula (hereinafter, H-K6 and F4 are used as "normal glasses")
P x,y ＝m x,y ·v d +b x,y (2)
This linear relationship is P x,y Is ordinate, v d Expressed on the abscissa, where m x,y Is the slope, b x,y Is the intercept.
It is known that the correction of the secondary spectrum, i.e. the achromatization of more than two wavelengths, requires at least one glass which does not conform to the above formula (2) (i.e. its P) x,y Value deviation from Abbe's empirical formula) by Δ P x,y Indicates that each P is x,y -v d The point being shifted by Δ P with respect to a "normal line" corresponding to the above formula (2) x,y Amount of such a.DELTA.P of each glass x,y The numerical value can be obtained by the following equation (3):
P x,y ＝m x,y ·v d +b x,y +ΔP x,y (3)
thus Δ P x,y Quantitatively indicating the deviation behavior of the specific dispersion when compared to "normal glass".
Therefore, from the above, relative partial dispersion (P) can be obtained g,F ) And negative anomalous dispersion (Δ P) g,F ) Are the following formulas (4) and (5):
P g,F ＝(n g -n F )/(n F -n C ) (4)
ΔP g,F ＝P g,F -0.6457+0.001703v d (5)
negative anomalous dispersion (. DELTA.P) of the glasses of the invention g,F ) ≦ 0.001, preferably Δ P g,F ≦ 0.002, more preferably Δ P g,F ≦ 0.003, more preferably Δ P g,F ≤-0.004。
The refractive index, Abbe number and negative anomalous dispersion of the optical glass meet the relational expression: delta P g,F +0.1×n d /v d ≧ 0.003, preferably satisfying the relationship: delta P g,F +0.1×n d /v d More preferably, ≧ 0.001, the relationship: delta P g,F +0.1×n d /v d 0 or more, further preferably satisfies the relation: delta P g,F +0.1×n d /v d ≥0.0001。
< stability against moisture >
The moisture Resistance (RC) of the glass (surface method) was tested according to the method specified in GB/T7962.15-2010.
The glass of the present invention has a moisture resistance stability (RC) (surface method) of 3 or more types, preferably 2 or more types.
< stability against acid >
The acid Resistance (RA) of the glass (surface method) was tested according to the method specified in GB/T7962.14-2010.
The glass of the present invention has an acid resistance stability (RA) (surface method) of 2 or more, preferably 1.
< degree of bubbling >
The bubble degree of the glass is tested according to the method specified in GB/T7962.8-2010.
The glass of the present invention has a bubble content of class B or more, preferably class A or more, more preferably class A 0 More preferably A or more 00 And (4) stage.
< transition temperature >
Transition temperature (T) of glass g ) The test was carried out according to the method specified in GB/T7962.16-2010.
Transition temperature (T) of the glasses according to the invention g ) Is 550 ℃ or lower, preferably 540 ℃ or lower, and more preferably 530 ℃ or lower.
[ method for producing glass ]
The manufacturing method of the glass of the invention is as follows: 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 1250-1400 ℃ 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 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 the excellent characteristics of the glass of the present invention; the optical element of the present invention has the excellent characteristics of the glass of the present invention, and can provide various optical elements such as 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 glass or 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 glass production method. Further, 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, in which SiO is represented by K1 2 /B 2 O 3 K2 denotes SiO 2 /La 2 O 3 K3 denotes SiO 2 /(La 2 O 3 +B 2 O 3 ) Denoted by K4 (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) K5 denotes B 2 O 3 /La 2 O 3 Denoted by K6 (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) Denoted by K7 (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO), K8 represents Nb 2 O 5 /SiO 2 。
TABLE 1
| Example (wt%) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| SiO 2 | 42.5 | 41.1 | 33.68 | 40.4 | 35.3 | 34.25 | 43.5 | 39.5 | 45.2 | 43.23 |
| B 2 O 3 | 8.3 | 5.2 | 3.8 | 5.55 | 4.75 | 5.15 | 5.47 | 4.85 | 8.5 | 6.25 |
| La 2 O 3 | 4.24 | 4.25 | 4.35 | 7.2 | 6.45 | 6 | 6.25 | 7.24 | 5.16 | 6.34 |
| Nb 2 O 5 | 26.6 | 21.34 | 27.6 | 23.42 | 23.5 | 24.7 | 23.3 | 24.1 | 22.15 | 20.37 |
| ZrO 2 | 6.25 | 4.5 | 3.2 | 2.51 | 4.24 | 5.26 | 7.15 | 3.34 | 4.6 | 5.2 |
| Li 2 O | 2.2 | 6.5 | 1.25 | 3.3 | 4.3 | 5.42 | 2.24 | 2.57 | 1 | 3.5 |
| Na 2 O | 8.5 | 13.26 | 18.3 | 11.25 | 17.5 | 7.35 | 8.8 | 14 | 9.35 | 12.7 |
| K 2 O | 0 | 0 | 0.85 | 0 | 0 | 2.5 | 0 | 0 | 0 | 0 |
| MgO | 0 | 0 | 0 | 1.6 | 0 | 0 | 0 | 0 | 2.24 | 0 |
| CaO | 0 | 0 | 0 | 0 | 0 | 3.5 | 0 | 0 | 0 | 0 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 1.31 | 3.8 | 6.75 | 0.77 | 2.24 | 5.5 | 3.2 | 4.4 | 1.8 | 2.31 |
| ZnO | 0 | 0 | 0.2 | 2.5 | 0 | 0 | 0 | 0 | 0 | 0 |
| Al 2 O 3 | 0 | 0 | 0 | 1.3 | 0 | 0.24 | 0 | 0 | 0 | 0 |
| P 2 O 5 | 0 | 0 | 0 | 0 | 1.57 | 0 | 0 | 0 | 0 | 0 |
| Sb 2 O 3 | 0.1 | 0.05 | 0.02 | 0.2 | 0.15 | 0.13 | 0.09 | 0 | 0 | 0.1 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| K1 | 5.12 | 7.904 | 8.863 | 7.279 | 7.432 | 6.65 | 7.952 | 8.144 | 5.318 | 6.917 |
| K2 | 10.02 | 9.671 | 7.743 | 5.611 | 5.473 | 5.708 | 6.96 | 5.456 | 8.76 | 6.819 |
| K3 | 3.389 | 4.349 | 4.133 | 3.169 | 3.152 | 3.072 | 3.712 | 3.267 | 3.309 | 3.434 |
| K4 | 3.494 | 4.751 | 4.961 | 3.229 | 3.352 | 3.565 | 3.985 | 3.631 | 3.441 | 3.617 |
| K5 | 1.958 | 1.224 | 0.874 | 0.771 | 0.736 | 0.858 | 0.875 | 0.67 | 1.647 | 0.986 |
| K6 | 2.306 | 1.799 | 1.731 | 2.048 | 1.414 | 2.218 | 2.829 | 2.049 | 2.493 | 2.029 |
| K7 | 2.735 | 1.097 | 1.171 | 1.693 | 1.154 | 1.64 | 2.138 | 1.309 | 2.202 | 1.381 |
| K8 | 0.626 | 0.519 | 0.819 | 0.58 | 0.666 | 0.721 | 0.536 | 0.61 | 0.49 | 0.471 |
| n d | 1.71255 | 1.63543 | 1.65224 | 1.64533 | 1.66354 | 1.67215 | 1.67416 | 1.66425 | 1.64753 | 1.65025 |
| v d | 40.25 | 37.25 | 38.12 | 36.17 | 37.55 | 40.13 | 39.55 | 38.85 | 37.55 | 39.15 |
| ΔP g,F | -0.00385 | -0.00425 | -0.00271 | -0.00424 | -0.00305 | -0.00316 | -0.00505 | -0.00415 | -0.00427 | -0.00336 |
| ΔP g,F +0.1×n d /v d | 0.00040 | 0.00014 | 0.00162 | 0.00031 | 0.00138 | 0.00101 | -0.00082 | 0.00013 | 0.00012 | 0.00086 |
| T g (℃) | 533.5 | 512.3 | 511.5 | 530.5 | 515.1 | 521.2 | 527.2 | 524.5 | 528.6 | 526.1 |
| Degree of bubbling | A 00 | A 00 | A | A 0 | A 0 | A 0 | A 00 | A 0 | A 0 | A 00 |
| RA | Class 2 | Class 2 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 2 | Class 1 |
| RC | Class 3 | Class 2 | Class 2 | Class 2 | Class 2 | Class 2 | Class 2 | Class 1 | Class 3 | Class 2 |
TABLE 2
< 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 glass examples 1 to 20 by means of, for example, polishing or press molding such as reheat press molding and precision press molding.
< optical element example >
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.
< 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 (11)
1. Optical glass, characterized in that its components, expressed in weight percent, contain: SiO 2 2 ：32～49％；B 2 O 3 ：2～12％；La 2 O 3 ：2～12％；Nb 2 O 5 ：20～28％；ZrO 2 ：1～8％；BaO：0.5～7％；Li 2 O：0.5～8％；Na 2 O: 5 to 20% of SiO 2 /B 2 O 3 2.0 to 9.0; SiO 2 2 /La 2 O 3 4.0 to 12.0; b is 2 O 3 /La 2 O 3 0.5 to 2.0; (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.0 to 3.0; nb 2 O 5 /SiO 2 0.3 to 1.5.
2. The optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: ZnO: 0 to 5 percent; and/or K 2 O: 0-6%; and/or MgO: 0-6%; and/or CaO: 0-6%; and/or SrO: 0-6%; and/or Al 2 O 3 : 0 to 5 percent; and/or P 2 O 5 : 0 to 5 percent; and/or Sb 2 O 3 ：0～1％。
3. An optical glass according to claim 1 or 2, characterised in that its composition, expressed in weight percent, comprises: SiO 2 2 : 36-45%, preferably SiO 2 : 36-42%; and/or B 2 O 3 : 3 to 10%, preferably B 2 O 3 : greater than 5% but less than or equal to 10%; and/or La 2 O 3 : 3-10%, preferably La 2 O 3 : 4-9%; and/orNb 2 O 5 : 22-28%; and/or ZrO 2 : 2-7%; and/or BaO: greater than 1% but less than or equal to 6%; and/or Li 2 O: 1-6%; and/or Na 2 O: 10-16%; and/or ZnO: 0 to 3 percent; and/or K 2 O: 0 to 3 percent; and/or MgO: 0 to 3 percent; and/or CaO: 0 to 3 percent; and/or SrO: 0 to 3 percent; and/or Al 2 O 3 : 0 to 3 percent; and/or P 2 O 5 : 0 to 3 percent; and/or Sb 2 O 3 ：0～0.5％。
4. An optical glass according to claim 1 or 2, characterised in that its composition, expressed in weight percentages, is such that: SiO 2 2 /B 2 O 3 4.0 to 9.0, preferably SiO 2 /B 2 O 3 5.0 to 8.5; and/or SiO 2 /La 2 O 3 4.5 to 10.0, preferably SiO 2 /La 2 O 3 5.0 to 9.0, more preferably SiO 2 /La 2 O 3 6.0 to 8.3; and/or B 2 O 3 /La 2 O 3 0.6 to 1.5, preferably B 2 O 3 /La 2 O 3 0.7 to 1.2, and more preferably B 2 O 3 /La 2 O 3 Greater than or equal to 0.8 but less than 1.0; and/or (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.2 to 2.5, preferably (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.2, more preferably (BaO + SiO) 2 )/(Li 2 O+Na 2 O+B 2 O 3 ) 1.5 to 2.0; and/or Nb 2 O 5 /SiO 2 0.4 to 1.2, preferably Nb 2 O 5 /SiO 2 0.5 to 1.0, more preferably Nb 2 O 5 /SiO 2 0.5 to 0.8; and/or SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.0 to 8.0, preferably SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 7.0, more preferably SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 6.0, and more preferably SiO 2 /(La 2 O 3 +B 2 O 3 ) 3.5 to 5.5; and/or (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 2.0 to 10.0, preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 3.0 to 8.0, more preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) 3.5 to 7.0, and more preferably (BaO + SiO) 2 )/(La 2 O 3 +B 2 O 3 ) Is greater than 4.0 but less than or equal to 6.0; and/or (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.0 to 5.0, preferably (Nb) 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.3 to 3.0, and (Nb) is more preferable 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.5, and (Nb) is more preferable 2 O 5 +ZrO 2 )/(Li 2 O+Na 2 O + BaO) is 1.5 to 2.0.
5. An optical glass according to claim 1 or 2, characterised in that the glass has a Δ P g,F ≦ 0.001, preferably Δ P g,F ≦ 0.002, more preferably Δ P g,F ≦ 0.003, more preferably Δ P g,F ≤-0.004。
6. An optical glass according to claim 1 or 2, characterised in that the refractive index n of the glass is d 1.62 to 1.72, preferably 1.63 to 1.70, and more preferably 1.64 to 1.69; abbe number v d 35 to 42, preferably 36 to 41, and more preferably 37 to 40.
7. An optical glass according to claim 1 or 2, wherein the relation: delta P g,F +0.1×n d /v d ≧ 0.003, preferably satisfying the relationship: delta P g,F +0.1×n d /v d More preferably, ≧ 0.001, the relationship: delta P g,F +0.1×n d /v d 0 or more, further preferably satisfies the relation: delta P g,F +0.1×n d /v d ≥0.0001。
8. An optical glass according to claim 1 or 2, characterised in that the glass has a transition temperature T g Is 550 ℃ or lower, preferably 540 ℃ or lower, more preferably 530 ℃ or lower; and/or the degree of bubbling is class A or more, preferably class A 0 More preferably A or more 00 Stage (2); and/or acid stability RA is 2 or more, preferably 1; and/or the moisture resistance stability RC is of 3 or more, preferably 2 or more.
9. A glass preform made of the optical glass according to any one of claims 1 to 8.
10. An optical element produced from the optical glass according to any one of claims 1 to 8 or the glass preform according to claim 9.
11. An optical device comprising the optical glass according to any one of claims 1 to 8 or the optical element according to claim 10.
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| CN110204199B (en) * | 2019-06-27 | 2022-05-17 | 成都光明光电股份有限公司 | Glass with negative anomalous dispersion |
| CN111204970A (en) * | 2020-03-06 | 2020-05-29 | 成都光明光电股份有限公司 | Optical glass, glass preform and optical element |
| CN111204972A (en) * | 2020-03-06 | 2020-05-29 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
| CN111204969A (en) * | 2020-03-06 | 2020-05-29 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
| CN112047625B (en) * | 2020-09-17 | 2022-04-15 | 成都光明光电股份有限公司 | Ultraviolet-transmitting optical glass |
| CN113264675B (en) * | 2021-06-24 | 2022-04-15 | 成都光明光电股份有限公司 | Optical glass, optical element and optical instrument |
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