CN115304274A - High-refraction high-dispersion optical glass - Google Patents
High-refraction high-dispersion optical glass Download PDFInfo
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- CN115304274A CN115304274A CN202211031612.8A CN202211031612A CN115304274A CN 115304274 A CN115304274 A CN 115304274A CN 202211031612 A CN202211031612 A CN 202211031612A CN 115304274 A CN115304274 A CN 115304274A
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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
- C03C4/00—Compositions for glass with special properties
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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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Abstract
The invention provides high-refraction high-dispersion optical glass, which comprises the following components in percentage by weight: siO 2 2 +B 2 O 3 ：8～28％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：46～70％；ZrO 2 ：1～12％；Nb 2 O 5 ：4～20％；TiO 2 :4 to 18 percent of which is TiO 2 /Y 2 O 3 0.3 to 4.0. Through reasonable component design, the optical glass has excellent weather resistance and abrasion resistance while having the expected refractive index and dispersion.
Description
Technical Field
The present invention relates to an optical glass, and more particularly to a high-refractive-index, high-dispersion optical glass having excellent weatherability and abrasion resistance.
Background
In recent years, digitalization and high definition of optical devices have been rapidly advanced, and there has been a demand for reduction in weight and size of optical elements used in various optical devices such as imaging devices such as digital cameras and video cameras, and projection devices such as projectors and projection televisions. Under the same curvature radius, the higher the refractive index of the glass, the larger the obtained imaging field of view is, which is beneficial to reducing the number of optical elements in the optical instrument, and along with the development trend of miniaturization of the optical instrument, the demand trend of the high refractive index glass is more and more obvious. Meanwhile, with the rapid development of the fields of monitoring security, vehicle-mounted imaging and the like, the high-refractive-index optical glass is also widely applied to the fields of monitoring, vehicle-mounted imaging and the like, and the optical glass applied to the fields needs to have excellent weather resistance so as to prolong the service life of the optical glass in severe environments.
In the optical element processing, it is required that the optical glass has good processability and excellent abrasion resistance by producing a glass preform by performing mechanical processing such as grinding and polishing on the optical glass, or by producing a preform for press molding from the optical glass, and then performing grinding after performing reheat press molding on the preform, or by performing precision press molding on the preform obtained by performing grinding.
Disclosure of Invention
The technical problem to be solved by the invention is to provide high-refraction high-dispersion optical glass with excellent weather resistance and abrasion resistance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) High-refractive high-dispersive optical glass, the composition of which is expressed by weight percentage and comprises: siO 2 2 +B 2 O 3 ：8～28％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：46～70％；ZrO 2 ：1～12％；Nb 2 O 5 ：4～20％；TiO 2 :4 to 18 percent of which is TiO 2 /Y 2 O 3 0.3 to 4.0.
(2) The high-refractive-index and high-dispersion optical glass according to (1), which comprises the following components in percentage by weight: ta 2 O 5 :0 to 8 percent; and/or RO:0 to 9 percent; and/or Rn 2 O:0 to 6 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0-2%, RO is one or more of MgO, caO, srO and BaO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(3) High refractive index, high dispersion optical glass containing ZrO 2 、Nb 2 O 5 、TiO 2 The components of the material are expressed by weight percentage and contain 8 to 28 percent of SiO 2 +B 2 O 3 And 46 to 70% of La 2 O 3 +Y 2 O 3 +Gd 2 O 3 In which TiO is 2 /Y 2 O 3 0.3 to 4.0, the refractive index n of the high-refractive-index high-dispersion optical glass d Is 1.92 to 1.98, abbe number v d 29 to 36, abrasion degree F A 80 to 130, and has a weather resistance CR of 2 or more types.
(4) The high-refractive-index and high-dispersion optical glass according to (3), which comprises the following components in percentage by weight: zrO (ZrO) 2 :1 to 12 percent; and/or Nb 2 O 5 :4 to 20 percent; and/or TiO 2 :4 to 18 percent; and/or Ta 2 O 5 :0 to 8 percent; and/or RO:0 to 9 percent; and/or Rn 2 O:0 to 6 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 2 percent of RO, rn and one or more of MgO, caO, srO and BaO 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(5) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), whose composition, expressed in weight percentage, satisfies one or more of the following 9 cases:
1)La 2 O 3 /(TiO 2 +Nb 2 O 5 ) 1.2 to 6.0, preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 1.5 to 5.0, more preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 2.0 to 4.0, and La is more preferable 2 O 3 /(TiO 2 +Nb 2 O 5 ) 2.5 to 3.5;
2)TiO 2 /Y 2 O 3 0.5 to 3.0, preferably TiO 2 /Y 2 O 3 0.6 to 2.0, more preferably TiO 2 /Y 2 O 3 0.75 to 1.5;
3)Y 2 O 3 /B 2 O 3 0.4 to 3.0, preferably Y 2 O 3 /B 2 O 3 Is 0.5 to 2.5, more preferably Y 2 O 3 /B 2 O 3 Is 0.6 to 1.5, and Y is more preferably 2 O 3 /B 2 O 3 0.7 to 1.2;
4)(B 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.0 to 10.0, preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.0 to 8.0, more preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.5 to 7.0, more preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 2.0 to 5.0;
5)(Ta 2 O 5 +Gd 2 O 3 )/Y 2 O 3 is 1.0 or less, preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.6 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.4 or less, and (Ta) is more preferable 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.1 or less;
6)TiO 2 /(Nb 2 O 5 +WO 3 ) 0.3 to 3.0, preferably TiO 2 /(Nb 2 O 5 +WO 3 ) Is 0.4 to 2.0, more preferably TiO 2 /(Nb 2 O 5 +WO 3 ) Is 0.6 to 1.5, and TiO is more preferable 2 /(Nb 2 O 5 +WO 3 ) 0.8 to 1.3;
7)ZnO/(SiO 2 +B 2 O 3 ) Is 0.5 or less, and ZnO/(SiO) is preferred 2 +B 2 O 3 ) Is 0.3 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.2 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.1 or less;
8)(Gd 2 O 3 +ZnO)/Y 2 O 3 is 1.0 or less, preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.6 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.3 or less, and (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.1 or less;
9)WO 3 /Y 2 O 3 is 0.8 or less, preferably WO 3 /Y 2 O 3 Is 0.6 or less, and WO is more preferable 3 /Y 2 O 3 Is 0.02 to 0.5, and WO is more preferable 3 /Y 2 O 3 0.05 to 0.3.
(6) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: la 2 O 3 +Y 2 O 3 +Gd 2 O 3 :50 to 68%, preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :55 to 65 percent; and/or SiO 2 +B 2 O 3 :10 to 25%, preferably SiO 2 +B 2 O 3 :12 to 20 percent; and/or ZrO 2 :3 to 10%, preferably ZrO 2 :4 to 9 percent; and/or Nb 2 O 5 :5 to 15%, preferably Nb 2 O 5 :7 to 12 percent; and/or Ta 2 O 5 :0 to 4%, preferably Ta 2 O 5 :0 to 2 percent; and/or TiO 2 :5 to 13%, preferably TiO 2 :6 to 12 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 4%, preferably Rn 2 O:0 to 1 percent; and/or WO 3 :0 to 4%, preferably WO 3 :0.5 to 3 percent; and/or ZnO:0 to 4%, preferably ZnO:0 to 2 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 1 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(7) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: siO 2 2 :1 to 12%, preferably SiO 2 :2 to 10%, more preferably SiO 2 :4 to 9 percent; and/or B 2 O 3 :5 to 18%, preferably B 2 O 3 :6 to 14%, more preferably B 2 O 3 :7 to 12 percent; and/or La 2 O 3 :40 to 60%, preferably La 2 O 3 :43 to 58%, more preferably La 2 O 3 :46 to 53 percent; and/or Y 2 O 3 :4 to 20%, preferably Y 2 O 3 :5 to 15%, more preferably Y 2 O 3 :6 to 12 percent; and/or Gd 2 O 3 :0 to 9%, preferably Gd 2 O 3 :0 to 5%, more preferably Gd 2 O 3 :0 to 3%, and Gd is more preferable 2 O 3 ：0～1％。
(8) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), wherein the composition thereof is, in terms of weight percent, siO 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 88% or more, and SiO is preferred 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 90% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (2) is 92% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 95% or more.
(9) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), which does not contain Ta in its composition 2 O 5 (ii) a And/or does not contain Yb 2 O 3 (ii) a And/or does not contain RO; and/or does not contain Rn 2 O; and/or no ZnO; and/or does not contain Al 2 O 3 (ii) a And/or does not contain GeO 2 The RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
(10) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), wherein the refractive index n of the high-refractive-index, high-dispersion optical glass d Is 1.92 to 1.98, preferably 1.93 to 1.97, more preferably 1.94 to 1.96, abbe number v d Is 29 to 36, preferably 30 to 35, more preferably 31 to 34.
(11) The high-refractive-index, high-dispersion optical glass according to any one of (1) to (4), wherein the density ρ of the high-refractive-index, high-dispersion optical glass is 5.10g/cm 3 Below, preferably 5.00g/cm 3 Hereinafter, more preferably 4.95g/cm 3 The following; and/or coefficient of thermal expansion alpha -30/70℃ Is 85X 10 -7 Preferably 80X 10 or less,/K -7 A value of not more than 75X 10 -7 A value of 70X 10 or less in terms of/K or less -7 below/K; and/or stability against water action D W Is 2 or more, preferably 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or lambda 70 Is 425nm or less, preferably lambda 70 Is 420nm or less, more preferably lambda 70 415nm or less; and/or lambda 5 Is 375nm or less, preferably lambda 5 Is 370nm or less, more preferably λ 5 Is less than 365 nm; and/or the weather resistance CR is of class 2 or more, preferably of class 1; and/or Knoop hardness H K Is 650 x 10 7 Pa or more, preferably 660X 10 7 Pa or more, more preferably 670X 10 7 Pa or more, more preferably 680X 10 7 Pa is above; and/or a Young's modulus E of 11000X 10 7 Pa～15000×10 7 Pa, preferably 11500X 10 7 Pa～14500×10 7 Pa, more preferably 12000X 10 7 Pa～14000×10 7 Pa, more preferably 12500X 10 7 Pa～13500×10 7 Pa; and/or the degree of bubbling is class A or more, preferably class A 0 More than grade, more preferablyIs A 00 A stage; and/or degree of wear F A Is 80 to 130, preferably 90 to 120, more preferably 95 to 115.
(12) A glass preform made of the high-refractive-index, high-dispersive optical glass according to any one of (1) to (11).
(13) An optical element produced from the high-refractive-index, high-dispersion optical glass according to any one of (1) to (11), or the glass preform according to (12).
(14) An optical device comprising the high-refractive-index, high-dispersion optical glass according to any one of (1) to (11), and/or comprising the optical element according to (13).
The invention has the beneficial effects that: through reasonable component design, the optical glass has excellent weather resistance and abrasion resistance while having the expected refractive index and dispersion.
Detailed Description
The embodiments of the high-refractive-index, high-dispersion optical glass 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. In addition, although the description of the overlapping description may be appropriately omitted, the high-refractive high-dispersive optical glass of the present invention is sometimes simply referred to as optical glass or glass in the following description without restricting the gist of the invention.
[ high-refractive high-dispersive optical glass ]
The ranges of the respective components (ingredients) of the high-refractive high-dispersive optical glass of the present invention are described below. In the present invention, the contents and total contents of the respective components are all expressed in weight percent (wt%), that is, the contents and total contents of the respective components are expressed in weight percent with respect to the total amount of the glass substance 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%.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
B 2 O 3 In the present invention, the network-forming component improves the thermal stability of the glass and improves the meltability of the glass, and the content of B in the glass composition is 5% or more 2 O 3 To obtain the above effects, B is preferable 2 O 3 The content of (B) is 6% or more, more preferably B 2 O 3 The content of (A) is more than 7%. When B is present 2 O 3 When the content of (2) is too large, the refractive index of the glass decreases, and the chemical stability deteriorates. Thus, in the present invention B 2 O 3 The upper limit of the content of (B) is 18%, preferably 14%, more preferably 12%.
SiO 2 Has the effects of improving the chemical stability of the glass, maintaining the viscosity suitable for the molding of the molten glass, and reducing the erosion of the refractory, and if the content is too high, the difficulty of melting the glass increases, and the lowering of the transition temperature of the glass is not favorable. Thus, siO in the present invention 2 The content of (B) is 1 to 12%, preferably 2 to 10%, more preferably 4 to 9%.
In some embodiments, by oxidizing SiO 2 And B 2 O 3 SiO in total content 2 +B 2 O 3 The content of the glass transition metal is controlled within the range of 8-28%, so that the abrasion degree and weather resistance of the glass can be optimized while the glass forming stability of the glass is maintained, and the devitrification resistance of the glass is prevented from being reduced. Therefore, siO is preferable 2 +B 2 O 3 8 to 28%, more preferably SiO 2 +B 2 O 3 In the range of 10 to 25%, siO is more preferable 2 +B 2 O 3 Is 12 to 20 percent.
La 2 O 3 Is effective component for increasing glass refractive index, and improving chemical stability and resistance of glassThe devitrification effect is obvious, and if the content of the devitrification effect is less than 40 percent, the required optical constant is difficult to achieve; if the content is more than 60%, devitrification tendency of the glass is rather increased and thermal stability is deteriorated. Thus, la 2 O 3 The content of (B) is limited to 40 to 60%, preferably 43 to 58%, more preferably 46 to 53%.
Y 2 O 3 The invention can improve the refractive index and devitrification resistance of the glass and adjust the Young's modulus of the glass by containing more than 4 percent of Y 2 O 3 To obtain the above-mentioned effect; if the content exceeds 20%, the chemical stability and weather resistance of the glass are deteriorated. Thus, Y in the present invention 2 O 3 The content is 4 to 20%, preferably 5 to 15%, more preferably 6 to 12%.
In some embodiments, Y is 2 O 3 Content of (A) and (B) 2 O 3 Ratio Y between contents of 2 O 3 /B 2 O 3 The control range of 0.4-3.0 is favorable for obtaining proper Young's modulus of the glass. Therefore, Y is preferred 2 O 3 /B 2 O 3 Is 0.4 to 3.0, more preferably Y 2 O 3 /B 2 O 3 0.5 to 2.5. Further, by adding Y 2 O 3 /B 2 O 3 The control is in the range of 0.6-1.5, which is beneficial to further reducing the thermal expansion coefficient of the glass and optimizing the bubble degree of the glass. Therefore, Y is more preferable 2 O 3 /B 2 O 3 Is 0.6 to 1.5, and Y is more preferably 2 O 3 /B 2 O 3 0.7 to 1.2.
Gd 2 O 3 The refractive index and chemical stability of the glass can be improved, but if the content is too high, the devitrification resistance and abrasion resistance of the glass are deteriorated, and the cost of the glass is increased. Thus, gd 2 O 3 The content of (b) is 0 to 9%, preferably 0 to 5%, more preferably 0 to 3%, and still more preferably 0 to 1%.
In some embodiments, by passing La 2 O 3 、Y 2 O 3 And Gd 2 O 3 The total content La of 2 O 3 +Y 2 O 3 +Gd 2 O 3 The control in the range of 46 to 70% makes it easier to obtain the desired refractive index and Abbe number of the glass and to optimize the resistance to devitrification and weather resistance of the glass. Therefore, la is preferable 2 O 3 +Y 2 O 3 +Gd 2 O 3 46 to 70%, more preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 50 to 68%, more preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 Is 55 to 65 percent.
Yb 2 O 3 And is a component imparting high-refractivity, low-dispersion properties to the glass, and if the content thereof exceeds 10%, the devitrification resistance of the glass is lowered. Thus, yb 2 O 3 The content of (B) is 0 to 10%, preferably 0 to 5%, more preferably 0 to 1%, and further preferably no Yb 2 O 3 。
ZrO 2 The viscosity, hardness, refractive index and chemical stability of the optical glass can be improved, and the thermal expansion coefficient of the glass can be reduced; when ZrO 2 When the content of (b) is too high, devitrification resistance of the glass is lowered, melting difficulty is increased, melting temperature is increased, and inclusions appear in the glass and light transmittance is lowered. Thus, zrO in the invention 2 The content of (B) is 1 to 12%, preferably 3 to 10%, more preferably 4 to 9%.
TiO 2 Is a high-refraction high-dispersion component, can obviously improve the refractive index and dispersion of glass in the glass, and the inventor researches and discovers that a proper amount of TiO is contained 2 The stability of the glass can be improved; but if too much TiO content is contained 2 The transmittance of the glass is significantly reduced, and the chemical stability of the glass tends to be deteriorated. Thus, tiO in the present invention 2 The content of (B) is 4 to 18%, preferably 5 to 13%, more preferably 6 to 12%.
In some embodiments, the TiO is 2 Content of (2) and Y 2 O 3 Ratio between contents of TiO 2 /Y 2 O 3 The abrasion degree and the weather resistance of the glass can be optimized by controlling the content of the glass to be within the range of 0.3-4.0. Therefore, tiO is preferred 2 /Y 2 O 3 0.3 to 4.0, more preferably TiO 2 /Y 2 O 3 0.5 to 3.0. Further, control of TiO 2 /Y 2 O 3 In the range of 0.6 to 2.0, the chemical stability and the bubble degree of the glass can be further improved. Therefore, tiO is more preferable 2 /Y 2 O 3 0.6 to 2.0, and TiO is more preferable 2 /Y 2 O 3 0.75 to 1.5.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and the devitrification resistance of the glass and reduce the thermal expansion coefficient of the glass, and the invention contains more than 4 percent of Nb 2 O 5 To obtain the above effects, nb is preferable 2 O 5 The lower limit of the content of (B) is 5%, and the more preferable lower limit is 7%. If Nb 2 O 5 More than 20%, the glass is lowered in thermal stability and weather resistance and the light transmittance is lowered, so that Nb in the present invention is contained 2 O 5 The upper limit of the content of (B) is 20%, preferably 15%, more preferably 12%.
In some embodiments, la is 2 O 3 In relation to TiO 2 And Nb 2 O 5 Of the total content of La 2 O 3 /(TiO 2 +Nb 2 O 5 ) The Young's modulus of the glass is favorably improved and the light transmittance of the glass is prevented from being reduced by controlling the content of the additive to be within the range of 1.2-6.0. Therefore, la is preferable 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 1.2 to 6.0, more preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 1.5 to 5.0. Further, control La 2 O 3 /(TiO 2 +Nb 2 O 5 ) In the range of 2.0 to 4.0, the density and thermal expansion coefficient of the glass can be further reduced. Therefore, la is more preferable 2 O 3 /(TiO 2 +Nb 2 O 5 ) 2.0 to 4.0, more preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 2.5 to 3.5.
Alkaline earth metal oxide RO (RO is one or more of MgO, caO, srO, and BaO) can adjust optical constants of the glass and optimize chemical stability of the glass, but when the content is high, devitrification resistance of the glass is lowered. Therefore, the RO content is limited to 0 to 9%, preferably 0 to 4%, and more preferably 0 to 2%. In some embodiments, it is further preferred that no RO is present.
Alkali metal oxide Rn 2 O(Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O) can lower the transition temperature of the glass, adjust the optical constant and high-temperature viscosity of the glass, and improve the meltability of the glass, but when the content is high, the devitrification resistance and chemical stability of the glass are lowered. Thus, rn in the present invention 2 The content of O is 0 to 6%, preferably 0 to 4%, more preferably 0 to 1%. In some embodiments, it is further preferred that Rn not be present 2 O。
WO 3 Can improve the refractive index and mechanical strength of the glass, if WO 3 When the content of (B) exceeds 6%, the glass is deteriorated in thermal stability and devitrification resistance. Thus, WO 3 The content of (B) is 0 to 6%, preferably 0 to 4%, more preferably 0.5 to 3%.
In some embodiments, WO is 3 Content of (2) and Y 2 O 3 Ratio between contents of WO 3 /Y 2 O 3 The control is below 0.8, which is beneficial to improving the chemical stability and crystallization resistance of the glass. Thus, WO is preferred 3 /Y 2 O 3 Is 0.8 or less, and WO is more preferable 3 /Y 2 O 3 Is 0.6 or less. Further, control of WO 3 /Y 2 O 3 In the range of 0.02 to 0.5, the hardness and the bubble degree of the glass can be further optimized. Therefore, WO is further preferred 3 /Y 2 O 3 0.02 to 0.5, and further preferably WO 3 /Y 2 O 3 0.05 to 0.3.
In some embodiments, the TiO is 2 Content of (2) and Nb 2 O 5 And WO 3 Total content of (B) Nb 2 O 5 +WO 3 Ratio of TiO to 2 /(Nb 2 O 5 +WO 3 ) The density of the glass can be reduced by controlling the concentration to be within the range of 0.3-3.0And simultaneously, the light transmittance of the glass is prevented from being reduced. Therefore, tiO is preferred 2 /(Nb 2 O 5 +WO 3 ) Is 0.3 to 3.0, more preferably TiO 2 /(Nb 2 O 5 +WO 3 ) 0.4 to 2.0. Further, control of TiO 2 /(Nb 2 O 5 +WO 3 ) Within the range of 0.6 to 1.5, the Young's modulus and weather resistance of the glass can be further optimized. Therefore, tiO is more preferable 2 /(Nb 2 O 5 +WO 3 ) 0.6 to 1.5, and TiO is more preferable 2 /(Nb 2 O 5 +WO 3 ) 0.8 to 1.3.
ZnO can adjust the refractive index and dispersion of the glass, and reduce the high-temperature viscosity and transition temperature of the glass. If the content of ZnO is too high, the glass forming difficulty is increased, and the devitrification resistance is deteriorated. Therefore, the content of ZnO is 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that no ZnO is present.
In some embodiments, the content of ZnO is related to SiO 2 And B 2 O 3 SiO (total content) 2 +B 2 O 3 Ratio between ZnO/(SiO) 2 +B 2 O 3 ) Controlling the content of the carbon black to be less than 0.5 can improve the meltability of the glass, improve the bubble degree and optimize the abrasion degree. Therefore, znO/(SiO) is preferable 2 +B 2 O 3 ) Is 0.5 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.3 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.2 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.1 or less.
In some embodiments, B is 2 O 3 And TiO 2 Total content of (B) 2 O 3 +TiO 2 With SiO 2 And the total content of ZnO SiO 2 + ZnO ratio (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is controlled within the range of 1.0 to 10.0, the chemical stability of the glass can be improved, and the light transmittance of the glass can be prevented from being reduced. Therefore, (B) is preferred 2 O 3 +TiO 2 )/(SiO 2 + ZnO) of 1.0E10.0, more preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.0 to 8.0. Further, by controlling (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is in the range of 1.5 to 7.0, and can further improve the hardness of the glass and reduce the thermal expansion coefficient of the glass. Therefore, (B) is more preferable 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.5 to 7.0, more preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 2.0 to 5.0.
In some embodiments, the method comprises administering Gd to the subject 2 O 3 And ZnO in total 2 O 3 + ZnO and Y 2 O 3 Ratio between contents of (Gd) 2 O 3 +ZnO)/Y 2 O 3 The thermal expansion coefficient of the glass can be reduced and the abrasion degree of the glass can be optimized by controlling the thermal expansion coefficient to be less than 1.0. Therefore, (Gd) is preferable 2 O 3 +ZnO)/Y 2 O 3 Is 1.0 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.6 or less. Further, control (Gd) 2 O 3 +ZnO)/Y 2 O 3 When the value is 0.3 or less, the glass can be more easily provided with an appropriate Young's modulus, and the hardness of the glass can be prevented from being lowered. Therefore, (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.3 or less, and (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.1 or less.
Ta 2 O 5 The glass has the effects of improving the refractive index and improving the devitrification resistance of the glass, but if the content of the glass is too high, the thermal stability of the glass is reduced, and the density is increased; on the other hand, ta is compared with other components 2 O 5 The price of (2) is very expensive, and the amount of use should be minimized from the practical and cost viewpoints. Thus, ta in the invention 2 O 5 The content of (b) is limited to 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that Ta is not included 2 O 5 。
In some embodiments, ta 2 O 5 And Gd 2 O 3 Total content Ta of 2 O 5 +Gd 2 O 3 And Y 2 O 3 Ratio between contents of (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 The control below 1.0 is beneficial to obtaining proper abrasion degree of the glass, optimizing the density and Young modulus of the glass and preventing the chemical stability of the glass from being deteriorated. Therefore, (Ta) is preferable 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 1.0 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.6 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.4 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.1 or less.
Al 2 O 3 The chemical stability of the glass can be improved, but when the content exceeds 5%, the melting property and light transmittance of the glass are deteriorated. Therefore, al in the present invention 2 O 3 The content of (b) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that Al is absent 2 O 3 。
GeO 2 Has the functions of improving the refractive index and resisting devitrification, but if the content is too high, the chemical stability of the glass is reduced; on the other hand, geO is compared with other components 2 The price of (2) is very expensive, and the amount of use thereof should be minimized from the practical and cost viewpoints. Accordingly, geO in the present invention 2 The content of (b) is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no GeO is contained 2 。
In the invention, 0 to 2 percent of Sb is contained 2 O 3 、SnO、SnO 2 、CeO 2 One or more components in the glass can be used as a clarifying agent to improve the clarifying effect of the glass and improve the bubble degree of the glass, and the content of the clarifying agent is preferably 0 to 1 percent, and more preferably 0 to 0.5 percent. The optical glass has reasonable component types and content design and excellent bubble degree, and is characterized by comprising the following componentsIt is further preferred in some embodiments that the clarifying agent is absent. When Sb is present 2 O 3 At contents exceeding 2%, the glass tends to have a reduced fining ability, and since the strong oxidizing action promotes the corrosion of the platinum or platinum alloy vessel from which the glass is melted and the deterioration of the forming mold, sb is preferred in the present invention 2 O 3 The content of (B) is 0 to 2%, more preferably 0 to 1%, still more preferably 0 to 0.5%, and still more preferably Sb is not contained 2 O 3 . SnO and SnO 2 However, when the content exceeds 2%, the glass tends to be colored more, or when the glass is heated, softened, press-molded or the like and then reformed, sn becomes a starting point of crystal nucleus formation, and the glass tends to be devitrified. Thus the SnO of the invention 2 The content of (B) is preferably 0 to 2%, more preferably 0 to 1%, still more preferably 0 to 0.5%, and still more preferably not containing SnO 2 (ii) a The SnO content is preferably 0 to 2%, more preferably 0 to 1%, still more preferably 0 to 0.5%, and still more preferably no SnO. CeO (CeO) 2 The function and content ratio of (A) and (B) of SnO 2 The content is preferably 0 to 2%, more preferably 0 to 1%, even more preferably 0 to 0.5%, and even more preferably no CeO 2 。
In some embodiments, siO is preferred for achieving lower coefficient of thermal expansion and density, higher light transmission and bubble rating, and suitable abrasion and Young's modulus for the high refractive high dispersive optical glass of the present invention 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (2) is 88% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 90% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (2) is more than 92%, more preferablySiO 2 is selected 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 95% or more.
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, cr, mn, fe, co, ni, cu, ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances under control, and measures for protecting the environment are required not only in the glass production process but also in the processing process and in the disposal after the production of products. 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 disposed of without taking special measures for environmental measures.
To be environmentally friendly, the high-refractive high-dispersive optical glass of the invention preferably does not contain As 2 O 3 And PbO.
"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the high-refractive high-dispersive optical glass of the present invention; however, it is within the scope of the present invention that certain impurities or components which are not intentionally added may be present as raw materials and/or equipment for producing the optical glass and may be contained in the final optical glass in small or trace amounts.
The performance of the high-refractive high-dispersion optical glass of the present invention will be described below.
< refractive index and Abbe number >
Refractive index (n) of optical glass d ) And Abbe number (. Nu.) d ) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the high refractive high dispersive optical glass of the present invention d ) The lower limit of (b) is 1.92, preferably 1.93, more preferably 1.94.
In some embodiments, the refractive index (n) of the high refractive high dispersive optical glass of the present invention d ) The upper limit of (2) is 1.98, preferably the upper limit is 1.97, and more preferably the upper limit is 1.96.
In some embodiments, the high-refractive, high-dispersion optical glass of the invention has an Abbe number (v) d ) The lower limit of (2) is 29, preferably 30, and more preferably 31.
In some embodiments, the Abbe number (v) of the high refractive, high dispersive optical glass of the present invention d ) The upper limit of (2) is 36, preferably 35, and more preferably 34.
< Density >
The density (. Rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
In some embodiments, the high-refractive high-dispersive optical glass of the invention has a density (. Rho.) of 5.10g/cm 3 Hereinafter, preferably 5.00g/cm 3 Hereinafter, more preferably 4.95g/cm 3 The following.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass -30/70℃ ) The data at-30 to 70 ℃ were tested according to the method specified in GB/T7962.16-2010.
In some embodiments, the high refractive high dispersive optical glass of the present invention has a coefficient of thermal expansion (α) -30/70℃ ) Is 85X 10 -7 Preferably 80X 10 or less,/K -7 A value of less than or equal to K, more preferably 75X 10 -7 A value of 70X 10 or less in terms of/K or less -7 The ratio of the sulfur to the sulfur is below K.
< stability against Water action >
Stability to Water of optical glass (D) W ) (powder method) the test was carried out according to the method described in GB/T17129.
In some embodiments, the high refractive high dispersive optical glass of the present invention has a water stability (D) W ) Is 2 or more, preferably 1.
< stability against acid Effect >
Stability of acid resistance of optical glasses (D) A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the high refractive high dispersive optical glass of the present invention has stability to acid action (D) A ) Is 2 or more, preferably 1.
< degree of coloration >
Coloring degree (. Lamda.) for short-wave transmission spectral characteristics of the glass of the present invention 70 And λ 5 ) And (4) showing. Lambda [ alpha ] 70 The wavelength corresponding to the glass transmittance of 70% is meant. Lambda 70 Is measured by measuring the spectral transmittance in a wavelength region from 280nm to 700nm using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished and exhibiting a wavelength of 70% transmittance. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass in Light transmitted through the glass and having an intensity I emitted from a plane out In the case of light of (1) through (I) out /I in The quantities 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 the high refractive index glass, λ 70 A small value of (A) means that the glass itself is colored very little and has a high light transmittance.
In some embodiments, the λ of the high refractive high dispersive optical glass of the present invention 70 Is 425nm or less, preferably lambda 70 Is 420nm or less, more preferably lambda 70 Is 415nm or less.
In some embodiments, the lambda of the high-refractive high-dispersive optical glass of the invention 5 Is 375nm or less, preferably lambda 5 Is 370nm or less, more preferably λ 5 Is 365nm or less.
< weather resistance >
The test method of the weatherability (CR) of the optical glass is as follows: the sample is placed in a test box in a saturated water vapor environment with the relative humidity of 90 percent, and is circulated alternately at intervals of 1h at the temperature of 40-50 ℃ for 15 periods. The weather resistance categories were classified according to the amount of change in turbidity before and after the sample was left, and the weather resistance categories are shown in table 1:
table 1.
In some embodiments, the high-refractive high-dispersive optical glass of the present invention has a weatherability (CR) of 2 or more, preferably 1.
< Knoop hardness >
Knoop hardness (H) of optical glass K ) The test was carried out according to the test method specified in GB/T7962.18-2010.
In some embodiments, the Knoop hardness (H) of the high-refractive high-dispersive optical glass of the present invention K ) Is 650 x 10 7 Pa or more, preferably 660X 10 7 Pa or more, more preferably 670X 10 7 Pa or more, more preferably 680X 10 7 Pa or above.
< Young's modulus >
The Young modulus (E) is obtained by testing the longitudinal wave speed and the transverse wave speed of the Young modulus by adopting ultrasonic waves and then calculating according to the following formula.
G＝V S 2 ρ
In the formula: e is Young's modulus, pa;
g is shear modulus, pa;
V T is the transverse wave velocity, m/s;
V S is the longitudinal wave velocity, m/s;
rho is the density of the glass, g/cm 3 。
In some embodiments, the Young's modulus of the high-refractive high-dispersive optical glass of the present inventionThe lower limit of the amount (E) is 11000X 10 7 Pa, preferably lower limit of 11500X 10 7 Pa, more preferably a lower limit of 12000X 10 7 Pa, more preferably a lower limit of 12500X 10 7 Pa。
In some embodiments, the high refractive high dispersive optical glass of the present invention has a Young's modulus (E) with an upper limit of 15000X 10 7 Pa, preferably upper limit of 14500X 10 7 Pa, more preferably 14000X 10 7 Pa, more preferably 13500X 10 7 Pa。
< degree of bubbling >
The bubble degree of the optical glass was measured according to the method specified in GB/T7962.8-2010.
In some embodiments, the high refractive high dispersive optical glass of the present invention has a bubble size of class A or greater, preferably A 0 More preferably A or more 00 And (4) stages.
< degree of wear >
Degree of abrasion (F) of optical glass A ) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the ratio is expressed as follows:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
in the formula: v, the volume abrasion loss of the measured sample;
V 0 -the amount of wear of the standard sample volume;
w is the abrasion loss of the quality of the sample to be measured;
W 0 -abrasion loss of standard sample mass;
rho is the density of the sample to be measured;
ρ 0 -standard sample density.
In some embodiments, the high refractive high dispersive optical glass of the present invention has an abrasion (F) A ) The lower limit of (2) is 80, preferably 90, and more preferably 95.
In some embodiments, the high-refractive high-dispersive optical glass of the present invention has an abrasion loss (F) A ) Has an upper limit of 130, preferably an upper limit of 120, more preferablyAn upper limit of 115 is selected.
[ method for producing optical glass ]
The manufacturing method of the high-refraction high-dispersion optical glass comprises the following steps: the glass of the invention is produced by adopting conventional raw materials and processes, including but not limited to oxides, hydroxides, composite salts (such as carbonates, nitrates, sulfates and the like) and boric acid and the like as raw materials, after being mixed by a conventional method, the mixed furnace materials are put into a smelting furnace (such as a platinum or platinum alloy crucible) with the temperature of 1200-1450 ℃ for smelting, and after clarification and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mould 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 made from the high-refractive high-dispersive optical glass produced by press molding such as direct gob casting, grinding, or hot press molding. That is, a glass preform can be produced by direct precision gob-molding of molten optical glass into a glass precision preform, or by mechanical processing such as grinding and polishing, or by producing a preform for press molding from optical glass, subjecting the preform to reheat press molding, and then performing polishing processing. It should be noted that the means for producing the glass preform is not limited to the above means.
As described above, the high-refractive-index, high-dispersion 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 high-refractive-index, high-dispersion optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform and the optical element of the present invention are each formed of the above-described high-refractive high-dispersive optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of high-refractive-index, high-dispersion optical glass, 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 element formed by the high-refraction high-dispersion optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of high refractive index and high dispersive 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, high-refractive and high-dispersive optical glasses having compositions shown in tables 2 to 4 were obtained by the above-described method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 2 to 4.
Table 2.
Table 3.
Table 4.
< glass preform example >
Various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, and preforms such as prisms were prepared by press molding the glasses obtained in examples 1 to 24# of the high-refractive high-dispersive optical glasses by means of, for example, grinding or hot press molding or precision press molding.
< optical element example >
The preforms obtained from the above glass preform examples were annealed to reduce the internal stress of the glass and to fine-tune the refractive index so that the optical properties such as refractive index reached 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 embodiment >
The optical element produced by the above-described optical element embodiment can be used, for example, for imaging apparatuses, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips by forming an optical component or optical assembly by using one or more optical elements through optical design.
Claims (14)
1. High-refractive-index, high-dispersive optical glass, characterized in that its composition, expressed in weight percentages, comprises: siO 2 2 +B 2 O 3 ：8～28％；La 2 O 3 +Y 2 O 3 +Gd 2 O 3 ：46～70％；ZrO 2 ：1～12％；Nb 2 O 5 ：4～20％；TiO 2 :4 to 18 percent of which is TiO 2 /Y 2 O 3 0.3 to 4.0.
2. A high-refractive-index, high-dispersive optical glass according to claim 1, characterized in that it further comprises, in percentages by weight: ta 2 O 5 :0 to 8 percent; and/or RO:0 to 9 percent; and/or Rn 2 O:0 to 6 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0-2%, RO is one or more of MgO, caO, srO and BaO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
3. High-refractive-index high-dispersion optical glass characterized by containing ZrO 2 、Nb 2 O 5 、TiO 2 The components of the material are expressed by weight percentage and contain 8 to 28 percent of SiO 2 +B 2 O 3 And 46 to 70% of La 2 O 3 +Y 2 O 3 +Gd 2 O 3 In which TiO is 2 /Y 2 O 3 0.3 to 4.0, the refractive index n of the high-refractive high-dispersion optical glass d Is 1.92 to 1.98, abbe number v d 29 to 36, abrasion degree F A 80 to 130, and has a weather resistance CR of 2 or more types.
4. According to claim 3The high-refractive-index and high-dispersive optical glass is characterized by comprising the following components in percentage by weight: zrO (ZrO) 2 :1 to 12 percent; and/or Nb 2 O 5 :4 to 20 percent; and/or TiO 2 :4 to 18 percent; and/or Ta 2 O 5 :0 to 8 percent; and/or RO:0 to 9 percent; and/or Rn 2 O:0 to 6 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 5 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0-2%, RO is one or more of MgO, caO, srO and BaO, rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
5. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, whose composition, expressed in weight percentage, satisfies one or more of the following 9 conditions:
1)La 2 O 3 /(TiO 2 +Nb 2 O 5 ) 1.2 to 6.0, preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 1.5 to 5.0, more preferably La 2 O 3 /(TiO 2 +Nb 2 O 5 ) Is 2.0 to 4.0, and La is more preferable 2 O 3 /(TiO 2 +Nb 2 O 5 ) 2.5 to 3.5;
2)TiO 2 /Y 2 O 3 0.5 to 3.0, preferably TiO 2 /Y 2 O 3 Is 0.6 to 2.0, more preferably TiO 2 /Y 2 O 3 0.75 to 1.5;
3)Y 2 O 3 /B 2 O 3 0.4 to 3.0, preferably Y 2 O 3 /B 2 O 3 Is 0.5 to 2.5, more preferably Y 2 O 3 /B 2 O 3 Is 0.6 to 1.5, and Y is more preferably 2 O 3 /B 2 O 3 0.7 to 1.2;
4)(B 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.0 to 10.0, preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.0 to 8.0, more preferably (B) 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 1.5 to 7.0, and (B) is more preferable 2 O 3 +TiO 2 )/(SiO 2 + ZnO) is 2.0 to 5.0;
5)(Ta 2 O 5 +Gd 2 O 3 )/Y 2 O 3 is 1.0 or less, preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.6 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.4 or less, and (Ta) is more preferable 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.1 or less;
6)TiO 2 /(Nb 2 O 5 +WO 3 ) 0.3 to 3.0, preferably TiO 2 /(Nb 2 O 5 +WO 3 ) 0.4 to 2.0, more preferably TiO 2 /(Nb 2 O 5 +WO 3 ) Is 0.6 to 1.5, and TiO is more preferable 2 /(Nb 2 O 5 +WO 3 ) 0.8 to 1.3;
7)ZnO/(SiO 2 +B 2 O 3 ) Is 0.5 or less, preferably ZnO/(SiO) 2 +B 2 O 3 ) Is 0.3 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.2 or less, and ZnO/(SiO) is more preferable 2 +B 2 O 3 ) Is 0.1 or less;
8)(Gd 2 O 3 +ZnO)/Y 2 O 3 is 1.0 or less, preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.6 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.3 or less, and (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.1 or less;
9)WO 3 /Y 2 O 3 is 0.8 or less, preferably WO 3 /Y 2 O 3 Is 0.6 or moreHereinafter, WO is more preferable 3 /Y 2 O 3 Is 0.02 to 0.5, and WO is more preferable 3 /Y 2 O 3 0.05 to 0.3.
6. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, having the composition, in weight percent, wherein: la 2 O 3 +Y 2 O 3 +Gd 2 O 3 :50 to 68%, preferably La 2 O 3 +Y 2 O 3 +Gd 2 O 3 :55 to 65 percent; and/or SiO 2 +B 2 O 3 :10 to 25%, preferably SiO 2 +B 2 O 3 :12 to 20 percent; and/or ZrO 2 :3 to 10%, preferably ZrO 2 :4 to 9 percent; and/or Nb 2 O 5 :5 to 15%, preferably Nb 2 O 5 :7 to 12 percent; and/or Ta 2 O 5 :0 to 4%, preferably Ta 2 O 5 :0 to 2 percent; and/or TiO 2 :5 to 13%, preferably TiO 2 :6 to 12 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 4%, preferably Rn 2 O:0 to 1 percent; and/or WO 3 :0 to 4%, preferably WO 3 :0.5 to 3 percent; and/or ZnO:0 to 4%, preferably ZnO:0 to 2 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 1 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 1 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
7. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the components are as given in weight percentThe method comprises the following steps: siO 2 2 :1 to 12%, preferably SiO 2 :2 to 10%, more preferably SiO 2 :4 to 9 percent; and/or B 2 O 3 :5 to 18%, preferably B 2 O 3 :6 to 14%, more preferably B 2 O 3 :7 to 12 percent; and/or La 2 O 3 :40 to 60%, preferably La 2 O 3 :43 to 58%, more preferably La 2 O 3 :46 to 53 percent; and/or Y 2 O 3 :4 to 20%, preferably Y 2 O 3 :5 to 15%, more preferably Y 2 O 3 :6 to 12 percent; and/or Gd 2 O 3 :0 to 9%, preferably Gd 2 O 3 :0 to 5%, more preferably Gd 2 O 3 :0 to 3%, more preferably Gd 2 O 3 ：0～1％。
8. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, whose composition, expressed in weight percentage, is SiO 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (2) is 88% or more, and SiO is preferred 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (2) is 90% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 92% or more, and SiO is more preferable 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The total content of (A) is 95% or more.
9. A high-refractive-index, high-dispersive optical glass according to any one of claims 1 to 4, characterised in that it does not contain Ta 2 O 5 (ii) a And/or does not containHas Yb 2 O 3 (ii) a And/or does not contain RO; and/or does not contain Rn 2 O; and/or no ZnO; and/or does not contain Al 2 O 3 (ii) a And/or does not contain GeO 2 The RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
10. A high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive-index, high-dispersion optical glass has a refractive index n d Is 1.92 to 1.98, preferably 1.93 to 1.97, more preferably 1.94 to 1.96, abbe number v d Is 29 to 36, preferably 30 to 35, more preferably 31 to 34.
11. The high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 4, wherein the density p of the high-refractive-index, high-dispersion optical glass is 5.10g/cm 3 Hereinafter, preferably 5.00g/cm 3 Hereinafter, more preferably 4.95g/cm 3 The following; and/or coefficient of thermal expansion alpha -30/70℃ Is 85X 10 -7 A value of 80X 10 or less, preferably below/K -7 A value of not more than 75X 10 -7 A value of 70X 10 or less in terms of/K or less -7 below/K; and/or stability against water action D W Is 2 or more, preferably 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or lambda 70 Is 425nm or less, preferably lambda 70 Is 420nm or less, more preferably lambda 70 415nm or less; and/or lambda 5 Is 375nm or less, preferably lambda 5 Is 370nm or less, more preferably λ 5 Is less than 365 nm; and/or the weather resistance CR is of class 2 or more, preferably of class 1; and/or Knoop hardness H K Is 650 x 10 7 Pa or more, preferably 660X 10 7 Pa or more, more preferably 670X 10 7 Pa or more, more preferably 680X 10 7 Pa or above; and/or a Young's modulus E of 11000X 10 7 Pa～15000×10 7 Pa, preferably 11500X 10 7 Pa～14500×10 7 Pa, more preferably 12000X 10 7 Pa～14000×10 7 Pa, more preferably 12500X 10 7 Pa～13500×10 7 Pa; and/or the degree of bubbling is class A or more, preferably class A 0 More preferably A or more 00 A stage; and/or degree of wear F A Is 80 to 130, preferably 90 to 120, more preferably 95 to 115.
12. A glass preform made of the high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 11.
13. An optical element, characterized by being made of the high-refractive-index, high-dispersion optical glass of any one of claims 1 to 11, or the glass preform of claim 12.
14. An optical device comprising the high-refractive-index, high-dispersion optical glass according to any one of claims 1 to 11 and/or comprising the optical element according to claim 13.
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| CN202211031612.8A CN115304274A (en) | 2022-08-26 | 2022-08-26 | High-refraction high-dispersion optical glass |
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| CN202211031612.8A CN115304274A (en) | 2022-08-26 | 2022-08-26 | High-refraction high-dispersion optical glass |
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