CN115677209A - Special dispersion optical glass - Google Patents
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- CN115677209A CN115677209A CN202211272912.5A CN202211272912A CN115677209A CN 115677209 A CN115677209 A CN 115677209A CN 202211272912 A CN202211272912 A CN 202211272912A CN 115677209 A CN115677209 A CN 115677209A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 105
- 239000006185 dispersion Substances 0.000 title claims abstract description 100
- 239000011521 glass Substances 0.000 claims description 134
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 48
- 230000003287 optical effect Effects 0.000 claims description 32
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- 239000008395 clarifying agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention provides special dispersion optical glass, which comprises the following components in percentage by weight: siO 2 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；BaO：6～20％；Na 2 O:3 to 18 percent of (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 2.5-10.0. Through reasonable component design, the special dispersion optical glass obtained by the invention has the expected refractive index and Abbe number and simultaneously has lower thermal expansion coefficientAnd relative partial dispersion P g,F And negative anomalous dispersion, thereby meeting the application of high-end photoelectric products.
Description
Technical Field
The invention relates to an optical glass, in particular to a special dispersion optical glass with low relative partial dispersion and negative anomalous dispersion and low thermal expansion coefficient.
Background
In recent years, with the rapid development of the fields of smart phones, vehicle-mounted imaging, monitoring security and the like, optical glass with the refractive index of 1.68-1.76 and the abbe number of 30-39 is widely applied. In order to improve the degree of freedom in designing optical systems, optical glasses having various properties are expected, and therefore optical glasses having properties suitable for eliminating or possibly eliminating residual chromatic aberration of the secondary spectrum are attracting attention, particularly having low relative partial dispersion (P) g,F ) And anomalous dispersion in the negative directionAn optical glass. On the other hand, the optical glass is easy to break in the processing process due to larger thermal expansion coefficient, and the yield of glass processing is reduced. Meanwhile, the large thermal expansion coefficient causes the glass to have poor thermal shock resistance, thereby limiting the application of the optical glass.
Therefore, a material with a low thermal expansion coefficient, a refractive index of 1.68-1.76, an Abbe number of 30-39 and a low relative partial dispersion (P) is developed g,F ) And negative anomalous dispersion optical glass, which is of great significance to the development of the photoelectric field.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a thermal expansion coefficient and relative partial dispersion (P) g,F ) Low-content special dispersion optical glass with negative anomalous dispersion.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) The special dispersion optical glass comprises the following components in percentage by weight: siO 2 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；BaO：6～20％；Na 2 O:3 to 18 percent of (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 2.5-10.0.
(2) The special dispersion optical glass according to (1), which comprises the following components in percentage by weight: b is 2 O 3 :0 to 10 percent; and/or MgO:0 to 6 percent; and/or CaO:0 to 10 percent; and/or SrO:0 to 6 percent; and/or Li 2 O:0 to 5 percent; and/or K 2 O:0 to 8 percent; and/or WO 3 :0 to 5 percent; and/or Ta 2 O 5 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(3) Optical glass with special dispersion, containing SiO 2 、Nb 2 O 5 、ZrO 2 、BaO、Na 2 O, the composition of which is expressed in weight percent, (SiO) 2 +Nb 2 O 5 ) The ratio of BaO to n is 2.5-10.0, the refractive index of the special dispersion optical glass is n d 1.68 to 1.76, abbe number v d 30 to 39, relative partial dispersion P g,F Is 0.7500 or less, and has a relative partial dispersion deviation value Δ P g,F Is less than 0, coefficient of thermal expansion alpha -30/70℃ Is 95X 10 -7 and/K is less than or equal to.
(4) The special dispersion optical glass according to (3), which comprises the following components in percentage by weight: siO 2 2 :26 to 42 percent; and/or Nb 2 O 5 :21 to 40 percent; and/or ZrO 2 :0.5 to 12 percent; and/or BaO:6 to 20 percent; and/or Na 2 O:3 to 18 percent; and/or B 2 O 3 :0 to 10 percent; and/or MgO:0 to 6 percent; and/or CaO:0 to 10 percent; and/or SrO:0 to 6 percent; and/or Li 2 O:0 to 5 percent; and/or K 2 O:0 to 8 percent; and/or WO 3 :0 to 5 percent; and/or Ta 2 O 5 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(5) The special dispersion optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: and (3) RO:7 to 35%, preferably RO:11 to 30%, more preferably RO:13 to 25 percent; and/or RO/SiO 2 0.2 to 1.2, preferably RO/SiO 2 Is 0.25 to 1.0, and RO/SiO is more preferable 2 Is 0.3 to 0.8, and R is more preferablyO/SiO 2 0.4 to 0.7; and/or RO/Nb 2 O 5 0.2 to 1.5, preferably RO/Nb 2 O 5 Is 0.3 to 1.2, and RO/Nb is more preferable 2 O 5 0.4 to 1.0, and RO/Nb is more preferable 2 O 5 0.4 to 0.8, and the RO is the total content of MgO, caO, srO and BaO.
(6) The special dispersion optical glass according to any one of (1) to (4), which has a composition, expressed in weight percent, satisfying one or more of the following 7 cases:
1)B 2 O 3 /SiO 2 is 0.3 or less, preferably B 2 O 3 /SiO 2 Is 0.25 or less, more preferably B 2 O 3 /SiO 2 Is 0.2 or less, and B is more preferably B 2 O 3 /SiO 2 0.01 to 0.15;
2)B 2 O 3 a ratio of/BaO of 1.4 or less, preferably B 2 O 3 A value of/BaO of 1.0 or less, and B is more preferably 2 O 3 A value of/BaO of 0.8 or less, and further preferably B 2 O 3 BaO is 0.1 to 0.5;
3)(ZrO 2 + ZnO)/BaO is 0.05 to 1.5, preferably (ZrO) 2 + ZnO)/BaO is 0.1 to 1.0, more preferably (ZrO) 2 + ZnO)/BaO is 0.15 to 0.8, and (ZrO) is more preferable 2 + ZnO)/BaO is 0.2-0.6;
4)(SiO 2 +Nb 2 O 5 ) A ratio of/BaO of 3.0 to 8.0, preferably (SiO) 2 +Nb 2 O 5 ) A value of/BaO is 3.5 to 7.0, more preferably (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 4.0-6.0;
5)(BaO+CaO)/Na 2 o is 0.5 to 5.0, preferably (BaO + CaO)/Na 2 O is 0.8 to 4.0, and (BaO + CaO)/Na is more preferable 2 O is 1.0 to 3.0, and (BaO + CaO)/Na is more preferable 2 O is 1.2 to 2.5;
6)(Na 2 O+Nb 2 O 5 )/SiO 2 0.6 to 2.0, preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.7 to 1.7, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.8 to 1.5, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 1.0 to 1.5;
7)(B 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less, preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less, and (B) is more preferable 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
(7) The special dispersion optical glass according to any one of (1) to (4), which comprises the following components in percentage by weight: siO 2 2 :28 to 40%, preferably SiO 2 :30 to 37 percent; and/or B 2 O 3 :0 to 6%, preferably B 2 O 3 :0.5 to 5 percent; and/or Nb 2 O 5 :25 to 35%, preferably Nb 2 O 5 :27 to 33 percent; and/or ZrO 2 :1 to 10%, preferably ZrO 2 :2 to 8 percent; and/or BaO:8 to 18%, preferably BaO:10 to 16 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or CaO:0.5 to 8%, preferably CaO:1 to 6 percent; and/or SrO:0 to 3%, preferably SrO:0 to 1 percent; and/or Na 2 O:5 to 15%, preferably Na 2 O:7 to 13 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2 percent; and/or K 2 O:0 to 5%, preferably K 2 O:0 to 3 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 3%, preferably Ta 2 O 5 :0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or ZnO:0 to 4%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or a clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(8) The special dispersion optical glass according to any one of (1) to (4), which does not contain TiO in its composition 2 (ii) a And/or does not contain WO 3 (ii) a And/or does not contain Ta 2 O 5 (ii) a And/or no ZnO; and/or does not contain Ln 2 O 3 (ii) a And/or do not contain Li 2 O; and/or does not contain Al 2 O 3 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of (a).
(9) The special dispersion optical glass according to any one of (1) to (4), wherein the refractive index n of the special dispersion optical glass d 1.68 to 1.76, preferably 1.69 to 1.75, more preferably 1.70 to 1.74, still more preferably 1.705 to 1.735, and/or Abbe number v d Is 30 to 39, preferably 31 to 38, more preferably 32 to 37, and still more preferably 33.50 to 36.50.
(10) Relative partial dispersion P of the special dispersion optical glass according to any one of (1) to (4) g,F Is 0.7500 or less, preferably 0.7000 or less, more preferably 0.6500 or less, further preferably 0.6000 or less, and/or a relative partial dispersion deviation value Δ P g,F Is less than 0, preferably-0.0001 or less, more preferably-0.0005 or less, and further preferably-0.0010 or less.
(11) The special dispersion optical glass according to any one of (1) to (4) having a density ρ of 3.8g/cm 3 Hereinafter, it is preferably 3.7g/cm 3 Hereinafter, more preferably 3.6g/cm 3 The following; and/or coefficient of thermal expansion alpha -30/70℃ Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than 85X 10 -7 below/K; and/or lambda 80 Less than or equal to 400nm, preferably lambda 80 Less than or equal to 390nm, more preferably lambda 80 Is less thanOr equal to 385nm; and/or lambda 5 Less than or equal to 350nm, preferably lambda 5 Less than or equal to 340nm, more preferably lambda 5 Less than or equal to 335nm; and/or the weather resistance CR is of class 2 or more, preferably of class 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or Knoop hardness H K Is 500X 10 7 Pa or more, preferably 510X 10 7 Pa or more, more preferably 520X 10 7 Pa is above; and/or degree of wear F A 180 to 220, preferably 185 to 215, more preferably 190 to 210; and/or a Young's modulus E of 8000X 10 7 ～11000×10 7 Pa, preferably 8500X 10 7 ～10500×10 7 Pa, more preferably 9000X 10 7 ～10000×10 7 Pa。
(12) A glass preform made of the special dispersion optical glass according to any one of (1) to (11).
(13) An optical element produced from the special dispersion optical glass according to any one of (1) to (11), or the glass preform according to (12).
(14) An optical device comprising the special dispersion optical glass according to any one of (1) to (11) and/or the optical element according to (13).
The invention has the beneficial effects that: through reasonable component design, the special dispersion optical glass obtained by the invention has the expected refractive index and Abbe number, and simultaneously has lower thermal expansion coefficient and relative partial dispersion (P) g,F ) And negative anomalous dispersion, thereby meeting the application of high-end photoelectric products.
Detailed Description
The following describes in detail embodiments of the special dispersion optical glass of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the invention is not limited thereto, and the special dispersion optical glass of the present invention may be simply referred to as an optical glass or a glass herein.
[ Special Dispersion optical glass ]
The ranges of the respective components (ingredients) of the special dispersion optical glass of the present invention are explained 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 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%.
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 >
SiO 2 Is an essential component of the optical glass of the present invention, is a skeleton of the optical glass of the present invention, and can improve the acid resistance and viscosity of the glass and reduce the abrasion degree of the glass, in the present invention, by containing SiO in an amount of 26% or more 2 To obtain the above effects, it is preferable to contain 28% or more of SiO 2 More preferably, it contains 30% or more of SiO 2 . On the other hand, if SiO 2 When the content of (B) is too large, the melting property of the glass is deteriorated, the high-temperature viscosity is increased, and inclusions such as bubbles and stones are liable to appear in the glass. Thus, siO in the present invention 2 The upper limit of the content of (b) is 42%, preferably 40%, more preferably 37%.
B 2 O 3 Has the effect of improving the thermal stability and melting property of the glass, but when the content thereof is more than 10%, the chemical stability, weather resistance and devitrification resistance of the glass are lowered. Thus, in the present invention B 2 O 3 In a content of0 to 10%, preferably 0 to 6%, more preferably 0.5 to 5%.
In some embodiments, B is 2 O 3 Content of (D) and SiO 2 Ratio B between the contents of 2 O 3 /SiO 2 The control of the content of the organic silicon compound is below 0.3, which is beneficial to improving the weather resistance and Young modulus of the glass and improving the light transmittance of the glass. Therefore, B is preferred 2 O 3 /SiO 2 Is 0.3 or less, and B is more preferably 2 O 3 /SiO 2 Is 0.25 or less, and B is more preferably B 2 O 3 /SiO 2 Is 0.2 or less, and further preferably B 2 O 3 /SiO 2 0.01 to 0.15.
ZrO 2 Can improve the refractive index of the glass, simultaneously improve the chemical stability of the glass, adjust the short-wave special dispersion and reduce the delta P of the glass g,F If the content is too large, the difficulty of melting the glass increases, the melting temperature increases, and inclusions in the glass and the light transmittance decrease. Thus, zrO 2 The content of (B) is 0.5 to 12%, preferably 1 to 10%, more preferably 2 to 8%.
In some embodiments, controlling the content of alkaline earth oxide RO (RO being the total content of MgO, caO, srO, and BaO) to be in the range of 7 to 35% makes it easier for the glass to obtain desired optical constants, and optimizes the chemical stability and abrasion of the glass. Therefore, RO is preferably 7 to 35%, more preferably 11 to 30%, and still more preferably 13 to 25%.
In some embodiments, the amount of RO is related to SiO 2 Ratio between contents of RO/SiO 2 The hardness of the glass can be improved and the chemical stability of the glass can be prevented from being deteriorated by controlling the hardness to be within the range of 0.2-1.2. Therefore, RO/SiO is preferable 2 Is 0.2 to 1.2, and RO/SiO is more preferable 2 0.25 to 1.0. Further, control of RO/SiO 2 In the range of 0.3 to 0.8, the abrasion degree and Young's modulus of the glass can be further optimized. Therefore, RO/SiO is more preferable 2 0.3 to 0.8, and RO/SiO is more preferable 2 0.4 to 0.7.
MgO can reduce the relative partial dispersion of the glass, but when the content of MgO is too much, the refractive index of the glass is difficult to meet the design requirement, and the anti-crystallization performance and the stability of the glass are reduced. Therefore, the content of MgO is limited to 0 to 6%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, it is further preferred that no MgO be present.
CaO can adjust the optical constant of the glass, improve the chemical stability of the glass, improve the processability of the glass, reduce the high-temperature viscosity and the surface tension of the glass, reduce the production difficulty of the glass, and reduce the devitrification resistance of the glass if the content of CaO is too high. Therefore, the content of CaO is 0 to 10%, preferably 0.5 to 8%, more preferably 1 to 6%.
SrO can adjust the refractive index and abbe number of the glass, but if the content is too large, the chemical stability of the glass is lowered and the cost of the glass is rapidly increased. Therefore, the content of SrO is limited to 0 to 6%, preferably 0 to 3%, and more preferably 0 to 1%. In some embodiments, it is further preferred that SrO is absent.
BaO increases the refractive index, melting property, and thermal stability of the glass, improves the abrasion resistance and light transmittance of the glass, and when the content is too high, the density of the glass increases, and the devitrification resistance decreases. Therefore, the content of BaO is 6 to 20%, preferably 8 to 18%, more preferably 10 to 16%.
In some embodiments, B is 2 O 3 Ratio B between the content of (B) and the content of BaO 2 O 3 The content of/BaO is controlled to 1.4 or less, so that the chemical stability and Young's modulus of the glass can be improved, and the hardness of the glass can be prevented from being deteriorated. Therefore, B is preferred 2 O 3 A value of/BaO of 1.4 or less, more preferably B 2 O 3 A BaO of 1.0 or less, and further preferably B 2 O 3 A value of/BaO of 0.8 or less, and further preferably B 2 O 3 The ratio of/BaO is 0.1-0.5.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index, dispersion and devitrification resistance of the glass, reduce the thermal expansion coefficient of the glass and does not obviously improve P g,F Value sum Δ P g,F Value, if Nb 2 O 5 Too much content of (A), lowering the thermal stability and weather resistance of the glass, and light transmittanceAnd (5) reducing. Thus, nb 2 O 5 The content of (b) is in the range of 21 to 40%, preferably 25 to 35%, more preferably 27 to 33%.
In some embodiments, the amount of RO is related to Nb 2 O 5 Ratio between contents of RO/Nb 2 O 5 The control range of 0.2 to 1.5 can reduce the density of the glass and improve the light transmittance of the glass. Therefore, RO/Nb is preferable 2 O 5 0.2 to 1.5, and RO/Nb is more preferable 2 O 5 0.3 to 1.2. Further, control of RO/Nb 2 O 5 In the range of 0.4 to 1.0, the abrasion degree and the thermal expansion coefficient of the glass can be further optimized. Therefore, RO/Nb is more preferable 2 O 5 0.4 to 1.0, and RO/Nb is more preferable 2 O 5 0.4 to 0.8.
In some embodiments, the SiO is 2 And Nb 2 O 5 SiO in total content 2 +Nb 2 O 5 Ratio to the content of BaO (SiO) 2 +Nb 2 O 5 ) The content of/BaO is controlled within the range of 2.5-10.0, so that the glass has lower P g,F Value sum Δ P g,F At the same time, the thermal expansion coefficient of the glass is reduced. Therefore, (SiO) is preferable 2 +Nb 2 O 5 ) The ratio of/BaO is 2.5 to 10.0, more preferably (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 3.0-8.0. Further, control (SiO) 2 +Nb 2 O 5 ) the/BaO is in the range of 3.5-7.0, and the abrasion degree and the weather resistance of the glass can be further optimized. Therefore, (SiO) is more preferable 2 +Nb 2 O 5 ) The ratio of/BaO is 3.5 to 7.0, more preferably (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 4.0-6.0.
Li 2 O can lower the glass transition temperature, adjust the high-temperature viscosity of the glass and improve the meltability of the glass, but the high content of O is unfavorable for the glass stability and the cost economy. Thus, li in the present invention 2 The content of O is 5% or less, preferably 3% or less, and more preferably 2% or less. In some embodiments, it is further preferred not to contain Li 2 O。
Na 2 O has the function of improving the meltability of the glass, can improve the melting effect of the glass and is also beneficial to reducing the P of the glass g,F Value sum Δ P g,F The amount of Na contained in the composition is 3% or more 2 O to obtain the above effect. If Na 2 The content of O exceeds 18%, the chemical stability and weather resistance of the glass are lowered, and therefore Na 2 The content of O is 3 to 18%, preferably Na 2 The content of O is 5 to 15%, more preferably Na 2 The content of O is 7 to 13 percent.
In some embodiments, na is substituted with sodium hydroxide 2 O and Nb 2 O 5 Total content of (3) Na 2 O+Nb 2 O 5 With SiO 2 Ratio between contents of (Na) 2 O+Nb 2 O 5 )/SiO 2 The content of the P in the glass can be controlled within the range of 0.6-2.0 g,F Value sum Δ P g,F The abrasion degree of the glass is optimized at the same time of the value. Therefore, (Na) is preferred 2 O+Nb 2 O 5 )/SiO 2 Is 0.6 to 2.0, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.7 to 1.7. Further, control (Na) 2 O+Nb 2 O 5 )/SiO 2 In the range of 0.8 to 1.5, the weather resistance of the glass can be further improved, and the density of the glass can be prevented from increasing. Therefore, (Na) is more preferable 2 O+Nb 2 O 5 )/SiO 2 Is 0.8 to 1.5, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 1.0 to 1.5.
In some embodiments, the combined content of BaO and CaO is BaO + CaO and Na 2 The ratio between the contents of O (BaO + CaO)/Na 2 The O is controlled within the range of 0.5 to 5.0, so that the glass has lower P g,F Value sum Δ P g,F At the same time, the chemical stability of the glass is improved, and the increase of the glass density is prevented. Therefore, (BaO + CaO)/Na is preferable 2 O is 0.5 to 5.0, more preferably (BaO + CaO)/Na 2 O is 0.8 to 4.0. Further, control of (BaO + CaO)/Na 2 O is in the range of 1.0 to 3.0, and the Young modulus and the weather resistance of the glass can be further optimized. Therefore, (BaO + CaO)/Na is more preferable 2 O is 1.0 to 3.0, and (BaO + CaO)/Na is more preferable 2 O is 1.2 to 2.5.
K 2 O has an effect of improving the thermal stability and melting property of the glass, but if the content thereof exceeds 8%, devitrification resistance and chemical stability of the glass deteriorate. Therefore, K in the present invention 2 The content of O is 0 to 8%, preferably K 2 The content of O is 0 to 5%, more preferably 0 to 3%.
WO 3 Can improve the refractive index and mechanical strength of the glass, if WO 3 When the content of (B) exceeds 5%, the glass is deteriorated in thermal stability and devitrification resistance. Thus, WO 3 The upper limit of the content of (B) is 5%, preferably 3%, more preferably 1%. In some embodiments, it is further preferred that WO is absent 3 。
Ta 2 O 5 The glass has the effects of improving the refractive index and improving the devitrification resistance of the glass, but the content of the glass is too high, the thermal stability of the glass is reduced, the density is increased, and the optical constant is difficult to control to a desired range; 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 thereof should be minimized from the practical and cost viewpoints. Thus, ta in the present invention 2 O 5 The content of (b) is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably Ta is not contained 2 O 5 。
TiO 2 Has the function of improving the refractive index and dispersion of the glass, and can stabilize the glass and reduce the viscosity of the glass by proper content. If TiO 2 The content of (B) exceeds 5%, the glass tends to be more devitrified, the transition temperature rises, and P of the glass rises g,F Value sum Δ P g,F The value becomes large. Thus, tiO in the present invention 2 The content of (A) is 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably contains no TiO 2 。
In some embodiments, B is 2 O 3 、Li 2 O、TiO 2 Total content of (B) 2 O 3 +Li 2 O+TiO 2 With BaO and Nb 2 O 5 Total content of (B) BaO + Nb 2 O 5 Ratio (B) between 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Controlling the content of the metal oxide to be less than 0.5 can improve the chemical stability of the glass and prevent the light transmittance of the glass from being reduced. Therefore, (B) is preferred 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less. Further, controlling (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Below 0.2, the hardness and thermal expansion coefficient of the glass can be further optimized. Therefore, (B) is more preferable 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
ZnO can adjust the refractive index and dispersion of the glass, reduce the high-temperature viscosity and transition temperature of the glass, and enable the glass to be smelted at a lower temperature, thereby improving the light transmittance of the glass. If the content of ZnO is too high, the difficulty of glass forming is increased, the devitrification resistance is deteriorated, and the negative anomalous dispersion of the glass is not favorably obtained. Therefore, the content of ZnO is 0 to 8%, preferably 0 to 4%, more preferably 0 to 1%. In some embodiments, it is further preferred that no ZnO is present.
In some embodiments, zrO is reacted with 2 And ZnO in total 2 Ratio between content of + ZnO and BaO (ZrO) 2 The content of + ZnO)/BaO is controlled within the range of 0.05-1.5, so that the glass can have lower P g,F Value sum Δ P g,F The value prevents the Young's modulus of the glass from deteriorating. Therefore, (ZrO) 2 + ZnO)/BaO is 0.05 to 1.5, more preferably (ZrO) 2 + ZnO)/BaO is 0.1-1.0. Further, control (ZrO) 2 The content of + ZnO)/BaO is within the range of 0.15-0.8, and the thermal expansion coefficient of the glass can be further reduced, and the hardness of the glass can be improved. Therefore, (ZrO) is more preferable 2 + ZnO)/BaO is 0.15 to 0.8, more preferably (ZrO) 2 +ZnO)/BaO is 0.2-0.6.
Ln 2 O 3 (Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more) is a component for improving the refractive index and chemical stability of the glass by adding Ln 2 O 3 The content of (B) is controlled to 5% or less, and deterioration of devitrification resistance of the glass can be prevented, and Ln is preferred 2 O 3 The upper limit of the content range of (B) is 3%, and the more preferable upper limit is 1%. In some embodiments, it is further preferred that Ln is absent 2 O 3 。
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 。
In the invention, 0 to 1 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 0.8 percent, and more preferably 0 to 0.5 percent. When Sb is present 2 O 3 At contents exceeding 1%, 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 1%, more preferably 0 to 0.8%, and still more preferably 0 to 0.5%. SnO and SnO 2 However, when the content exceeds 1%, 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 1%, more preferably 0 to 0.8%, and further preferably 0 to 0.5%; the content of SnO is preferably 0 to 1%, more preferably0 to 0.8%, and more preferably 0 to 0.5%. CeO (CeO) 2 The function and content ratio of (A) and (B) of SnO 2 The content is preferably 0 to 1%, more preferably 0 to 0.8%, even more preferably 0 to 0.5%, and even more preferably no CeO 2 。
< component which should not be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, cr, mn, fe, co, ni, cu, ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the optical glass of the present invention as a raw material; 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 properties of the special 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 (v) 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 special dispersion optical glass of the present invention d ) The lower limit of (b) is 1.68, preferably 1.69, more preferably 1.70, and still more preferably 1.705. In some embodiments, the refractive index (n) of the optical glass of the present invention d ) The upper limit of (a) is 1.76, preferably 1.75, more preferably 1.74, and still more preferably 1.735.
In some embodiments, the Abbe number (v) of the particular dispersive optical glass of the present invention d ) The lower limit of (2) is 30, preferably 31, more preferably 32, and still more preferably 33.50. In some embodiments, the Abbe number (v) of the optical glass of the present invention d ) The upper limit of (2) is 39, preferably 38, more preferably 37, and still more preferably 36.50.
< Density >
The density (. Rho.) of the optical glass was measured according to the method specified in GB/T7962.20-2010.
In some embodiments, the specially dispersive optical glasses of the present invention have a density (. Rho.) of 3.8g/cm 3 Hereinafter, it is preferably 3.7g/cm 3 Hereinafter, more preferably 3.6g/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 measured according to the method specified in GB/T7962.16-2010.
In some embodiments, the specific dispersion optical glass of the present invention has a coefficient of thermal expansion (α) -30/70℃ ) Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than 85X 10 -7 and/K is less than or equal to.
< degree of coloration >
The coloring degree (lambda) for the short-wave transmission spectrum characteristic of the special dispersion optical glass of the invention 80 And λ 5 ) And (4) showing. Lambda [ alpha ] 80 Refers to the corresponding wavelength when the transmittance of the glass reaches 80 percent。λ 80 Was measured using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished, measuring the spectral transmittance in the wavelength region from 280nm to 700nm and showing a wavelength of transmittance of 80%. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the 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 quantity expressed and also the transmission of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in the glass, λ 80 A small value of (A) means that the glass itself is rarely colored and has a high light transmittance.
In some embodiments, the special dispersion optical glasses of the present invention have a lambda 80 Less than or equal to 400nm, preferably lambda 80 Less than or equal to 390nm, more preferably lambda 80 Less than or equal to 385nm.
In some embodiments, the special dispersion optical glasses of the present invention have a lambda 5 Less than or equal to 350nm, preferably lambda 5 Less than or equal to 340nm, more preferably lambda 5 Less than or equal to 335nm.
< weather resistance >
The optical glass was tested for weatherability (CR) 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 alternately circulated at intervals of 1h at the temperature of 40-50 ℃ for 15 periods. Weather resistance categories were classified according to the amount of change in haze before and after the sample was left, and the weather resistance categories are shown in table 1:
table 1.
In some embodiments, the special dispersion 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 ) According to GB/T7962.18-2010.
In some embodiments, the Knoop hardness (H) of the special dispersion optical glasses of the present invention K ) Is 500X 10 7 Pa or more, preferably 510X 10 7 Pa or more, more preferably 520X 10 7 Pa or above.
< relative partial dispersion and relative partial dispersion deviation value >
The relative partial dispersion (P) is illustrated by the following equation g,F ) And relative partial dispersion deviation value (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 a 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 Indicate, then each P 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 relative partial dispersion deviation value (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)
in some embodiments, the relative partial dispersion (P) of the special dispersion optical glasses of the present invention g,F ) Is 0.7500 or less, preferably 0.7000 or less, more preferably 0.6500 or less, and further preferably 0.6000 or less.
In some embodiments, the relative partial dispersion deviation value (Δ P) of the special dispersion optical glass of the present invention g,F ) Is less than 0, preferably-0.0001 or less, more preferably-0.0005 or less, and further preferably-0.0010 or less.
< degree of abrasion >
Degree of abrasion (F) of optical glass A ) The abrasion loss of the sample is multiplied by 100 under the same conditions, and the value is expressed by the following formula:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
in the formula: v is the volume abrasion amount of the sample to be measured;
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 degree of abrasion (F) of the particular dispersive optical glass of the present invention A ) Has a lower limit of 180, preferably 185, more preferably 190, and a degree of wear (F) A ) Is 220, preferably 215, more preferably 210.
< stability against Water Effect >
Stability to Water of optical glass (D) W ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the water stability of the special dispersing optical glasses of the present invention (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 described in GB/T17129.
In some embodiments, the special dispersion optical glasses of the present invention are stable against acid action (D) A ) Is 2 or more, preferably 1.
< Young's modulus >
The Young modulus (E) is obtained by measuring the longitudinal wave velocity and the transverse wave velocity of the Young modulus by ultrasonic waves and 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 lower limit of the Young's modulus (E) of the special dispersion optical glass of the present invention is 8000X 10 7 Pa, preferably lower limit of 8500X 10 7 Pa or more, and more preferably 9000X 10 as the lower limit 7 Pa or above.
In some embodiments, the Young's modulus (E) of the special dispersion optical glass of the present invention has an upper limit of 11000X 10 7 Pa, preferably upper limit of 10500X 10 7 Pa, more preferably upper limit of 10000X 10 7 Pa。
[ method for producing optical glass ]
The method for manufacturing the special 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 1200-1500 ℃ for smelting, and after being clarified and homogenized, 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 produced from the optical glass produced by direct gob casting, grinding, or press molding such as 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 optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for reheat press forming, precision press forming, or the like to produce optical elements such as lenses, prisms, or the like.
The glass preform of the present invention and the optical element are each formed of the above-described optical glass of the present invention. The glass preform of the present invention has excellent characteristics possessed by optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide optical elements such as various lenses and prisms having high optical values.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a double convex lens, a double concave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments ]
The optical element formed by the special 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
< specific Dispersion optical glass example >
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, special dispersion optical glasses having compositions shown in tables 2 to 4 were obtained by the above-mentioned optical glass production method. 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 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 by using glasses obtained in examples 1 to 24# of special dispersion optical glasses by means of polishing or press molding such as hot press molding and 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 coated with an antireflection film.
< optical Instrument example >
The optical element produced by the above-described optical element embodiments can be used, for example, for imaging devices, sensors, microscopes, medical technology, digital projection, communication, optical communication technology/information transmission, optics/illumination in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, by optical design, by forming an optical component or optical assembly using one or more optical elements.
Claims (14)
1. Special dispersion optical glass, characterized in that the components are given in weight percentThe method comprises the following steps: siO 2 2 ：26～42％；Nb 2 O 5 ：21～40％；ZrO 2 ：0.5～12％；BaO：6～20％；Na 2 O:3 to 18 percent of (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 2.5-10.0.
2. The special dispersion optical glass according to claim 1, wherein the composition, expressed in weight percent, further comprises: b is 2 O 3 :0 to 10 percent; and/or MgO:0 to 6 percent; and/or CaO:0 to 10 percent; and/or SrO:0 to 6 percent; and/or Li 2 O:0 to 5 percent; and/or K 2 O:0 to 8 percent; and/or WO 3 :0 to 5 percent; and/or Ta 2 O 5 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
3. Special dispersion optical glass characterized by containing SiO 2 、Nb 2 O 5 、ZrO 2 、BaO、Na 2 O, the composition of which is expressed in weight percent, (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 2.5-10.0, and the refractive index n of the special dispersion optical glass d 1.68 to 1.76, abbe number v d 30 to 39, relative partial dispersion P g,F A relative partial dispersion deviation value Δ P of 0.7500 or less g,F Is less than 0 and has a coefficient of thermal expansion alpha -30/70℃ Is 95X 10 -7 and/K is less than or equal to.
4. A specific dispersion optical glass according to claim 3, having the composition, expressed in weight percent, comprising: siO 2 2 :26 to 42 percent; and/or Nb 2 O 5 :21 to 40 percent; and/or ZrO 2 :0.5 to 12 percent; and/or BaO:6 to 20 percent; and/or Na 2 O:3 to 18 percent; and/or B 2 O 3 :0 to 10 percent; and/or MgO:0 to 6 percent; and/or CaO:0 to 10 percent; and/or SrO:0 to 6 percent; and/or Li 2 O:0 to 5 percent; and/or K 2 O:0 to 8 percent; and/or WO 3 :0 to 5 percent; and/or Ta 2 O 5 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or ZnO:0 to 8 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or Al 2 O 3 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
5. The special dispersion optical glass according to any one of claims 1 to 4, wherein the components are expressed in weight percent, wherein: and (3) RO:7 to 35%, preferably RO:11 to 30%, more preferably RO:13 to 25 percent; and/or RO/SiO 2 0.2 to 1.2, preferably RO/SiO 2 Is 0.25 to 1.0, and RO/SiO is more preferable 2 0.3 to 0.8, and further preferably RO/SiO 2 0.4 to 0.7; and/or RO/Nb 2 O 5 0.2 to 1.5, preferably RO/Nb 2 O 5 0.3 to 1.2, and RO/Nb is more preferable 2 O 5 0.4 to 1.0, and RO/Nb is more preferable 2 O 5 0.4 to 0.8, and the RO is the total content of MgO, caO, srO and BaO.
6. A specific dispersion optical glass according to any one of claims 1 to 4, wherein the composition, expressed in weight percent, satisfies one or more of the following 7 conditions:
1)B 2 O 3 /SiO 2 is 0.3 or less, preferably B 2 O 3 /SiO 2 Is 0.25 or less, more preferably B 2 O 3 /SiO 2 Is 0.2 or less, and B is more preferably B 2 O 3 /SiO 2 0.01 to 0.15;
2)B 2 O 3 a ratio of/BaO of 1.4 or less, preferably B 2 O 3 BaO is 1.0 or less, and B is more preferably 2 O 3 BaO is 0.8 or less, and B is more preferable 2 O 3 The ratio of/BaO is 0.1-0.5;
3)(ZrO 2 + ZnO)/BaO is 0.05 to 1.5, preferably (ZrO) 2 + ZnO)/BaO is 0.1 to 1.0, more preferably (ZrO) 2 + ZnO)/BaO is 0.15 to 0.8, and (ZrO) is more preferable 2 + ZnO)/BaO is 0.2-0.6;
4)(SiO 2 +Nb 2 O 5 ) A ratio of/BaO of 3.0 to 8.0, preferably (SiO) 2 +Nb 2 O 5 ) A value of/BaO is 3.5 to 7.0, more preferably (SiO) 2 +Nb 2 O 5 ) The ratio of/BaO is 4.0-6.0;
5)(BaO+CaO)/Na 2 o is 0.5 to 5.0, preferably (BaO + CaO)/Na 2 O is 0.8 to 4.0, more preferably (BaO + CaO)/Na 2 O is 1.0 to 3.0, and (BaO + CaO)/Na is more preferable 2 O is 1.2 to 2.5;
6)(Na 2 O+Nb 2 O 5 )/SiO 2 0.6 to 2.0, preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.7 to 1.7, more preferably (Na) 2 O+Nb 2 O 5 )/SiO 2 Is 0.8 to 1.5, and (Na) is more preferable 2 O+Nb 2 O 5 )/SiO 2 1.0 to 1.5;
7)(B 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.5 or less, preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.3 or less, more preferably (B) 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) Is 0.2 or less, and (B) is more preferable 2 O 3 +Li 2 O+TiO 2 )/(BaO+Nb 2 O 5 ) 0.01 to 0.15.
7. The special dispersion optical glass according to any one of claims 1 to 4, wherein the components are expressed in weight percent, wherein: siO 2 2 :28 to 40%, preferably SiO 2 :30 to 37 percent; and/or B 2 O 3 :0 to 6%, preferably B 2 O 3 :0.5 to 5 percent; and/or Nb 2 O 5 :25 to 35%, preferably Nb 2 O 5 :27 to 33 percent; and/or ZrO 2 :1 to 10%, preferably ZrO 2 :2 to 8 percent; and/or BaO:8 to 18%, preferably BaO:10 to 16 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or CaO:0.5 to 8%, preferably CaO:1 to 6 percent; and/or SrO:0 to 3%, preferably SrO:0 to 1 percent; and/or Na 2 O:5 to 15%, preferably Na 2 O:7 to 13 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 2 percent; and/or K 2 O:0 to 5%, preferably K 2 O:0 to 3 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or Ta 2 O 5 :0 to 3%, preferably Ta 2 O 5 :0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or ZnO:0 to 4%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 3%, preferably Al 2 O 3 :0 to 1 percent; and/or a clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of Sb as clarifying agent 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
8. Special dispersion optical glass according to any one of claims 1 to 4, characterised in that it does not contain TiO in its composition 2 (ii) a And/or does not contain WO 3 (ii) a And/or does not contain Ta 2 O 5 (ii) a And/or does not contain ZnO(ii) a And/or does not contain Ln 2 O 3 (ii) a And/or do not contain Li 2 O; and/or does not contain Al 2 O 3 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of (a).
9. Specific dispersion optical glass according to any one of claims 1 to 4, wherein the refractive index n of the specific dispersion optical glass d 1.68 to 1.76, preferably 1.69 to 1.75, more preferably 1.70 to 1.74, still more preferably 1.705 to 1.735, and/or Abbe number v d Is 30 to 39, preferably 31 to 38, more preferably 32 to 37, and still more preferably 33.50 to 36.50.
10. A special dispersion optical glass according to any one of claims 1 to 4, characterized in that the relative partial dispersion P of the special dispersion optical glass g,F Is 0.7500 or less, preferably 0.7000 or less, more preferably 0.6500 or less, further preferably 0.6000 or less, and/or a relative partial dispersion deviation value Δ P g,F Is less than 0, preferably-0.0001 or less, more preferably-0.0005 or less, and further preferably-0.0010 or less.
11. The special dispersion optical glass as claimed in any one of claims 1 to 4, wherein the density p of the special dispersion optical glass is 3.8g/cm 3 Hereinafter, it is preferably 3.7g/cm 3 Hereinafter, more preferably 3.6g/cm 3 The following; and/or coefficient of thermal expansion alpha -30/70℃ Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than 85X 10 -7 below/K; and/or lambda 80 Less than or equal to 400nm, preferably lambda 80 Less than or equal to 390nm, more preferably lambda 80 Less than or equal to 385nm; and/or lambda 5 Less than or equal to 350nm, preferably lambda 5 Less than or equal to 340nm, more preferably lambda 5 Less than or equal to 335nm; and/or the weather resistance CR is of class 2 or more,preferably of class 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or Knoop hardness H K Is 500X 10 7 Pa or more, preferably 510X 10 7 Pa or more, more preferably 520X 10 7 Pa is above; and/or degree of wear F A 180 to 220, preferably 185 to 215, more preferably 190 to 210; and/or a Young's modulus E of 8000X 10 7 ～11000×10 7 Pa, preferably 8500X 10 7 ～10500×10 7 Pa, more preferably 9000X 10 7 ～10000×10 7 Pa。
12. A glass preform made of the special dispersion optical glass according to any one of claims 1 to 11.
13. Optical element, characterized in that it is made of a special dispersion optical glass according to any one of claims 1 to 11 or of a glass preform according to claim 12.
14. Optical instrument comprising a specific dispersion optical glass according to any one of claims 1 to 11 and/or comprising an optical element according to claim 13.
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| CN202211272912.5A CN115677209A (en) | 2022-10-18 | 2022-10-18 | Special dispersion optical glass |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225903A (en) * | 1998-02-10 | 1999-08-18 | 株式会社小原 | Optical glass having negative abnormal dispersion |
| JP2016088758A (en) * | 2014-10-29 | 2016-05-23 | 株式会社オハラ | Optical glass, preform and optical element |
| CN111183122A (en) * | 2017-10-02 | 2020-05-19 | 株式会社小原 | Optical glass, preform, and optical element |
| CN113264675A (en) * | 2021-06-24 | 2021-08-17 | 成都光明光电股份有限公司 | Optical glass, optical element and optical instrument |
| CN113292242A (en) * | 2021-06-24 | 2021-08-24 | 成都光明光电股份有限公司 | Special dispersion optical glass |
-
2022
- 2022-10-18 CN CN202211272912.5A patent/CN115677209A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225903A (en) * | 1998-02-10 | 1999-08-18 | 株式会社小原 | Optical glass having negative abnormal dispersion |
| JP2016088758A (en) * | 2014-10-29 | 2016-05-23 | 株式会社オハラ | Optical glass, preform and optical element |
| CN111183122A (en) * | 2017-10-02 | 2020-05-19 | 株式会社小原 | Optical glass, preform, and optical element |
| CN113264675A (en) * | 2021-06-24 | 2021-08-17 | 成都光明光电股份有限公司 | Optical glass, optical element and optical instrument |
| CN113292242A (en) * | 2021-06-24 | 2021-08-24 | 成都光明光电股份有限公司 | Special dispersion optical glass |
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