CN117185653A - High-refraction high-dispersion optical glass and optical element - Google Patents
High-refraction high-dispersion optical glass and optical element Download PDFInfo
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- 239000005304 optical glass Substances 0.000 title claims abstract description 94
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 91
- 239000011521 glass Substances 0.000 claims description 122
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 41
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- 238000000034 method Methods 0.000 claims description 28
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- 239000008395 clarifying agent Substances 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 11
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Abstract
The invention provides high-refraction high-dispersion optical glass, which comprises the following components in percentage by weight: p (P) 2 O 5 ：16～33％；Nb 2 O 5 ：40～55％；TiO 2 ：1～13％；BaO：1～15％；Na 2 O:0.5 to 15 percent, wherein TiO 2 BaO is 0.2-8.0. Through reasonable component design, the optical glass obtained by the invention has low thermal expansion coefficient while having the optical performance of high refractive index and high dispersion, and meets the use requirement of high-performance optical instruments.
Description
Technical Field
The present invention relates to an optical glass, and more particularly, to a high-refractive high-dispersion optical glass, and an optical element made of the same.
Background
The optical glass with the refractive index of 1.86-1.93 and the Abbe number of 16-24 belongs to high-refraction high-dispersion optical glass, and the high-refraction high-dispersion optical glass can be coupled with low-dispersion optical glass for use, so that chromatic aberration and secondary spectrum can be effectively eliminated, meanwhile, the optical total length of a lens can be effectively shortened, and an imaging system is miniaturized, so that the glass has a very wide application prospect. Chinese patent CN1915876A discloses a high-refraction high-dispersion optical glass with refractive index of 1.86-1.95 and Abbe number of 19-24, its composition contains more than 10-30% of WO 3 High content WO 3 The light transmittance of the optical glass is not good.
An optical element mounted in an optical device for a vehicle and an optical element mounted in an optical device for generating heat such as a projector, a copier, a laser printer, or the like are used in an environment where a temperature change is large, and if the thermal expansion coefficient of an optical glass is excessively large, thermal expansion of the optical element occurs due to a change in the environmental temperature. Because of the difference in expansion coefficient from the optical element fixing jig, stress is generated in the optical element, and birefringence is generated, so that imaging characteristics are changed. Accordingly, it is desirable for the optical glass to have a low thermal expansion coefficient.
Disclosure of Invention
The invention aims to provide high-refraction high-dispersion optical glass with low thermal expansion coefficient.
The technical scheme adopted for solving the technical problems is as follows:
(1) The high-refraction high-dispersion optical glass comprises the following components in percentage by weight: p (P) 2 O 5 ：16～33％；Nb 2 O 5 ：40～55％；TiO 2 ：1～13％；BaO：1～15％；Na 2 O:0.5 to 15 percent, wherein TiO 2 BaO is 0.2-8.0.
(2) The high-refraction high-dispersion optical glass according to (1), which comprises the following components in percentage by weight: caO: 0-8%; and/or MgO: 0-5%; and/or SrO: 0-5%; and/or ZnO: 0-8%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 0-5%; and/or Al 2 O 3 :0 to 3 percent; and/or WO 3 :0 to 3 percent; and/or ZrO 2 : 0-5%; and/or Bi 2 O 3 :0 to 3 percent; and/or TeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One of (a)One or more.
(3) The high-refraction high-dispersion optical glass contains P in its component 2 O 5 、Nb 2 O 5 、TiO 2 BaO and Na 2 O, the components of which are expressed in weight percent, wherein TiO 2 BaO is 0.2-8.0, and the refractive index n of the optical glass d Is 1.86 to 1.93, and Abbe number v d Is 16 to 24, the thermal expansion coefficient alpha 100/300℃ 95X 10 -7 and/K or below.
(4) The high-refraction high-dispersion optical glass according to (3), comprising, in weight percent: p (P) 2 O 5 : 16-33%; and/or Nb 2 O 5 : 40-55%; and/or TiO 2 :1 to 13 percent; and/or BaO: 1-15%; and/or Na 2 O: 0.5-15%; and/or CaO: 0-8%; and/or MgO: 0-5%; and/or SrO: 0-5%; and/or ZnO: 0-8%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 0-5%; and/or Al 2 O 3 :0 to 3 percent; and/or WO 3 :0 to 3 percent; and/or ZrO 2 : 0-5%; and/or Bi 2 O 3 :0 to 3 percent; and/or TeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(5) The high-refraction high-dispersion optical glass according to any one of (1) to (4), wherein the components thereof are expressed in weight percent, satisfying one or more of the following 6 cases:
1)TiO 2 BaO is 0.3 to 5.0, preferably TiO 2 BaO is 0.5 to 3.0, more preferably TiO 2 BaO is 0.6-1.5;
2)ZnO/TiO 2 at most 3.0, preferably ZnO/TiO 2 From 0.01 to 2.0, more preferably ZnO/TiO 2 0.1 to 1.5, znO/TiO is more preferable 2 0.2 to 0.8;
3)ZnO/(Na 2 O+TiO 2 ) At most 2.0, znO/(Na) is preferable 2 O+TiO 2 ) Is 0.01 to 1.5, more preferably ZnO/(Na) 2 O+TiO 2 ) In the range of 0.05 to 0.8, znO/(Na) is more preferable 2 O+TiO 2 ) 0.05 to 0.4;
4)TiO 2 CaO is 0.5 to 10.0, preferably TiO 2 CaO is 1.0 to 8.0, more preferably TiO 2 CaO is 2.0 to 7.0, and TiO is more preferable 2 CaO is 2.5 to 6.0;
5) ZnO/BaO is 3.0 or less, preferably 0.05 to 2.0, more preferably 0.1 to 1.5, and still more preferably 0.2 to 0.8;
6)(P 2 O 5 +BaO)/(ZnO+CaO) is 2.0 or more, preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 3.0 to 20.0, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 5.0 to 15.0, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 8.0 to 12.0.
(6) The high-refraction high-dispersion optical glass according to any one of (1) to (4), wherein the components thereof are expressed in weight percent, satisfying one or more of the following 7 cases:
1)(B 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 2.0 or less, preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 1.0 or less, more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 0.5 or less, and more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is less than 0.2;
2)(B 2 O 3 +Li 2 O+K 2 O)/ZnO is 2.0 or less, preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 1.0 or less, more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.5 or less, and more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.2 or less;
3)(Na 2 O+K 2 O)/Nb 2 O 5 is 0.05 to 0.45, preferably (Na 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.4, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.3, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 0.1 to 0.25;
4)(BaO+K 2 O+ZnO)/(Na 2 O+CaO) is 0.1 to 8.0, preferably (BaO+K) 2 O+ZnO)/(Na 2 O+CaO) is 0.2 to 5.0, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+CaO) is 0.3 to 2.5, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+cao) is 0.5 to 1.5;
5)(TiO 2 +K 2 O)/P 2 O 5 is 0.05 to 0.8, preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.6, more preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.5, more preferably (TiO) 2 +K 2 O)/P 2 O 5 0.15 to 0.4;
6)(WO 3 +TiO 2 )/Nb 2 O 5 is 0.02 to 0.3, preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.25, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.2, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 0.07 to 0.17;
7)(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 is 0.8 or less, preferably
(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.5 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.3 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 At 0.1 toThe Ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
(7) The high-refraction high-dispersion optical glass according to any one of (1) to (4), wherein the components are represented by weight percent: p (P) 2 O 5 :20 to 30%, preferably P 2 O 5 : 22-28%; and/or Nb 2 O 5 :45 to 55%, preferably Nb 2 O 5 : 46-53%; and/or TiO 2 :3 to 10%, preferably TiO 2 : 4-8%; and/or BaO: 2-12%, preferably BaO: 3-9%; and/or Na 2 O:3 to 12%, preferably Na 2 O: 6-10%; and/or CaO: greater than 0 but less than or equal to 6%, preferably CaO:1 to 4 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or ZnO: greater than 0 but less than or equal to 6%, preferably ZnO:1 to 4 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 1 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or SiO 2 :0 to 3%, preferably SiO 2 :0 to 1 percent; and/or B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 2%, preferably Al 2 O 3 :0 to 1 percent; and/or WO 3 :0 to 2%, preferably WO 3 :0 to 1 percent; and/or ZrO 2 :0 to 3%, preferably ZrO 2 :0 to 1 percent; and/or Bi 2 O 3 :0 to 2%, preferably Bi 2 O 3 :0 to 1 percent; and/or TeO 2 :0 to 3%, preferably TeO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(8) The high-refractive high-dispersion optical glass according to any one of (1) to (4), wherein MgO is not contained in the composition; and/or does not contain SrO; and/or does not contain Li 2 O; and/or does not contain K 2 O; and/or does not contain Ln 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or no clarifying agent, said Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
(9) The high-refractive high-dispersion optical glass according to any one of (1) to (4), which has a refractive index n d 1.86 to 1.93, preferably 1.87 to 1.92, more preferably 1.88 to 1.91; abbe number v d 16 to 24, preferably 17 to 23, more preferably 18 to 22.
(10) The high-refractive high-dispersion optical glass according to any one of (1) to (4), which has a coefficient of thermal expansion α 100/300℃ 95X 10 -7 Preferably 90X 10, and K is less than or equal to -7 Preferably not more than/K, more preferably 85X 10 -7 and/K or below; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or stability against water action D W More than 2 types, preferably 1 type; and/or relative partial dispersion P g,F From 0.58 to 0.72, preferably from 0.60 to 0.68, more preferably from 0.63 to 0.66; and/or relative partial dispersion deviation value ΔP g,F Is 0.08 or less, preferably 0.01 to 0.06, more preferably 0.02 to 0.05; and/or transition temperature T g 670 ℃ or lower, preferably 660 ℃ or lower, more preferably 650 ℃ or lower; and/or abrasion degree F A 230 to 270, preferably 240265, more preferably 245 to 260; and/or density ρ of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following are set forth; and/or lambda 70 Is 440nm or less, preferably lambda 70 Is 430nm or less, more preferably lambda 70 425nm or less; and/or lambda 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 385nm or less; and/or weather resistance CR is 2 or more, preferably 1; and/or Young's modulus E of 8000X 10 7 Pa or more, preferably 9000×10 7 Pa or more, more preferably 9500×10 7 Pa or more; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage.
(11) A glass preform produced by using the high-refractive high-dispersion optical glass according to any one of (1) to (10).
(12) An optical element made of the high-refractive high-dispersion optical glass according to any one of (1) to (10), or made of the glass preform according to (11).
(13) An optical device comprising the high-refractive high-dispersion optical glass according to any one of (1) to (10), or the optical element according to (12).
The beneficial effects of the invention are as follows: through reasonable component design, the optical glass obtained by the invention has low thermal expansion coefficient while having the optical performance of high refractive index and high dispersion, and meets the use requirement of high-performance optical instruments.
Detailed Description
The following describes embodiments of the high-refractive high-dispersion optical glass of the present invention in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the description of the repetitive description, the high refractive high dispersion optical glass of the present invention is sometimes referred to simply as an optical glass or glass in the following description, although description is omitted appropriately, without limiting the gist of the present invention.
[ optical glass ]
The ranges of the respective components (ingredients) of the optical glass of the present invention are described below. In the present invention, unless otherwise specified, the content and the total content of each component are all expressed in weight percent (wt%), that is, the content and the total content of each component are expressed in weight percent with respect to the total amount of the glass substance converted into the composition of oxide. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the optical glass composition of the present invention is 100% when the oxide, the composite salt, the hydroxide, and the like are melted and decomposed and converted into oxide.
Unless otherwise indicated in a particular context, the numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "and/or" as used herein is inclusive, e.g. "a and/or B", meaning either a alone, B alone, or both a and B.
< essential Components and optional Components >
P 2 O 5 Compared with silicate glass, the phosphate glass can be melted at low temperature, so that the light transmittance of the glass is improved; if P 2 O 5 If the content of (c) is too high, it is difficult to obtain a high refractive index of the glass. Thus, P in the present invention 2 O 5 The content of (2) is 16 to 33%, preferably 20 to 30%, more preferably 22 to 28%.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and devitrification resistance of the glass, and has the effect of reducing the relative partial dispersion (P g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) In the present invention, the content of Nb is 40% or more 2 O 5 To obtain the above effect, nb is preferable 2 O 5 The lower limit of the content of (2) is 45%, and more preferably the lower limit is 46%. If Nb is 2 O 5 The content of (2) exceeds 55%, the thermal stability and chemical stability of the glass are lowered, and the light transmittance is lowered. Thus, nb in the present invention 2 O 5 The upper limit of the content of (2) is 55%, preferably 53%。
TiO 2 Has high refractive and high dispersion properties, and can improve the chemical stability of glass and adjust the relative partial dispersion (P) g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) If the content is too high, the devitrification resistance and the light transmittance of the glass decrease. Thus, tiO 2 The content of (2) is 1 to 13%, preferably 3 to 10%, more preferably 4 to 8%.
BaO can improve devitrification resistance and hardness of the glass, and can reduce the temperature coefficient of refractive index and thermal expansion coefficient of the glass, and in the present invention, it is preferable that BaO is contained in an amount of not less than 1% to obtain the above-mentioned effects, and the BaO content is not less than 2%, more preferably not less than 3%. On the other hand, by setting the content of BaO to 15% or less, it is possible to prevent a decrease in chemical stability due to an excessively high BaO content. Therefore, the content of BaO is 15% or less, preferably 12% or less, and more preferably 9% or less.
In some embodiments, tiO is used 2 Ratio between the content of (A) and the content of BaO (A) TiO (A) 2 BaO is controlled within the range of 0.2-8.0, which is favorable for improving the chemical stability of the glass and reducing the thermal expansion coefficient of the glass. Therefore, tiO is preferred 2 BaO is 0.2 to 8.0, more preferably TiO 2 BaO is 0.3-5.0. Further, control TiO 2 BaO is in the range of 0.5-3.0, and the abrasion degree of the glass can be further optimized, so that the glass is easier to obtain the expected P g,F Value sum delta P g,F Values. Therefore, tiO is further preferred 2 BaO is 0.5 to 3.0, and TiO is more preferable 2 BaO is 0.6-1.5.
CaO contributes to adjusting the optical constants of the glass and improving the processability and weather resistance of the glass, but when the content of CaO is too large, the crystallization resistance of the glass is deteriorated. Therefore, the CaO content is 0 to 8%, preferably greater than 0 but less than or equal to 6%, more preferably 1 to 4%.
In some embodiments, tiO is used 2 Ratio between the content of (2) and the content of CaO TiO 2 CaO is controlled within the range of 0.5-10.0, which is favorable for reducing the thermal expansion coefficient of the glass and optimizing the Young modulus and the Young modulus of the glassAbrasion degree. Therefore, tiO is preferred 2 CaO is 0.5 to 10.0, more preferably TiO 2 CaO is 1.0 to 8.0, and TiO is more preferable 2 CaO is 2.0 to 7.0, and TiO is more preferable 2 CaO is 2.5 to 6.0.
SrO can adjust the refractive index and dispersion of glass, but if it is contained too much, the chemical stability of glass decreases and the cost of glass increases. Therefore, the SrO content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that SrO is absent.
MgO is favorable for reducing the density and melting temperature of the glass, but when the MgO content is excessive, the refractive index of the glass is difficult to reach the design requirement, and the crystallization resistance and the stability of the glass are reduced. Accordingly, the MgO content is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that MgO is not contained.
ZnO can reduce the glass transition temperature and the melting temperature, improve the chemical stability of the glass, reduce the high-temperature viscosity of the glass, and if the ZnO content is too high, the crystallization resistance of the glass is poor and devitrification is easily caused due to the too low viscosity. Accordingly, the content of ZnO in the present invention is 0 to 8%, preferably greater than 0 but less than or equal to 6%, more preferably 1 to 4%.
In some embodiments, the content of ZnO is compared with Na 2 O and TiO 2 Is the total content Na of 2 O+TiO 2 Ratio between ZnO/(Na) 2 O+TiO 2 ) The bubble degree of the glass can be improved while preventing the glass transition temperature from rising by controlling the temperature to 2.0 or less. Therefore, znO/(Na) is preferable 2 O+TiO 2 ) Is 2.0 or less, more preferably ZnO/(Na) 2 O+TiO 2 ) 0.01 to 1.5. Further, znO/(Na) is controlled 2 O+TiO 2 ) In the range of 0.05 to 0.8, the abrasion degree and weather resistance of the glass can be further optimized. Therefore, znO/(Na) is more preferable 2 O+TiO 2 ) In the range of 0.05 to 0.8, znO/(Na) is more preferable 2 O+TiO 2 ) 0.05 to 0.4.
In some embodiments, P 2 O 5 And the total content of BaOP 2 O 5 The ratio between +BaO and the sum of ZnO and CaO content ZnO+CaO (P 2 O 5 +BaO)/(ZnO+CaO) is controlled to 2.0 or more, whereby the light transmittance of the glass can be improved and deterioration of the transition temperature can be prevented. Therefore, it is preferable that (P 2 O 5 +BaO)/(ZnO+CaO) is 2.0 or more, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 3.0 to 20.0. Further, control (P 2 O 5 The Young's modulus and the bubble degree of the glass can be further optimized in the range of 5.0 to 15.0. Therefore, it is more preferable that (P 2 O 5 +BaO)/(ZnO+CaO) is 5.0 to 15.0, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 8.0 to 12.0.
In some embodiments, controlling the ratio ZnO/BaO between the content of ZnO and the content of BaO to be 3.0 or less is advantageous in improving the weatherability of the glass. Therefore, znO/BaO is preferably 3.0 or less. Furthermore, the ZnO/BaO is controlled within the range of 0.05-2.0, and the abrasion degree of the glass can be optimized while the transition temperature of the glass is reduced. Therefore, znO/BaO is more preferably 0.05 to 2.0, still more preferably 0.1 to 1.5, still more preferably 0.2 to 0.8.
In some embodiments, the ZnO content is compared with TiO 2 Ratio between the contents of ZnO/TiO 2 The abrasion degree and chemical stability of the glass can be optimized and the transition temperature of the glass can be prevented from rising by controlling the abrasion degree and chemical stability below 3.0. Therefore, znO/TiO is preferable 2 Is 3.0 or less, more preferably ZnO/TiO 2 0.01 to 2.0, znO/TiO is more preferable 2 From 0.1 to 1.5, znO/TiO being more preferred 2 0.2 to 0.8.
Li 2 O can improve the meltability of the glass, reduce the transformation temperature, and if the content is too high, the refractive index of the glass is difficult to meet the design requirement, and the chemical stability of the glass is poor. Thus, li in the present invention 2 The content of O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that Li is not contained 2 O。
Na 2 O can improve the meltability and the formability of the glass, optimize the light transmittance of the glass,if the content is too high, it is disadvantageous in terms of the thermal expansion coefficient and chemical stability of the glass. Thus, na 2 The O content is 0.5 to 15%, preferably 3 to 12%, more preferably 6 to 10%.
K 2 O has an effect of improving the thermal stability and meltability of the glass, but if it is contained in an excessively high amount, the devitrification resistance of the glass is lowered. Thus, K is 2 The content of O is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that K is absent 2 O。
In some embodiments, na 2 O and K 2 Total content of O Na 2 O+K 2 O and Nb 2 O 5 Ratio between the contents of (Na) 2 O+K 2 O)/Nb 2 O 5 Controlled within the range of 0.05-0.45, which is favorable for obtaining high refraction and high dispersion and expected P of the glass g,F Value sum delta P g,F And (3) optimizing the crystallization resistance and abrasion resistance of the glass. Therefore, it is preferable that (Na 2 O+K 2 O)/Nb 2 O 5 Is 0.05 to 0.45, more preferably (Na 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.4, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.3, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 0.1 to 0.25.
In some embodiments, tiO is used 2 And K 2 Total content of O TiO 2 +K 2 O and P 2 O 5 Ratio between the contents of (TiO) 2 +K 2 O)/P 2 O 5 Controlled within a range of 0.05 to 0.8 to enable the glass to have the expected P g,F Value sum delta P g,F When the glass is used, the light transmittance and Young's modulus of the glass are prevented from being deteriorated. Therefore, it is preferable that (TiO 2 +K 2 O)/P 2 O 5 Is 0.05 to 0.8, more preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.6, more preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.5, more preferably (TiO) 2 +K 2 O)/P 2 O 5 0.15 to 0.4.
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more) are components that increase the refractive index of the glass, and are optional components in the optical glass of the present invention. By combining Ln 2 O 3 The content of (2) is controlled to 5% or less, and the devitrification resistance of the glass can be prevented from being lowered. Thus, in the present invention, ln 2 O 3 The content of (2) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that Ln is not present 2 O 3 。
By containing SiO in phosphate glass 2 The glass grid can be more compact, and the chemical stability and the mechanical strength of the glass are improved. But phosphate glass grid vs. SiO 2 Is not compatible with SiO 2 When the content is too high, the phase separation is likely to occur. Thus, siO in the present invention 2 The content of (2) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%.
B 2 O 3 Has the effect of improving the thermal stability and meltability of the glass, but when the content thereof is high, the chemical stability and devitrification resistance of the glass are reduced. Thus, in the present invention B 2 O 3 The content of (2) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that B is absent 2 O 3 。
In some embodiments, B 2 O 3 、Li 2 O and K 2 Total content of O B 2 O 3 +Li 2 O+K 2 Ratio between O and ZnO content (B 2 O 3 +Li 2 O+K 2 The O)/ZnO is controlled to be less than 2.0, so that the glass can obtain the expected P g,F Value sum delta P g,F The value and Young's modulus, and the chemical stability and the bubble degree of the glass are prevented from deteriorating. Therefore, (B) is preferable 2 O 3 +Li 2 O+K 2 O)/ZnO is 2.0 or less, more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 1.0 or less, and more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.5 or less, and more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.2 or less.
In some embodiments, baO, K 2 Total content of O and ZnO BaO+K 2 O+ZnO and Na 2 Total content of O and CaO Na 2 Ratio between O+CaO (BaO+K) 2 O+ZnO)/(Na 2 O+cao) is in the range of 0.1 to 8.0, which is advantageous for reducing the density and thermal expansion coefficient of the glass. Therefore, (BaO+K) is preferred 2 O+ZnO)/(Na 2 O+CaO) is 0.1 to 8.0, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+cao) is 0.2 to 5.0. Further, control (BaO+K 2 O+ZnO)/(Na 2 O+cao) is in the range of 0.3 to 2.5, and the abrasion degree and weather resistance of the glass can be further optimized. Therefore, (BaO+K) is more preferable 2 O+ZnO)/(Na 2 O+CaO) is 0.3 to 2.5, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+cao) is 0.5 to 1.5.
Al 2 O 3 The chemical stability of the glass can be improved, but when the content exceeds 3%, the melting property and light transmittance of the glass become poor. Thus, al in the present invention 2 O 3 The content of (2) is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%. In some embodiments, it is further preferred that Al is absent 2 O 3 。
WO 3 Is an optional component capable of adjusting the optical constant and devitrification resistance of the glass, but when the content is high, the transmittance and devitrification resistance of the glass decrease. Thus, WO 3 The content of (2) is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%. In some embodiments, it is further preferred that WO is not included 3 。
In some embodiments, WO is used 3 And TiO 2 Is the sum of WO 3 +TiO 2 With Nb 2 O 5 The ratio between the contents of (WO) 3 +TiO 2 )/Nb 2 O 5 The control of the glass is within the range of 0.02 to 0.3, which is beneficial to reducing the density of the glass and optimizing the Young modulus of the glassAnd abrasion. Therefore, it is preferable (WO 3 +TiO 2 )/Nb 2 O 5 Is 0.02 to 0.3, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.25, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.2, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 0.07 to 0.17.
Proper amount of ZrO 2 Can increase the mechanical strength and hardness of the glass, improve the crystallization resistance of the glass and adjust the P of the glass g,F Value sum delta P g,F Values. But ZrO 2 Is refractory to phosphate glass, and when the content is too high, the melting difficulty is caused. Thus, zrO in the present invention 2 The content of (2) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. In some embodiments, it is further preferred that ZrO-free 2 。
Bi 2 O 3 Can increase the refractive index of glass, but Bi 2 O 3 The density of the glass is large, and the lightweight design of the glass is not facilitated. Accordingly, bi in the present invention 2 O 3 The content of (2) is 0 to 3%, preferably 0 to 2%, more preferably 0 to 1%. In some embodiments, it is further preferred that Bi is not contained 2 O 3 。
In some embodiments, B 2 O 3 、WO 3 And Bi (Bi) 2 O 3 Total content B of (2) 2 O 3 +WO 3 +Bi 2 O 3 Ratio to ZnO content (B 2 O 3 +WO 3 +Bi 2 O 3 ) The ZnO is controlled below 2.0, which is favorable for obtaining the expected P of the glass g,F Value sum delta P g,F While optimizing the light transmittance and bubble degree of the glass, the density of the glass is prevented from rising. Therefore, (B) is preferable 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 2.0 or less, more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 1.0 or less, and more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 0.5 or less, and more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 0.2 or less.
In some embodiments, ln 2 O 3 、Li 2 O、K 2 O、WO 3 And Bi (Bi) 2 O 3 Is the sum Ln of (3) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 With TiO 2 Ratio between the contents of (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Controlled below 0.8, the glass has the expected P g,F Value sum delta P g,F While optimizing the values, the chemical stability and the bubble degree of the glass. Therefore, preference is given to
(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.8 or less, more preferably
(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.5 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.3 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.1 or less.
TeO 2 Is an optional component for improving the refractive index of the glass and reducing the transition temperature of the glass, and when the content of the optional component is too high, the optional component is easy to react with a platinum vessel, the service life of the platinum vessel is reduced, platinum particles are easy to enter the glass, the transmittance of the glass is reduced, volatile stripes are easy to generate, and the internal quality of the glass is reduced. Thus, teO 2 The content of (2) is limited to 5% or less, preferably 3% or less, and more preferably 1% or less. In some embodiments, it is further preferred that the TeO is absent 2 。
In the invention, 0 to 1 percent of Sb is contained 2 O 3 、SnO 2 、CeO 2 One or more components of the glass as a clarifying agent, can improve the clarification of the glassThe cleaning effect improves the bubble degree of the glass, the content of the clarifier is preferably 0 to 0.5 percent, and more preferably the content of the clarifier is 0 to 0.1 percent. Since the optical glass of the present invention has a reasonable design of the types and contents of components and is excellent in bubble degree, it is further preferable that a clarifier is not contained in some embodiments. When Sb is 2 O 3 If the content exceeds 1%, the glass tends to be degraded in fining property, and the strong oxidation promotes corrosion of platinum or platinum alloy vessels for melting the glass and deterioration of molding dies, so that Sb is preferable in the present invention 2 O 3 The content of (C) is 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%, and still more preferably no Sb is contained 2 O 3 。SnO 2 When the content exceeds 1%, the glass tends to be colored, or when the glass is heated, softened, and subjected to press molding or the like to be reformed, sn becomes a starting point of nucleation and devitrification tends to occur. Thus SnO of the present invention 2 The content of (2) is preferably 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.1%, and still more preferably no SnO is contained 2 。CeO 2 Action and content ratio of (2) and SnO 2 The content thereof is preferably 0 to 1%, more preferably 0 to 0.5%, even more preferably 0 to 0.1%, and even more preferably no CeO is contained 2 。
< component not to be contained >
In the glass of the present invention, V, cr, mn, fe, co, ni, cu, ag and oxides of transition metals such as Mo are colored even when they are contained in small amounts, either alone or in combination, and absorb at a specific wavelength in the visible light range, so that the property of the present invention of improving the visible light transmittance effect is impaired, and therefore, in particular, an optical glass having a wavelength transmittance in the visible light range is preferably practically not contained.
Th, cd, tl, os, be and Se oxides have a tendency to be used in a controlled manner as harmful chemical substances in recent years, and are required to provide environmental protection not only in the glass manufacturing process but also in the processing steps and disposal after production. Therefore, in the case where the influence on the environment is emphasized, it is preferable that they are not substantially contained except for unavoidable mixing. As a result, the optical glass becomes practically free from environmental pollutants. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures against the environment.
In order to achieve environmental friendliness, the optical glass of the present invention preferably does not contain As 2 O 3 And PbO.
The term "not containing" or "0%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing optical glass that are not intentionally added, and that may be present in small or trace amounts in the final optical glass.
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) d ) With Abbe number (v) d ) Tested according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n d ) The lower limit of (2) is 1.86, preferably 1.87, more preferably 1.88.
In some embodiments, the refractive index (n d ) The upper limit of (2) is 1.93, preferably 1.92, more preferably 1.91.
In some embodiments, the Abbe number (. Nu.) of the high refractive high dispersion optical glass of the present invention d ) The lower limit of (2) is 16, preferably 17, more preferably 18.
In some embodiments, the Abbe number (. Nu.) of the high refractive high dispersion optical glass of the present invention d ) The upper limit of (2) is 24, preferably 23, more preferably 22.
< coefficient of thermal expansion >
Heat of optical glassCoefficient of expansion (alpha) 100/300℃ ) Data at 100-300℃were tested according to the procedure prescribed in GB/T7962.16-2010.
In some embodiments, the high refractive high dispersion optical glass of the present invention has a coefficient of thermal expansion (α 100/300℃ ) 95X 10 -7 Preferably 90X 10, and K is less than or equal to -7 Preferably not more than/K, more preferably 85X 10 -7 and/K or below.
< stability against acid action >
Acid action resistance stability of optical glass (D A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the acid action resistance stability (D A ) More than 2 kinds, preferably 1 kind.
< stability against Water action >
Stability against Water action of optical glass (D W ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the high refractive high dispersion optical glass of the present invention has water resistance stability (D W ) More than 2 kinds, preferably 1 kind.
< relative partial Dispersion and relative partial Dispersion deviation value >
The relative partial dispersion (P) is described by the following formula g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) Is derived from (a).
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)
according to Abbe's number formula, the following formula (2) is true for most of so-called "normal glasses" (hereinafter H-K6 and F4 are selected as "normal glasses")
P x,y ＝m x,y ·v d +b x,y (2)
The linear relationship is represented by P x,y Is in ordinate, v d Represented by the abscissa, where m x,y Is a slope, b x,y Is the intercept.
It is known that correction of the secondary spectrum, i.e. achromatizing to more than two wavelengths, requires at least one glass which does not correspond to formula (2) above (i.e. P x,y Value deviation from Abbe's empirical formula), which is a deviation from the value ΔP x,y Representation, then each P x,y -v d The point is shifted by ΔP with respect to the "normal line" conforming to the above formula (2) x,y The amount of ΔP of each glass x,y The numerical value can be obtained by the following formula (3):
P x,y ＝m x,y ·v d +b x,y +ΔP x,y (3)
thus DeltaP x,y The deviation characteristic of the special dispersion when compared with "normal glass" is quantitatively expressed.
Thus, the relative partial dispersion (P g,F ) And relative partial dispersion deviation value (DeltaP) g,F ) The calculation formulas of (a) 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 g,F ) The lower limit of (2) is 0.58, preferably 0.60, more preferably 0.63.
In some embodiments, the relative partial dispersion (P g,F ) The upper limit of (2) is 0.72, preferably 0.68, more preferably 0.66.
In some embodiments, the relative partial dispersion deviation value (ΔP of the high refractive high dispersion optical glass of the present invention g,F ) The lower limit of (2) is 0.01, preferably 0.02.
In some embodiments, the relative partial dispersion deviation value (ΔP of the high refractive high dispersion optical glass of the present invention g,F ) The upper limit of (2) is 0.08, preferably 0.06, more preferably 0.05.
< transition temperature >
Rotation of optical glassTemperature change (T) g ) The test was carried out according to the method prescribed in GB/T7962.16-2010.
In some embodiments, the high refractive high dispersion optical glass of the present invention has a transition temperature (T g ) The temperature is 670℃or lower, preferably 660℃or lower, and more preferably 650℃or lower.
< abrasion degree >
Abrasion degree (F) of optical glass A ) The abrasion loss of the sample and the abrasion loss (volume) of the standard sample (H-K9 glass) are multiplied by 100 under the identical conditions, and the values are expressed as follows:
F A ＝V/V 0 ×100＝(W/ρ)/(W 0 /ρ 0 )×100
wherein: v-the volume abrasion of the sample to be measured;
V 0 -standard sample volume attrition;
w is the mass abrasion quantity of the sample to be measured;
W 0 -standard sample mass abrasion;
ρ -the measured sample density;
ρ 0 standard sample density.
In some embodiments, the abrasion degree (F A ) The lower limit of (2) is 230, preferably 240, more preferably 245.
In some embodiments, the abrasion degree (F A ) The upper limit of (2) is 270, preferably 265, more preferably 260.
< Density >
The density (. Rho.) was measured according to the method prescribed in GB/T7962.20-2010.
In some embodiments, the high refractive high dispersion optical glass of the present invention has a density (ρ) of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following is given.
< coloring degree >
The short wave transmission spectrum characteristics of the glass of the invention are usedChromaticity (lambda) 70 And lambda (lambda) 5 ) And (3) representing. Lambda (lambda) 70 Refers to the wavelength corresponding to when the glass transmittance reaches 70%. Lambda (lambda) 70 Is to measure spectral transmittance in a wavelength range from 280nm to 700nm and to exhibit a wavelength of 70% transmittance using glass having a thickness of 10.+ -. 0.1mm having two opposite planes which are parallel to each other and optically polished. The spectral transmittance or transmittance is the intensity I at right angles to the surface of the glass in Transmits through glass and emits intensity I from a plane out In the case of light passing through I out /I in The indicated amounts, and also the transmittance of the surface reflection losses on the above-mentioned surface of the glass. The higher the refractive index of the glass, the greater the surface reflection loss. Thus, in high refractive index glass, λ 70 The small value of (2) means that the glass itself is extremely little colored and the light transmittance is high.
In some embodiments, λ of the high refractive high dispersion optical glass of the present invention 70 Is 440nm or less, preferably lambda 70 Is 430nm or less, more preferably lambda 70 425nm or less.
In some embodiments, λ of the high refractive high dispersion optical glass of the present invention 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 Is 385nm or less.
< weather resistance >
The weather resistance (CR) test method of the optical glass is as follows: the sample is placed in a test box in a saturated steam environment with the relative humidity of 90 percent, and the sample is alternately circulated at the temperature of 40-50 ℃ for 15 cycles every 1 hour. Weather resistance categories were classified according to the amount of turbidity change before and after sample placement, and weather resistance classification conditions are shown in table 1:
table 1.
In some embodiments, the high refractive high dispersion optical glass of the present invention has a weatherability (CR) of 2 or more, preferably 1.
< Young's modulus >
Young's modulus (E) is obtained by measuring longitudinal wave velocity and transverse wave velocity by ultrasonic wave and calculating according to the following formula.
G＝V S 2 ρ
Wherein: e is Young's modulus, pa;
g is the shear modulus, pa;
V T is transverse wave speed, m/s;
V S is longitudinal wave speed, m/s;
ρ is the density of the glass, g/cm 3 。
In some embodiments, the high refractive high dispersion optical glass of the present invention has a Young's modulus (E) of 8000X 10 7 Pa or more, preferably 9000×10 7 Pa or more, more preferably 9500×10 7 Pa or more.
< bubble degree >
The bubble degree of the optical glass was measured according to the method prescribed in GB/T7962.8-2010.
In some embodiments, the high refractive high dispersion optical glass of the present invention has a bubble degree of class A or more, preferably class A 0 Above the stage, more preferably A 00 A stage.
[ method for producing optical glass ]
The method for manufacturing the high-refraction high-dispersion optical glass comprises the following steps: the glass of the present invention is produced by conventional raw materials and processes, including but not limited to using oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, phosphates, metaphosphates, etc.), boric acid, etc. as raw materials, after being dosed according to conventional methods, the dosed charge is put into a melting furnace (such as a platinum or platinum alloy crucible) at 1050-1250 ℃, preferably 1100-1200 ℃, and after clarification and homogenization, a homogeneous molten glass free of bubbles and undissolved substances is obtained, which is cast and annealed in a mold. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by direct drop molding, grinding, or compression molding such as hot press molding. That is, the glass preform may be produced by directly precision drop molding a 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 an optical glass, and then performing hot press molding and polishing on the preform. The means for producing the glass preform is not limited to the above-described 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 performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include 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, each of which has a spherical or aspherical lens surface.
[ optical instrument ]
The optical element formed by the optical glass can be used for manufacturing optical instruments such as photographic equipment, image pickup equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 2 to 4 were obtained by using the above-described method for producing high-refraction and high-dispersion optical glass. The characteristics of each glass were measured by the test method of the present invention, and the measurement results are shown in tables 2 to 4.
Table 2.
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Table 3.
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Table 4.
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< example of glass preform >
The glasses obtained in examples 1 to 21 were subjected to polishing, re-hot press molding, and press molding such as precision press molding to prepare various kinds of 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.
< example of optical element >
The glass preforms obtained in the above examples were annealed, and the refractive index was fine-tuned while reducing the internal stress of the glass so that the optical characteristics such as refractive index reached the desired values.
Next, each preform was ground and polished to produce various lenses and prisms such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens. The surface of the obtained optical element may be coated with an antireflection film.
< example of optical instrument >
The optical elements produced by the above-described optical element embodiments are useful, for example, in imaging devices, sensors, microscopes, medical technology, digital projection, communications, 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 optical components or optical assemblies using one or more optical elements.
Claims (13)
1. The high-refraction high-dispersion optical glass is characterized by comprising the following components in percentage by weight: p (P) 2 O 5 ：16～33％；Nb 2 O 5 ：40～55％；TiO 2 ：1～13％；BaO：1～15％；Na 2 O:0.5 to 15 percent, wherein TiO 2 BaO is 0.2-8.0.
2. The high-refraction high-dispersion optical glass according to claim 1, further comprising, in weight percent: caO: 0-8%; and/orMgO: 0-5%; and/or SrO: 0-5%; and/or ZnO: 0-8%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 0-5%; and/or Al 2 O 3 :0 to 3 percent; and/or WO 3 :0 to 3 percent; and/or ZrO 2 : 0-5%; and/or Bi 2 O 3 :0 to 3 percent; and/or TeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
3. A high-refraction high-dispersion optical glass characterized by comprising P in the components 2 O 5 、Nb 2 O 5 、TiO 2 BaO and Na 2 O, the components of which are expressed in weight percent, wherein TiO 2 BaO is 0.2-8.0, and the refractive index n of the optical glass d Is 1.86 to 1.93, and Abbe number v d Is 16 to 24, the thermal expansion coefficient alpha 100/300℃ 95X 10 -7 and/K or below.
4. The high-refraction high-dispersion optical glass according to claim 3, wherein the composition comprises, in weight percent: p (P) 2 O 5 : 16-33%; and/or Nb 2 O 5 : 40-55%; and/or TiO 2 :1 to 13 percent; and/or BaO: 1-15%; and/or Na 2 O: 0.5-15%; and/or CaO: 0-8%; and/or MgO: 0-5%; and/or SrO: 0-5%; and/or ZnO: 0-8%; and/or Li 2 O: 0-5%; and/or K 2 O: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or SiO 2 : 0-5%; and/or B 2 O 3 : 0-5%; and/or Al 2 O 3 ：0～3%; and/or WO 3 :0 to 3 percent; and/or ZrO 2 : 0-5%; and/or Bi 2 O 3 :0 to 3 percent; and/or TeO 2 : 0-5%; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
5. The high-refractive high-dispersion optical glass according to any one of claims 1 to 4, wherein the composition thereof, expressed in weight percent, satisfies one or more of the following 6 cases:
1)TiO 2 BaO is 0.3 to 5.0, preferably TiO 2 BaO is 0.5 to 3.0, more preferably TiO 2 BaO is 0.6-1.5;
2)ZnO/TiO 2 at most 3.0, preferably ZnO/TiO 2 From 0.01 to 2.0, more preferably ZnO/TiO 2 0.1 to 1.5, znO/TiO is more preferable 2 0.2 to 0.8;
3)ZnO/(Na 2 O+TiO 2 ) At most 2.0, znO/(Na) is preferable 2 O+TiO 2 ) Is 0.01 to 1.5, more preferably ZnO/(Na) 2 O+TiO 2 ) In the range of 0.05 to 0.8, znO/(Na) is more preferable 2 O+TiO 2 ) 0.05 to 0.4;
4)TiO 2 CaO is 0.5 to 10.0, preferably TiO 2 CaO is 1.0 to 8.0, more preferably TiO 2 CaO is 2.0 to 7.0, and TiO is more preferable 2 CaO is 2.5 to 6.0;
5) ZnO/BaO is 3.0 or less, preferably 0.05 to 2.0, more preferably 0.1 to 1.5, and still more preferably 0.2 to 0.8;
6)(P 2 O 5 +BaO)/(ZnO+CaO) is 2.0 or more, preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 3.0 to 20.0, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 5.0 to 15.0, more preferably (P) 2 O 5 +BaO)/(ZnO+CaO) is 8.0 to 12.0.
6. The high-refractive high-dispersion optical glass according to any one of claims 1 to 4, wherein the components thereof are expressed in weight percent satisfying one or more of the following 7 cases:
1)(B 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 2.0 or less, preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 1.0 or less, more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is 0.5 or less, and more preferably (B) 2 O 3 +WO 3 +Bi 2 O 3 ) ZnO is less than 0.2;
2)(B 2 O 3 +Li 2 O+K 2 O)/ZnO is 2.0 or less, preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 1.0 or less, more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.5 or less, and more preferably (B) 2 O 3 +Li 2 O+K 2 O)/ZnO is 0.2 or less;
3)(Na 2 O+K 2 O)/Nb 2 O 5 is 0.05 to 0.45, preferably (Na 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.4, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 Is 0.1 to 0.3, more preferably (Na) 2 O+K 2 O)/Nb 2 O 5 0.1 to 0.25;
4)(BaO+K 2 O+ZnO)/(Na 2 O+CaO) is 0.1 to 8.0, preferably (BaO+K) 2 O+ZnO)/(Na 2 O+CaO) is 0.2 to 5.0, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+CaO) is 0.3 to 2.5, more preferably (BaO+K) 2 O+ZnO)/(Na 2 O+cao) is 0.5 to 1.5;
5)(TiO 2 +K 2 O)/P 2 O 5 is 0.05 to 0.8, preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.6, more preferably (TiO) 2 +K 2 O)/P 2 O 5 Is 0.1 to 0.5, more preferably (TiO) 2 +K 2 O)/P 2 O 5 0.15 to 0.4;
6)(WO 3 +TiO 2 )/Nb 2 O 5 is 0.02 to 0.3, preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.25, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 Is 0.05 to 0.2, more preferably (WO) 3 +TiO 2 )/Nb 2 O 5 0.07 to 0.17;
7)(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 is 0.8 or less, preferably
(Ln 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.5 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.3 or less, more preferably (Ln) 2 O 3 +Li 2 O+K 2 O+WO 3 +Bi 2 O 3 )/TiO 2 Is 0.1 or less, ln is the same as that of the above 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the following.
7. The high-refraction high-dispersion optical glass according to any one of claims 1 to 4, wherein the components thereof are represented by weight percent, wherein: p (P) 2 O 5 :20 to 30%, preferably P 2 O 5 : 22-28%; and/or Nb 2 O 5 :45 to 55%, preferably Nb 2 O 5 : 46-53%; and/or TiO 2 :3 to 10%, preferably TiO 2 : 4-8%; and/or BaO: 2-12%, preferably BaO: 3-9%; and/or Na 2 O:3 to 12%, preferably Na 2 O: 6-10%; and/or CaO: greater than 0 but less than or equal to 6%, preferably CaO:1 to 4 percent; and/or MgO:0 to 3%, preferably MgO:0 to 1 percent; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or ZnO:greater than 0 but less than or equal to 6%, preferably ZnO:1 to 4 percent; and/or Li 2 O:0 to 3%, preferably Li 2 O:0 to 1 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or SiO 2 :0 to 3%, preferably SiO 2 :0 to 1 percent; and/or B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 1 percent; and/or Al 2 O 3 :0 to 2%, preferably Al 2 O 3 :0 to 1 percent; and/or WO 3 :0 to 2%, preferably WO 3 :0 to 1 percent; and/or ZrO 2 :0 to 3%, preferably ZrO 2 :0 to 1 percent; and/or Bi 2 O 3 :0 to 2%, preferably Bi 2 O 3 :0 to 1 percent; and/or TeO 2 :0 to 3%, preferably TeO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
8. The high-refraction high-dispersion optical glass according to any one of claims 1 to 4, wherein the composition does not contain MgO; and/or does not contain SrO; and/or does not contain Li 2 O; and/or does not contain K 2 O; and/or does not contain Ln 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Bi 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or no clarifying agent, said Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 、Lu 2 O 3 One or more of the clarifying agents is Sb 2 O 3 、SnO 2 、CeO 2 One or more of the following.
9. The high-refractive high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refractive high-dispersion optical glass has a refractive index n d 1.86 to 1.93, preferably 1.87 to 1.92, more preferably 1.88 to 1.91; abbe number v d 16 to 24, preferably 17 to 23, more preferably 18 to 22.
10. The high-refraction high-dispersion optical glass according to any one of claims 1 to 4, wherein the high-refraction high-dispersion optical glass has a thermal expansion coefficient α 100/300℃ 95X 10 -7 Preferably 90X 10, and K is less than or equal to -7 Preferably not more than/K, more preferably 85X 10 -7 and/K or below; and/or acid action resistance stability D A More than 2 types, preferably 1 type; and/or stability against water action D W More than 2 types, preferably 1 type; and/or relative partial dispersion P g,F From 0.58 to 0.72, preferably from 0.60 to 0.68, more preferably from 0.63 to 0.66; and/or relative partial dispersion deviation value ΔP g,F Is 0.08 or less, preferably 0.01 to 0.06, more preferably 0.02 to 0.05; and/or transition temperature T g 670 ℃ or lower, preferably 660 ℃ or lower, more preferably 650 ℃ or lower; and/or abrasion degree F A 230 to 270, preferably 240 to 265, more preferably 245 to 260; and/or density ρ of 3.90g/cm 3 Hereinafter, it is preferably 3.80g/cm 3 Hereinafter, it is more preferably 3.70g/cm 3 The following are set forth; and/or lambda 70 Is 440nm or less, preferably lambda 70 Is 430nm or less, more preferably lambda 70 425nm or less; and/or lambda 5 Is 400nm or less, preferably lambda 5 Is 390nm or less, more preferably lambda 5 385nm or less; and/or weather resistance CR is 2 or more, preferably 1; and/or Young's modulus E of 8000X 10 7 Pa or more, preferably 9000×10 7 Pa or more, more preferably 9500×10 7 Pa or more; and/or the degree of air bubbles is a class A or more, preferably A 0 Above the stage, more preferably A 00 A stage.
11. A glass preform produced by using the high-refractive high-dispersion optical glass according to any one of claims 1 to 10.
12. An optical element, characterized in that it is made of the high-refraction high-dispersion optical glass according to any one of claims 1 to 10, or made of the glass preform according to claim 11.
13. An optical device comprising the high-refractive high-dispersion optical glass according to any one of claims 1 to 10, or the optical element according to claim 12.
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| CN202311149927.7A CN117185653A (en) | 2023-09-07 | 2023-09-07 | High-refraction high-dispersion optical glass and optical element |
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