CN115231817A - Optical glass, optical element and optical instrument - Google Patents
Optical glass, optical element and optical instrument Download PDFInfo
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- CN115231817A CN115231817A CN202211032836.0A CN202211032836A CN115231817A CN 115231817 A CN115231817 A CN 115231817A CN 202211032836 A CN202211032836 A CN 202211032836A CN 115231817 A CN115231817 A CN 115231817A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 95
- 230000003287 optical effect Effects 0.000 title claims description 41
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 40
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims description 107
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 12
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 11
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 10
- 239000008395 clarifying agent Substances 0.000 claims description 10
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 description 17
- 238000005299 abrasion Methods 0.000 description 15
- 238000004031 devitrification Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000005499 meniscus Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
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- 238000007496 glass forming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides an optical glass, which comprises the following components in percentage by weight: siO 2 2 ：1～12％；B 2 O 3 ：3～18％；La 2 O 3 ：45～65％；Y 2 O 3 ：1～13％；ZrO 2 ：1～13％；Nb 2 O 5 ：3～18％；TiO 2 :5 to 20% of (SiO) 2 +B 2 O 3 )/Nb 2 O 5 0.5 to 5.0. Through reasonable component design, the optical glass obtained by the invention has higher hardness and excellent weather resistance.
Description
Technical Field
The present invention relates to an optical glass, and particularly to an optical glass having high hardness and excellent weatherability.
Background
With the continuous fusion of optics and electronic information science and new material science, the application of optical glass as a photoelectron base material in the technical fields of light transmission, light storage, photoelectric display and the like is rapidly advanced. Optical elements and optical instruments are rapidly developed in digitalization, integration and high refinement, and higher demands are made on the performance of optical glass used for optical elements of optical instruments and apparatuses. Under the same curvature radius, the higher the refractive index of the glass, the larger the obtained imaging field of view is, which is beneficial to reducing the number of optical elements in the optical instrument. With the development of the times, high refractive index optical glass is widely applied to the fields of vehicle-mounted imaging, monitoring and security protection and the like, but the optical glass applied to the fields needs to have higher hardness and excellent weather resistance so as to resist abrasion and attack of sand and stone in the driving process of a vehicle and respond to a severe environment so as to prolong the service life of the optical glass.
Disclosure of Invention
The invention aims to provide optical glass with higher hardness and excellent weather resistance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) The optical glass comprises the following components in percentage by weight: siO 2 2 ：1～12％；B 2 O 3 ：3～18％；La 2 O 3 ：45～65％；Y 2 O 3 ：1～13％；ZrO 2 ：1～13％；Nb 2 O 5 ：3～18％；TiO 2 :5 to 20 percent of (SiO) 2 +B 2 O 3 )/Nb 2 O 5 0.5 to 5.0.
(2) The optical glass according to (1), which comprises the following components in percentage by weight: ta 2 O 5 :0 to 8 percent; and/or Gd 2 O 3 :0 to 8 percent; and/or RO:0 to 8 percent; and/or Rn 2 O:0 to 8 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 8 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(3) Optical glass containing SiO 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The components of which are expressed in weight percent, wherein (SiO) 2 +B 2 O 3 )/Nb 2 O 5 0.5 to 5.0, the refractive index n of the optical glass d Is more than 1.97, abbe number v d 26 to 33, and the weather resistance CR is of the type 2 or moreUpper Knoop hardness H K Is 670 multiplied by 10 7 Pa or above.
(4) The optical glass according to (3), which comprises the following components in percentage by weight: siO 2 2 :1 to 12 percent; and/or B 2 O 3 :3 to 18 percent; and/or La 2 O 3 :45 to 65 percent; and/or Y 2 O 3 :1 to 13 percent; and/or ZrO 2 :1 to 13 percent; and/or Nb 2 O 5 :3 to 18 percent; and/or TiO 2 :5 to 20 percent; and/or Ta 2 O 5 :0 to 8 percent; and/or Gd 2 O 3 :0 to 8 percent; and/or RO:0 to 8 percent; and/or Rn 2 O:0 to 8 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 8 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(5) The optical glass according to any one of (1) to (4), which has a composition satisfying, in terms of weight percent, one or more of the following 7 conditions:
1)(Ta 2 O 5 +Gd 2 O 3 )/Y 2 O 3 is 1.0 or less, preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.8 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.5 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.2 or less;
2)La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 3.0 to 14.0, preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 4.0 to 12.0, more preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 5.0 to 9.0, more preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) 5.2 to 7.5;
3)(Gd 2 O 3 +ZnO)/Y 2 O 3 is 1.0 or less, preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.8 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.5 or less, and (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.2 or less;
4)(WO 3 +Gd 2 O 3 )/TiO 2 is not more than 2.0, preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.5 or less, more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.0 or less, and is more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is less than 0.5;
5)La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 4.0 to 30.0, preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) 5.0 to 20.0, more preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 7.0 to 15.0, and La is more preferable 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) 8.0 to 11.0;
6)La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 3.0 to 15.0, preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 4.0 to 10.0, more preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 5.0 to 8.0, and La is more preferable 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) 5.5 to 7.5;
7)(SiO 2 +B 2 O 3 )/Nb 2 O 5 0.8 to 3.5, preferably (SiO) 2 +B 2 O 3 )/Nb 2 O 5 Is 1.0 to 2.5, more preferably (SiO) 2 +B 2 O 3 )/Nb 2 O 5 Is 1.2 to 2.0 percent,
the RO is one or more of MgO, caO, srO and BaO.
(6) The optical glass according to any one of (1) to (4), which comprises, in terms of weight percent: siO 2 2 :2 to 10%, preferably SiO 2 :3 to 8 percent; and/or B 2 O 3 :5 to 15%, preferably B 2 O 3 :6 to 12 percent; and/or La 2 O 3 :47 to 60%, preferably La 2 O 3 :50 to 56 percent; and/or Y 2 O 3 :2 to 12%, preferably Y 2 O 3 :4 to 10 percent; and/or ZrO 2 :2 to 10%, preferably ZrO 2 :3 to 9 percent; and/or Nb 2 O 5 :5 to 15%, preferably Nb 2 O 5 :6 to 12 percent; and/or Ta 2 O 5 :0 to 5%, preferably Ta 2 O 5 :0 to 1 percent; and/or Gd 2 O 3 :0 to 4%, preferably Gd 2 O 3 :0 to 2 percent; and/or TiO 2 :8 to 18%, preferably TiO 2 :11 to 17 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 4%, preferably Rn 2 O:0 to 2 percent; and/or WO 3 :0 to 4%, preferably WO 3 :0 to 3 percent; and/or ZnO:0 to 5%, preferably ZnO:0 to 1 percent; and/or Al 2 O 3 :0 to 5%, preferably Al 2 O 3 :0 to 2 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 2 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 1 percent; and/or a clarifying agent: 0 to 0.5%, preferably clarifying agent: 0 to 0.2 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
(7) The optical glass according to any one of (1) to (4), wherein Ta is not contained in the component 2 O 5 (ii) a And/or no ZnO; and/or does not contain Rn 2 O; and/or does not contain Gd 2 O 3 (ii) a And/or does not contain Yb 2 O 3 (ii) a And/or does not contain GeO 2 Rn of the formula 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
(8) The optical glass according to any one of (1) to (4), wherein the refractive index n of the optical glass d Is 1.97 or more, preferably 1.98 or more, more preferably 1.99 or more, further preferably 1.99 to 2.10, further preferably 1.99 to 2.05, abbe number v d From 26 to 33, preferably from 27 to 32, more preferably from 28 to 31.
(9) The optical glass according to any one of (1) to (4), wherein the optical glass has a thermal expansion coefficient α 20/120℃ Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than 85X 10 -7 A value of 80X 10 or less, more preferably 80K or less -7 below/K; and/or stability against water action D W Is 2 or more, preferably 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or the weather resistance CR is of class 2 or more, preferably of class 1; and/or Knoop hardness H K Is 670X 10 7 Pa or more, preferably 680X 10 7 Pa or more, more preferably 690X 10 7 Pa or above; and/or a Young's modulus E of 11000X 10 7 Pa or more, preferably 12000X 10 7 Pa or more, more preferably 12500X 10 7 Pa or more, more preferably 12800X 10 7 Pa or above; and/or lambda 70 Is 450nm or less, preferably lambda 70 445nm or less, more preferably λ 70 Is 440nm or less; and/or lambda 5 Is 390nm or less, preferably lambda 5 Is 385nm or less, more preferably lambda 5 Is 380nm or less; and/or degree of wear F A From 70 to 120, preferably from 80 to 110, more preferably from 85 to 105; and/or the degree of bubbling is class A or higher, preferably class A 0 More preferably A or more 00 And (4) stages.
(10) A glass preform made of the optical glass according to any one of (1) to (9).
(11) An optical element produced from the optical glass according to any one of (1) to (9), or the glass preform according to (10).
(12) An optical device comprising the optical glass according to any one of (1) to (9) and/or the optical element according to (11).
The invention has the beneficial effects that: through reasonable component design, the optical glass obtained by the invention has higher hardness and excellent weather resistance.
Detailed Description
The optical glass of the present invention is obtained by the following steps, which are not limited to the above-described embodiments, and can be appropriately modified within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the gist of the present invention is not limited thereto, and the optical glass of the present invention may be simply referred to as glass in the following description.
[ optical glass ]
The ranges of the respective components (components) of the 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 the glass substance converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the optical glass composition component of the present invention are decomposed and converted to oxides when melted, the total amount of the oxides is 100%.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
< essential Components and optional Components >
B 2 O 3 Is a component for forming glass network, and has the functions of raising glass meltability and devitrification resistance and reducing glass transition temperature and density, and the invention contains more than 3% of B 2 O 3 In order to obtain the above effects, it is preferable to contain 5% or more of B 2 O 3 More preferably, it contains 6% or more of B 2 O 3 (ii) a However, if the content exceeds 18%, the glass is deteriorated in stability and the refractive index is lowered, and it is difficult to obtain the high refractive index of the present invention. Thus, in the present invention B 2 O 3 The upper limit of the content of (B) is 18%, preferably 15%, more preferably 12%.
SiO 2 The glass is also a network forming component, can adjust the thermal expansion coefficient of the glass, improves the devitrification resistance and the chemical stability of the glass, and also has the function of improving the thermal stability and the high-temperature viscosity of the glass; if the content exceeds 12%, the melting property of the glass tends to deteriorate and the transition temperature rises. Thus, siO in the present invention 2 The content of (B) is 1 to 12%, preferably 2 to 10%, more preferably 3 to 8%.
La 2 O 3 The glass is an effective component for improving the refractive index of the glass, has obvious effects on improving the chemical stability and the devitrification resistance of the glass, and cannot reach the required optical constant if the content of the glass is less than 45 percent; if the content is more than 65%, devitrification tendency of the glass is rather increased and thermal stability is deteriorated. Thus, la 2 O 3 The content of (b) is limited to 45 to 65%, preferably 47 to 60%, more preferably 50 to 56%.
Y 2 O 3 The invention can improve the refractive index and devitrification resistance of the glass and adjust the Young's modulus of the glass by containing more than 1 percent of Y 2 O 3 To obtain the above-mentioned effect; if the content exceeds 13%, the chemical stability and weather resistance of the glass are deteriorated. Thus, Y in the present invention 2 O 3 The content is 1 to 13%, preferably 2 to 12%, more preferably 4 to 10%.
Gd 2 O 3 The refractive index and chemical stability of the glass can be improved, but if the content thereof is more than 8%, devitrification resistance and abrasion resistance of the glass are deteriorated. Thus, gd 2 O 3 In an amount of0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that no Gd is present 2 O 3 。
Yb 2 O 3 And is a component imparting high-refractivity, low-dispersion properties to the glass, and if the content thereof exceeds 8%, the devitrification resistance of the glass is lowered. Thus, yb 2 O 3 The content of (B) is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%, and further preferably Yb is not contained 2 O 3 。
ZrO 2 The viscosity, hardness, refractive index and chemical stability of the optical glass can be improved, and the thermal expansion coefficient of the glass can be reduced; when ZrO 2 When the content of (b) is too high, devitrification resistance of the glass is lowered, melting difficulty is increased, melting temperature is increased, and inclusions appear in the glass and light transmittance is lowered. Thus, zrO in the invention 2 The content of (B) is 1 to 13%, preferably 2 to 10%, more preferably 3 to 9%.
TiO 2 The component is a high-refraction high-dispersion component, can obviously improve the refractive index and dispersion of glass in the glass, and is found by the research of the inventor that a proper amount of TiO is contained 2 The glass stability can be increased; but if too much TiO content is contained 2 The transmittance of the glass is significantly reduced, and the chemical stability of the glass tends to be deteriorated. Thus, tiO in the present invention 2 The content of (B) is 5 to 20%, preferably 8 to 18%, more preferably 11 to 17%.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and the devitrification resistance of the glass and reduce the thermal expansion coefficient of the glass, and the invention contains more than 3 percent of Nb 2 O 5 To obtain the above effects, it is preferable to contain 5% or more of Nb 2 O 5 More preferably 6% or more of Nb 2 O 5 . If Nb 2 O 5 More than 18%, the glass is lowered in thermal stability and weather resistance and the light transmittance is lowered, so that Nb in the present invention is contained 2 O 5 The upper limit of the content of (B) is 18%, preferably 15%, more preferably 12%.
In some embodiments of the present invention, the substrate is,mixing SiO 2 And B 2 O 3 SiO in total content 2 +B 2 O 3 And Nb 2 O 5 In the middle of ratio of (SiO) 2 +B 2 O 3 )/Nb 2 O 5 The control range is 0.5-5.0, which is beneficial to improving the hardness and weather resistance of the glass. Therefore, (SiO) is preferable 2 +B 2 O 3 )/Nb 2 O 5 Is 0.5 to 5.0, more preferably (SiO) 2 +B 2 O 3 )/Nb 2 O 5 0.8 to 3.5. Further, mixing (SiO) 2 +B 2 O 3 )/Nb 2 O 5 The abrasion degree and the bubble degree of the glass can be further optimized by controlling the abrasion degree and the bubble degree of the glass within the range of 1.0-2.5. Therefore, (SiO) is more preferable 2 +B 2 O 3 )/Nb 2 O 5 Is 1.0 to 2.5, and (SiO) is more preferable 2 +B 2 O 3 )/Nb 2 O 5 Is 1.2 to 2.0.
The alkaline earth metal oxide RO (RO is one or more of MgO, caO, srO, and BaO) can adjust the optical constants of the glass to optimize the chemical stability of the glass, but when the content thereof is high, the devitrification resistance of the glass is lowered. Therefore, the RO content is limited to 0 to 8%, preferably 0 to 4%, and more preferably 0 to 2%.
In some embodiments, la is 2 O 3 With RO and Nb 2 O 5 、Gd 2 O 3 Total content of RO + Nb 2 O 5 +Gd 2 O 3 Ratio La between 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) The light transmittance and the bubble degree of the glass can be improved by controlling the content within the range of 3.0-14.0. Therefore, la is preferable 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 3.0 to 14.0, more preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 4.0 to 12.0. Further, control La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) In the range of 5.0-9.0, the abrasion degree of the glass can be further optimized, and the heat of the glass is reducedCoefficient of expansion. Therefore, la is more preferable 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) 5.0 to 9.0, more preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) 5.2 to 7.5.
Alkali metal oxide Rn 2 O(Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O) can lower the glass transition temperature, adjust the optical constant and high-temperature viscosity of the glass, and improve the glass meltability, but when the content is high, the glass has reduced devitrification resistance and chemical stability, and the refractive index decreases. Thus, rn in the present invention 2 The content of O is 0 to 8%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, it is further preferred that Rn is absent 2 O。
WO 3 Can improve the refractive index and mechanical strength of the glass, if WO 3 When the content of (2) exceeds 6%, the glass is deteriorated in thermal stability and devitrification resistance. Thus, WO 3 The content of (b) is 0 to 6%, preferably 0 to 4%, more preferably 0 to 3%.
In some embodiments, WO is 3 And Gd 2 O 3 WO in total 3 +Gd 2 O 3 With TiO 2 Ratio between contents of (WO) 3 +Gd 2 O 3 )/TiO 2 The control below 2.0 can improve the weather resistance and chemical stability of the glass and prevent the light transmittance from decreasing. Therefore, preferred is (WO) 3 +Gd 2 O 3 )/TiO 2 Is not more than 2.0, more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.5 or less. Further, will (WO) 3 +Gd 2 O 3 )/TiO 2 The thermal expansion coefficient of the glass can be further reduced by controlling the thermal expansion coefficient to be less than 1.0. Therefore, further preferred (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.0 or less, more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 0.5 or less.
ZnO can adjust the refractive index and dispersion of the glass, and reduce the high-temperature viscosity and transition temperature of the glass. If the content of ZnO is too high, the glass forming difficulty is increased, and the devitrification resistance is deteriorated. Therefore, the content of ZnO is 0 to 8%, preferably 0 to 5%, more preferably 0 to 1%. In some embodiments, it is further preferred that ZnO is absent.
In some embodiments, the composition is prepared by reacting Gd 2 O 3 And total content Gd of ZnO 2 O 3 + ZnO and Y 2 O 3 Ratio between contents of (Gd) 2 O 3 +ZnO)/Y 2 O 3 The thermal expansion coefficient of the glass can be reduced and the abrasion degree of the glass can be optimized by controlling the thermal expansion coefficient to be less than 1.0. Therefore, (Gd) is preferable 2 O 3 +ZnO)/Y 2 O 3 Is 1.0 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.8 or less. Further, control (Gd) 2 O 3 +ZnO)/Y 2 O 3 When the value is 0.5 or less, the glass can be more easily provided with an appropriate Young's modulus, and the hardness of the glass can be prevented from being lowered. Therefore, (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.5 or less, and more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.2 or less.
Ta 2 O 5 The glass has the effects of improving the refractive index and the devitrification resistance of the glass, but if the content of the glass is too high, the thermal stability of the glass is reduced, and the density is increased; on the other hand, ta is compared with other components 2 O 5 The price of (2) is very expensive, and the amount of use thereof should be minimized from the practical and cost viewpoints. Thus, ta in the invention 2 O 5 The content of (b) is limited to 0 to 8%, preferably 0 to 5%, more preferably 0 to 1%. In some embodiments, it is further preferred that Ta is not included 2 O 5 。
In some embodiments, ta 2 O 5 And Gd 2 O 3 Total content Ta of 2 O 5 +Gd 2 O 3 And Y 2 O 3 Ratio between contents of (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 The concentration is controlled below 1.0, which is beneficial to obtaining the glassThe proper abrasion degree, the optimized density and Young modulus of the glass and the prevention of the deterioration of the chemical stability of the glass. Therefore, (Ta) is preferable 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 1.0 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.8 or less, and (Ta) is more preferable 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.5 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.2 or less.
In some embodiments, la is 2 O 3 With Ta 2 O 5 And Nb 2 O 5 Total content Ta of 2 O 5 +Nb 2 O 5 Ratio La between 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) The bubble degree and the hardness of the glass can be improved by controlling the content of the glass to be within the range of 3.0-15.0. Therefore, la is preferable 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 3.0 to 15.0, more preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 4.0 to 10.0. Further, la 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) The thermal expansion coefficient of the glass can be further reduced and the weather resistance can be improved by controlling the temperature within the range of 5.0-8.0. Therefore, la is more preferable 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) 5.0 to 8.0, more preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) 5.5 to 7.5.
Al 2 O 3 The chemical stability of the glass can be improved, but when the content thereof exceeds 8%, 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 8%, preferably 0 to 5%, more preferably 0 to 2%.
In some embodiments, la is 2 O 3 Content of (A) and Y 2 O 3 And Al 2 O 3 Total content of (A) Y 2 O 3 +Al 2 O 3 Ratio La between 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) The Young's modulus and the bubble degree of the glass can be improved and the chemical stability can be prevented from being reduced by controlling the content of the additive in the range of 4.0-30.0. Therefore, la is preferable 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 4.0 to 30.0, more preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 5.0 to 20.0, more preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 7.0 to 15.0, more preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) 8.0 to 11.0.
GeO 2 Has the functions of improving the refractive index and resisting devitrification, but if the content is too high, the chemical stability of the glass is reduced; on the other hand, geO is compared with other components 2 The price of (2) is very expensive, and the amount of use should be minimized from the practical and cost viewpoints. Accordingly, geO in the present invention 2 The content of (b) is limited to 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no GeO is contained 2 。
In the invention, 0 to 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 0.5 percent, and more preferably 0 to 0.2 percent. Since the optical glass of the present invention is excellent in the degree of foaming due to its rational component kinds and contents, it is further preferable in some embodiments that no fining agent is contained. 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 0.5%, still more preferably 0 to 0.2%, and still more preferably not containingSb 2 O 3 . 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 0.5%, still more preferably 0 to 0.2%, and still more preferably not containing SnO 2 (ii) a The SnO content is preferably 0 to 1%, more preferably 0 to 0.5%, still more preferably 0 to 0.2%, and still more preferably no SnO. CeO (CeO) 2 Action and content ratio of (B) and SnO 2 The content is preferably 0 to 1%, more preferably 0 to 0.5%, even more preferably 0 to 0.2%, and even more preferably no CeO 2 。
< Components not to be contained >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, cr, mn, fe, co, ni, cu, ag, and Mo is contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances under control, and measures for protecting the environment are required not only in the glass production process but also in the processing process and in the disposal after the production of products. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thereby, the optical glass becomes practically free from substances contaminating the environment. Therefore, the optical glass of the present invention can be manufactured, processed, and disposed of without taking special measures for environmental measures.
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 performance of the 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 optical glass of the present invention d ) The lower limit of (b) is 1.97, preferably 1.98, more preferably 1.99, and still more preferably 1.995.
In some embodiments, the refractive index (n) of the optical glass of the present invention d ) The upper limit of (2) is 2.10, preferably 2.05, more preferably 2.02.
In some embodiments, the Abbe number (. Nu.s) of the optical glass of the present invention d ) The lower limit of (2) is 26, the lower limit is preferably 27, and the lower limit is more preferably 28.
In some embodiments, the Abbe number (v) of the optical glass of the present invention d ) The upper limit of (3) is 33, the upper limit is preferably 32, and the upper limit is more preferably 31.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of optical glass 20/120℃ ) The data at 20-120 ℃ were tested according to the method specified in GB/T7962.16-2010.
In some embodiments, the optical glass of the present invention has a coefficient of thermal expansion (α) 20/120℃ ) Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than K, more preferably 85X 10 -7 A value of 80X 10 or less, more preferably 80K or less -7 and/K is less than or equal to.
< stability against Water action >
Stability to Water of optical glass (D) W ) (powder method) according toTest according to the method specified in GB/T17129.
In some embodiments, the optical glass of the present invention has stability to water effects (D) W ) Is 2 or more, preferably 1.
< stability against acid Effect >
Stability of acid resistance of optical glass (D) A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
In some embodiments, the stability against acid action of the optical glasses of the invention (D) A ) Is 2 or more, preferably 1.
< weather resistance >
The test method of the weatherability (CR) of the optical glass is as follows: the sample is placed in a test box in a saturated water vapor environment with the relative humidity of 90 percent, and is 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 optical glass of the present invention has a weatherability (CR) of 2 or more, preferably 1.
< Knoop hardness >
Knoop hardness (H) of optical glass K ) The test was carried out according to the test method specified in GB/T7962.18-2010.
In some embodiments, the Knoop hardness (H) of the optical glasses of the present invention K ) Is 670 multiplied by 10 7 Pa or more, preferably 680X 10 7 Pa or more, more preferably 690X 10 7 Pa or above.
< 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 optical glass of the present invention has a Young's modulus (E) of 11000X 10 7 Pa or more, preferably 12000X 10 7 Pa or more, more preferably 12500X 10 7 Pa or more, more preferably 12800X 10 7 Pa or above.
< 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 ratio is expressed as follows:
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 optical glass of the present invention has an abrasion loss (F) A ) The lower limit of (2) is 70, preferably 80, and more preferably 85.
In some embodiments, the optical glass of the present invention has an abrasion degree (F) A ) The upper limit of (3) is 120, preferably the upper limit is 110, and more preferably the upper limit is 105.
< degree of coloration >
Coloring degree (. Lamda.) for short-wave transmission spectral characteristics of the glass of the present invention 70 And λ 5 ) And (4) showing. Lambda [ alpha ] 70 The wavelength corresponding to the glass transmittance of 70% is meant. Lambda [ alpha ] 70 Is measured by measuring the spectral transmittance in a wavelength region from 280nm to 700nm using a glass having a thickness of 10. + -. 0.1mm with two opposing planes parallel to each other and optically polished and exhibiting a wavelength of 70% transmittance. The spectral transmittance or transmittance is the intensity I of light incident perpendicularly to the surface of the glass in Light transmitted through the glass and having an intensity I emitted from a plane out Under the condition of light of (1) through 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 high refractive index glasses, λ 70 A small value of (A) means that the glass itself is rarely colored and has a high light transmittance.
In some embodiments, the lambda of the optical glass of the present invention 70 Is 450nm or less, preferably lambda 70 445nm or less, more preferably λ 70 Is 440nm or less.
In some embodiments, the λ of the optical glass of the present invention 5 Is 390nm or less, preferably lambda 5 Is 385nm or less, more preferably lambda 5 Is 380nm or less.
< degree of bubbling >
The bubble degree of the optical glass is measured according to the method specified in GB/T7962.8-2010.
In some embodiments, the optical glass of the present invention has a bubble degree of class A or more, preferably class A 0 More preferably A or more 00 And (4) stage.
[ method for producing optical glass ]
The method for manufacturing the 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 optical glass can be used for manufacturing optical instruments such as photographic equipment, camera equipment, projection equipment, display equipment, vehicle-mounted equipment, monitoring equipment and the like.
Examples
< example of optical glass >
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, optical glasses having compositions shown in tables 2 to 4 were obtained by the above-mentioned method for producing optical glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 2 to 4.
Table 2.
Table 3.
Table 4.
< glass preform example >
The glasses obtained in examples 1 to 24# of the optical glasses were subjected to press molding such as polishing or reheat press molding or precision press molding to prepare preforms for various lenses such as concave meniscus lenses, convex meniscus lenses, biconvex lenses, biconcave lenses, plano-convex lenses and plano-concave lenses, prisms and the like.
< 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 embodiment can be used, for example, for imaging apparatuses, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips by forming an optical component or optical assembly by using one or more optical elements through optical design.
Claims (12)
1. Optical glass, characterized in that its composition, expressed in weight percentage, contains: siO 2 2 ：1～12％；B 2 O 3 ：3～18％；La 2 O 3 ：45～65％；Y 2 O 3 ：1～13％；ZrO 2 ：1～13％；Nb 2 O 5 ：3～18％；TiO 2 :5 to 20% of (SiO) 2 +B 2 O 3 )/Nb 2 O 5 0.5 to 5.0.
2. An optical glass according to claim 1, characterized in that its composition, expressed in weight percent, further comprises: ta 2 O 5 :0 to 8 percent; and/or Gd 2 O 3 :0 to 8 percent; and/or RO:0 to 8 percent; and/or Rn 2 O：0～8 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 8 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of RO, rn and one or more of MgO, caO, srO and BaO 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
3. An optical glass characterized by containing SiO 2 、B 2 O 3 、La 2 O 3 、Y 2 O 3 、ZrO 2 、Nb 2 O 5 、TiO 2 The components of which are expressed in weight percent, wherein 2 +B 2 O 3 )/Nb 2 O 5 0.5 to 5.0, the refractive index n of the optical glass d Is more than 1.97, abbe number v d 26 to 33, a weather resistance CR of 2 or more, a Knoop hardness H K Is 670X 10 7 Pa or above.
4. An optical glass according to claim 3, characterised in that its composition, expressed in weight percentage, comprises: siO 2 2 :1 to 12 percent; and/or B 2 O 3 :3 to 18 percent; and/or La 2 O 3 :45 to 65 percent; and/or Y 2 O 3 :1 to 13 percent; and/or ZrO 2 :1 to 13 percent; and/or Nb 2 O 5 :3 to 18 percent; and/or TiO 2 :5 to 20 percent; and/or Ta 2 O 5 :0 to 8 percent; and/or Gd 2 O 3 :0 to 8 percent; and/or RO:0 to 8 percent; and/or Rn 2 O:0 to 8 percent; and/or WO 3 :0 to 6 percent; and/or ZnO:0 to 8 percent; and/or Al 2 O 3 :0 to 8 percent; and/or Yb 2 O 3 :0 to 10 percent; and/or GeO 2 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent, the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
5. An optical glass according to any one of claims 1 to 4, characterised in that its composition, expressed in weight percentage, satisfies one or more of the following 7 conditions:
1)(Ta 2 O 5 +Gd 2 O 3 )/Y 2 O 3 is 1.0 or less, preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.8 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.5 or less, more preferably (Ta) 2 O 5 +Gd 2 O 3 )/Y 2 O 3 Is 0.2 or less;
2)La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 3.0 to 14.0, preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 4.0 to 12.0, more preferably La 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) Is 5.0 to 9.0, and La is more preferable 2 O 3 /(RO+Nb 2 O 5 +Gd 2 O 3 ) 5.2 to 7.5;
3)(Gd 2 O 3 +ZnO)/Y 2 O 3 is 1.0 or less, preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.8 or less, more preferably (Gd) 2 O 3 +ZnO)/Y 2 O 3 Is 0.5 or less, and (Gd) is more preferable 2 O 3 +ZnO)/Y 2 O 3 Is 0.2 or less;
4)(WO 3 +Gd 2 O 3 )/TiO 2 is not more than 2.0, preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.5 or less, more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is 1.0 or less, and is more preferably (WO) 3 +Gd 2 O 3 )/TiO 2 Is less than 0.5;
5)La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 4.0 to 30.0, preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) 5.0 to 20.0, more preferably La 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) Is 7.0 to 15.0, and La is more preferable 2 O 3 /(Y 2 O 3 +Al 2 O 3 ) 8.0 to 11.0;
6)La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 3.0 to 15.0, preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 4.0 to 10.0, more preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) Is 5.0 to 8.0, more preferably La 2 O 3 /(Ta 2 O 5 +Nb 2 O 5 ) 5.5 to 7.5;
7)(SiO 2 +B 2 O 3 )/Nb 2 O 5 0.8 to 3.5, preferably (SiO) 2 +B 2 O 3 )/Nb 2 O 5 Is 1.0 to 2.5, more preferably (SiO) 2 +B 2 O 3 )/Nb 2 O 5 Is 1.2 to 2.0 percent,
the RO is one or more of MgO, caO, srO and BaO.
6. An optical glass according to any one of claims 1 to 4, characterized in that its composition, expressed in weight percentages, is such that: siO 2 2 :2 to 10%, preferably SiO 2 :3 to 8 percent; and/or B 2 O 3 :5 to 15%, preferably B 2 O 3 :6 to 12 percent; and/or La 2 O 3 :47 to 60%, preferably La 2 O 3 :50 to 56 percent; and/or Y 2 O 3 :2 to 12%, preferably Y 2 O 3 :4 to 10 percent; and/or ZrO 2 :2 to 10%, preferably ZrO 2 :3 to 9 percent; and/or Nb 2 O 5 : 5-15%, excellenceSelecting Nb 2 O 5 :6 to 12 percent; and/or Ta 2 O 5 :0 to 5%, preferably Ta 2 O 5 :0 to 1 percent; and/or Gd 2 O 3 :0 to 4%, preferably Gd 2 O 3 :0 to 2 percent; and/or TiO 2 :8 to 18%, preferably TiO 2 :11 to 17 percent; and/or RO:0 to 4%, preferably RO:0 to 2 percent; and/or Rn 2 O:0 to 4%, preferably Rn 2 O:0 to 2 percent; and/or WO 3 :0 to 4%, preferably WO 3 :0 to 3 percent; and/or ZnO:0 to 5%, preferably ZnO:0 to 1 percent; and/or Al 2 O 3 :0 to 5%, preferably Al 2 O 3 :0 to 2 percent; and/or Yb 2 O 3 :0 to 5%, preferably Yb 2 O 3 :0 to 2 percent; and/or GeO 2 :0 to 3%, preferably GeO 2 :0 to 1 percent; and/or a clarifying agent: 0 to 0.5%, preferably a clarifying agent: 0 to 0.2 percent of the total weight of the catalyst, wherein the RO is one or more of MgO, caO, srO and BaO, and Rn 2 O is Li 2 O、Na 2 O、K 2 One or more of O and Sb as clarifier 2 O 3 、SnO、SnO 2 、CeO 2 One or more of (a).
7. An optical glass according to any one of claims 1 to 4, characterised in that it does not contain Ta in its composition 2 O 5 (ii) a And/or no ZnO; and/or does not contain Rn 2 O; and/or does not contain Gd 2 O 3 (ii) a And/or does not contain Yb 2 O 3 (ii) a And/or does not contain GeO 2 Rn of the formula 2 O is Li 2 O、Na 2 O、K 2 One or more of O.
8. An optical glass according to any one of claims 1 to 4, wherein the refractive index n of the optical glass is d Is 1.97 or more, preferably 1.98 or more, more preferably 1.99 or more, further preferably 1.99 to 2.10, further preferably 1.99 to 2.05, abbe number v d From 26 to 33, preferably from 27 to 32, more preferably from 28 to 31.
9. The optical glass according to any one of claims 1 to 4, wherein the optical glass has a coefficient of thermal expansion α 20/120℃ Is 95X 10 -7 Preferably 90X 10 or less,/K -7 A value of not more than 85X 10 -7 A value of 80X 10 or less, more preferably 80K or less -7 below/K; and/or stability against water action D W Is 2 or more, preferably 1; and/or stability against acid action D A Is 2 or more, preferably 1; and/or the weather resistance CR is of class 2 or more, preferably of class 1; and/or Knoop hardness H K Is 670 multiplied by 10 7 Pa or more, preferably 680X 10 7 Pa or more, more preferably 690X 10 7 Pa is above; and/or a Young's modulus E of 11000X 10 7 Pa or more, preferably 12000X 10 7 Pa or more, more preferably 12500X 10 7 Pa or more, more preferably 12800X 10 7 Pa is above; and/or lambda 70 Is 450nm or less, preferably lambda 70 445nm or less, more preferably λ 70 Is 440nm or less; and/or lambda 5 Is 390nm or less, preferably lambda 5 Is 385nm or less, more preferably lambda 5 Is 380nm or less; and/or degree of wear F A From 70 to 120, preferably from 80 to 110, more preferably from 85 to 105; and/or the degree of bubbling is class A or more, preferably class A 0 More preferably A or more 00 And (4) stages.
10. A glass preform, characterized by being made of the optical glass according to any one of claims 1 to 9.
11. An optical element, characterized in that it is made of the optical glass of any one of claims 1 to 9 or the glass preform of claim 10.
12. An optical device comprising the optical glass according to any one of claims 1 to 9 and/or comprising the optical element according to claim 11.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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