WO2018230124A1 - Verre optique, préforme et élément optique - Google Patents

Verre optique, préforme et élément optique Download PDF

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Publication number
WO2018230124A1
WO2018230124A1 PCT/JP2018/015070 JP2018015070W WO2018230124A1 WO 2018230124 A1 WO2018230124 A1 WO 2018230124A1 JP 2018015070 W JP2018015070 W JP 2018015070W WO 2018230124 A1 WO2018230124 A1 WO 2018230124A1
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WIPO (PCT)
Prior art keywords
component
glass
less
refractive index
optical
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PCT/JP2018/015070
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English (en)
Japanese (ja)
Inventor
岩▲崎▼菜那
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株式会社 オハラ
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Priority claimed from JP2018034031A external-priority patent/JP7233844B2/ja
Application filed by 株式会社 オハラ filed Critical 株式会社 オハラ
Priority to CN201880039982.1A priority Critical patent/CN110770183A/zh
Priority to EP18816712.6A priority patent/EP3640222A1/fr
Priority to US16/622,786 priority patent/US20200131076A1/en
Publication of WO2018230124A1 publication Critical patent/WO2018230124A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • 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

Definitions

  • the present invention relates to an optical glass, a preform, and an optical element.
  • optical elements incorporated in in-vehicle optical devices such as in-vehicle cameras and optical elements incorporated in optical devices that generate a lot of heat, such as projectors, copiers, laser printers, and broadcasting equipment, have higher temperatures.
  • Use in the environment is increasing. In such a high temperature environment, the temperature at the time of use of the optical element constituting the optical system is likely to fluctuate greatly, and the temperature often reaches 100 ° C. or more.
  • the adverse effect on the imaging characteristics and the like of the optical system due to temperature fluctuation is so large that it cannot be ignored, it is required to construct an optical system in which the imaging characteristics and the like are hardly affected even by temperature fluctuation.
  • an optical element made of glass whose refractive index decreases when the temperature rises and the temperature coefficient of the relative refractive index becomes negative.
  • the combined use of an optical element made of glass that increases the refractive index when the temperature rises and has a positive temperature coefficient of relative refractive index can correct the influence on the imaging characteristics and the like due to the temperature change. This is preferable.
  • Patent Document 1 As a glass developed by paying attention to the temperature coefficient of the relative refractive index, for example, a glass composition represented by Patent Document 1 is known.
  • the glass described in Patent Document 1 is a glass containing a lot of components that provide a high refractive index, and is intended to increase the temperature coefficient of the relative refractive index.
  • a glass having a small temperature coefficient of relative refractive index has not been obtained.
  • a glass having a negative temperature coefficient of the relative refractive index and a glass having a small absolute value of the temperature coefficient of the relative refractive index are desired.
  • a low-refractive index low-dispersion glass material and a high-refractive index high-dispersion glass material may be joined. If the difference in the average linear thermal expansion coefficient of the glass materials combined at the time of joining becomes small, the joining becomes good.
  • low-refractive index low-dispersion glass materials containing fluorine are known to have a large average linear thermal expansion coefficient, but there are almost no glass materials with a high average refractive index and high-dispersion glass material that have a high average linear thermal expansion coefficient. Therefore, a glass material having a large average linear thermal expansion coefficient is demanded.
  • the glass described in Patent Document 1 has a small average linear thermal expansion coefficient, and it is difficult to say that the glass sufficiently satisfies such a requirement.
  • the optical glass according to the present invention can be manufactured at a lower cost because a glass having excellent transmittance in visible light can be obtained without going through the steps of reheating and heat treatment to remove the coloring of the glass. be able to.
  • the present invention has been made in view of the above problems, and the object of the present invention is to take a small value of the temperature coefficient of the relative refractive index and contribute to the correction of the influence on the imaging characteristics due to the temperature change.
  • the object is to obtain a preform and an optical element using optical glass having an average linear thermal expansion coefficient suitable for bonding between optical glass and a low refractive index and low dispersion glass material.
  • the present inventor has conducted earnest test research, and as a result, contains the P 2 O 5 component and the Nb 2 O 5 component, and contains a predetermined amount of the Na 2 O component and the K 2 O component.
  • the present invention provides the following.
  • An optical device including the optical element according to (6).
  • an optical glass that has a small temperature coefficient of relative refractive index, can contribute to correction of influence on imaging characteristics due to temperature change, and has good transmittance in visible light, and the same are used. Preforms and optical elements can be obtained at lower costs.
  • the optical glass of the present invention is, by mass%, 20.0% to 40.0% of P 2 O 5 component, 25.0% to 50.0% in total of Nb 2 O 5 component, Na 2 O component And the K 2 O component has a mass sum of 3.0% or more and 30.0% or less, and the temperature coefficient (40 to 60 ° C.) of the relative refractive index (589.29 nm) is + 3.0 ⁇ 10 ⁇ 6 to ⁇ 10. Within the range of 0 ⁇ 10 ⁇ 6 (° C. ⁇ 1 ).
  • a glass material glass having a small temperature coefficient of relative refractive index and a large average linear thermal expansion coefficient can be obtained.
  • the transmittance in visible light is good
  • the temperature coefficient of the relative refractive index takes a small value, and it can contribute to the correction of the influence on the imaging characteristics due to the temperature change, and the bonding property with the low refractive index and low dispersion glass material
  • the composition range of each component constituting the optical glass of the present invention is described below.
  • the contents of the respective components are all expressed in mass% with respect to the total mass of the oxide equivalent composition.
  • the “oxide equivalent composition” is based on the assumption that the oxide, composite salt, metal fluoride, etc. used as the raw material of the glass component of the present invention are all decomposed and changed into oxides during melting. It is the composition which described each component contained in glass by making the total mass number of production
  • the P 2 O 5 component is an essential component as a glass-forming oxide.
  • the content of the P 2 O 5 component is preferably 20.0% or more, more preferably more than 21.0%, and even more preferably more than 22.0%.
  • the desired refractive index and dispersion can be maintained by setting the content of the P 2 O 5 component to 40.0% or less.
  • the content of the P 2 O 5 component is preferably 40.0% or less, more preferably 35.0% or less, and even more preferably less than 30.0%.
  • the P 2 O 5 component uses Al (PO 3 ) 3 , Ca (PO 3 ) 2 , Ba (PO 3 ) 2 , BPO 4 , H 3 PO 4, NaH 2 PO 4 , KH 2 PO 4, etc. as raw materials. be able to.
  • the Nb 2 O 5 component is an essential component as a high refractive index and high dispersion component.
  • the content of the Nb 2 O 5 component is preferably 25.0% or more, more preferably more than 28.0%, still more preferably more than 30.0%.
  • the content of the Nb 2 O 5 component is preferably 50.0% or less, more preferably 47.0% or less.
  • Nb 2 O 5 or the like can be used as a raw material.
  • the Na 2 O component When the Na 2 O component is contained in an amount of more than 0%, it is an optional component that can improve the meltability of the glass raw material, improve the transmittance, and reduce the temperature coefficient of the relative refractive index. Therefore, the content of the Na 2 O component is preferably more than 0%, more preferably more than 0.1%, still more preferably more than 0.5%, still more preferably more than 1.0%, still more preferably 1.5%. %, More preferably more than 2.0%. In particular, when the content exceeds 10.0%, the effect of reducing the temperature coefficient of the relative refractive index is enhanced, and the meltability of the glass is also improved.
  • the content of the Na 2 O component is preferably 35.0% or less, more preferably less than 30.0%, even more preferably less than 25.0%, and even more preferably less than 20.0%.
  • the Na 2 O component Na 2 CO 3 , NaNO 3 , NaF, Na 2 SiF 6 or the like can be used as a raw material.
  • the K 2 O component is an optional component that, when contained in excess of 0%, has a large average linear thermal expansion coefficient, good transmittance, and a small temperature coefficient of relative refractive index. Therefore, the content of the K 2 O component is preferably more than 0%, more preferably 0.5% or more, still more preferably more than 1.0%, and even more preferably more than 2.0%. In particular, when the content exceeds 5.0%, the effect of reducing the temperature coefficient of the relative refractive index is enhanced, and the stability of the glass is also improved. On the other hand, when the content of the K 2 O component is 30.0% or less, the stability of the glass can be maintained and the decrease in the refractive index can be suppressed.
  • the content of the K 2 O component is preferably 30.0% or less, more preferably less than 25.0%, further preferably less than 20.0%, and further preferably less than 15.0%.
  • K 2 O component K 2 CO 3 , KNO 3 , KF, KHF 2 , K 2 SiF 6 or the like can be used.
  • the BaO component is an optional component that can increase the meltability of the glass raw material, reduce the devitrification of the glass, increase the refractive index, and decrease the temperature coefficient of the relative refractive index when it contains more than 0%.
  • the content of the BaO component is preferably more than 0%, more preferably more than 0.1%, still more preferably more than 1.0%, still more preferably more than 2.0%.
  • the content of the BaO component is 20.0% or less, the average linear thermal expansion coefficient is large, and a decrease in the refractive index of the glass due to excessive content and devitrification can be reduced.
  • the content of the BaO component is preferably 20.0% or less, more preferably less than 19.0%, and even more preferably less than 18.0%.
  • BaO component BaCO 3 , Ba (NO 3 ) 2 , Ba (PO 3 ) 2 , BaF 2 and the like can be used as raw materials.
  • the TiO 2 component is a component that can increase the refractive index of the glass, reduce the Abbe number, and can easily obtain a stable glass when it contains more than 0%. Therefore, the content of the TiO 2 component is preferably more than 0%, more preferably more than 1.0%, still more preferably more than 3.0%, and even more preferably 5.0% or more. On the other hand, by setting the content of the TiO 2 component to 30.0% or less, the average linear thermal expansion coefficient is large, the temperature coefficient of the relative refractive index can be reduced, and devitrification due to excessive inclusion of the TiO 2 component is reduced. It is possible to suppress a decrease in transmittance of glass with respect to visible light (particularly, a wavelength of 500 nm or less).
  • the content of the TiO 2 component is preferably 30.0% or less, more preferably less than 26.0%, even more preferably less than 23.0%, and even more preferably less than 20.0%.
  • TiO 2 component TiO 2 or the like can be used as a raw material.
  • the SiO 2 component is a glass-forming oxide component that can improve the viscosity of the molten glass when it exceeds 0%. Therefore, the content of the SiO 2 component is preferably more than 0%, more preferably more than 0.1%, still more preferably more than 0.3%. On the other hand, when the content of the SiO 2 component is 5.0% or less, an increase in the glass transition point can be suppressed and a decrease in the refractive index can be suppressed. Therefore, the content of the SiO 2 component is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably less than 1.0%. As the SiO 2 component, SiO 2 , K 2 SiF 6 , Na 2 SiF 6 or the like can be used as a raw material.
  • the B 2 O 3 component when ultra containing 0%, is optionally component used as a glass-forming oxide which can increase the melting property of the glass.
  • the content of the B 2 O 3 component is preferably 5.0% or less, more preferably 3.0% or less, more preferably less than 1.5%, and still more preferably less than 1.3%.
  • the refractive index can be increased, the Abbe number can be lowered, the glass transition point can be lowered, and the loss can be reduced while reducing the coloration of the glass by other components that bring about a high refractive index. It is an optional component that can reduce see-through.
  • the content of the WO 3 component can be 10.0% or less, the temperature coefficient of the relative refractive index can be reduced, and devitrification during reheat pressing can be suppressed.
  • the visible light transmittance can be increased by reducing the coloring of the glass by the WO 3 component.
  • the content of the WO 3 component is preferably 10.0% or less, more preferably less than 9.0%, even more preferably less than 8.0%, still more preferably less than 6.5%, still more preferably 5. It may be less than 0%.
  • WO 3 component WO 3 or the like can be used as a raw material.
  • the ZnO component When the ZnO component is contained in an amount of more than 0%, the ZnO component is an optional component that enhances the meltability of the raw material, promotes defoaming from the melted glass, and enhances the stability of the glass. It is also a component that can lower the glass transition point and improve chemical durability.
  • the content of the ZnO component less than 5.0%, the temperature coefficient of the relative refractive index can be reduced, the expansion due to heat can be reduced, the decrease in the refractive index can be suppressed, and the excessive viscosity can be reduced. Devitrification due to the reduction can be reduced.
  • the content of the ZnO component is preferably less than 5.0%, more preferably less than 4.0%, further preferably less than 2.0%, more preferably less than 1.0%, and still more preferably 0.5%. It may be less than%. Moreover, it is not necessary to contain a ZnO component.
  • ZnO component ZnO, ZnF 2 or the like can be used as a raw material.
  • the ZrO 2 component is an optional component that can increase the refractive index of the glass and reduce devitrification when it contains more than 0%. Therefore, the content of the ZrO 2 component is preferably more than 0%, more preferably more than 0.5%, and even more preferably more than 1.0%. On the other hand, by setting the content of the ZrO 2 component to 5.0% or less, the temperature coefficient of the relative refractive index can be reduced, and devitrification due to excessive inclusion of the ZrO 2 component can be reduced. Therefore, the content of the ZrO 2 component is preferably 5.0% or less, more preferably 3.0% or less, still more preferably less than 1.0%, and even more preferably less than 0.5%. Further, the ZrO 2 component may not be contained. As the ZrO 2 component, ZrO 2 , ZrF 4 or the like can be used as a raw material.
  • the MgO component, CaO component, and SrO component are optional components that can adjust the refractive index, meltability, and devitrification resistance of the glass when the content exceeds 0%.
  • the contents of the MgO component, the CaO component and the SrO component are each preferably 5.0% or less, more preferably 3.5% or less, and even more preferably less than 2.0%.
  • the Li 2 O component is an optional component that can improve the meltability of the glass and lower the glass transition point.
  • the content of the Li 2 O component is preferably 5.0% or less, more preferably less than 3.0%, further preferably 1.0% or less, and further preferably less than 0.5%.
  • Li 2 O component Li 2 CO 3 , LiNO 3 , LiF, or the like can be used as a raw material.
  • the Al 2 O 3 component and the Ga 2 O 3 component are optional components that can improve the devitrification resistance of the molten glass when the content exceeds 0%.
  • the content of the Al 2 O 3 component and the Ga 2 O 3 component is preferably 10.0% or less, more preferably less than 5.0%, still more preferably less than 3.0%, and still more preferably 1.%. It may be less than 0%.
  • Al 2 O 3 component is a raw material as Al 2 O 3, Al (OH ) can be used 3, AlF 3, etc., Ga 2 O 3 may be used as component Ga 2 O 3 or the like as raw materials.
  • the Sb 2 O 3 component is an optional component that can degas the molten glass when it contains more than 0%.
  • the content of the Sb 2 O 3 component is preferably 1.0% or less, more preferably less than 0.5%, more preferably less than 0.2%, and even more preferably less than 0.1%.
  • Sb 2 O 3 component Sb 2 O 3 , Sb 2 O 5 , Na 2 H 2 Sb 2 O 7 .5H 2 O, or the like can be used as a raw material.
  • the total content of the Na 2 O component and the K 2 O component is preferably 3.0% or more.
  • the mass sum (Na 2 O + K 2 O) is preferably 3.0% or more, more preferably more than 4.0%, more preferably more than 5.0%, and still more preferably more than 6.0%.
  • the mass sum (Na 2 O + K 2 O) is preferably 30.0% or less, more preferably less than 25.0%, and even more preferably less than 23.0%.
  • the total content of the Na 2 O component, K 2 O component and BaO component is preferably 10.0% or more.
  • the mass sum (Na 2 O + K 2 O + BaO) is preferably 10.0% or more, more preferably more than 12.0%, more preferably more than 14.0%, more preferably more than 16.0%, even more preferably Is over 17.5%.
  • the mass sum (Na 2 O + K 2 O + BaO) is preferably 35.0%, more preferably 33.0% or less, and even more preferably less than 30.0%.
  • the total content of the Nb 2 O 5 component and the TiO 2 component is preferably 30.0% or more.
  • the mass sum (Nb 2 O 5 + TiO 2 ) is preferably 30.0% or more, more preferably 35.0% or more, and further preferably 40.0% or more.
  • the mass sum (Nb 2 O 5 + TiO 2 ) is preferably 65.0% or less, more preferably 63.0% or less, and even more preferably 60.0 or less.
  • the ratio of the Na 2 O component, the K 2 O component and the BaO component to the total content of the B 2 O 3 component and the TiO 2 component is preferably more than 0.5.
  • the mass ratio (Na 2 O + K 2 O + BaO) / (B 2 O 3 + TiO 2 ) is preferably more than 0.5, more preferably more than 0.7, and still more preferably more than 1.0.
  • the mass ratio (Na 2 O + K 2 O + BaO) / (B 2 O 3 + TiO 2 ) is preferably less than 5.5, more preferably less than 5.0, and even more preferably less than 4.8.
  • the sum (mass sum) of the content of RO components (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is more than 0%, so that the refractive index of the glass is increased.
  • the meltability and devitrification resistance can be increased. Therefore, the lower limit of the sum (mass sum) of the RO component contents is preferably more than 0%, more preferably more than 0.5%, and still more preferably more than 1.0%.
  • the sum of the RO component contents (mass sum) is preferably 30.0% or less, more preferably 25.0% or less, and still more preferably 20.0% or less.
  • the refractive index of the glass can be increased and the loss resistance can be increased. It is an optional component that can increase the permeability.
  • the content of La 2 O 3 component, Gd 2 O 3 component, Y 2 O 3 component, Yb 2 O 3 component and Ta 2 O 5 component 5.0% or less, the raw material of optical glass The cost can be reduced, and the melting temperature of the raw material is lowered, and the energy required for melting the raw material is reduced. Therefore, the manufacturing cost of the optical glass can also be reduced. Therefore, the content of each of these components is preferably 5.0% or less, more preferably less than 3.0%, more preferably less than 2.0%, and even more preferably less than 1.0%.
  • the GeO 2 component is an optional component that can increase the refractive index of the glass and improve the devitrification resistance when it contains more than 0%.
  • the raw material price of GeO 2 is high, and the production cost increases when the content is large. Therefore, the content of the GeO 2 component is preferably 10.0% or less, more preferably less than 5.0%, more preferably less than 3.0%, and even more preferably less than 1.0%.
  • the GeO 2 component GeO 2 or the like can be used as a raw material.
  • the Bi 2 O 3 component is an optional component that can increase the refractive index, lower the Abbe number, and lower the glass transition point when it contains more than 0%.
  • the content of the Bi 2 O 3 component is preferably 5.0% or less, more preferably less than 3.0%, and even more preferably less than 1.0%. In particular, it is preferably not contained from the viewpoint of obtaining a glass with good transmittance.
  • Bi 2 O 3 component Bi 2 O 3 or the like can be used as a raw material.
  • the TeO 2 component is an optional component that can increase the refractive index and lower the glass transition point when it exceeds 0%.
  • TeO 2 has a problem that it can be alloyed with platinum when melting a glass raw material in a crucible made of platinum or a melting tank in which a portion in contact with molten glass is formed of platinum. Therefore, the content of the TeO 2 component is preferably 10.0% or less, more preferably less than 5.0%, more preferably less than 3.0%, and even more preferably less than 1.0%.
  • TeO 2 component can use TeO 2 or the like as a raw material.
  • the SnO 2 component When the SnO 2 component is contained in an amount of more than 0%, the SnO 2 component is an optional component that can be refined by reducing the oxidation of the molten glass and can increase the visible light transmittance of the glass.
  • the content of the SnO 2 component is 3.0% or less, the coloring of the glass due to the reduction of the molten glass and the devitrification of the glass can be reduced.
  • the alloying of the SnO 2 component and the melting equipment especially a noble metal such as Pt
  • the content of the SnO 2 component is preferably 3.0% or less, more preferably less than 1.0%, further preferably less than 0.5%, and further preferably less than 0.1%.
  • SnO 2 component SnO, SnO 2 , SnF 2 , SnF 4 or the like can be used as a raw material.
  • the components for clarifying and defoaming the glass are not limited to the above-described Sb 2 O 3 component and SnO 2 component, and well-known fining agents, defoaming agents or combinations thereof in the field of glass production are used. be able to.
  • the F component is an optional component that can increase the glass Abbe number, lower the glass transition point, and improve the devitrification resistance when it is contained in excess of 0%.
  • the content of the F component that is, the total amount of F substituted for a part or all of one or more oxides of each of the above metal elements exceeds 10.0%
  • F Since the volatilization amount of the component increases, it becomes difficult to obtain a stable optical constant, and it becomes difficult to obtain a homogeneous glass.
  • the Abbe number rises more than necessary. Therefore, the content of the F component is preferably 10.0% or less, more preferably less than 5.0%, more preferably less than 3.0%, and even more preferably less than 1.0%.
  • the F component can be contained in the glass by using, for example, ZrF 4 , AlF 3 , NaF, CaF 2 or the like as a raw material.
  • the mass ratio (SiO 2 + Al 2 O 3 + ZnO) / (B 2 O 3 + Rn 2 O) is preferably 15.0 or less, more preferably 12.0 or less, more preferably 10.0 or less, more preferably Is 8.0 or less, more preferably 6.0 or less, and still more preferably less than 5.0.
  • the mass ratio (SiO 2 + Al 2 O 3 + ZnO) / (B 2 O 3 + Rn 2 O) can be greater than zero.
  • the temperature coefficient of relative refractive index can be reduced and the average linear thermal expansion coefficient can be increased. Therefore, the mass ratio (SiO 2 + Al 2 O 3 + ZnO) / (B 2 O 3 + Rn 2 O) is preferably more than 0, more preferably more than 1.0, and still more preferably more than 2.0.
  • Rn 2 O component (wherein Rn is one or more selected from the group consisting of Li, Na, K), the sum (mass sum) of the content is more than 1.0%, the relative refractive index And the average linear thermal expansion coefficient can be increased. Accordingly, the sum (mass sum) of the contents of the Rn 2 O component is preferably more than 1.0%, more preferably more than 1.5%, and still more preferably more than 2.0%. On the other hand, by setting the sum to 30.0% or less, devitrification due to a decrease in the viscosity of the glass can be reduced while maintaining a desired refractive index and dispersion. Therefore, the sum (mass sum) of the contents of the Rn 2 O component is preferably 30.0% or less, more preferably less than 25.0%, and even more preferably less than 23.0%.
  • the optical glass of the present invention preferably contains two or more components among the above-mentioned Rn 2 O components. This eliminates the need for a reheating and heat treatment step to reduce the temperature coefficient of the relative refractive index and improve the transmittance.
  • the Rn 2 O component to contain two or more components containing Na 2 O component and K 2 O component is a large average linear thermal expansion coefficient, the transmittance was improved, the temperature coefficient of the relative refractive index Is preferable in that it can be reduced.
  • the sum (mass sum) of the contents of the Ln 2 O 3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, Yb, and Lu) is preferably 5.0% or less. Thereby, it is possible to obtain a glass having excellent devitrification resistance and good transmittance. Therefore, the sum (mass sum) of the contents of the Ln 2 O 3 component is preferably 5.0% or less, more preferably 3.5% or less, and still more preferably less than 2.0%.
  • each transition metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, excluding Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, is independent of each other. Or, even when it is contained in a small amount in combination, the glass is colored and has the property of causing absorption at a specific wavelength in the visible range. .
  • lead compounds such as PbO and arsenic compounds such as As 2 O 3 are components with high environmental loads, it is desirable that they are not substantially contained, that is, not contained at all except for inevitable mixing.
  • each component of Th, Cd, Tl, Os, Be, and Se has tended to be refrained from being used as a harmful chemical material in recent years, and not only in the glass manufacturing process, but also in the processing process and disposal after commercialization. Until then, environmental measures are required. Therefore, when importance is placed on the environmental impact, it is preferable that these are not substantially contained.
  • the optical glass of the present invention is produced, for example, as follows. That is, as the raw materials for the above components, high purity raw materials used for ordinary optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphate compounds, etc. Mix uniformly so as to be within the range of the content of metal, put the prepared mixture into a platinum crucible, and melt in a temperature range of 1000-1500 ° C for 1-10 hours in an electric furnace depending on the difficulty of melting the glass raw material After stirring and homogenizing, the temperature is lowered to an appropriate temperature, cast into a mold, and slowly cooled.
  • high purity raw materials used for ordinary optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphate compounds, etc.
  • the optical glass of the present invention preferably has a high refractive index and a low Abbe number (high dispersion).
  • the refractive index (n d ) of the optical glass of the present invention is preferably 1.65 or more, more preferably 1.67 or more, and further preferably 1.69 or more.
  • This refractive index (n d ) is preferably 2.00 or less, more preferably 1.98 or less, still more preferably 1.96 or less, and even more preferably 1.95 or less.
  • the Abbe number ( ⁇ d ) of the optical glass of the present invention is preferably 10.0 or more, more preferably 13.0 or more, further preferably 15.0 or more, and further preferably 17.0 or more.
  • the Abbe number ( ⁇ d ) is preferably 35.0 or less, more preferably 34.0 or less, still more preferably 32.0 or less, and even more preferably 30.0 or less.
  • the Abbe number ( ⁇ d ) is preferably 35.0 or less, more preferably 34.0 or less, still more preferably 32.0 or less, and even more preferably 30.0 or less.
  • the optical glass of the present invention has a low temperature coefficient (dn / dT) of relative refractive index. More specifically, the temperature coefficient of the relative refractive index of the optical glass of the present invention is preferably + 3.0 ⁇ 10 ⁇ 6 ° C. ⁇ 1 , more preferably + 1.5 ⁇ 10 ⁇ 6 ° C. ⁇ 1 , more preferably The upper limit value is + 1.0 ⁇ 10 ⁇ 6 ° C. ⁇ 1 , and this upper limit value or a lower value (minus side) can be taken. On the other hand, the temperature coefficient of the relative refractive index of the optical glass of the present invention is preferably ⁇ 10.0 ⁇ 10 ⁇ 6 ° C.
  • glasses having a low temperature coefficient of relative refractive index are present as glasses having a refractive index (n d ) of 1.65 or more and an Abbe number ( ⁇ d ) of 10 or more and 35 or less. Therefore, it is possible to expand the options for correction such as image formation deviation due to temperature change, and to make the correction easier.
  • the temperature coefficient of the relative refractive index of the optical glass of the present invention is the temperature coefficient of the refractive index (589.29 nm) in air at the same temperature as the optical glass, and when the temperature is changed from 40 ° C. to 60 ° C. Of change per 1 ° C. (° C. ⁇ 1 ).
  • the average linear thermal expansion coefficient ⁇ at 100 to 300 ° C. is preferably 80 (10 ⁇ 7 ° C. ⁇ 1 ) or more. That is, the average linear thermal expansion coefficient ⁇ at 100 to 300 ° C. of the optical glass of the present invention is preferably 80 (10 ⁇ 7 ° C. ⁇ 1 ) or more, more preferably 85 (10 ⁇ 7 ° C. ⁇ 1 ) or more, more preferably Is 90 (10 ⁇ 7 ° C. ⁇ 1 ) or more. In general, if the average linear thermal expansion coefficient ⁇ is large, cracks are likely to occur when glass is processed. Therefore, it is desirable that the average linear thermal expansion coefficient ⁇ is small.
  • the glass material and the average linear thermal expansion coefficient ⁇ are the same or approximate. It is desirable.
  • glass having a refractive index (n d ) of 1.65 or more and an Abbe number ( ⁇ d ) of 10 or more and 35 or less has few glass materials having a large average linear thermal expansion coefficient ⁇ , and has a low refractive index.
  • the average linear thermal expansion coefficient ⁇ has a large value as in the present invention.
  • the optical glass of the present invention has high visible light transmittance, in particular, high transmittance of light on the short wavelength side of visible light, and thereby less coloring.
  • the shortest wavelength ( ⁇ 80 ) showing a spectral transmittance of 80% in a sample having a thickness of 10 mm is preferably 460 nm or less, more preferably 450 nm or less, and even more preferably. Is 440 nm or less.
  • the shortest wavelength ( ⁇ 70 ) having a spectral transmittance of 70% in a 10 mm thick sample is preferably 430 nm or less, more preferably 420 nm or less, and even more preferably 410 nm or less.
  • the shortest wavelength ( ⁇ 5 ) having a spectral transmittance of 5% in a 10 mm thick sample is preferably 400 nm or less, more preferably 390 nm or less, and even more preferably 380 nm or less.
  • this optical glass can be preferably used for an optical element that transmits light such as a lens.
  • a glass molded body can be produced from the produced optical glass by means of, for example, polishing or molding press molding such as reheat press molding or precision press molding.
  • polishing or molding press molding such as reheat press molding or precision press molding.
  • optical glass is subjected to mechanical processing such as grinding and polishing to produce a glass molded body, or a preform for mold press molding is produced from optical glass, and reheat press molding is performed on this preform.
  • polishing is performed to produce a glass molded body, or precision preforming is performed on a preform formed by polishing or a preform formed by known floating molding, etc., to form a glass molded body.
  • the means for producing the glass molded body is not limited to these means.
  • the optical glass of the present invention is useful for various optical elements and optical designs.
  • a preform having a large diameter can be formed, so that it is possible to realize high-definition and high-precision imaging characteristics and projection characteristics when used in an optical apparatus while increasing the size of the optical element.
  • the glass molded body made of the optical glass of the present invention can be used for applications of optical elements such as lenses, prisms, mirrors, etc., and typically tends to become high temperature such as in-vehicle optical devices, projectors, and copiers. Can be used for equipment.
  • Tables 1 to 8 show the results of temperature coefficient (dn / dT), average linear thermal expansion coefficient (100 to 300 ° C.), and transmittance ( ⁇ 80, ⁇ 70, ⁇ 5 ).
  • the following examples are merely for illustrative purposes and are not limited to these examples.
  • the glasses of the examples and comparative examples of the present invention are used for ordinary optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, and metaphosphate compounds corresponding to the raw materials of the respective components.
  • a high-purity raw material is selected, weighed so as to have the composition ratio of each example shown in the table, and mixed uniformly, and then put into a platinum crucible, which is 800 in an electric furnace according to the difficulty of melting the glass raw material. It was melted at a temperature range of ⁇ 1300 ° C. for 1 to 10 hours, homogenized with stirring, cast into a mold or the like, and slowly cooled.
  • the refractive index (n d ) and Abbe number ( ⁇ d ) of the glass of the example and the comparative example are shown as measured values with respect to the d-line (587.56 nm) of the helium lamp.
  • the Abbe number ( ⁇ d ) is the refractive index of the d line, the refractive index (n F ) for the F lamp (486.13 nm) of the hydrogen lamp, and the refractive index (n C ) for the C line (656.27 nm).
  • the Abbe number ( ⁇ d ) [(n d ⁇ 1) / (n F ⁇ n C )].
  • the temperature coefficient (dn / dT) of the relative refractive index of the glass of Examples and Comparative Examples is a method described in Japanese Optical Glass Industry Association Standard JOGIS18-2008 “Measurement Method of Temperature Coefficient of Refractive Index of Optical Glass”
  • the value of the temperature coefficient of the relative refractive index at 40 to 60 ° C. for light having a wavelength of 589.29 nm was measured by the interferometry.
  • the average linear thermal expansion coefficient (100-300 ° C.) of the glass of the example and the comparative example is the temperature and the elongation of the sample according to Japan Optical Glass Industry Association Standard JOGIS08-2003 “Measurement Method of Thermal Expansion of Optical Glass”. From the thermal expansion curve obtained by measuring the relationship of.
  • the transmittance of the glass of the example was measured according to Japan Optical Glass Industry Association Standard JOGIS02-2003.
  • the presence / absence and degree of coloration of the glass were determined by measuring the transmittance of the glass.
  • a face parallel polished product having a thickness of 10 ⁇ 0.1 mm was measured for a spectral transmittance of 200 to 800 nm in accordance with JISZ8722, and ⁇ 80 (wavelength at 80% transmittance), ⁇ 70 (transmittance). (Wavelength at 70%) and ⁇ 5 (wavelength at 5% transmittance) were determined.
  • the optical glass of the example of the present invention contains a P 2 O 5 component and a Nb 2 O 5 component, and contains a predetermined amount of a Na 2 O component and a K 2 O component, so that the temperature coefficient of the relative refractive index is small.
  • An inexpensive glass with a value can be obtained.
  • the temperature coefficient of the relative refractive index is within the range of + 1.0 ⁇ 10 ⁇ 6 to ⁇ 10.0 ⁇ 10 ⁇ 6 (° C. ⁇ 1 ). Specifically, it was within the range of + 3.0 ⁇ 10 ⁇ 6 to ⁇ 10.0 ⁇ 10 ⁇ 6 (° C. ⁇ 1 ), and was within the desired range.
  • optical glasses of the examples all had a refractive index (n d ) of 1.65 or more, and were within a desired range. Further, the optical glasses of the examples of the present invention all had an Abbe number ( ⁇ d ) in the range of 10 or more and 35 or less, and were in a desired range.
  • optical glasses of the examples all had an average linear thermal expansion coefficient (100-300 ° C.) of 80 (10 ⁇ 7 ° C. ⁇ 1 ) or more.
  • the optical glass of the example had a transmittance ( ⁇ 80 ) of 460 nm or less, a transmittance ( ⁇ 70 ) of 430 nm or less, and a transmittance ( ⁇ 5 ) of 400 nm or less.
  • the optical glass of the example formed a stable glass, and devitrification hardly occurred at the time of glass production.
  • the glass of Comparative Example A did not vitrify because devitrification occurred.
  • the optical glass of the example has a refractive index (n d ) and an Abbe number ( ⁇ d ) within desired ranges, and takes a value with a small temperature coefficient of relative refractive index, and can be obtained at a lower material cost. It became clear. Therefore, the optical glass of the embodiment of the present invention contributes to miniaturization of an optical system such as an in-vehicle optical device or a projector used in a high temperature environment, and contributes to correction of a shift in imaging characteristics due to a temperature change. It is inferred that
  • a glass block was formed using the optical glass of the example of the present invention, and this glass block was ground and polished to be processed into the shape of a lens and a prism. As a result, it was possible to stably process into various lens and prism shapes.

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  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

L'invention concerne : un verre optique qui présente un faible coefficient de température de l'indice de réfraction relatif et qui peut contribuer à corriger les effets sur les caractéristiques d'imagerie dus à un changement de température ; et une préforme et un élément optique utilisant ledit verre optique. Le verre optique comprend, en % en masse, 20,0 à 40,0 % d'un constituant P2O5, 25,0 à 50,0 % d'un constituant Nb2O5 et 3,0 à 30,0 % d'une somme de masse (Na2O+K2O), et présente un coefficient de température (40 à 60 °C) de l'indice de réfraction relatif (589,29 nm) dans une plage de +3,0×10-6 à -10,0×10-6 (°C-1).
PCT/JP2018/015070 2017-06-16 2018-04-10 Verre optique, préforme et élément optique WO2018230124A1 (fr)

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CN201880039982.1A CN110770183A (zh) 2017-06-16 2018-04-10 光学玻璃、预成形体以及光学元件
EP18816712.6A EP3640222A1 (fr) 2017-06-16 2018-04-10 Verre optique, préforme et élément optique
US16/622,786 US20200131076A1 (en) 2017-06-16 2018-04-10 Optical glass, preform, and optical element

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022159275A1 (fr) * 2021-01-22 2022-07-28 Corning Incorporated Verres phosphatés à indice de réfraction élevé et à dispersion réduite
EP3943458A4 (fr) * 2019-03-18 2022-12-07 Hikari Glass Co., Ltd. Verre optique, élément optique, système optique, lentille interchangeable et dispositif optique
WO2023286630A1 (fr) * 2021-07-16 2023-01-19 株式会社 オハラ Verre de phosphate, verre optique et élément optique

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Publication number Priority date Publication date Assignee Title
JP2007106611A (ja) 2005-10-11 2007-04-26 Ohara Inc 光学ガラス
JP2011144063A (ja) * 2010-01-13 2011-07-28 Ohara Inc 光学ガラス、プリフォーム、及び光学素子
JP2014185075A (ja) * 2013-02-19 2014-10-02 Hoya Corp 光学ガラス、光学ガラスブランク、プレス成型用ガラス素材、光学素子、およびそれらの製造方法

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Publication number Priority date Publication date Assignee Title
JP2007106611A (ja) 2005-10-11 2007-04-26 Ohara Inc 光学ガラス
JP2011144063A (ja) * 2010-01-13 2011-07-28 Ohara Inc 光学ガラス、プリフォーム、及び光学素子
JP2014185075A (ja) * 2013-02-19 2014-10-02 Hoya Corp 光学ガラス、光学ガラスブランク、プレス成型用ガラス素材、光学素子、およびそれらの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3943458A4 (fr) * 2019-03-18 2022-12-07 Hikari Glass Co., Ltd. Verre optique, élément optique, système optique, lentille interchangeable et dispositif optique
WO2022159275A1 (fr) * 2021-01-22 2022-07-28 Corning Incorporated Verres phosphatés à indice de réfraction élevé et à dispersion réduite
US11472731B2 (en) 2021-01-22 2022-10-18 Corning Incorporated Phosphate glasses with high refractive index and reduced dispersion
WO2023286630A1 (fr) * 2021-07-16 2023-01-19 株式会社 オハラ Verre de phosphate, verre optique et élément optique

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