WO2016068125A1 - 光学ガラス、光学素子および光学ガラス素材 - Google Patents

光学ガラス、光学素子および光学ガラス素材 Download PDF

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WO2016068125A1
WO2016068125A1 PCT/JP2015/080231 JP2015080231W WO2016068125A1 WO 2016068125 A1 WO2016068125 A1 WO 2016068125A1 JP 2015080231 W JP2015080231 W JP 2015080231W WO 2016068125 A1 WO2016068125 A1 WO 2016068125A1
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glass
content
optical
temperature
optical glass
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PCT/JP2015/080231
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English (en)
French (fr)
Japanese (ja)
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奈緒美 松本
藤原　康裕
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Hoya株式会社
奈緒美 松本
藤原　康裕
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Application filed by Hoya株式会社, 奈緒美 松本, 藤原　康裕 filed Critical Hoya株式会社
Priority to CN201580057947.9A priority Critical patent/CN107148403B/zh
Priority to JP2016556579A priority patent/JP6669663B2/ja
Publication of WO2016068125A1 publication Critical patent/WO2016068125A1/ja

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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
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • 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 a phosphate optical glass having a refractive index (nd) of 1.625 to 1.680 and an Abbe number ( ⁇ d) of 58 to 65. Moreover, this invention relates to the optical element and optical glass raw material which consist of this optical glass.
  • phosphate optical glass having a predetermined refractive index and low dispersibility is effectively used as an optical element material for these imaging devices.
  • phosphate optical glasses described in Patent Document 1 and Patent Document 2 are known.
  • optical glass is widely used as an optical element such as an optical lens or an optical glass material for an optical element.
  • Glass is a viscous material above the glass transition temperature Tg (hereinafter sometimes simply referred to as “glass transition temperature”, “Tg” or “temperature Tg”), and has a property that the viscosity decreases as the temperature rises, ie, more than Tg. It has the property of softening when heated to a high temperature.
  • a press forming method is known in which heat-softened glass is pressed into a desired shape.
  • Such press molding methods are roughly classified into three methods: a direct press molding method, a reheat press molding method, and a precision press molding method (also referred to as a mold press molding method).
  • the direct press molding method and the reheat press molding method are press molding a melted or softened glass material in a short time to mold an optical element blank that approximates the target optical element shape, and then In this method, the optical element blank is ground and polished to finish the optical element.
  • the precision press molding method is a method for producing a target optical element by transferring a precisely processed molding surface shape to glass softened in a non-oxidizing atmosphere. No grinding / polishing is required.
  • the direct press molding method is a method of pressing molten glass without producing a glass material, whereas the reheat press molding method and the precision press molding method are once solidified by cooling the molten glass. After forming the glass material, the glass material is reheated and softened and press-molded.
  • the glass material that has been solidified is reheated and softened, such as the reheat press method and precision press molding method
  • the heating temperature is too high, defects due to crystallization occur in the molded product after pressing. There is. Therefore, if the heating temperature is too low to avoid crystallization of the glass, the viscosity of the glass is high. Therefore, the glass has a defective shape due to insufficient deformation of the glass during press molding, or the glass is increased due to an increase in press pressure for deforming the glass. Defects such as cracks may occur.
  • glass crystals include surface crystals that frequently occur on the glass surface and internal crystals that are generated from the glass surface to the inside.
  • internal crystals For optical glass, it is preferred that there are no or very few surface crystals and internal crystals.
  • the thermal stability of the glass includes devitrification resistance when the glass melt is formed and devitrification resistance when the glass once solidified is reheated.
  • the present inventors have found a phosphate optical glass having a high refractive index and a low dispersibility and excellent thermal stability. Specifically, the present inventors have invented a phosphate optical glass having a high refractive index while giving priority to ensuring thermal stability to the extent that no internal crystals of the glass are produced during reheat press molding.
  • An object of the present invention is to provide a phosphate optical glass having a relatively high refractive index nd and excellent thermal stability. Furthermore, an object of this invention is to provide the optical element and optical glass raw material which consist of this optical glass.
  • the gist of the present invention is as follows.
  • One or more selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 , B content of the mass ratio of P 2 O 5 to the content of 2 O 3 [P 2 O 5 / B 2 O 3] is 1 super-15.0
  • the mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 3.0 or less
  • Mass ratio ⁇ 1 of total content of P 2 O 5 , B 2 O 3 and Al 2 O 3 with respect to the total content of Gd 2 O 3 is
  • the total content [Gd 2 O 3 + Y 2 O 3 + La 2 O 3 + Yb 2 O 3 ] of Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 is 0.5 to 11
  • an optical glass having a relatively high refractive index (refractive index nd is 1.625 or more), even when reheated under harsh conditions due to excellent thermal stability
  • refractive index nd is 1.625 or more
  • an optical glass that hardly causes crystallization can be obtained.
  • an optical element and an optical glass material made of the optical glass are obtained.
  • the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
  • the optical glass of the first embodiment has a total content [P 2 O 5 + B 2 O 3 + Al 2 O 3 ] of P 2 O 5 , B 2 O 3 and Al 2 O 3 of 55% by mass or less.
  • Any one or more selected from BaO, MgO, CaO, ZnO and SrO, and selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 one or more and include a B 2 O 3 mass ratio of the content of P 2 O 5 to the content of [P 2 O 5 / B 2 O 3] is 1 super ⁇ 15.0, MgO,
  • the mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] of the content of BaO to the total content of CaO, ZnO and SrO is 3.0 or less, and Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 the total content of P 2 O 5, B 2 O 3 and Al 2 O
  • the components constituting the glass can be roughly classified into a network component that forms a glass network structure and a modifying component that controls the characteristics of the glass.
  • the network component mainly contributes to the stability of the glass (for example, structural stability, thermal stability, and glass meltability). Therefore, from the viewpoint of obtaining a stable glass, it is desirable to relatively increase the proportion of network components in the glass.
  • the modifying component mainly contributes to the functionality of the glass (for example, optical properties such as refractive index and dispersibility and chemical durability such as weather resistance). For this reason, it is desirable to appropriately select and adjust the type and amount of the modifying component depending on the function and characteristics required of the glass.
  • the ratio of the modifying component in the glass increases, the ratio of the network component decreases as a result, so that the stability as the glass may decrease.
  • Some modifying components are effective from the viewpoint of improving the characteristics, but may significantly reduce the stability of the glass by adding a small amount.
  • the stability and functionality of glass are greatly influenced by the balance between network components and modifying components.
  • phosphate glass has been expected to be used as an optical element such as an optical lens because of its high refractive index and low dispersibility, but it has low weather resistance and cannot be used as a glass for press molding. It was.
  • BaO is added as a modifying component, and the ratio of BaO in the glass is increased to increase the refractive index (refractive index nd is 1.). 625 or more), and the weather resistance was improved.
  • a large amount of BaO and ZnO are introduced as modifying components to improve the weather resistance while ensuring a relatively high refractive index.
  • Such an optical glass has improved weather resistance and is suitable as a glass for precision press molding, but crystallization due to a modifying component (for example, BaO) introduced in a large amount is likely to occur. There was a problem that the thermal stability deteriorated. Therefore, even if the glass has been solidified once, if it is softened again under severe conditions, crystals may be formed in the cooled glass.
  • a modifying component for example, BaO
  • Such glass is an optical element such as a reheat press molding method. It was unsuitable for the production method.
  • the present inventors have increased the proportion of modifying components in the glass and decreased the proportion of network components (P 2 O 5 , B 2).
  • the total content of O 3 and Al 2 O 3 be [P 2 O 5 + B 2 O 3 + Al 2 O 3] is less 55 mass%), blended well balanced and BaO, and other divalent component
  • the thermal stability of the glass can be improved, and the present invention has been completed.
  • the optical glass according to the first embodiment includes BaO and includes at least one selected from MgO, CaO, ZnO and SrO, and BaO with respect to the total content of MgO, CaO, ZnO and SrO. It is one feature that the mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] of the content of Al is 3.0 or less.
  • Such an optical glass according to the first embodiment can effectively prevent the generation of internal crystals of glass in reheat press molding performed in an air atmosphere where precise temperature control is difficult.
  • the optical glass according to the first embodiment has Gd 2 O 3 , Y 2 O 3 in order to effectively increase the refractive index (nd) and achieve low dispersion while maintaining thermal stability.
  • Gd 2 O 3 , Y 2 O 3 in order to effectively increase the refractive index (nd) and achieve low dispersion while maintaining thermal stability.
  • 2 O 3 + Yb 2 O 3 )] is 4.80 or more.
  • Total content of network components P 2 O 5 , B 2 O 3 and Al 2 O 3 ) relative to the total content of the rare earth elements (Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 )
  • the ratio of the amount (mass ratio ⁇ 1) in the above range the balance of the total content of the network component and the rare earth element can be kept moderate, the refractive index of the glass can be increased, and the Abbe number can be increased.
  • the thermal stability of the glass can be increased.
  • Such an optical glass according to the first embodiment is particularly suitable for producing an optical element having a high refractive index by using a reheat press molding method.
  • the optical glass in the first embodiment is a glass composition containing a plurality of metal oxides, and forms (lumps, plates, spheres, etc.) and uses (materials for optical elements, optical elements, etc.) ) Regardless of whether or not.
  • the glass composition can be determined by a method such as ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry).
  • ICP-AES analysis quantitative analysis is first performed for each element, and then converted into oxide notation based on the quantitative analysis value.
  • the analysis value obtained by ICP-AES may include a measurement error of about ⁇ 5% of the analysis value. Therefore, the oxide notation value converted from the analysis value may also contain an error of about ⁇ 5%.
  • the content of the constituent component (notation of oxide) is 0% or does not contain or does not introduce, which means that the constituent component is not substantially contained, and that the constituent component is contained.
  • the amount shall be less than or equal to the impurity level.
  • P 2 O 5 is a network component that forms a network structure of glass, and is an essential component for imparting thermal stability that can be produced to glass.
  • the glass transition temperature, the yield point, and the melting temperature of the glass increase, and the refractive index and weather resistance tend to decrease.
  • the content of P 2 O 5 is too small, the Abbe number ( ⁇ d) of the glass is reduced and the low dispersibility is impaired, and the tendency of the glass to become devitrified becomes strong and the glass tends to become unstable. .
  • the upper limit of the content of P 2 O 5 is preferably 43%, and more preferably in the order of 40%, 37%, 36%, 35%, and 34%. Further, the lower limit of the content of P 2 O 5 is preferably 25%, and more preferably 27%, 29%, 30%, 31%, and 32% in this order.
  • B 2 O 3 is a very effective component for improving the meltability of glass and homogenizing glass, and at the same time, improving the devitrification resistance and weather resistance of glass, increasing the refractive index, and promoting low dispersion. It is an effective ingredient above.
  • the upper limit of the content of B 2 O 3 is preferably 15%, and more preferably in the order of 12%, 10%, 9%, 8%, and 7%. Further, meltability and devitrification resistance of the glass when the content of B 2 O 3 is too small decreases.
  • the lower limit of the content of B 2 O 3 is preferably 2%, and more preferably in the order of 3%, 4%, and 4.5%.
  • B 2 O 3 in the optical glass of the present invention, to form a network structure of the glass together with P 2 O 5, from the viewpoint of the stability of the glass is preferably contained as an essential component.
  • Al 2 O 3 is a network component that forms a network structure of glass, and is used as an effective component for improving the weather resistance of glass.
  • the upper limit of the content of Al 2 O 3 is preferably 10%, and more preferably 7%, 5%, and 3% in this order.
  • the lower limit of the content of Al 2 O 3 is preferably 0%, and more preferably in the order of 0.1%, 0.5%, 1.0%, and 1.5%.
  • the refractive index decreases and the glass melting temperature. There is a risk that the quality will deteriorate due to the increase of the glass and the volatilization of glass. On the other hand, if the total content of these components is too small, devitrification resistance deteriorates and vitrification becomes difficult, and low dispersibility may be impaired.
  • the upper limit of the total content [P 2 O 5 + B 2 O 3 + Al 2 O 3 ] is 55%, and further 50%, 47%, 45%, 44%, 43%, It is preferable in the order of 42%.
  • the lower limit of the total content [P 2 O 5 + B 2 O 3 + Al 2 O 3 ] is preferably 33%, and more preferably 35%, 37%, 39%, and 40% in this order.
  • the content of P 2 O 5 with respect to the content of B 2 O 3 is compatible from the viewpoint of imparting low dispersibility to the glass and enhancing the thermal stability.
  • the ratio: mass ratio [P 2 O 5 / B 2 O 3 ] is more than 1 to 15.0.
  • the upper limit of this mass ratio [P 2 O 5 / B 2 O 3 ] is 15.0, more preferably 12.0, 10.0, 9.0, 8.0, 7.5.
  • the lower limit of the mass ratio [P 2 O 5 / B 2 O 3 ] is more than 1, and more preferably 1.7, 2.0, 3.0, 3.5, and 4.0 in this order.
  • BaO is a very effective essential component for increasing the refractive index of glass and improving weather resistance by introducing an appropriate amount.
  • the amount introduced is too large, the thermal stability of the glass is remarkably impaired, the glass transition temperature rises, and the low dispersibility tends to be impaired.
  • the amount introduced is too small, the desired refractive index cannot be obtained, and the weather resistance is further deteriorated. Therefore, in the optical glass of the present invention, BaO is an essential component, and the upper limit of the content is preferably 45%, and more preferably in the order of 42%, 40%, 38%, 37%, and 36%. .
  • the lower limit of the BaO content is preferably 15%, and more preferably 20%, 23%, 26%, and 28% in this order.
  • the upper limit of the total content of BaO and P 2 O 5 [BaO + P 2 O 5 ] is preferably 78%, and further 75% and 72%. 70% in order.
  • the lower limit of the total content [BaO + P 2 O 5 ] is preferably 50%, and more preferably in the order of 52%, 55%, 58%, and 60%.
  • the proportion of BaO content to the content of B 2 O 3 is preferably Is 10.0, more preferably in the order of 9.0, 8.0, 7.5, 7.0.
  • the lower limit of the mass ratio [BaO / B 2 O 3 ] is preferably 1.0, and more preferably 2.0, 3.0, 3.5, and 4.0 in this order.
  • MgO is a component introduced in order to achieve both high weather resistance and low dispersibility of glass.
  • the introduction of a small amount of MgO has the effect of lowering the glass transition temperature, yield point or liquidus temperature.
  • the upper limit of the content of MgO is preferably 8%, and more preferably in the order of 6%, 5%, and 4.5%.
  • the lower limit of the content of MgO is preferably 0%, and more preferably in the order of 0.5%, 1.0%, 1.5%, and 2.0%.
  • the optical glass of the present invention contains at least 2% of any one component of MgO, B 2 O 3 and Li 2 O. It is preferable to introduce.
  • the lower limit of the content of any one of MgO, B 2 O 3 and Li 2 O is preferable in the order of 3%, 4% and 5%.
  • the upper limit of the CaO content is preferably 12%, and more preferably in the order of 10%, 9%, and 8%.
  • the lower limit of the CaO content is preferably 0%, and more preferably in the order of 2%, 3%, 4%, and 5%.
  • the upper limit of the total content [MgO + CaO] of MgO and CaO in the optical glass of the present invention is preferably 20% from the viewpoint of achieving both low dispersibility, thermal stability, and weather resistance of the glass. Is preferably in the order of 17%, 15%, 12%, and 11%. Further, the lower limit of the total content [MgO + CaO] is preferably 3%, and more preferably 4%, 5%, 6%, and 7% in this order.
  • the upper limit of the SrO content is preferably 8%, more preferably 6% and 5% in this order.
  • the lower limit of the SrO content is preferably 0%, and more preferably in the order of 0.1%, 1.0%, and 1.5%.
  • the upper limit of the ZnO content is preferably 15%, and more preferably in the order of 13%, 12%, 11%, 10%, and 9%.
  • the lower limit of the content of ZnO is preferably 0%, further 1%, and further preferably 2%, 3%, and 4% in this order.
  • the optical glass of the present invention contains one or more selected from MgO, CaO, ZnO and SrO as a divalent component.
  • the upper limit of the total content R1 [MgO + CaO + ZnO + SrO + BaO] of MgO, CaO, ZnO, SrO and BaO is preferably 65%, and Is preferred in the order of 62%, 60%, 57%, 55%.
  • the lower limit of the total content R1 is preferably 38%, and more preferably in the order of 40%, 43%, 46%, and 48%.
  • the ratio of the content of BaO to the total content of MgO, CaO, ZnO and SrO: mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] is set to 3.0 or less.
  • the upper limit with preferable mass ratio (alpha) 1 is 2.9, Furthermore, it is preferable in order of 2.8, 2.7, 2.6, and 2.5.
  • the lower limit of the mass ratio ⁇ 1 is preferably 1.0, and more preferably in the order of 1.2, 1.3, 1.4, and 1.5.
  • the BaO content is not excessively introduced with respect to the content of the other divalent components, so that the precipitation of crystals due to BaO can be suppressed. Therefore, even when BaO and other divalent components are blended in a balanced manner, the component that increases the refractive index is increased, and the component that forms the network structure is decreased. Can be improved.
  • the optical glass of the present invention satisfying the mass ratio ⁇ 1 of 3.0 or less may be referred to as a crystallization peak temperature Tc (hereinafter simply referred to as “crystallization peak temperature”, “Tc”, or “temperature Tc”). ) And the glass transition temperature Tg (Tc ⁇ Tg) are relatively large, and both Tc ⁇ Tg are 150 ° C. or higher.
  • Tc-Tg crystallization peak temperature
  • the upper limit of the ratio of the content of BaO to the total content of MgO and SrO: mass ratio [BaO / (MgO + SrO)] is preferably 45, 42, 40, and 38 are preferred in this order.
  • the lower limit of the mass ratio [BaO / (MgO + SrO)] is preferably 1, and more preferably 2, 3, 4, and 5 in this order.
  • the ratio of the total content of SrO and BaO to the total content of MgO and CaO is preferably 1.0, and more preferably 2.0, 2.5, and 3.0 in this order.
  • the upper limit of the ratio of the content of ZnO to the content of BaO: mass ratio [ZnO / BaO] is preferably 0.33, Furthermore, it is preferable in the order of 0.30, 0.28, and 0.27. Further, the lower limit of the mass ratio [ZnO / BaO] is preferably 0.10, and more preferably in the order of 0.15, 0.18, and 0.20.
  • Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 are all components that contribute to improving the weather resistance and increasing the refractive index of the glass. However, if these components are introduced excessively, the thermal stability and homogeneity of the glass may be deteriorated, and the low dispersibility will be significantly impaired. Therefore, in the optical glass of the present invention, the upper limit of the content of Gd 2 O 3 is preferably 10%, and more preferably 9.0%, 8.5%, and 8.0% in this order. Moreover, the lower limit of the content of Gd 2 O 3 is preferably 0%, and more preferably in the order of 0.1%, 0.5%, 1.0%, 2.0%, and 3.0%.
  • the upper limit of the content of Y 2 O 3 is preferably 10%, and more preferably 8%, 7%, and 6% in this order. Further, the lower limit of the content of Y 2 O 3 is preferably 0%, and more preferably 0.5% and 1.0% in this order. The upper limit of the content of La 2 O 3 is preferably 10%, and more preferably 7%, 5%, and 4% in this order. Further, the lower limit of the content of La 2 O 3 is preferably 0%, more preferably 0.05%. The upper limit of the content of Yb 2 O 3 is preferably 7%, and more preferably in the order of 5%, 2% and 1%. Moreover, the lower limit of the content of Yb 2 O 3 is preferably 0%, more preferably 0.05%. Since Yb 2 O 3 has an absorptivity in the near infrared region, it is preferably not introduced when using light rays in the near infrared region.
  • the rare earth elements such as Gd 2 O 3 , Y 2 O 3 , La 2 O 3, and Yb 2 O 3 are preferably introduced appropriately from the viewpoint of effectively increasing the refractive index. Therefore, the optical glass of the present invention contains one or more selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 .
  • the thermal stability of the glass deteriorates and the low dispersibility tends to be remarkably impaired.
  • the upper limit of the total content Re1 [Gd 2 O 3 + Y 2 O 3 + La 2 O 3 + Yb 2 O 3 ] of Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 is preferably Is 11%, and further preferably 9.0%, 8.5%, and 8.0% in this order.
  • the lower limit of the total content Re1 is preferably 0.5%, and further 0.7%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0% Are preferred in this order.
  • the thermal stability of the glass may be improved by introducing two or more rare earth elements rather than introducing a single rare earth element.
  • the optical glass of the present invention preferably contains any two or more rare earth elements selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 .
  • the optical glass according to the present invention has a P 2 with respect to the total content Re1 of rare earth elements from the viewpoint of ensuring the thermal stability of the glass and effectively increasing the refractive index while keeping the mass ratio ⁇ 1 within a predetermined range.
  • Ratio of total content of O 5 , B 2 O 3 and Al 2 O 3 Mass ratio ⁇ 1 [(P 2 O 5 + B 2 O 3 + Al 2 O 3 ) / Re1] is 4.80 or more.
  • the lower limit of the mass ratio ⁇ 1 is 4.80, and further preferably 4.90, 4.95, 5.00, 5.05, 5.10.
  • sample 35A with the smallest total content Re1 of rare earth elements among the optical glasses according to the examples of the present invention described later includes 1.12% by mass of Gd 2 O 3 (molecular weight: 362), and the mass ratio The value of ⁇ 1 is 37.73.
  • the mass ratio ⁇ 1 is a value representing a relative relationship between P 2 O 5 + B 2 O 3 + Al 2 O 3 and Re1, a relatively light rare earth element such as Y 2 O 3 is selected as Re1. In this case, the value of ⁇ 1 becomes relatively large.
  • the value of the mass ratio ⁇ 1 becomes about 60.
  • the upper limit of the mass ratio ⁇ 1 is preferably 65, and more preferably in the order of 60, 50, 40, 30, 20, 15, 12, 10, and 8.
  • the mass ratio ⁇ 1 and the mass ratio ⁇ 1 are closely related from the viewpoint of obtaining desired optical characteristics and improving the thermal stability of the glass. This will be described below.
  • the thermal stability of the glass is relatively small. Specifically, the thermal stability is improved by suppressing the total content Re1 of rare earth elements as the denominator of the mass ratio ⁇ 1 and adjusting the components so that the mass ratio ⁇ 1 is 4.80 or more.
  • the thermal stability of the glass is improved, but the refractive index decreases as the total content Re1 of rare earth elements decreases. Therefore, in the optical glass according to the present invention, the amount of BaO introduced is made relatively large so that the action of BaO is effectively expressed to improve the refractive index. However, if the introduction amount of BaO with respect to the total content of MgO, CaO, ZnO and SrO is too large, the thermal stability is adversely impaired. Therefore, in the present invention, the upper limit of the mass ratio ⁇ 1 is specified (the mass ratio ⁇ 1 is 3 0.0 or less).
  • the glass composition so that the mass ratio ⁇ 1 and the mass ratio ⁇ 1 are within a predetermined range, desired optical characteristics can be obtained and the thermal stability of the glass can be improved.
  • SiO 2 is an effective component for improving chemical durability while maintaining low dispersibility. However, if the amount introduced is too large, the glass transition temperature and yield point tend to increase and the refractive index tends to decrease. Therefore, in the optical glass of the present invention, the upper limit of the content of SiO 2 is preferably 3%, more preferably 2%, still more preferably 1%, and even more preferably 0.5%.
  • SiO 2 is a network component with P 2 O 5, B 2 O 3, Al 2 O 3, it is not necessarily introduced SiO 2 in the optical glass of the present invention.
  • Li 2 O is a component that lowers the glass transition temperature and the yield point and is effective for lowering the dispersion.
  • coexistence of P 2 O 5 , B 2 O 3 and Li 2 O is very effective for reducing the dispersion of glass.
  • the upper limit of the content of Li 2 O is preferably 6%, and further 5%, 4%, 3%, 2%, 1.8%, 1.5% Are preferred in this order.
  • the lower limit of the content of Li 2 O is preferably 0%, and more preferably smaller in the order of 0.3%, 0.5%, 1.0%, 1.3%. In the case of preparing an optical element by using a reheat press molding, it may not substantially introduce Li 2 O.
  • Na 2 O and K 2 O are optional components introduced to improve the devitrification resistance of the glass, lower the glass transition temperature, yield point, and liquidus temperature, and improve the meltability of the glass. is there.
  • the introduction of appropriate amounts of Na 2 O and K 2 O improves the stability of the glass and leads to a decrease in the liquidus temperature and transition temperature.
  • the upper limit of the Na 2 O content is preferably 5%, and more preferably in the order of 3%, 2%, and 1.5%.
  • the upper limit of the content of K 2 O is preferably 3%, and more preferably in the order of 2% and 1%. It is particularly preferable that Na 2 O and K 2 O are not substantially introduced.
  • the upper limit of the total content R 2 1 [Li 2 O + Na 2 O + K 2 O] of Li 2 O, Na 2 O and K 2 O is preferably 10%, 7%, 5%, 3%, 2%, 1.8%, and 1.5% in this order.
  • the lower limit of the total content R 2 1 is preferably 0%, further 0.1%, preferably from about 0.5% smaller in the order of 1.0%.
  • Li 2 O, Na 2 O and K 2 the total content R 2 1 of O is preferably at most 2.0%, 1.0 % Or less, more preferably 0.5% or less, even more preferably 0.3% or less, still more preferably 0.1% or less, and substantially no introduction. It is particularly preferred.
  • Cs 2 O is an alkali metal oxide is not necessarily required, but rather required because adverse terms of raw material cost. Further, Cs 2 O lowers the refractive index and remarkably impairs the weather resistance, so it is preferable not to introduce Cs 2 O.
  • the ratio of P 2 O 5 content to the total content R 2 1 of the alkali metal oxide mass ratio [P 2 O 5 / R 2 1] from the viewpoint of achieving both glass meltability and thermal stability.
  • the upper limit is preferably 120, and more preferably 110, 100, and 90 in this order.
  • the lower limit of the mass ratio [P 2 O 5 / R 2 1] is preferably set to 7, and more preferably in the order of 10, 15, 17, and 20.
  • the optical glass of the present invention does not substantially contain Pb, As, Cd, U, Th, and Tl from the viewpoint of reducing the load on the environment.
  • the optical glass of the present invention can contain halogen, that is, F, Cl, Br, and I as optional components.
  • the content can be represented by the mass fraction of anions (for example, [F / (O + F)]).
  • the upper limit of the F content is preferably 8%, and more preferably 5%, 3%, 2%, 1%, 0.5%, and 0.1% in this order.
  • the upper limit of the content of Cl, Br, and I is preferably 5%, respectively, and more preferably in the order of 3%, 2%, 1%, 0.5%, and 0.1%.
  • the upper limit of B 2 O 3 in the glass is preferably 8% in order to suppress the volatilization of the glass, more preferably in the order of 5%, 3%, and 1%, and most preferably. Is substantially not contained. However, this does not apply when a small amount of halogen of 1% or less is added. In particular, in order to suppress the volatilization of components from the glass and improve the homogeneity of the glass, it is preferable that the halogen is not substantially contained.
  • an easily reducing component composed of WO 3 , TiO 2 , Bi 2 O 3 and Nb 2 O 5 can be contained as an optional component.
  • These easily reducing components are effective components for increasing the refractive index.
  • W, Ti, Bi, and Nb significantly reduce the glass Abbe number ( ⁇ d). Therefore, the upper limit of the content of the easily reducing component is preferably 4%, more preferably 3%, 2%, and 1%. In addition, it is particularly preferable not to substantially introduce the easily reducing component.
  • the optical glass of the present invention as described above is basically composed of P 2 O 5 , B 2 O 3 , SiO 2 , Al 2 O 3 , Li 2 O, Na 2 O, K 2 O, MgO, CaO, ZnO. , SrO, BaO, Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 .
  • the total content of these components is 95% or more Preferably, it is 98% or more, more preferably 99% or more, and still more preferably 100%.
  • optical glass of this invention is fundamentally comprised by the said component, in the range which does not prevent the effect of this invention, it is also possible to introduce
  • substantially not containing can be taken as a guide that the content is less than 0.2% by mass. Since components and additives that are not substantially contained are preferably not contained in the glass, the content is preferably less than 0.1% by mass, more preferably less than 0.08% by mass, It is further preferably less than 0.05% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.005% by mass.
  • the optical glass of the present invention is composed of the above components and the total amount is 100% by mass, even if a refining agent such as Sb 2 O 3 , SnO 2 , or CeO 2 is introduced in an external ratio within 4% by mass. Good.
  • the upper limit of the content of Sb 2 O 3 is preferably 4% by mass, and more preferably 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, and 0.1% by mass in this order.
  • the lower limit of the content of Sb 2 O 3 is preferably 0%, and more preferably in the order of 0.01% by mass, 0.02% by mass, and 0.04% by mass.
  • SnO 2 and CeO 2 may deteriorate the transmittance of the glass, so that introduction of 1% by mass or less is preferable, and it is particularly preferable not to introduce substantially.
  • the upper limit of the refractive index nd of the optical glass of the present invention is 1.680, and further preferably 1.670, 1.665, 1.660. Further, the lower limit of the refractive index nd is 1.625, and more preferably in the order of 1.630 and 1.635.
  • the upper limit of the Abbe number ⁇ d of the optical glass of the present invention is 65, and 63 and 62.5 are more preferable in this order.
  • the lower limit of the Abbe number ⁇ d is 58, and 59 and 60 are more preferable in this order.
  • an optical system is constructed, so that the optical system can be made compact, highly functional, and improved in chromatic aberration.
  • the thermal stability of glass includes devitrification resistance when forming a glass melt and devitrification resistance when glass that has been solidified once is reheated.
  • the devitrification resistance when molding the glass melt is based on the liquidus temperature, and the lower the liquidus temperature, the better the devitrification resistance.
  • the temperature of the glass melt In glass with a high liquidus temperature, the temperature of the glass melt must be maintained at a high temperature in order to prevent devitrification, which leads to deterioration in quality and productivity due to volatilization of glass components. May end up. Therefore, the optical glass of the present invention preferably has a liquidus temperature of 1350 ° C. or lower, more preferably 1300 ° C. or lower, further preferably 1250 ° C. or lower, and further preferably 1200 ° C. or lower. Preferably, the temperature is 1100 ° C. or lower.
  • Tc ⁇ Tg the temperature difference between the crystallization peak temperature Tc and the glass transition temperature Tg.
  • the “softening point” of glass is a temperature at which the glass starts to deform significantly due to its own weight, and corresponds to a viscosity of about 10 7.6 dPa ⁇ s.
  • “temperature Tp at which glass is softened” (hereinafter simply referred to as “temperature at which glass is softened”, “Tp” or “temperature Tp”) is higher than “softening point”. This is the temperature at which the viscosity of the glass corresponds to a viscosity of 10 4 to 10 6 dPa ⁇ s.
  • the temperature corresponding to a viscosity of 10 4 to 10 6 dPa ⁇ s can be uniquely determined by a viscosity curve.
  • Crystallization start temperature Tx (hereinafter, simply referred to as “crystallization start temperature”, “Tx”, or “temperature Tx”) will be described with reference to FIG.
  • FIG. 1 is a schematic diagram showing a differential scanning calorimetric curve of optical glass (phosphate optical glass).
  • the horizontal axis represents temperature
  • the vertical axis represents the amount of differential heat corresponding to the exothermic heat absorption of the glass.
  • the glass transition temperature Tg, the endothermic peak temperature Tk accompanying the glass transition, the crystallization start temperature Tx, and the crystallization peak temperature Tc are all measured by a differential scanning calorimeter [DSC (Differential Scanning Calorimetry)].
  • the endothermic peak temperature Tk accompanying the glass transition means the temperature of the peak of the endothermic reaction occurring in the vicinity of Tg to (Tg + 100 ° C.).
  • the crystallization peak temperature Tc means a temperature showing the lowest crystallization exothermic peak when glass is powdered and differential scanning calorimetry is performed from room temperature to a predetermined temperature at a heating rate of 10 ° C./min.
  • the crystallization start temperature Tx means the rising temperature on the low temperature side of the crystallization peak.
  • the glass transition temperature Tg of the optical glass of the present invention is preferably within the following range. That is, the upper limit of Tg is preferably 650 ° C, and more preferably in the order of 630 ° C, 620 ° C, 610 ° C, 600 ° C, and 590 ° C. Moreover, although the minimum of Tg is not specifically limited, 420 degreeC is preferable, Furthermore, 440 degreeC, 460 degreeC, 480 degreeC, 500 degreeC, 530 degreeC, and 560 degreeC are preferable in order.
  • the crystallization peak temperature Tc of the optical glass of the present invention is preferably within the following range. That is, the lower limit of Tc is preferably 650 ° C, and more preferably in the order of 670 ° C, 680 ° C, 690 ° C, and 700 ° C. Further, the upper limit of Tc is preferably 820 ° C, and more preferably in the order of 810 ° C, 800 ° C, and 790 ° C.
  • the glass material is heated and adjusted to have a viscosity suitable for press molding.
  • the reheat press molding method deforms the glass in a shorter time than the precision press molding method, so it is common to reheat the glass at a relatively high temperature so that good press molding can be performed, and sufficiently reduce the viscosity of the glass. Is.
  • the heating temperature is insufficient and the glass viscosity is high, the molded product may crack due to pressure during pressing, and shape defects may occur due to insufficient deformation. May decrease. Therefore, in order to perform good press molding, particularly in the reheat press molding method, it is necessary to sufficiently heat the glass material and adjust it to an appropriate temperature (temperature corresponding to a glass viscosity of 10 4 to 10 6 dPa ⁇ s). There is.
  • glass that is easily crystallized in the reheat press molding method often has a small temperature difference between Tg and Tc, and when heated to a temperature suitable for press molding, the temperature may exceed Tc.
  • the optical glass of the present invention has excellent Tc-Tg of 150 ° C. or higher, no internal crystals are generated by reheating, and is excellent in thermal stability, as shown in Examples described later. That is, since the temperature Tc of the optical glass of the present invention is sufficiently higher than the temperature Tg, the glass material is softened at a temperature lower than the crystallization peak temperature Tc and no crystal is generated at the time of reheat press molding. .
  • the crystallization peak temperature Tc of the optical glass of the present invention is sufficiently higher than the temperature Tp at which the glass softens.
  • Tp the temperature at which the glass softens.
  • the temperature difference (Tc ⁇ Tg) is higher than the temperature Tg. Therefore, the temperature difference (Tc ⁇ Tg) is higher than the temperature difference (Tc ⁇ Tg). It is more preferable that the temperature difference is larger than Tp). Since the optical glass of the present invention has the above-described glass composition, the temperature difference (Tc ⁇ Tg) is appropriately secured and the thermal stability is improved, and the temperature difference (Tc ⁇ Tp) is increased. The productivity (for example, easy temperature control) of reheat press molding is improved.
  • the temperature difference (Tc ⁇ Tg) between the temperature Tc and the temperature Tg is preferably 150 ° C. or more, more preferably 160 ° C. or more, and further preferably 180 ° C. or more. Especially preferably, it is 200 degreeC or more.
  • the temperature difference (Tc ⁇ Tp) between the temperature Tc and the temperature Tp is preferably 1 ° C. or more, and the temperature difference (Tc ⁇ Tp) is preferably 10 ° C. or more, more preferably 20 ° C. or more. Yes, more preferably 30 ° C or higher, still more preferably 50 ° C or higher, and even more preferably 70 ° C or higher.
  • the optical glass of the present invention has a crystallization peak in a reheat press molding method in which a glass material is heated to a temperature higher than Tg to soften the glass material to an appropriate viscosity (about 10 4 to 10 6 dPa ⁇ s). Since it is sufficiently softened at a temperature lower than the temperature Tc, the generation of internal crystals can be effectively prevented. Further, since the optical glass of the present invention is excellent in thermal stability, it can be applied to a reheat press molding method in an open atmosphere where precise temperature control is difficult.
  • the thermal stability of the glass obtained from a differential scanning calorimeter can also be evaluated by the peak intensity ⁇ of crystallization.
  • the height of the crystallization peak can also be calculated from the difference between the calorific value at the peak temperature and the baseline of the differential scanning calorimeter. In this case, since it depends on how to draw the baseline, in the present embodiment, the former is used.
  • the peak intensity ⁇ of crystallization was calculated by the method described above.
  • the peak intensity ⁇ is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, still more preferably 2 or less, and even more preferably 1 or less.
  • the crystallization peak is not observed and the peak intensity cannot be defined. Even when the peak intensity ⁇ is relatively large, if the temperature difference [Tc ⁇ Tg] between the temperature Tc and the temperature Tg is 150 ° C. or higher, crystallization occurs even if the glass is heated to lower the viscosity. Therefore, crystallization in reheat press molding hardly occurs.
  • the optical glass of the present invention is also excellent in weather resistance.
  • the weather resistance of glass can be expressed using a haze value (haze) as an index.
  • the haze value is the degree of cloudiness of the glass when the glass is held for a predetermined time in a high temperature and high humidity environment.
  • the haze value is the ratio of the scattered light intensity to the total transmitted light intensity when white light is transmitted perpendicular to the polished surface of the glass flat plate subjected to double-side optical polishing, that is, [scattered light intensity / transmitted light intensity. ] In%.
  • the optical glass of the present invention preferably has a haze value of 10 or less, more preferably a haze value of 5 or less, further preferably a haze value of 2 or less, more preferably a haze value of less than 1.
  • a glass with a high haze value is a glass with low chemical durability, in which the glass is easily eroded by water droplets and water vapor adhering to the glass and various chemical components in the use environment, and a reaction product is easily generated on the glass surface. It is.
  • a glass having a small haze value such as the optical glass of the present invention, is a glass having high chemical durability (weather resistance).
  • the optical glass according to the present invention will be described based on the content ratio of each component in cation% display.
  • each content is expressed in cation% unless otherwise specified.
  • the cation% indicates the ratio of individual cations to all cations contained in the glass in terms of mole percentage.
  • the optical glass of the second embodiment is an oxide glass, the anion is mainly oxygen (O 2 ⁇ ), but a part of the anion other than oxygen (for example, halogen) may be substituted. it can.
  • the optical glass of the second embodiment is an oxide glass having a total content [P 5+ + B 3+ + Al 3+ ] of P 5+ , B 3+ and Al 3+ of 65% or less, Any one or more selected from Ba 2+ , Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ and selected from Gd 3+ , Y 3+ , La 3+ and Yb 3+ anda any one or more, the content of the cation ratio of P 5+ to the content of B 3+ [P 5+ / B 3+ ] is 1 super ⁇ 10.0, Mg 2+, Ca Cation ratio ⁇ 2 [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] of the content of Ba 2+ with respect to the total content of 2+ , Zn 2+ and Sr 2+ is 1.50 or less in and, Gd 3+, Y 3+, P 5+ to the total content of La 3+ and Yb 3+, B
  • the components constituting the glass can be roughly classified into a network component that forms a glass network structure and a modifying component that controls the characteristics of the glass.
  • the network component mainly contributes to the stability of the glass (for example, structural stability, thermal stability, and glass meltability). Therefore, from the viewpoint of obtaining a stable glass, it is desirable to relatively increase the proportion of network components in the glass.
  • the modifying component mainly contributes to the functionality of the glass (for example, optical properties such as refractive index and dispersibility and chemical durability such as weather resistance). For this reason, it is desirable to appropriately select and adjust the type and amount of the modifying component depending on the function and characteristics required of the glass.
  • the ratio of the modifying component in the glass increases, the ratio of the network component decreases as a result, so that the stability as the glass may decrease.
  • Some modifying components are effective from the viewpoint of improving the characteristics, but may significantly reduce the stability of the glass by adding a small amount.
  • the stability and functionality of glass are greatly influenced by the balance between network components and modifying components.
  • phosphate optical glass has been expected to be used as an optical element such as an optical lens because of its high refractive index and low dispersibility, but it has low weather resistance and can be used as a glass for press molding. There wasn't.
  • Ba 2+ is added as a modifying component, and the ratio of Ba 2+ in the glass is increased to increase the refractive index (refractive index).
  • the weather resistance was improved while ensuring nd of 1.625 or more.
  • a large amount of Ba 2+ and Zn 2+ are introduced as modifying components to improve the weather resistance while ensuring a relatively high refractive index.
  • Such an optical glass has improved weather resistance and is suitable as a glass for precision press molding, but crystallization due to a modifying component (for example, Ba 2+ ) introduced in a large amount tends to occur. There was a problem that the thermal stability of the glass deteriorated. Therefore, even if the glass has been solidified once, if it is softened again under severe conditions, crystals may be formed in the cooled glass.
  • a modifying component for example, Ba 2+
  • Such glass is an optical element such as a reheat press molding method. It was unsuitable for the production method.
  • the present inventors have increased the proportion of the modifying component in the glass and decreased the proportion of the network component (P 5+ , B 3+ And Al 3+ total content [P 5+ + B 3+ + Al 3+ ] of 65% or less), by mixing Ba 2+ with other divalent components in a balanced manner, The present inventors have found that the thermal stability can be improved and have completed the present invention.
  • the optical glass according to the present invention contains Ba 2+ and contains at least one selected from Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ , and Mg 2+ , Ca 2.
  • the cation ratio ⁇ 2 [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] of the content of Ba 2+ to the total content of + , Zn 2+ and Sr 2+ is 1.50 or less Is one of the characteristics.
  • Such an optical glass according to the present invention can effectively prevent the generation of internal crystals of glass in reheat press molding performed in an air atmosphere where precise temperature control is difficult.
  • the optical glass according to the present invention provides Gd 3+ , Y 3+ , La 3+ and La 3+ in order to effectively increase the refractive index (nd) and achieve low dispersion while maintaining thermal stability.
  • Ratio of total content of network components (P 5+ , B 3+ and Al 3+ ) to total content of the rare earth elements (Gd 3+ , Y 3+ , La 3+ and Yb 3+ ) (cation ratio ⁇ 2 ) within the above range, the balance of the total content of the network component and the rare earth element can be maintained appropriately, the refractive index of the glass can be increased, the Abbe number can be increased, and the thermal stability of the glass. Can be increased.
  • Such an optical glass according to the second embodiment is particularly suitable for producing an optical element having a high refractive index using a reheat press molding method.
  • the optical glass in the second embodiment is a glass composition containing a plurality of metal oxides, and has a form (lump shape, plate shape, spherical shape, etc.) and application (a material for optical elements, an optical element, etc.) ) Regardless of whether or not.
  • the content rate of the constituent components of the glass can be measured by a method such as ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry).
  • an analysis value (for example, atomic% notation) obtained by performing a quantitative analysis for each element based on the ICP-AES analysis may include a measurement error of about ⁇ 5% of the analysis value. Moreover, based on the said analysis value, it can convert into the value of an oxide description, and it can convert the cation component in glass into the value of a cation% description, The conversion method is mentioned later.
  • the content of the constituent component is 0% or does not contain or is not introduced, which means that the constituent component is substantially not contained, and the content of the constituent component is about the impurity level.
  • P 5+ is a network component that forms a network structure of glass, and is an essential component for imparting thermal stability that can be produced to glass.
  • the glass transition temperature, the yield point, and the melting temperature of the glass increase, and the refractive index and weather resistance tend to decrease.
  • the content of P 5+ is too small, the Abbe number ( ⁇ d) of the glass is reduced, and the low dispersibility is impaired. Further, the tendency of the glass to devitrify becomes strong and the glass tends to become unstable. Therefore, in the optical glass of the present invention, the upper limit of the P 5+ content is preferably 50%, and more preferably in the order of 45%, 42%, 40%, 39%, and 38%. Further, the lower limit of the content of P 5+ is preferably 20%, and more preferably in the order of 25%, 27%, 30%, 32%, 34%.
  • B 3+ is a very effective component for improving the glass meltability and homogenizing the glass, and at the same time, improving the devitrification resistance and weather resistance of the glass, increasing the refractive index, and promoting low dispersion. It is an effective ingredient.
  • the upper limit of the B 3+ content is preferably 25%, and more preferably 22%, 20%, 18%, 17%, and 16% in this order.
  • the meltability and devitrification resistance of glass will fall.
  • the lower limit of the B 3+ content is preferably 1%, and further 2.0%, 3.0%, 5.0%, 8.0%, 10% Are preferred in this order.
  • B 3+ forms a glass network structure together with P 5+ , and therefore is preferably contained as an essential component from the viewpoint of glass stability.
  • Al 3+ is a network component that forms a network structure of glass, and is used as an effective component for improving the weather resistance of glass.
  • the upper limit of the content of Al 3+ is preferably 13%, and more preferably in the order of 10%, 8%, 7%, and 6%.
  • the lower limit of the content of Al 3+ is preferably 0%, and more preferably in the order of 0.1%, 0.5%, 1.0%, and 2.0%.
  • the upper limit of the total content [P 5+ + B 3+ + Al 3+ ] is 65%, and further preferably 60%, 58%, 57%, and 56%.
  • the lower limit of the total content [P 5+ + B 3+ + Al 3+ ] is preferably 40%, and more preferably in the order of 45%, 47%, 49%, and 50%.
  • the ratio of the content of P 5+ to the content of B 3+ from the viewpoint of both imparting low dispersibility to the glass and enhancing the thermal stability is more than 1 to 10.0. Further, the preferable upper limit of the cation ratio [P 5+ / B 3+] is 8.0, more preferably in the order of 6.0,5.0,4.5,4.0,3.7. Moreover, the preferable lower limit of the cation ratio [P 5+ / B 3+] is 1.2, more preferably in the order of 1.5 and 2.0.
  • excellent thermal stability is achieved while achieving low dispersion by balancing the proportion of P 5+ and B 3+ that predominantly affect the formation of the glass network structure. Can be obtained.
  • Ba 2+ is an essential component that is very effective for increasing the refractive index of glass and improving weather resistance by introducing an appropriate amount.
  • the amount introduced is too large, the thermal stability of the glass is remarkably impaired, the glass transition temperature rises, and the low dispersibility tends to be impaired.
  • the amount introduced is too small, the desired refractive index cannot be obtained, and the weather resistance is further deteriorated. Therefore, in the optical glass of the present invention, Ba 2+ is an essential component, and the upper limit of its content is preferably 30%, and further 27%, 25%, 22%, 20%, 19%, It is preferable in the order of 18%.
  • the lower limit of the Ba 2+ content is preferably 5.0%, and more preferably 8.0%, 10%, 12%, and 14% in this order.
  • the upper limit of the total content of Ba 2+ and P 5+ [Ba 2+ + P 5+ ] is preferably 65%, and more preferably 60%. , 58% and 56% in this order.
  • the lower limit of the total content [Ba 2+ + P 5+ ] is preferably 40%, and more preferably in the order of 42%, 45%, 48%, and 50%.
  • the upper limit of the ratio of the Ba 2+ content to the B 3+ content: cation ratio [Ba 2+ / B 3+ ] is , Preferably 3.0, and more preferably 2.5, 2.0, 1.8, and 1.7 in this order.
  • the lower limit of the cation ratio [Ba 2+ / B 3+ ] is preferably 0.5, and more preferably in the order of 0.6, 0.8, and 1.0.
  • Mg 2+ is a component introduced to achieve both high weather resistance and low dispersibility of glass.
  • the introduction of a small amount of Mg 2+ has the effect of lowering the glass transition temperature, yield point or liquidus temperature.
  • the upper limit of the Mg 2+ content is preferably 20%, and more preferably in the order of 15%, 12%, 10%, and 9%.
  • the lower limit of the Mg 2+ content is preferably 0%, and more preferably in the order of 0.5%, 1.0%, 1.5%, and 2.0%.
  • the upper limit of the content of Ca 2+ is preferably 22%, and more preferably in the order of 18%, 15%, 12%, 11%, and 10%.
  • the lower limit of the Ca 2+ content is preferably 0%, and more preferably in the order of 1.0%, 3.0%, 5.0%, 6.0%, and 7.0%.
  • the upper limit of the total content of Mg 2+ and Ca 2+ [Mg 2+ + Ca 2+ ] in the optical glass of the present invention is from the viewpoint of achieving both low dispersibility, thermal stability, and weather resistance of the glass. , Preferably 30%, and more preferably in the order of 27%, 25%, 22%, 20%, 18%.
  • the lower limit of the total content [Mg 2+ + Ca 2+ ] is preferably 2%, and more preferably 3.0%, 5.0%, 8.0% and 10% in this order.
  • the upper limit of the Sr 2+ content is preferably 10%, and more preferably in the order of 8%, 5%, 4%, and 3%.
  • the lower limit of the Sr 2+ content is preferably 0%, and more preferably in the order of 0.5%, 1.0%, 1.5%, and 2.0%.
  • the Zn 2+ is a component used for increasing the refractive index of glass by appropriate introduction, improving the thermal stability of the glass, and lowering the liquidus temperature and the glass transition temperature.
  • the upper limit of the Zn 2+ content is preferably 15%, and more preferably in the order of 13%, 12%, 10%, and 9%.
  • the lower limit of the Zn 2+ content is preferably 0%, and more preferably 0.5%, 1.0%, 2.0%, and 3.0% in this order.
  • the optical glass of the present invention contains at least one selected from Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ as a divalent component in addition to Ba 2+ .
  • the total content of Mg 2+ , Ca 2+ , Zn 2+ , Sr 2+ and Ba 2+ R2 [Mg 2+ + Ca
  • the upper limit of 2+ + Zn 2+ + Sr 2+ + Ba 2+ ] is preferably 53%, and more preferably in the order of 50%, 47%, 45%, and 43%.
  • the lower limit of the total content R2 is preferably 25%, and more preferably 28%, 31%, 33%, and 35% in this order.
  • the content of Ba 2+ with respect to the total content of Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ from the viewpoint of improving the thermal stability of the glass while increasing the refractive index.
  • Amount ratio The cation ratio ⁇ 2 [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] is 1.50 or less.
  • the upper limit with preferable cation ratio (alpha) 2 is 1.4, Furthermore, 1.2, 1.1, and 1.0 are preferable in order.
  • the cation ratio ⁇ 2 is preferably more than 0, and the lower limit of the cation ratio ⁇ 2 is 0.1, 0.2, 0.3, 0.5, It is preferable in order of 0.6.
  • the Ba 2+ content is not excessively introduced with respect to the content of the other divalent components, so that the precipitation of crystals due to Ba 2+ can be suppressed. Therefore, even when Ba2 + and other divalent components are blended in a balanced manner, the component that increases the refractive index is increased and the component that forms the network structure is decreased. Stability can be improved.
  • the optical glass of the present invention satisfying the cation ratio ⁇ 2 of 1.50 or less has a relatively large temperature difference (Tc ⁇ Tg) between the crystallization peak temperature Tc and the glass transition temperature Tg, and all of the Tc ⁇ Tg are 150. More than °C.
  • the ratio of the content of Ba 2+ to the total content of Mg 2+ and Sr 2+ : cation ratio [Ba 2+ / (Mg 2+ + Sr 2+ ) ] Is preferably 3.0, and more preferably in the order of 2.5, 2.0, 1.8, and 1.7.
  • the lower limit of the cation ratio [Ba 2+ / (Mg 2+ + Sr 2+ )] is preferably 0.3, and more preferably 0.5, 0.7, and 0.8 in this order.
  • the ratio of the total content of Sr 2+ and Ba 2+ to the total content of Mg 2+ and Ca 2+ cation ratio [(Sr The upper limit of ( 2+ + Ba 2+ ) / (Mg 2+ + Ca 2+ )] is preferably 3.0, and more preferably 2.5, 2.0, 1.8, and 1.7 in this order. Further, the lower limit of the cation ratio [(Sr 2+ + Ba 2+ ) / (Mg 2+ + Ca 2+ )] is preferably 0.3, and further 0.5, 0.7, 0.8, 1 0.0 is preferred.
  • the upper limit of the ratio of the Zn 2+ content to the Ba 2+ content: cation ratio [Zn 2+ / Ba 2+ ] is Preferably it is 0.60, and further preferably in the order of 0.55 and 0.50. Further, the lower limit of the cation ratio [Zn 2+ / Ba 2+ ] is preferably 0.10, and more preferably in the order of 0.15, 0.20, and 0.25.
  • Gd 3+ , Y 3+ , La 3+ and Yb 3+ are all components that contribute to improving the weather resistance and increasing the refractive index of the glass. However, if these components are introduced excessively, the thermal stability and homogeneity of the glass may be deteriorated, and the low dispersibility will be significantly impaired. Therefore, in the optical glass of the present invention, the upper limit of the content of Gd 3+ is preferably 13%, and more preferably in the order of 10%, 7%, 5%, and 4%. Further, the lower limit of the content of Gd 3+ is preferably 0%, and more preferably in the order of 0.5%, 1.0%, and 2.0%.
  • the upper limit of the content of Y 3+ is preferably 10%, and more preferably 7.0%, 5.0%, 4.0%, and 3.0% in this order.
  • the lower limit of the content of Y 3+ is preferably 0%, and more preferably in the order of 0.5% and 1.0%.
  • the upper limit of the La 3+ content is preferably 10%, further 7.0%, 5.0%, 3.0%, preferably in the order of 2.0%.
  • the lower limit of the La 3+ content is preferably 0%, more preferably 0.05%.
  • the upper limit of the Yb 3+ content is preferably 5.0%, and more preferably 3.0%, 2.0%, 1.5% and 1.0% in this order.
  • the lower limit of the content of Yb 3+ is preferably 0%, more preferably 0.05%. Since Yb 3+ has an absorptivity in the near infrared region, it is preferably not introduced when using light rays in the near infrared region.
  • the rare earth elements such as Gd 3+ , Y 3+ , La 3+, and Yb 3+ are preferably introduced appropriately from the viewpoint of effectively increasing the refractive index. Therefore, the optical glass of the present invention contains any one or more selected from Gd 3+ , Y 3+ , La 3+ and Yb 3+ .
  • the thermal stability of the glass deteriorates and the low dispersibility tends to be remarkably impaired.
  • the upper limit of the total content Re2 [Gd 3+ + Y 3+ + La 3+ + Yb 3+ ] of Gd 3+ , Y 3+ , La 3+ and Yb 3+ is preferably 5.0%, Furthermore, it is preferable in the order of 4.5%, 4.0%, and 3.5%. Further, the lower limit of the total content Re2 is preferably 0.1%, and more preferably in the order of 0.2%, 0.4%, 1.0%, 1.5%, and 2.0%. Note that the thermal stability of the glass may be improved by introducing two or more rare earth elements rather than introducing a single rare earth element. For this reason, the optical glass of the present invention preferably contains any two or more rare earth elements selected from Gd 3+ , Y 3+ , La 3+ and Yb 3+ .
  • the optical glass according to the present invention has a P 5 with respect to the total content Re2 of rare earth elements from the viewpoint of ensuring the thermal stability of the glass and effectively increasing the refractive index while keeping the cation ratio ⁇ 2 within a predetermined range.
  • Ratio of total content of + , B 3+ and Al 3+ : Cation ratio ⁇ 2 [(P 5+ + B 3+ + Al 3+ ) / Re2] is set to 14.0 or more.
  • the minimum with preferable cation ratio (beta) 2 is 14.1, Furthermore, it is preferable in order of 14.2, 14.4, 14.6, 14.8, 15.0.
  • the upper limit of the cation ratio ⁇ 2 is preferably 120.0, and more preferably 90.0, 70.0, 50.0, 40.0, 30.0, 20.0 in this order.
  • the cation ratio ⁇ 2 and the cation ratio ⁇ 2 are closely related from the viewpoint of obtaining desired optical characteristics and improving the thermal stability of the glass. This will be described below.
  • the thermal stability of the glass is relatively small. Specifically, the thermal stability is improved by suppressing the total content Re2 of rare earth elements as the denominator of the cation ratio ⁇ 2 and adjusting the components so that the cation ratio ⁇ 2 is 14.0 or more.
  • the thermal stability of the glass is improved, but the refractive index decreases as the total content Re2 of rare earth elements decreases. Therefore, in the optical glass according to the present invention, the amount of Ba 2+ introduced is relatively increased so that the action of Ba 2+ is effectively expressed and the refractive index is improved. However, if the introduction amount of Ba 2+ with respect to the total content of Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ is too large, the thermal stability is adversely affected. Therefore, in the present invention, the cation ratio ⁇ 2 The cation ratio ⁇ 2 is 1.50 or less.
  • the glass composition so that the cation ratio ⁇ 2 and the cation ratio ⁇ 2 are within a predetermined range, desired optical characteristics can be obtained and the thermal stability of the glass can be improved.
  • Si 4+ is an effective component for improving chemical durability while maintaining low dispersibility.
  • the upper limit of the content of Si 4+ is preferably 3.0%, and further 2.0%, 1.5%, 1.0%, and 0.5%. It is preferable in order.
  • Si 4+ is a network component together with P 5+ , B 3+ , and Al 3+ , but Si 4+ is not necessarily introduced into the optical glass of the present invention.
  • Li + is a component that lowers the glass transition temperature and the yield point and is effective for lowering the dispersion.
  • coexistence of P 5+ , B 3+ and Li + is very effective for reducing the dispersion of the glass.
  • the upper limit of the content of Li + is preferably 26%, and further 23%, 20%, 17%, 15%, 10%, 8%, 5%, 3% Are preferred in this order.
  • the lower limit of the Li + content is preferably 0%, and more preferably smaller in the order of 0.1%, 1.0%, 1.5%, 2.0%, 2.5%. .
  • Both Na + and K + are optional components introduced to improve the devitrification resistance of the glass, lower the glass transition temperature, yield point, and liquidus temperature, and improve the meltability of the glass.
  • the introduction of appropriate amounts of Na + and K + improves the stability of the glass and leads to a decrease in liquidus temperature and transition temperature.
  • the upper limit of the content of Na + and K + is preferably 8.0%, respectively, and further in the order of 5.0%, 4.0%, and 3.0%. preferable. It is particularly preferable that Na + and K + are not substantially introduced.
  • the upper limit of the total content R 2 2 [Li + + Na + + K + ] of Li + , Na + and K + is preferably 26%, and further 23%, 20 %, 17%, 15%, 10%, 8%, 5% in this order.
  • the lower limit of the total content R 2 2 is preferably 0%, further 0.5%, 1.0%, 1.5%, 2.0%, than smaller in the order of 3.0% preferable.
  • the total content R 2 2 of Li + , Na + and K + is preferably 10.0% or less, and is 5.0% or less. More preferably, it is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably not substantially introducing them.
  • the upper limit of the ratio of the P 5+ content to the total content R 2 2 of the alkali metal component: cation ratio [P 5+ / R 2 2] is that the glass has both meltability and thermal stability. , 50, more preferably 40, 30, 25, 20, 15, 10 in this order.
  • the lower limit of the cation ratio [P 5+ / R 2 2] is preferably 1.0, and more preferably in the order of 1.2, 1.5, 1.8, and 2.0.
  • the optical glass of the present invention does not substantially contain Pb, As, Cd, U, Th, and Tl from the viewpoint of reducing the load on the environment.
  • the optical glass of the present invention can contain halogen, that is, F ⁇ , Cl ⁇ , Br ⁇ , and I ⁇ as optional components.
  • the content can be represented by the anion fraction of anions (for example, [F ⁇ / (O 2 ⁇ + F ⁇ )]).
  • the upper limit of the content of F ⁇ is preferably 7%, more preferably 5%, 3%, 2%, 1%, 0.5%, and 0.1% in this order.
  • the upper limit of the content of Cl ⁇ , Br ⁇ and I ⁇ is preferably 5%, respectively, and more preferably in the order of 3%, 2%, 1%, 0.5% and 0.1%. .
  • the upper limit of B 3+ in the glass is preferably 15% in order to suppress the volatilization of the glass, more preferably in the order of 10%, 5%, 3%, and 1%. Preferably it is not substantially contained. However, this does not apply when a small amount of halogen of 1% or less is added. In particular, in order to suppress the volatilization of components from the glass and improve the homogeneity of the glass, it is preferable that the halogen is not substantially contained.
  • the optical glass of the present invention can contain an easily reducing component composed of W 6+ , Ti 4+ , Bi 3+ and Nb 5+ as an optional component.
  • These easily reducing components are effective components for increasing the refractive index.
  • W 6+ , Ti 4+ , Bi 3+ and Nb 5+ significantly reduce the glass Abbe number ( ⁇ d). Therefore, the upper limit of the total content [W 6+ + Ti 4+ + Bi 3+ + Nb 5+ ] of the above easily reducing components is preferably 4.0%, and more preferably 3.0%, 2.0%, It is preferable in the order of 1.0% and 0.5%. In addition, it is particularly preferable not to substantially introduce the easily reducing component.
  • the optical glass of the present invention basically has P 5+ , B 3+ , Si 4+ , Al 3+ , Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2. It is preferably constituted by a component selected from + , Sr 2+ , Ba 2+ , Gd 3+ , Y 3+ , La 3+ and Yb 3+ .
  • Total content of these components is preferably 95% or more, more preferably 98% or more, more preferably 99% or more, and still more preferably 100%.
  • optical glass of this invention is fundamentally comprised by the said component, in the range which does not prevent the effect of this invention, it is also possible to introduce
  • substantially not containing can be taken as a guide when the content is less than 0.2%.
  • the components and additives that are not substantially contained are preferably not contained in the glass. Therefore, the content is preferably less than 0.1%, more preferably less than 0.08%, and more preferably. It is further preferably less than 05%, more preferably less than 0.01%, and even more preferably less than 0.005%.
  • the optical glass of the present invention is composed of the above components and the total amount is 100% by mass, even if a refining agent such as Sb 2 O 3 , SnO 2 , or CeO 2 is introduced in an external ratio within 4% by mass. Good.
  • the upper limit of the content of Sb 2 O 3 is preferably 4% by mass, and more preferably 3% by mass, 2% by mass, 1% by mass, 0.5% by mass, and 0.1% by mass in this order.
  • the lower limit of the content of Sb 2 O 3 is preferably 0%, and more preferably 0.01% by mass, 0.02% by mass, and 0.04% by mass in this order.
  • SnO 2 and CeO 2 may deteriorate the transmittance of the glass, so that introduction of 1% by mass or less is preferable, and it is particularly preferable not to introduce substantially.
  • the glass composition of the optical glass is mainly described in terms of cation%, but the analysis values obtained by performing quantitative analysis for each component by ICP-AES analysis or the like are as follows. Can be converted to a cation% display by a simple method.
  • the content of the cation element in the glass component composed of the cation and the anion may be displayed as a percentage of atomic%.
  • Such composition display can be converted into the cation% display of the present invention by, for example, the following method.
  • each cation content (atomic%) of the quantified glass component is divided by the specific atomic weight to obtain the molar percentage of each cation, and the ratio of the cation to be obtained to all the cations contained Is expressed as a percentage by cation.
  • the content (atomic%) of n cations is quantified as m 1 , m 2 ,..., M i , ..., m n, and the atomic weight of each cation is M 1
  • the cation content (cation%) of one component (m i , M i ) can be obtained by the following equation. [(M i / M i ) / [(m 1 / M 1 ) + (m 2 / M 2 ) + ... + (m i / M i ) + ...
  • an anion element may be quantified by quantitative analysis, it can be converted into the anion content rate (anion%) of an anion in the same manner as described above.
  • the glass component may be expressed on an oxide basis, and the content of the glass component may be displayed in mass%.
  • Such composition display can be converted into cation% display by the following method, for example.
  • a m O n An oxide composed of a cation A and oxygen is denoted as “A m O n ”.
  • m and n are integers determined stoichiometrically.
  • the characteristics (optical characteristics and thermal stability) of the optical glass according to the present embodiment are the same as those described in the first embodiment. Therefore, description is abbreviate
  • optical glass according to the present invention may be produced according to a known glass production method by blending raw materials so as to have the above-mentioned predetermined composition.
  • the optical glass according to the present invention is melted to form a plate-like glass material, and the plate-like glass material is subdivided into a predetermined volume to produce a glass material for press molding. Or the glass lump of a predetermined volume is shape
  • a glass material for precision press molding is produced by hot forming molten glass, and an optical element is produced by heating and precision press molding the glass material.
  • a molten glass is directly molded (direct press molding) to produce a glass molded body, and this molded body is polished to produce an optical element.
  • the optical functional surface of the manufactured optical element may be coated with an antireflection film, a total reflection film or the like according to the purpose of use.
  • optical elements examples include spherical lenses, aspherical lenses, microlenses, various lenses such as a lens array, prisms, diffraction gratings, and the like.
  • Tables 1 to 5 show optical glasses (samples 1A to 50A) according to examples of the first embodiment of the present invention, and Table 6 shows optical glasses (sample ref1A) according to comparative examples of the present invention.
  • Samples 2A and 19A shown in Table 6 are the same as the samples shown in Tables 1 and 2, and are shown together for comparison between Examples and Comparative Examples.
  • optical glasses were produced by the following procedure and subjected to various evaluations. The results are shown in Tables 1-6.
  • the optical glasses (samples 1A to 50A) according to the examples of the present invention have a refractive index nd of 1.625 to 1.680 and an Abbe number ⁇ d of 58 to 65.
  • the glass is in a desired range ([P 2 O 5 / B 2 O 3 ] is more than 1 to 15.0, mass ratio ⁇ 1 is 3.0 or less, and mass ratio ⁇ 1 is 4.80 or more).
  • the average value of the temperature difference (Tc ⁇ Tg) between the temperature Tg and the temperature Tc is about 185 ° C., and the temperature Tp of each sample is higher than the crystallization peak temperature Tc. (That is, Tp ⁇ Tc), and it was confirmed that the solidified glass did not generate internal crystals and had high thermal stability.
  • Sample 19A in Tables 2 and 6 has the smallest temperature difference (Tc ⁇ Tg) among Samples 1A to 50A, but even in this case, no internal crystals are generated, and thermal It was confirmed that the stability was high.
  • sample 2A in Tables 1 and 6 is a sample very close to the sample ref1A (Comparative Example) in Table 6 in terms of refractive index and Abbe number, the temperature difference (Tc ⁇ Tg) is low. It was 178 ° C., no internal crystal was generated, and it was confirmed that the thermal stability was high as in other samples.
  • the sample ref1A in Table 6 which is an optical glass according to the comparative example of the present invention has a temperature difference (Tc ⁇ Tg) of 139 ° C., which is much higher than the crystallization peak temperature Tc (667 ° C.). Softened at a temperature Tp (710 ° C.). That is, in this sample ref1A, the temperature Tp and the temperature Tc have a relationship of Tp> Tc. And it was confirmed that the crystal
  • the optical glass according to the example of the present invention has a sufficiently large temperature difference (Tc ⁇ Tg). For this reason, glass can be reliably softened at a temperature Tp lower than the temperature Tc. Therefore, the optical glass of the present invention can be applied to reheat press molding where precise temperature control is difficult.
  • the optical glass according to the comparative example (sample ref1A in Table 6) has a relatively small temperature difference (Tc ⁇ Tg) and the softening temperature Tp is higher than the crystallization peak temperature Tc.
  • Tc ⁇ Tg the softening temperature
  • Tp the softening temperature
  • the optical glass according to this example (Sample 2A in Table 1 and Table 6) has no surface alteration and is transparent even after being treated for a long time under high temperature and high humidity. It was confirmed to be excellent. The haze value was 0.1%.
  • the optical glass according to the present invention has excellent weather resistance.
  • Tables 7 to 10 show optical glasses (samples 1B to 47B) according to examples of the second embodiment of the present invention
  • Table 11 shows optical glasses (sample ref1B) according to comparative examples of the present invention.
  • Samples 16B and 25B shown in Table 11 are the same as the samples shown in Table 8, and are shown together for comparison between Examples and Comparative Examples.
  • the optical glasses (samples 1B to 47B) according to the examples of the present invention have a refractive index nd of 1.625 to 1.680 and an Abbe number ⁇ d of 58 to 65.
  • the cation ratio [P 5+ / B 3+ ] the cation ratio ⁇ 2 [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] and the cation ratio ⁇ 2 [(P 5+ + B 3+ + Al 3+ ) / Re2] within a desired range ([P 5+ / B 3+ ] is more than 1 to 10.0, cation ratio ⁇ 2 is 1.50 or less, and cation ratio ⁇ 2 is 14.0 or more) It is in the glass.
  • the average value of the temperature difference (Tc ⁇ Tg) between the temperature Tg and the temperature Tc is about 185 ° C., and the temperature Tp of each sample is higher than the crystallization peak temperature Tc. (That is, Tp ⁇ Tc), and it was confirmed that the solidified glass did not generate internal crystals and had high thermal stability.
  • Sample 16B in Table 8 and Table 11 has the smallest temperature difference (Tc ⁇ Tg) among Samples 1B to 47B, but even in this case, no internal crystals are generated, and thermal It was confirmed that the stability was high.
  • the sample 25B in Table 8 and Table 11 has a temperature difference (Tc ⁇ Tg) although it is very close to the sample ref1B (Comparative Example) in Table 11 in terms of refractive index and Abbe number. It was 178 ° C., no internal crystal was generated, and it was confirmed that the thermal stability was high as in other samples.
  • the sample ref1B in Table 11 which is an optical glass according to the comparative example of the present invention has a temperature difference (Tc ⁇ Tg) of 139 ° C., which is much higher than the crystallization peak temperature Tc (667 ° C.). Softened at a temperature Tp (710 ° C.). That is, in this sample ref1B, the temperature Tp and the temperature Tc have a relationship of Tp> Tc. And it was confirmed that the crystal
  • the optical glass according to the example of the present invention has a sufficiently large temperature difference (Tc ⁇ Tg). For this reason, glass can be reliably softened at a temperature Tp lower than the temperature Tc. Therefore, the optical glass of the present invention can be applied to reheat press molding where precise temperature control is difficult.
  • the optical glass according to the comparative example (sample ref1B in Table 11) has a relatively small temperature difference (Tc ⁇ Tg) and the softening temperature Tp is higher than the crystallization peak temperature Tc.
  • Tc ⁇ Tg temperature difference
  • Tp crystallization peak temperature
  • the optical glass according to this example (sample 25B in Table 8 and Table 11) has no surface alteration and is transparent after being treated for a long time under high temperature and high humidity. It was confirmed to be excellent. The haze value was 0.1%.
  • the optical glass according to the present invention has excellent weather resistance.
  • Example 2 An optical lens was manufactured using the optical glass (samples 1A to 50A and samples 1B to 47B) manufactured in Example 1A and Example 1B. Specifically, each optical glass of Example 1A and Example 1B was processed into a predetermined shape to produce an optical glass material. Next, the optical glass material is heated and softened, press-molded into a shape that approximates the shape of the target lens, and after press molding, the glass is annealed (annealed) and finished into an optical lens through processing steps including a polishing step. It was. In addition, what is necessary is just to apply a well-known method suitably for the press molding method, annealing method, and processing process of glass.
  • optical lens thus obtained can be obtained as a good optical lens without crystallization of the glass even when heated at a relatively high temperature during reheat press molding.
  • Comparative Example 2 In the same manner as in Example 2, an attempt was made to produce an optical lens using the optical glass (sample ref1A in Table 6 and sample ref1B in Table 11) produced in Comparative Example 1A and Comparative Example B.
  • the thermal stability was low, crystallization occurred due to heating during reheat press molding, and internal crystals were generated in the obtained optical lens.
  • the optical glass of the first embodiment has a total content of P 2 O 5 , B 2 O 3 and Al 2 O 3 [P 2 O 5 + B 2 O 3 + Al 2 O 3 ] is 55% by mass or less glass, BaO, Any one or more selected from MgO, CaO, ZnO and SrO; One or more selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 , B content of the mass ratio of P 2 O 5 to the content of 2 O 3 [P 2 O 5 / B 2 O 3] is 1 super-15.0, The mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 3.0 or less, Mass ratio ⁇ 1 of total content of P 2 O 5 , B 2 O 3 and Al 2
  • the optical glass of the first embodiment described above has a total content of Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 [Gd 2 O 3 + Y 2 O 3 + La 2 O 3. + Yb 2 O 3 ] is 0.5 to 11% by mass.
  • the optical glass of the first embodiment preferably has a P 2 O 5 content of 25 to 43% by mass.
  • the optical glass of the first embodiment preferably has a BaO content of 15 to 45% by mass.
  • the mass ratio [ZnO / BaO] of the ZnO content to the BaO content is preferably 0.10 to 0.33.
  • the Li 2 O content is preferably 0 to 2.0% by mass.
  • the optical element is made of the optical glass of the first embodiment.
  • the optical glass material is the optical glass of the first embodiment.
  • the optical glass of the first embodiment has a total content of P 2 O 5 , B 2 O 3 and Al 2 O 3 [P 2 O 5 + B 2 O 3 + Al 2. O 3 ] is 55% by mass or less of glass, BaO, Any one or more selected from MgO, CaO, ZnO and SrO; One or more selected from Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3 , The content of ZnO is 15% by mass or less, The mass ratio ⁇ 1 [BaO / (MgO + CaO + ZnO + SrO)] of the content of BaO to the total content of MgO, CaO, ZnO and SrO is 3.0 or less, Mass ratio ⁇ 1 of total content of P 2 O 5 , B 2 O 3 and Al 2 O 3 with respect to the total content of Gd 2 O 3 , Y 2 O 3 , La 2 O 3 and Yb 2 O 3
  • the optical glass of the second embodiment has a total content of P 5+ , B 3+ and Al 3+ [P 5+ + B 3+ + Al 3+ ] is 65 cation% or less glass, Ba 2+ Any one or more selected from Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ ; Any one or more selected from Gd 3+ , Y 3+ , La 3+ and Yb 3+ ,
  • the cation ratio [P 5+ / B 3+ ] of the P 5+ content to the B 3+ content is more than 1 to 10.0, Cation ratio ⁇ 2 of Ba 2+ content to the total content of Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] Is 1.50 or less, Cation ratio ⁇ 2 of the total content of P 5+ , B 3+
  • the total content [Gd 3+ + Y 3+ + La 3+ + Yb 3+ ] of Gd 3+ , Y 3+ , La 3+ and Yb 3+ is 0. 1 to 5.0 cation% is satisfied.
  • the total content [P 5+ + B 3+ + Al 3+ ] of P 5+ , B 3+ and Al 3+ is 49 to 65 cation%. preferable.
  • the optical glass of the second embodiment preferably has a P 5+ content of 20 to 50 cation%.
  • the Ba 2+ content is preferably 5 to 30 cation%.
  • the cation ratio [Zn 2+ / Ba 2+ ] of the Zn 2+ content to the Ba 2+ content is 0.10 to 0.60. Is preferred.
  • the cation ratio ⁇ 2 is preferably 14.1 to 120.0.
  • the optical glass of the second embodiment described above it is preferable that the content of Li + is 0 to 10.0 cationic%.
  • the optical element is made of the optical glass of the second embodiment.
  • the optical glass material is the optical glass of the second embodiment.
  • the optical glass of the second embodiment has a total content of P 5+ , B 3+ and Al 3+ [P 5+ + B 3+ + Al 3+ ] of 65 cations. % Or less glass, Ba 2+ Any one or more selected from Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ ; Any one or more selected from Gd 3+ , Y 3+ , La 3+ and Yb 3+ , Zn 2+ content is 15 cation% or less, Cation ratio ⁇ 2 of Ba 2+ content to the total content of Mg 2+ , Ca 2+ , Zn 2+ and Sr 2+ [Ba 2+ / (Mg 2+ + Ca 2+ + Zn 2+ + Sr 2+ )] Is 1.50 or less, Cation ratio ⁇ 2 of the total content of P 5+ , B 3+ and Al 3+ to the total content of Gd 3+ , Y 3+ , La 3+

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