(19)
(11)EP 3 578 524 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
11.12.2019 Bulletin 2019/50

(21)Application number: 18748622.0

(22)Date of filing:  22.01.2018
(51)International Patent Classification (IPC): 
C03C 3/068(2006.01)
G02B 1/00(2006.01)
C03C 3/062(2006.01)
(86)International application number:
PCT/JP2018/001748
(87)International publication number:
WO 2018/142980 (09.08.2018 Gazette  2018/32)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
MA MD TN

(30)Priority: 01.02.2017 JP 2017016998
19.06.2017 JP 2017119838
30.11.2017 JP 2017230027

(71)Applicant: Ohara Inc.
Chuo-ku Sagamihara-shi Kanagawa 252-5286 (JP)

(72)Inventors:
  • OGINO Michiko
    Sagamihara-shi Kanagawa 252-5286 (JP)
  • MUKOUGAWA Katsuyuki
    Sagamihara-shi Kanagawa 252-5286 (JP)

(74)Representative: Zumstein, Angela 
Maiwald Patentanwalts- und Rechtsanwaltsgesellschaft mbH Elisenhof Elisenstraße 3
80335 München
80335 München (DE)

  


(54)OPTICAL GLASS, PREFORM AND OPTICAL ELEMENT


(57) The purpose of the present invention is to obtain, at a lower cost: an optical glass that has a low temperature coefficient regarding the relative refractive index and that can contribute to correcting the effect of temperature change on image-forming characteristics; and a preform and an optical element that use such an optical glass. This optical glass contains, in mass%, 1.0-27.0% of a SiO2 component, a total of 5.0-34.0% of a Ln2O3 component (wherein, Ln represents at least one selected from the group consisting of La, Gd, Y, and Yb), and more than 30.0% but not more than 65.0% of a BaO component, wherein the contained amount of a B2O3 component is at most 25.0%, and the temperature coefficient (40-60°C) of the relative refractive index (589.29 nm) falls within the range between +3.0×10-6 and -10.0×10-6 (°C-1).




Description

TECHNICAL FIELD



[0001] The present invention relates to an optical glass, a preform, and an optical element.

BACKGROUND ART



[0002] In recent years, there has been an increase in the utilization in higher temperature environments of optical elements built into optical devices for vehicles such as vehicle cameras or the like, or optical elements built into optical devices which generate much heat, such as projectors, copy machines, laser printers, broadcast devices and the like. In such high temperature environments, the temperature during use of the optical elements constituting an optical system may greatly fluctuate, and these temperatures may often reach 100°C or more. At such times, the adverse effect on the imaging characteristics and the like of the optical system due to temperature fluctuations becomes so large that it cannot be ignored, and as a result there is demand for constituting optical systems where effect on the imaging characteristics and the like due to temperature fluctuations does not readily occur.

[0003] When constituting an optical system wherein temperature fluctuations do not readily affect the imaging characteristics and the like, the joint use of an optical element constituted from a glass with a negative temperature coefficient of the relative refractive index, whereby the refractive index becomes lower when the temperature increases, and an optical element constituted from a glass with a positive temperature coefficient of the relative refractive index, whereby the refractive index becomes higher when the temperature increases, is preferable from the point of correcting for the effect on the imaging characteristics and the like due to temperature fluctuations.

[0004] As glasses developed by focusing on the temperature coefficient of the relative refractive index, for example, glass compositions such as those represented by Patent Documents 1 to 3 are known.

Patent Document 1: Japanese Unexamined Patent Application, Publication No. 2013-100213

Patent Document 2: Japanese Unexamined Patent Application, Publication No. 2007-106611

Patent Document 3: Japanese Unexamined Patent Application, Publication No. 2008-232874


DISCLOSURE OF THE INVENTION


Problems to be Solved by the Invention



[0005] Among these, the glass disclosed in Patent Document 1 is a so-called fluorophosphate glass, wherein, when melting the glass raw materials, special production equipment is required because gasses containing fluorides are generated. Further, the removal of fluorides included in the gasses incurs costs, and therefore, the production cost of the glass disclosed in Patent Document 1 is high.

[0006] Further, the glasses disclosed in Patent Documents 2 and 3 are glasses which include many components brining about a high refractive index, and have the objective of increasing the temperature coefficient of the relative refractive index. On the other hand, in a glass including many components bringing about a high refractive index, a glass having a low temperature coefficient of the relative refractive index is not obtained. However, from the viewpoint of contributing to correcting for the effect on the imaging characteristics due to temperature fluctuations, a glass with a negative temperature coefficient of the relative refractive index, or a glass having a small absolute value of the temperature coefficient of the relative refractive index, is also desired.

[0007] In addition, it is desirable to make the raw material cost of the optical glass as low as possible. However, the glasses disclosed in Patent Documents 2 and 3 are ones including many expensive components among the components bringing about a high refractive index, and it is difficult to say that such a requirement is sufficiently addressed.

[0008] The present invention was made in consideration of the above described problems, and the objective thereof is to provide an optical glass which has the optical characteristics of a low value of the temperature coefficient of the relative refractive index, and can contribute to correcting for the effect on imaging characteristics due to temperature fluctuations, and a preform and optical element using the same.

Means for Solving the Problems



[0009] The present inventors, as a result of repeated diligent research in order to solve the above described problems, discovered that comprising a large amount of a BaO component can provide a low cost glass with a low value of the temperature coefficient of the relative refractive index, and further discovered that by comprising an SiO2 component and an Ln2O3 component, and adjusting the content of each component, a glass which does not require special production equipment can be obtained, and thereby completed the present invention. Specifically, the present invention provides the following.
  1. (1) An optical glass comprising, in mass%,
    an SiO2 component of 1.0% to 27.0%,
    an Ln2O3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) of 5.0% to 34.0%,
    a BaO component of more than 30.0% to 65.0%,
    and wherein
    a content of a B2O3 component is 25.0% or less, and
    a temperature coefficient (40 to 60°C) of a relative refractive index (589.29 nm), is within the range of +3.0 × 10-6 to - 10.0 × 10-6 (°C-1).
  2. (2) An optical glass according to (1), wherein, in mass%, a La2O3 component is 0 to 30.0%,
    a Gd2O3 component is 0 to 25.0%,
    a Y2O3 component is 0 to 25.0%,
    a Yb2O3 component is 0 to 10.0%
    a K2O component is 0 to 12.0%
    a ZnO component is 0 to less than 5.0%,
    a ZrO2 component is 0 to 15.0%,
    an Nb2O5 component is 0 to 25.0%,
    a WO3 component is 0 to 10.0%,
    a TiO2 component is 0 to 25.0%,
    a Ta2O5 component is 0 to 10.0%,
    an MgO component is 0 to 5.0%,
    a CaO component is 0 to 12.0%,
    an SrO component is 0 to 12.0%,
    a Li2O component is 0 to 5.0%,
    an Na2O component is 0 to 12.0%,
    a P2O5 component is 0 to 10.0%,
    a GeO2 component is 0 to 10.0%,
    an Al2O3 component is 0 to 12.0%,
    a Ga2O3 component is 0 to 10.0%,
    a Bi2O3 component is 0 to 10.0%,
    a TeO2 component is 0 to 10.0%,
    a SnO2 component is 0 to 3.0%,
    a Sb2O3 component is 0 to 1.0%
    and
    wherein a content as F of a fluoride partially or completely substituting an oxide of one or two or more of each of the above elements is 0 to 10.0 mass%.
  3. (3) An optical glass according to (1) or (2), wherein a mass sum (SiO2 + B2O3) is 7.0% to less than 37.0%.
  4. (4) An optical glass according to any one of (1) to (3), wherein a mass sum (BaO + K2O) is more than 30.0% to less than 62.0%.
  5. (5) An optical glass according to any one of (1) to (4), wherein a mass ratio (BaO + K2O)/(SiO2 + B2O3 + ZnO) is more than 1.00 to 5.00.
  6. (6) An optical glass according to any one of (1) to (5), wherein a mass sum TiO2 + ZrO2 + WO3 + Nb2O5 + Ta2O5 is 0.5% to 30.0% .
  7. (7) An optical glass according to any one of (1) to (6), wherein a mass sum ZrO2 + Ta2O5 is 15.0% or less.
  8. (8) An optical glass according to any one of (1) to (7), wherein a sum of a content of an RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn), in mass%, is more than 30.0% to 65.0%.
  9. (9) An optical glass according to any one of (1) to (8), wherein a sum of a content of an Rn2O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K), in mass%, is 12.0% or less.
  10. (10) An optical glass according to any one of (1) to (9), having an refractive index (nd) of 1.70 or more, and having an Abbe number (νd) of 20 to 50.
  11. (11) A preform material consisting of an optical glass according to any one of (1) to (10).
  12. (12) An optical element consisting of an optical glass according to any one of (1) to (10).
  13. (13) An optical device provided with the optical element according to (12).

Effects of the Invention



[0010] According to the present invention, it is possible to obtain at a lower cost an optical glass which has a low value of the temperature coefficient of the relative refractive index, and can contribute to correcting the effect on the imaging characteristics due to temperature fluctuations, and a preform and an optical element using the same.

BRIEF DESCRIPTION OF THE DRAWINGS



[0011] Fig. 1 is a figure showing the relationship between the refractive index (nd) and Abbe number (νd) for an optical glass of an embodiment of the present invention.

PREFERRED MODE FOR CARRYING OUT THE INVENTION



[0012] The optical glass of the present invention comprises, in mass%, an SiO2 component of 1.0% to 27.0%, an Ln2O3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) of 5.0% to 34.0%, a BaO component of more than 30.0% to 65.0%, and wherein a content of a B2O3 component is 25.0% or less, and a temperature coefficient (40 to 60°C) of a relative refractive index (589.29 nm) is within the range of +3.0 × 10-6 to -10.0 × 10-6 (°C-1). By comprising a large amount of the BaO component, it is possible to obtain a low cost glass with a low value of the temperature coefficient of the relative refractive index. Further, by comprising an SiO2 component and an Ln2O3 component, and adjusting the contents of each component, it is possible to obtain a glass which does not require special production equipment. Therefore, the temperature coefficient of the relative refractive index takes a low value, and an optical glass which can contribute to correcting the effect on the imaging characteristics due to temperature fluctuations, and a preform and an optical element using the same, can be obtained at lower cost.

[0013] Below, examples of the optical glass of the present invention are explained in detail. The present invention is not in any way limited by the examples below, and can be practiced with the addition of suitable modifications, within the scope of the objective of the present invention. Further, where the explanations overlap, the explanations may be suitably abridged, but this does not limit the intent of the invention.

[Glass Components]



[0014] The compositional range of each component constituting the optical glass of the present invention is explained below. In the present specification, the contents of each component, unless particularly noted, are all shown as mass% with respect to the total mass of an oxide converted composition. Herein, "oxide converted composition" is the composition shown wherein each component comprised in the glass, with a total mass number of the corresponding generated oxides taken as 100 mass%, when the oxides, complex salts, metal fluorides and the like used as raw materials of the glass constituent components of the present invention are all decomposed and converted to oxides when melted.

<Concerning the Required Components, Optional Components>



[0015] The SiO2 component is a required component as a glass-forming oxide. In particular, by comprising 1.0% or more of the SiO2 component, the chemical resistance, in particular the water resistance is increased, the viscosity of the molten glass is increased, and coloration of the glass can be reduced. Further, the stability of the glass is increased, and a glass which tolerates mass production can be readily obtained. Accordingly, the content of the SiO2 component is preferably 1.0% or more, even more preferably 3.0% or more, even more preferably 5.0% or more, even more preferably more than 7.0%, and even more preferably more than 9.0%. On the other hand, by making the content of the SiO2 component 27.0% or less, the temperature coefficient of the relative refractive index can be made small, an increase in the glass transition point can be suppressed, and further, a reduction in the refractive index can be suppressed. Accordingly, the content of the SiO2 component is preferably 27.0% or less, more preferably 25.0% or less, even more preferably 20.0% or less, even more preferably less than 17.0%, even more preferably less than 14.0%, and even more preferably less than 12.0%.

[0016] The sum (mass sum) of the content of the rare earth component, namely the Ln2O3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) is preferably 5.0% or more. In this way, is it possible to increase the refractive index of the glass, and to readily obtain a glass having the desired refractive index and Abbe number. Further, the chemical resistance, in particular the water resistance of the glass, can be increased. Accordingly, the mass sum of the Ln2O3 component is preferably 5.0% or more, more preferably more than 8.0%, even more preferably more than 10.0%, even more preferably more than 13.0%, even more preferably 16.8% or more. On the other hand, by making this sum 34.0% or less, because the liquidus temperature of the glass is lowered, devitrification of the glass can be reduced. Further, it is possible to suppress increases in the raw materials cost of the glass, and to suppress greater than necessary increases of the Abbe number. Accordingly, the mass sum of the Ln2O3 component is preferably 34.0% or less, more preferably less than 30.0%, even more preferably less than 28.0%, even more preferably less than 25.0%, and even more preferably less than 22.0%.

[0017] The BaO component is a required component which can increase the fusibility of the glass raw material, reduce the devitrification of the glass, increase the refractive index, and can make the temperature coefficient of the relative refractive index small. Further, it is a component which has a low raw material cost among the components which bring about a high refractive index, and is readily melted. Accordingly, the content of the BaO component is preferably more than 30.0%, more preferably more than 33.0%, even more preferably more than 35.0%, even more preferably more than 38.0%, even more preferably more than 40.0%, and even more preferably more than 45.0%. On the other hand, by making the content of the BaO component 65.0% or less, reduction of the refractive index due to excessive content, or reduction of the chemical resistance (water resistance), and devitrification can be reduced. Accordingly, the content of the BaO component is preferably 65.0% or less, more preferably less than 62.0%, even more preferably less than 60.0%, even more preferably less than 58.0%, even more preferably less than 55.0%, and even more preferably less than 53.0%.

[0018] The B2O3 component is an optionally used component as a glass-forming oxide. Accordingly, the content of the B2O3 component may be preferably more than 0%, more preferably 1.0% or more, even more preferably more than 3.0%, even more preferably more than 5.0%, and even more preferably more than 8.0%. On the other hand, by making the content of the B2O3 component 25.0% or less, an even larger refractive index can be readily obtained, the temperature coefficient of the relative refractive index can be made small, and further, deterioration of the chemical resistance can be suppressed. Accordingly, the content of the B2O3 component is preferably 25.0% or less, more preferably 24.0% or less, even more preferably 23.0% or less, even more preferably 22.0% or less, even more preferably less than 20.0%, even more preferably less than 18.0%, and even more preferably less than 15.0%.

[0019] The La2O3 component is an optional component which, if having a content of more than 0%, can increase the stability of the glass, and can increase the refractive index of the glass. Accordingly, the content of the La2O3 component is preferably more than 0%, more preferably more than 1.0%, even more preferably more than 4.0%, even more preferably more than 7.0%, even more preferably more than 10.0%, and even more preferably more than 13.0%. On the other hand, by making the content of the La2O3 component 30.0% or less, devitrification can be reduced by increasing the stability of the glass, and it is possible to suppress an increase in the Abbe number. Further, the fusibility of the glass raw materials can be increased. Accordingly, the content of the La2O3 component is preferably 30.0% or less, more preferably less than 25.0%, even more preferably less than 23.0%, and even more preferably less than 20.0%.

[0020] The Gd2O3 component and Yb2O3 component are optional components which, if having a content of more than 0%, can increase the refractive index of the glass. On the other hand, the Gd2O3 component and Yb2O3 component are costly raw materials even among rare earth elements, and if the content thereof is high, the production costs will increase. Further, by reducing the Gd2O3 component and Yb2O3 component, an increase of the Abbe number of the glass can be suppressed. Accordingly, the content of the Gd2O3 component may be preferably 25.0% or less, more preferably 20.0% or less, even more preferably 15.0% or less, even more preferably 10.0% or less, even more preferably less than 9.0%, even more preferably less than 5.0%, and even more preferably less than 3.0%. Further, the content of the Yb2O3 component may be preferably 10.0% or less, more preferably less than 6.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0021] The Y2O3 component is an optional component which, if having a content of more than 0%, can suppress raw material costs of the glass compared to other rare earth elements while maintaining a high refractive index of the glass, and can reduce the specific gravity of the glass. Accordingly, the content of the Y2O3 component may be preferably more than 0%, more preferably more than 1.0%, and even more preferably more than 2.0%. On the other hand, by making the content of the Y2O3 component 25.0% or less, it is possible to suppress a reduction of the refractive index of the glass, suppress an increase of the Abbe number of the glass, and further increase the stability of the glass. Further, degradation of the fusibility of the glass raw materials can be suppressed. Accordingly, the content of the Y2O3 component may be preferably 25.0% or less, more preferably 20.0% or less, even more preferably less than 15.0%, and even more preferably less than 12.0%. Further, the content of the Y2O3 component may be less than 10.0%, and may be less than 5.0%.

[0022] The ZnO component is an optional component which, if having a content of more than 0%, can increase the fusibility of the raw materials, can promote degassing from the molten glass, and further, can increase the stability of the glass. Further, it is a component which can reduce the glass transition point and further improve the chemical resistance. On the other hand, by making the content of the ZnO component less than 5.0%, the temperature coefficient of the relative refractive index can be made small, expansion due to heating can be reduced, lowering of the refractive index can be suppressed, and further, devitrification due to excessive lowering of the viscosity can be reduced. Accordingly, the content of the ZnO component may be preferably less than 5.0%, more preferably less than 4.0%, even more preferably less than 2.0%, even more preferably less than 1.0%, and even more preferably less than 0.5%. Further, the ZnO component may also not be contained.

[0023] The ZrO2 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, and further can reduce the devitrification. Accordingly, the content of the ZrO2 component may be preferably more than 0%, more preferably more than 0.5%, and even more preferably more than 1.0%. On the other hand, by making the content of the ZrO2 component 15.0% or less, the temperature coefficient of the relative refractive index can be made small, and devitrification due to excessive content of the ZrO2 component can be reduced. Accordingly, the content of the ZrO2 component may be preferably 15.0% or less, more preferably 13.0% or less, even more preferably 10.0% or less, even more preferably less than 7.0%, even more preferably less than 4.0%, and even more preferably less than 2.0%.

[0024] The Nb2O5 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, can lower the Abbe number, and further can increase the devitrification resistance of the glass by lowering the liquidus temperature of the glass. Accordingly, the content of the Nb2O5 component may be preferably more than 0%, more preferably more than 2.0%, and even more preferably more than 4.0%. On the other hand, by making the content of the Nb2O5 component 25.0% or less, the raw materials cost of the glass can be reduced, the temperature coefficient of the relative refractive index can be made small, devitrification due to excessive content of the Nb2O5 component can be reduced, and further, a reduction of the transmittance with respect to visible light (in particular wavelengths of 500 nm or less) of the glass can be suppressed. Accordingly, the content of the Nb2O5 component may be preferably 25.0% or less, more preferably 20.0% or less, even more preferably 15.0% or less, even more preferably 13.0% or less, even more preferably 10.0% or less, even more preferably less than 6.0%, even more preferably less than 4.0%, and even more preferably less than 2.0%.

[0025] The WO3 component is an optional component which, if having a content of more than 0%, can increase the refractive index, can lower the Abbe number, and reduce the glass transition point, while reducing coloration of the glass by other components which bring about a high refractive index, and further can reduce devitrification. On the other hand, by making the content of the WO3 component 10.0% or less, the temperature coefficient of the relative refractive index can be made small, and further the material costs can be suppressed. Further, the coloration of the glass due to the WO3 component can be reduced and the visible light transmittance can be increased. Accordingly, the content of the WO3 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 1.5%, and even more preferably less than 1.0%.

[0026] The TiO2 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, lower the Abbe number, readily provide a stable glass, and further can reduce the raw material costs. Accordingly, the content of the TiO2 component may be preferably more than 0%, more preferably more than 1.0%, even more preferably more than 3.0%, even more preferably more than 5.0%, even more preferably more than 8.0%, and even more preferably 10.0% or more. On the other hand, by making the content of the TiO2 component 25.0% or less, the temperature coefficient of the relative refractive index can be made small, devitrification due to excessive content of the TiO2 component can be reduced, and a reduction of the transmittance with respect to visible light (in particular wavelengths of 500 nm or less) of the glass can be suppressed. Accordingly, the content of the TiO2 component may be preferably 25.0% or less, more preferably less than 20.0%, even more preferably less than 17.0%, and even more preferably less than 15.0%.

[0027] The Ta2O5 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, and further, can increase the devitrification resistance. On the other hand, by making the content of the Ta2O5 component 10.0% or less, the raw material cost of the optical glass can be reduced, and further, the melting temperature of the raw materials can be lowered, and the energy required to melt the raw materials can be reduced, whereby the production cost of the optical glass can be reduced. Accordingly, the content of the Ta2O5 component may be preferably 10.0% or less, more preferably less than 7.0%, even more preferably less than 5.0%, even more preferably less than 2.0%, and even more preferably less than 1.0%. In particular, from the viewpoint of reducing material costs, it is most preferable that the Ta2O5 component is not comprised.

[0028] The MgO component, CaO component, and SrO component are optional components, and when having a content of more than 0%, the refractive index and fusibility and devitrification resistance of the glass can be adjusted. On the other hand, by making the content of the MgO component 5.0% or less, or the content of the CaO component or the content of the SrO component 12.0% or less, it is possible to suppress reduction of the refractive index, and further it is possible to reduce devitrification due to excessive contents of these components. Accordingly, the content of the MgO component is preferably 5.0% or less, more preferably less than 3.0%, and even more preferably less than 1.0%. Further, the content of the CaO component and the content of the SrO component are preferably respectively 12.0% or less, more preferably 10.0% or less, even more preferably less than 6.5%, even more preferably less than 4.0%, and even more preferably less than 2.0%.

[0029] The Li2O component, Na2O component, and K2O component are optional components which, if having a content of more than 0%, can improve the fusibility of the glass, and can lower the glass transition point. In particular, if the K2O component has a content of more than 0%, the temperature coefficient of the relative refractive index can be made smaller. On the other hand, by reducing the content of the Li2O component, Na2O component, and K2O component, the refractive index of the glass is not readily reduced, and further it is possible to reduce the devitrification of the glass. Further, by reducing the content of the Li2O component in particular, the viscosity of the glass can be increased, and the striation of the glass can be reduced. Further, by reducing the content of the K2O component, the chemical resistance of the glass can be increased. Accordingly, the content of the Li2O component may be preferably 5.0% or less, more preferably less than 3.0%, even more preferably 1.0% or less, and even more preferably less than 0.3%. Further, the content of the Na2O component may be preferably 12.0% or less, more preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%. Further, the content of the K2O component may be preferably 12.0% or less, more preferably less than 10.0%, even more preferably less than 8.0%, even more preferably less than 5.0%, and even more preferably 3.0% or less.

[0030] The P2O5 component is an optional component which, if having a content of more than 0%, can reduce the liquidus temperature of the glass and increase the devitrification resistance. On the other hand, by making the content of the P2O5 component 10.0% or less, a reduction in the chemical resistance of the glass, in particular the water resistance, can be suppressed. Accordingly, the content of the P2O5 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, even more preferably less than 1.0%, and the P2O5 component may not be included.

[0031] The GeO2 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, and further, can improve the devitrification resistance. However, GeO2 has a high raw material cost, and if the content thereof is high, the production costs increase. Accordingly, the content of the GeO2 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0032] The Al2O3 component and the Ga2O3 component are optional components which, if having a content of more than 0%, can improve the devitrification resistance of the molten glass. On the other hand, by making the content of the Al2O3 component 12.0% or less, or the content of the Ga2O3 component 10.0% or less, the liquidus temperature of the glass can be reduced, and the devitrification resistance can be increased. Accordingly, the content of the Al2O3 component may be preferably 12.0% or less, more preferably 10.0% or less, even more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%. Further, the content of the Ga2O3 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0033] The Bi2O3 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, can reduce the Abbe number, and further, can lower the glass transition point. On the other hand, by making the content of the Bi2O3 component 10.0% or less, the liquidus temperature of the glass can be lowered, and the devitrification resistance can be increased. Accordingly, the content of the Bi2O3 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0034] The TeO2 component is an optional component which, if having a content of more than 0%, can increase the refractive index of the glass, and further, can lower the glass transition point. On the other hand, the TeO2 component has the problem that it may alloy with the platinum when melting the glass raw materials in a platinum crucible or a melt tank which has components which contact the molten glass formed of platinum. Accordingly, the content of the TeO2 component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0035] The SnO2 component is an optional component which, if having a content of more than 0%, can clarify and decrease the oxides of the molten glass, and further, can increase the visible light transmittance of the glass. On the other hand, by making the content of the SnO2 component 3.0% or less, coloration of the glass due to reduction of the molten glass, or devitrification of the glass can be reduced. Further, because alloying between the SnO2 component and the melting equipment (in particular precious metals such as Pt and the like) can be reduced, it is possible to obtain longer lifetime of the melting equipment. Accordingly, the content of the SnO2 component is preferably 3.0% or less, more preferably less than 1.0%, even more preferably less than 0.5%, and even more preferably less than 0.1%.

[0036] The Sb2O3 component is an optional component which, if having a content of more than 0%, can degas the molten glass. On the other hand, by making the content of the Sb2O3 component 1.0% or less, reduction of the transmittance in the short wavelength region of the visible light region, or solarization or reduction of the quality of the inner portion of the glass can be suppressed. Accordingly, the content of the Sb2O3 component may be preferably 1.0% or less, more preferably less than 0.5%, and even more preferably less than 0.2%.

[0037] Further, a component which clarifies and degasses the glass is not limited to the above-described Sb2O3 component, and well-known clarifying agents and degassing agents in the field of glass production, or combinations thereof, may be used.

[0038] The F component is an optional component which, if having a content of more than 0%, can increase the Abbe number of the glass, lower the glass transition point, and further increase the devitrification resistance. However, if the content of the F component, namely the total amount as F of a fluoride partially or completely substituting an oxide of one or two or more of each of the above described metal elements, is more than 10.0%, the volatilization of the F component becomes large, and it becomes difficult to obtain stable optical constants, and it becomes difficult to obtain a homogenous glass. Further, the Abbe number is increased more than necessary. Accordingly, the content of the F component may be preferably 10.0% or less, more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 1.0%.

[0039] The total amount of the SiO2 component and the B2O3 component is preferably 10.0% or more. In this way, a stable glass is easily obtained. Accordingly, the mass sum (SiO2 + B2O3) is preferably 7.0% or more, more preferably 10.0% or more, even more preferably more than 12.0%, even more preferably more than 15.0%, even more preferably more than 18.0%, and even more preferably 20.0% or more. On the other hand, by making the total amount less than 37.0%, the temperature coefficient of the relative refractive index can be made small. Accordingly, the mass sum (SiO2 + B2O3) is preferably less than 37.0%, more preferably 35.0% or less, even more preferably less than 33.0%, even more preferably less than 30.0%, even more preferably less than 28.0%, even more preferably less than 25.0% or less, even more preferably 22.1% or less and even more preferably less than 21.0%.

[0040] The total content of BaO and K2O (mass total) is preferably more than 30.0%. By making this large, the temperature coefficient of the relative refractive index can be made small. Accordingly, the mass total (BaO + K2O) is preferably more than 30.0%, more preferably more than 33.0%, even more preferably more than 35.0%, even more preferably more than 38.0%, and even more preferably more than 41.0%. On the other hand, from the viewpoint of obtaining a stable glass, this mass total (BaO + K2O) may be preferably less than 62.0%, more preferably less than 60.0%, even more preferably less than 58.0%, even more preferably less than 55.0%, and even more preferably less than 53.0%.

[0041] A ratio (mass ratio) of the total content of the BaO and K2O components, with respect to a total content of the SiO2 component, B2O3 component, and ZnO component is preferably more than 1.00. By making this ratio large, the temperature coefficient of the relative refractive index can be made small. Accordingly, the mass ratio (BaO + K2O)/(SiO2 + B2O3 + ZnO) is preferably more than 1.00, more preferably more than 1.30, even more preferably more than 1.50, even more preferably more than 1.60, and even more preferably more than 1.80. On the other hand, from the viewpoint of obtaining a stable glass, this mass ratio mass ratio (BaO + K2O)/(SiO2 + B2O3 + ZnO) may be preferably 5.00 or less, more preferably less than 4.50, even more preferably less than 4.00, even more preferably less than 3.50, even more preferably less than 3.00, and even more preferably less than 2.60.

[0042] A total mass (mass total) of the TiO2 component, ZrO2 component, WO3 component, Nb2O5 component, and Ta2O5 component is preferably 0.5% or more. In this way, because is it possible to increase the refractive index of the glass, a desired high refractive index can be obtained. Accordingly, the mass total TiO2 + ZrO2 + WO3 + Nb2O5 + Ta2O5 is preferably 0.5% or more, more preferably 1.0% or more, even more preferably 3.0% or more, even more preferably 5.0% or more, even more preferably 8.0% or more, and even more preferably 10.0% or more. On the other hand, this total is preferably 30.0% or less. In this way, the stability of the glass can be increased. Accordingly, the mass sum TiO2 + ZrO2 + WO3 + Nb2O5 + Ta2O5 is preferably 30.0% or less, more preferably less than 25.0%, even more preferably less than 23.0%, even more preferably less than 20.0%, even more preferably less than 18.0%, and even more preferably less than 16.0%.

[0043] A total amount of the ZrO2 component and the Ta2O5 component is preferably 15.0% or less. In this way, because it is possible to increase the fusibility of the raw materials while also reducing the raw material costs of the glass, it is also possible to reduce the manufacturing costs of the glass. Accordingly, the mass total (ZrO2 + Ta2O5) is preferably 15.0% or less, more preferably 13.0% or less, even more preferably 10.0% or less, even more preferably less than 8.0%, even more preferably less than 5.0%, even more preferably less than 3.0%, and even more preferably less than 2.0%.

[0044] A sum (mass sum) of the content of the RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, and Ba) is preferably more than 30.0%. In this way, the devitrification of the glass can be reduced, and further, the temperature coefficient of the relative refractive index can be made small. Accordingly, the mass sum of the RO component is preferably more preferably more than 30.0%, more preferably more than 35.0%, even more preferably more than 38.0%, and even more preferably more than 40.0%. On the other hand, by making the mass sum of the RO component 65.0% or less, reductions in the refractive index can be suppressed, and further, the stability of the glass can be increased. Accordingly, the mass sum of the RO component is preferably 65.0% or less, more preferably less than 62.0%, even more preferably less than 60.0%, even more preferably less than 58.0%, even more preferably less than 55.0%, and even more preferably less than 53.0%.

[0045] A sum (mass sum) of the content of the Rn2O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K) is preferably 12.0% or less. In this way, reductions in the viscosity of the molten glass can be suppressed, the refractive index of the glass is not readily reduced, and further, devitrification of the glass can be reduced. Accordingly, the mass sum of the Rn2O component is preferably 12.0% or less, more preferably 10.0% or less, even more preferably less than 7.0%, even more preferably less than 4.0%, even more preferably less than 2.0%, and even more preferably less than 1.0%.

<Concerning the Components Which Should Not Be Contained>



[0046] Next, components which should not be included and components which are preferably not included in the optical glass of the present invention are explained.

[0047] Other components may be added as required within a range which does not harm the characteristics of the glass of the present invention. However, excluding Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, various transition metal components of V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Mo, and the like, even if respectively contained individually or combination in small amounts, have the property of coloring the glass, and giving rise to absorbance of specified wavelengths in the visible range, and therefore, in particular for optical glass used for wavelengths in the visible region, these are preferably substantially not included.

[0048] Further, lead compounds such as PbO and the like, and arsenic compounds such as As2O3 and the like are components having a high environmental burden, and therefore should substantially not be included, namely, they are desirably not included at all except for unavoidable impurities.

[0049] Furthermore, in recent years there has been a tendency to avoid use of all of the components of Th, Cd, Tl, Os, Be, and Se as harmful chemical materials, and steps for environmental measures are required not only in the production steps of the glass, but also in the processing steps, up until the disposal after having made the product. Accordingly, in the case of focusing on environmental impact, it is preferable that these are substantially not included.

[Production Method]



[0050] The optical glass of the present invention is manufactured, for example by a method such as the following. Namely, it is produced by uniformly mixing as raw materials of each of the above components, high purity raw materials usually used for optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphates and the like, so that the each component is within the predetermined content range, charging the produced mixture into a platinum crucible, and after melting for 1 to 10 hours in a temperature range of 1000 to 1500°C in an electric furnace in accordance with the degree of ease of melting the glass raw materials, with stirring and homogenizing, the temperature is lowered to a suitable level, casting in a mold, and annealing.

<Properties>



[0051] The optical glass of the present invention preferably has a high refractive index and a low Abbe number (high dispersion). In particular, the refractive index (nd) of the optical glass of the present invention preferably has a lower limit of 1.70, more preferably 1.75, even more preferably 1.77, and even more preferably 1.78. This refractive index (nd) may have an upper limit of preferably 2.10, more preferably 2.00, even more preferably 1.90, and even more preferably 1.85. Further, the Abbe number (νd) of the optical glass of the present invention preferably has a lower limit of 20, more preferably 25, even more preferably 30, and even more preferably 33. This Abbe number (νd) preferably has an upper limit of 50, more preferably 45, even more preferably 40, and even more preferably 38. By having such a high refractive index, even when designing thinner optical elements, it is possible to obtain a large diffraction amount of light. Further, by having such a high dispersion, the focus point according to the wavelength of the light when using a single lens can be suitably shifted. Therefore, for example when constituting an optical system by combining with optical elements having a low dispersion (high Abbe number), it is possible to reduce aberrations of this optical system as a whole and design for high imaging characteristics and the like. In such a way, the optical glass of the present invention is useful for optical design, and in particular, when constituting an optical system, it is possible to design size reduction of the optical system even while designing high imaging characteristics and the like, and it is possible to broaden the degree of freedom in optical design.

[0052] Herein, in the optical glass of the present invention, the refractive index (nd) and the Abbe number (νd) preferably satisfy the relationship (-0.0112νd + 2.10) ≤ nd ≤ (-0.0112νd + 2.30). In the glass with the composition specified by the present invention, by satisfying this relationship between the refractive index (nd) and the Abbe number (νd), a more stable glass can be obtained. Accordingly, in the optical glass of the present invention, the refractive index (nd) and the Abbe number (νd) preferably satisfy the relationship nd ≥ (-0.0112νd + 2.10), more preferably satisfy the relationship nd ≥ (-0.0112νd + 2.12), and even more preferably satisfy the relationship nd ≥ (-0.0112νd + 2.15). On the other hand, in the optical glass of the present invention, the refractive index (nd) and the Abbe number (νd) preferably satisfy the relationship nd ≤ (-0.0112νd + 2.30), more preferably satisfy the relationship nd ≤ (-0.0112νd + 2.28), even more preferably satisfy the relationship nd ≤ (-0.0112νd + 2.26), and even more preferably satisfy the relationship nd ≤ (-0.0112νd + 2.25).

[0053] The optical glass of the present invention has a low value of the temperature coefficient of the relative refractive index (dn/dT). More specifically, the temperature coefficient of the relative refractive index of the optical glass of the present invention preferably has an upper limit value of +4.0 × 10-6 °C-1, more preferably +3.0 × 10-6 °C-1, even more preferably +1.0 × 10-6 °C-1, and it is possible to obtain this upper limit or a lower value (on the negative side). On the other hand, the temperature coefficient of the relative refractive index of the optical glass of the present invention preferably has a lower limit value of -10.0 × 10-6 °C-1, more preferably-5.0 × 10-6 °C-1, and even more preferably -3.0 × 10-6 °C-1, it is possible to obtain this lower limit or a higher value (on the positive side). Among these, as a glass having a refractive index (nd) of 1.70 or more, and further an Abbe number (νd) of 20 to 50, a glass with a low temperature coefficient of the relative refractive index is unknown, and this broadens the options for correcting deviations and the like of an image due to temperature changes, and such corrections can be more easily made. Accordingly, by having such a range of the temperature coefficient of the relative refractive index, it becomes possible to contribute to correction of deviations and the like of an image due to temperature changes. The temperature coefficient of the relative refractive index of the optical glass of the present invention, is a temperature coefficient of the refractive index for light having a wavelength of 589.29 nm in air having the same temperature of the optical glass, and shows the amount of change per 1°C (°C-1) when changing the temperature from 40°C to 60°C.

[0054] The optical glass of the present invention preferably has a high devitrification resistance, more specifically, has a low liquidus temperature. Namely, the upper limit of the liquidus temperature of the optical glass of the present invention may be preferably 1200°C, more preferably 1180°C, and even more preferably 1150°C. In this way, even if flowing at a low temperature after melting the glass, because the crystallization of the prepared glass is reduced, devitrification when forming the glass from the fused state can be reduced, and the effects on the optical characteristics of optical elements using the glass can be reduced. Further, because the glass can be molded even when the fusion temperature of the glass is low, the consumption of energy when molding the glass can be suppressed, and the production costs of the glass can be reduced. On the other hand, the lower limit of the liquidus temperature of the optical glass of the present invention is not particularly limited, but the liquidus temperature of the glass obtained by the present invention is often roughly 800°C or more, specifically 850°C or more, and even more specifically 900°C or more. Further, in the present specification, "liquidus temperature" indicates the lowest temperature at which crystals are not recognized, when observing the presence/absence of crystals at the glass surface and in the glass directly after a 30 cc caret-shaped glass sample is inserted into a platinum crucible with a volume of 50 ml to reach a fully molten state at 1250°C, lowering the temperature to a predetermined temperature and holding for 1 hour, removing from the furnace and cooling. Herein, the predetermined temperature when lowering the temperature is a temperature between 1200°C and 800°C in increments of 10°C.

[Preform and Optical Element]



[0055] From the produced optical glass, for example, it is possible to manufacture a glass compact, using a polishing technique, or a technique of mold press molding such as reheat press molding or precision press molding or the like. Namely, it is possible to manufacture a glass compact by carrying out a mechanical process such as grinding and polishing or the like on the optical glass, or to manufacture a preform for mold press molding from the optical glass and manufacture a glass compact by carrying out a polishing technique after having carried out reheat press molding on this preform, or to manufacture a glass compact by carrying out precision press molding on a preform manufactured by carrying out an polishing technique or on a preform molded by a publicly known floating molding, or the like. Further, the technique of manufacturing the glass compact is not limited to these techniques.

[0056] In this way, the optical glass of the present invention is useful for a great variety of optical elements and optical designs. Among these, in particular, forming a preform from the optical glass of the present invention, carrying out reheat press molding or precision press molding or the like using this preform, and manufacturing an optical element such as a lens or prism or the like is preferable. In this way, it becomes possible to form a preform having a large diameter, whereby it is possible to design large optical elements, while realizing high resolution and high precision imaging characteristics and projection characteristics when used in an optical device.

[0057] The glass compact consisting of the optical glass of the present invention can be used, for example, for applications of optical elements such as lenses, prisms, mirrors and the like, and can also be used for devices which readily reach high temperatures, typically optical devices for vehicles, or projectors or copiers or the like.

EXAMPLES



[0058] The compositions of the Examples (No. 1 to No. 63) of the present invention and the Comparative Example (No. A) and the results of the refractive index (nd), Abbe number (νd), temperature coefficient of the relative refractive index (dn/dT) of these glasses are shown in Tables 1 to 9. Further, the below examples are provided only for exemplification, and these examples are in no way limiting.

[0059] The glasses of the Examples and Comparative Examples of the present invention were all prepared by selecting high purity raw materials usually used for optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, metaphosphates and the like, respectively corresponding to the raw material of each component, weighed so as to have the proportions of the compositions of each example shown in the table, and after uniformly mixing, were charged into a platinum crucible, and after melting for 1 to 10 hours in a temperature range of 1000 to 1500°C in an electric furnace in accordance with the degree of ease of melting the glass raw materials, and after stirring and homogenizing, were cast in a mold, and annealed.

[0060] The refractive index (nd) and Abbe number (νd) of the glasses of the examples and comparative examples show the measured values with respect to the d-line of a helium lamp (587.56 nm). Further, the Abbe number (νd) was calculated from the formula Abbe number (νd) = [(nd - 1)/(nF - nC)] using the values of the refractive index of the above mentioned d-line, and the refractive index (nF) with respect to the F-line (486.13 nm), and the refractive index (nC) with respect to the C-line (656.27 nm) of a hydrogen lamp. Then, from the values of the obtained refractive index (nd) and Abbe number (νd), the intercept b was determined when the slope a in the relational formula nd = -a × νd + b was 0.0112.

[0061] The temperature coefficient of the relative refractive index (dn/dT) of the glasses of the Examples and Comparative Examples is the measured value of the temperature coefficient of the relative refractive index when the temperature was changed from 40°C to 60°C for a wavelength of 589.29 nm, according to the interferometry method among the methods disclosed in "Measurement Method of Temperature Coefficient of the Relative Refractive Index of Optical Glass" JOGIS18-2008 by the Japan Optical Glass Manufacturers Association.
[Table 1]
(Units: mass%)Example
12345678
SiO2 10.38 9.46 11.46 9.98 10.17 9.16 9.16 10.46
B2O3 12.25 13.51 8.34 11.78 11.99 10.80 10.80 12.34
BaO 42.93 45.30 42.20 45.80 42.05 50.28 50.28 47.98
La2O3 19.51 13.25 21.52 18.76 19.11 17.21 13.90 14.93
Gd2O3                
Y2O3 2.81 3.10 3.10 2.70 2.75 2.48 2.48 2.83
K2O         2.75      
ZnO                
ZrO2                
Nb2O5   0.83            
WO3 0.75   0.83          
TiO2 11.36 12.54 12.54 10.93 11.13 10.02 13.33 11.45
CaO                
SrO                
Li2O                
Al2O3   2.00            
Sb2O3 0.01 0.01 0.01 0.05 0.05 0.04 0.04 0.01
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 22.32 16.35 24.63 21.47 21.86 19.69 16.38 17.76
Si+B 22.63 22.97 19.79 21.76 22.16 19.96 19.96 22.80
Ba+K 42.93 45.30 42.20 45.80 44.80 50.28 50.28 47.98
(Ba+K)/(Si+B+Zn) 1.90 1.97 2.13 2.10 2.02 2.52 2.52 2.10
Ti+Zr+W+Nb+Ta 12.11 13.37 13.37 10.93 11.13 10.02 13.33 11.45
Zr+Ta 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg+Ca+Sr+Ba 42.93 45.30 42.20 45.80 42.05 50.28 50.28 47.98
Li+Na+K 0.00 0.00 0.00 0.00 2.75 0.00 0.00 0.00
Refractive index (nd) 1.799 1.790 1.817 1.795 1.781 1.791 1.808 1.789
Abbe number (νd) 36.5 36.1 35.2 37.0 37.0 37.5 34.8 36.8
Intercept b (a=0.0112) 2.208 2.194 2.212 2.209 2.195 2.211 2.198 2.201
Temperature coefficient of the relative refractive index [× 10-6°C-1] -0.4 0.2 0.0 -0.8 -1.1 -2.2 -1.7 -0.6
[Table 2]
(Units: mass%)Example
910111213141516
SiO2 10.46 10.38 10.46 9.55 10.46 9.99 9.56 9.99
B2O3 9.50 12.25 12.34 11.27 12.34 9.98 11.27 11.78
BaO 43.26 42.93 43.26 48.14 52.70 45.82 48.15 45.82
La2O3 19.65 19.51 16.82 17.95 7.37 18.77 15.37 14.26
Gd2O3                
Y2O3 2.83 2.81 2.83 2.59 2.83 2.71 2.59 2.71
K2O                
ZnO                
ZrO2           1.80    
Nb2O5                
WO3   0.75            
TiO2 14.28 11.36 14.28 10.46 14.28 10.93 13.05 15.44
CaO                
SrO                
Li2O                
Sb2O3 0.01 0.01 0.01 0.04        
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 22.49 22.32 19.65 20.54 10.21 21.47 17.96 16.96
Si+B 19.96 22.63 22.80 20.82 22.80 19.97 20.83 21.77
Ba+K 43.26 42.93 43.26 48.14 52.70 45.82 48.15 45.82
(Ba+K)/(Si+B+Zn) 2.17 1. 90 1.90 2.31 2.31 2.29 2.31 2.10
Ti+Zr+W+Nb+Ta 14.28 12.11 14.28 10.46 14.28 12.74 13.05 15.44
Zr+Ta 0.00 0.00 0.00 0.00 0.00 1.80 0.00 0.00
Mg+Ca+Sr+Ba 43.26 42.93 43.26 48.14 52.70 45.82 48.15 45.82
Li+Na+K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.827 1.799 1.813 1.793 1.794 1.807 1.798 1.819
Abbe number (νd) 33.9 36.5 34.3 37.2 34.7 36.3 37.4 33.4
Intercept b (a=0.0112) 2.206 2.208 2.197 2.209 2.183 2.214 2.217 2.193
Temperature coefficient of the relative refractive index [× 10-6°C-1] 0.0 -0.4 0.2 -1.3 -1.9 -1.1 0.5 0.3
[Table 3]
(Units: mass%)Example
17 18 19 20 21 22 23 24
SiO2 9.99 9.72 9.99 10.02 9.66 10.71 9.99 10.46
B2O3 9.98 9.71 9.98 9.95 11.40 11.67 10.80 12.34
BaO 45.82 44.61 40.82 45.66 47.59 41.88 45.82 52.14
La2O3 16.96 16.52 16.67 18.82 15.43 17.71 16.72 8.28
Gd2O3     3.00          
Y2O3 2.71 2.63   2.71 2.62 2.90 2.71 2.83
K2O                
ZnO   1.95            
ZrO2 1.80 1.76 1.80     0.97 0.98  
Nb2O5                
WO3                
TiO2 12.74 12.40 12.74 12.83 13.30 14.14 12.98 13.94
CaO     2.00          
SrO     3.00          
Li2O   0.69            
Sb2O3 0.01 0.01 0.01 0.01   0.01   0.01
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 19.67 19.15 19.67 21.53 18.04 20.61 19.42 11.12
Si+B 19.97 19.44 19.97 19.97 21.06 22.38 20.79 22.80
Ba+K 45.82 44.61 40.82 45.66 47.59 41.88 45.82 52.14
(Ba+K)/(Si+B+Zn) 2.29 2.09 2.04 2.29 2.26 1.87 2.20 2.29
Ti+Zr+W+Nb+Ta 14.54 14.16 14.54 12.83 13.30 15.11 13.97 13.94
Zr+Ta 1.80 1.76 1.80 0.00 0.00 0.97 0.98 0.00
Mg+Ca+Sr+Ba 45.82 44.61 45.82 45.66 47.59 41.88 45.82 52.14
Li+Na+K 0.00 0.69 0.00 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.817 1.813 1.818 1.814 1.807 1.818 1.812 1.794
Abbe number (νd) 34.9 34.9 34.8 35.0 34.9 34.2 34.9 35.0
Intercept b (a=0.0112) 2.207 2.203 2.208 2.206 2.199 2.201 2.203 2.185
Temperature coefficient of the relative refractive index [× 10-6°C-1] -0.6 -0.6 -0.8 -1.0 -1.1 0.2 -0.2 -1.5
[Table 4]
(Units: mass%)Example
2526272829303132
SiO2 9.99 9.56 9.99 9.56 9.72 9.99 9.72 9.84
B2O3 10.80 9.55 10.80 11.27 9.71 9.98 10.51 11.61
BaO 45.82 48.15 45.82 48.15 47.24 45.82 47.24 46.57
La2O3 16.72 15.37 7.70 15.37 16.52 7.94 7.49 18.49
Gd2O3                
Y2O3 2.71 2.59 11.73 2.59 2.63 11.73 11.42 2.67
K2O                
ZnO                
ZrO2 0.98 1.73 0.98   1.76 1.80 0.96  
Nb2O5                
WO3                
TiO2 12.98 13.05 12.98 13.05 12.40 12.74 12.64 10.77
CaO                
SrO                
Li2O                
Sb2O3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.04
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 19.42 17.96 19.42 17.96 19.15 19.67 18.91 21.16
Si+B 20.79 19.10 20.79 20.83 19.44 19.97 20.24 21.45
Ba+K 45.82 48.15 45.82 48.15 47.24 45.82 47.24 46.57
(Ba+K)/(Si+B+Zn) 2.20 2.52 2.20 2.31 2.43 2.29 2.33 2.17
Ti+Zr+W+Nb+Ta 13.97 14.78 13.97 13.05 14.16 14.54 13.60 10.77
Zr+Ta 0.98 1.73 0.98 0.00 1.76 1.80 0.96 0.00
Mg+Ca+Sr+Ba 45.82 48.15 45.82 48.15 47.24 45.82 47.24 46.57
Li+Na+K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.812 1.818 1.808 1.798 1.815 1.813 1.807 1.795
Abbe number (νd) 34.9 34.6 35.2 37.4 35.0 35.2 35.3 37.0
Intercept b (a=0.0112) 2.203 2.205 2.202 2.217 2.207 2.206 2.202 2.209
Temperature coefficient of the relative refractive index [× 10-6°C-1] -1.0 -1.1 0.2 0.5 -1.3 -0.2 -0.2 -1.1
[Table 5]
(Units: mass%)Example
3334353637383940
SiO2 9.70 9.70 9.81 9.98 16.81 11.08 8.78 16.81
B2O3 11.45 11.45 11.57 11.78 5.85 11.65 14.87 5.85
BaO 47.32 47.32 44.99 45.80 40.19 41.78 41.37 40.19
La2O3 18.23 3.23 18.43 9.74 14.06 18.29 18.03 14.06
Gd2O3   15.00            
Y2O3 2.63 2.63 2.66 11.72 1.34 3.04 3.81 1.34
K2O     1.77   1.03     1.03
ZnO                
ZrO2         3.92 2.70 1.14 3.92
Nb2O5         3.66 1.91   3.66
WO3           0.32    
TiO2 10.62 10.62 10.74 10.93 13.11 9.20 11.99 13.11
CaO                
SrO                
Li2O                
Sb2O3 0.04 0.04 0.04 0.05 0.03 0.01 0.01 0.03
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 20.86 20.86 21.09 21.47 15.41 21.33 21.84 15.41
Si+B 21.15 21.15 21.38 21.76 22.66 22.74 23.65 22.66
Ba+K 47.32 47.32 46.76 45.80 41.22 41.78 41.37 41.22
(Ba+K)/(Si+B+Zn) 2.24 2.24 2.19 2.10 1.82 1.84 1.75 1.82
Ti+Zr+W+Nb+Ta 10.62 10.62 10.74 10.93 20.69 14.14 13.13 20.69
Zr+Ta 0.00 0.00 0.00 0.00 3.92 2.70 1.14 3.92
Mg+Ca+Sr+Ba 47.32 47.32 44.99 45.80 40.19 41.78 41.37 40.19
Li+Na+K 0.00 0.00 1.77 0.00 1.03 0.00 0.00 1.03
Refractive index (nd) 1.794 1.794 1.785 1.792 1.801 1.799 1.801 1.800
Abbe number (νd) 37.1 37.2 37.1 37.1 34.6 38.0 36.4 34.6
Intercept b (a=0.0112) 2.210 2.211 2.201 2.207 2.188 2.225 2.209 2.188
Temperature coefficient of the relative refractive index [× 10-6°C-1] -1.3 -0.8 -1.5 -0.4 0.4 -0.4 -0.5 0.3
[Table 6]
(Units: mass%)ExampleComparative Example
4142A
SiO2 9.97 19.19 6.09
B2O3 16.90   21.99
BaO 47.02 40.18 2.99
La2O3 20.49 17.11 32.04
Gd2O3     2.99
Y2O3 4.33   2.99
K2O   0.99  
ZnO     12.97
ZrO2 1.30 6.34 4.99
Nb2O5   5.92 9.03
WO3     3.69
TiO2   10.27  
CaO      
SrO      
Li2O     0.20
Al2O3      
Sb2O3     0.02
TOTAL 100.0 100.0 100.0
La+Gd+Y+Yb 24.82 17.11 38.02
Si+B 26.87 19.19 28.08
Ba+K 47.02 41.17 2.99
(Ba+K)/(Si+B+Zn) 1.75 2.15 0.07
Ti+Zr+W+Nb+Ta 1.30 22.53 17.71
Zr+Ta 1.30 6.34 4.99
Mg+Ca+Sr+Ba 47.02 40.18 2.99
Li+Na+K 0.00 0.99 0.20
Refractive index (nd) 1.717 1.795 1.806
Abbe number (νd) 47.7 35.8 40.9
Intercept b (a=0.0112) 2.251 2.196 2.264
Temperature coefficient of the relative refractive index [× 10-6°C-1] -1.1 0.9 7.2
[Table 7]
(Units: mass%)Example
4344454647484950
SiO2 9.70 12.33 9.70 9.70 9.70 9.70 9.70 9.70
B2O3 11.45 8.82 11.45 10.57 8.82 11.45 9.69 11.45
BaO 47.36 47.32 47.32 47.32 47.32 44.69 49.07 47.33
La2O3 12.98 14.73 7.72 5.97 5.97 5.97 5.97 7.72
Gd2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Y2O3 7.89 6.13 13.15 15.77 17.53 17.53 14.90 13.15
K2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ZnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ZrO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Nb2O5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 10.66
WO3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TiO2 10.62 10.62 10.62 10.62 10.62 10.62 10.62 0.00
CaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Li2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Al2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sb2O3 0.00 0.04 0.04 0.04 0.04 0.04 0.04 0.00
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 20.86 20.86 20.86 21.74 23.49 23.49 20.86 20.86
Si+B 21.15 21.15 21.15 20.27 18.52 21.15 19.40 21.15
Ba+K 47.36 47.32 47.32 47.32 47.32 44.69 49.07 47.33
(Ba+K)/(Si+B+Zn) 2.24 2.24 2.24 2.33 2.55 2.11 2.53 2.24
Ti+Zr+W+Nb+Ta 10.62 10.62 10.62 10.62 10.62 10.62 10.62 10.66
Zr+Ta 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg+Ca+Sr+Ba 47.36 47.32 47.32 47.32 47.32 44.69 49.07 47.33
Li+Na+K 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.792 1.793 1.790 1.794 1.802 1.793 1.795 1.767
Abbe number (νd) 37.2 37.1 37.3 37.2 37.0 37.4 37.2 42.4
Intercept b (a=0.0112) 2.209 2.209 2.208 2.211 2.216 2.212 2.211 2.242
Temperature coefficient of the relative refractive index [× 10-6°C-1] -0.8 -0.5 -0.5 -0.2 -0.4 -0.1 -0.6 -1.1
[Table 8]
(Units: mass%)Example
51525354555657
SiO2 9.46 9.50 9.70 9.70 9.74 7.96 9.71
B2O3 10.30 10.30 8.82 8.82 11.45 8.82 7.07
BaO 46.11 46.11 47.32 47.32 47.32 47.34 47.34
La2O3 5.81 5.81 7.72 7.72 7.72 7.72 7.72
Gd2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Y2O3 15.37 15.37 13.15 13.15 13.15 13.15 13.15
K2O 2.56 0.00 0.00 0.00 0.00 0.00 0.00
ZnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ZrO2 0.00 0.00 0.00 2.63 5.26 0.00 0.00
Nb2O5 10.35 10.35 13.25 10.62 5.36 15.01 13.26
WO3 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TiO2 0.00 0.00 0.00 0.00 0.00 0.00 1.75
CaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00
SrO 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Li2O 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na2O 0.00 2.56 0.00 0.00 0.00 0.00 0.00
Al2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sb2O3 0.04 0.00 0.04 0.04 0.00 0.00 0.00
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 21.18 21.18 20.86 20.86 20.86 20.87 20.87
Si+B 19.76 19.80 18.52 18.52 21.19 16.78 16.78
Ba+K 48.67 46.11 47.32 47.32 47.32 47.34 47.34
(Ba+K)/(Si+B+Zn) 2.46 2.33 2.55 2.55 2.23 2.82 2.82
Ti+Zr+W+Nb+Ta 10.35 10.35 13.25 13.25 10.62 15.01 15.01
Zr+Ta 0.00 0.00 0.00 2.63 5.26 0.00 0.00
Mg+Ca+Sr+Ba 46.11 46.11 47.32 47.32 47.32 47.34 47.34
Li+Na+K 2.56 2.56 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.760 1.755 1.789 1.787 1.762 1.805 1.824
Abbe number (νd) 42.4 42.4 40.3 41.1 44.0 39.1 37.3
Intercept b (a=0.0112) 2.235 2.230 2.240 2.247 2.255 2.243 2.242
Temperature coefficient of the relative refractive index [× 10-6°C-1] -1.6 -1.4 -1.2 -0.6 -0.5 -1.5 -1.4
[Table 9]
(Units: mass%)Example
585960616263
SiO2 10.22 9.77 10.22 7.32 7.45 5.50
B2O3 11.55 11.04 11.55 10.38 11.55 10.38
BaO 48.90 51.16 48.90 46.01 48.90 46.01
La2O3 7.98 7.63 7.98 10.88 7.98 12.70
Gd2O3            
Y2O3 7.38 7.06 7.38 3.82 7.38 3.82
K2O            
ZnO            
ZrO2       2.38   2.38
Nb2O5       19.18 16.73 19.18
WO3            
TiO2 13.96 13.35 13.96      
CaO            
SrO            
Li2O            
Na2O            
Al2O3            
Sb2O3       0.02   0.02
TOTAL 100.0 100.0 100.0 100.0 100.0 100.0
La+Gd+Y+Yb 15.36 14.69 15.36 14.70 15.36 16.52
Si+B 21.77 20.81 21.77 17.70 19.00 15.89
Ba+K 48.90 51.16 48.90 46.01 48.90 46.01
(Ba+K)/(Si+B+Zn) 2.25 2.46 2.25 2.60 2.57 2.90
Ti+Zr+W+Nb+Ta 13.96 13.35 13.96 21.56 16.73 21.56
Zr+Ta 0.00 0.00 0.00 2.38 0.00 2.38
Mg+Ca+Sr+Ba 48.90 51.16 48.90 46.01 48.90 46.01
Li+Na+K 0.00 0.00 0.00 0.00 0.00 0.00
Refractive index (nd) 1.804 1.801 1.773 1.821 1.795 1.830
Abbe number (νd) 34.6 35.0 40.8 36.7 38.8 36.4
Intercept b (a=0.0112) 2.191 2.193 2.230 2.232 2.230 2.237
Temperature coefficient of the relative refractive index [× 10-6°C-1] -0.4 -1.1 -0.6 -0.5 -0.8 -1.0


[0062] The optical glass of the Examples of the present invention has a high content of the BaO component which las a low materials cost among the components which contribute to a high refractive index, and on the other hand has a low content of Ln2O3 components which have a high cost, whereby it can provide a more inexpensive raw materials cost.

[0063] As shown in the tables, the optical glasses of the Examples all had a temperature coefficient of the relative refractive index within the range of +4.0 × 10-6 to -10.0 × 10-6 (°C- 1), and more specifically within the range of +1.0 × 10-6 to-3.0 × 10-6 (°C-1), which was within the desired range. On the other hand, the glass of the Comparative Example (No. A) had a temperature coefficient of the relative refractive index of +7.2 × 10-6 (°C-1), which is a high temperature coefficient of the relative refractive index.

[0064] Further, the optical glasses of the Examples all had a refractive index (nd) of 1.70 or more, more specifically 1.71 or more, and were within the desired range. Further, the optical glasses of the Examples of the present invention all had an Abbe number (νd) within the range of 20 to 50, more specifically 33 to 48, and were within the desired range. Further, for the optical glasses of Examples of the present invention, the refractive index (nd) and Abbe number (νd) satisfied the relationship (-0.0112νd + 2.10) ≤ nd ≤ (-0.0112νd + 2.30), and more specifically satisfied the relationship (-0.0112νd + 2.18) ≤ nd ≤ (-0.0112νd + 2.26). Further, the relationship between the refractive index (nd) and Abbe number (νd) of the optical glasses of the present application, is as shown in Fig. 1.

[0065] Further, the optical glasses of the Examples formed a stable glass, and devitrification did not readily occur when producing the glass.

[0066] Accordingly, it became clear that the optical glasses of the Examples had a refractive index (nd) and Abbe number (νd) within the desired range, and a low value of the temperature coefficient of the relative refractive index, and could be obtained with more inexpensive material costs. From this, it can be surmised that the optical glasses of the Examples of the present invention may contribute to reducing the size and reducing the weight of optical systems used in high temperature environments such as optical devices for automobiles or projectors or the like, and further may contribute to correction of deviations and the like of the imaging characteristics due to temperature fluctuations.

[0067] Furthermore, using the optical glasses of the Examples of the present invention, glass blocks were formed, and by carrying out grinding and polishing of these glass blocks, they were processed into lenses and prisms. As a result, they could be stably processed into various lens and prism shapes.

[0068] The present invention was explained in detail with the objective of exemplification, but the examples of the present invention have only the intention of exemplification, and one skilled in the art could understand that many modifications are possible within the concept and scope of the present invention.


Claims

1. An optical glass comprising, in mass%,
a SiO2 component of 1.0% to 27.0%,
a total Ln2O3 component (wherein Ln is one or more selected from the group consisting of La, Gd, Y, and Yb) of 5.0% to 34.0%,
a BaO component of more than 30.0% to 65.0%,
and wherein
a content of a B2O3 component is 25.0% or less, and
a temperature coefficient (40 to 60°C) of a relative refractive index (589.29 nm), is within the range of +3.0 × 10-6 to -10.0 × 10-6 (°C-1).
 
2. An optical glass according to claim 1, wherein, in mass%,
a La2O3 component is 0 to 30.0%,
a Gd2O3 component is 0 to 25.0%,
a Y2O3 component is 0 to 25.0%,
a Yb2O3 component is 0 to 10.0%
a K2O component is 0 to 12.0%
a ZnO component is 0 to less than 5.0%,
a ZrO2 component is 0 to 15.0%,
an Nb2O5 component is 0 to 25.0%,
a WO3 component is 0 to 10.0%,
a TiO2 component is 0 to 25.0%,
a Ta2O5 component is 0 to 10.0%,
an MgO component is 0 to 5.0%,
a CaO component is 0 to 12.0%,
an SrO component is 0 to 12.0%,
a Li2O component is 0 to 5.0%,
an Na2O component is 0 to 12.0%,
a P2O5 component is 0 to 10.0%,
a GeO2 component is 0 to 10.0%,
an Al2O3 component is 0 to 12.0%,
a Ga2O3 component is 0 to 10.0%,
a Bi2O3 component is 0 to 10.0%,
a TeO2 component is 0 to 10.0%,
a SnO2 component is 0 to 3.0%,
a Sb2O3 component is 0 to 1.0%,
and
wherein a content as F of a fluoride partially or completely substituting an oxide of one or two or more of each of the above elements is 0 to 10.0 mass%.
 
3. An optical glass according to claim 1 or 2, wherein a mass sum (SiO2 + B2O3) is 7.0% to less than 37.0%.
 
4. An optical glass according to any one of claims 1 to 3, wherein a mass sum (BaO + K2O) is more than 30.0% to less than 62.0%.
 
5. An optical glass according to any one of claims 1 to 4, wherein a mass ratio (BaO + K2O)/(SiO2 + B2O3 + ZnO) is more than 1.00 to 5.00.
 
6. An optical glass according to any one of claims 1 to 5, wherein a mass sum TiO2 + ZrO2 + WO3 + Nb2O5 + Ta2O5 is 0.5% to 30.0%.
 
7. An optical glass according to any one of claims 1 to 6, wherein a mass sum ZrO2 + Ta2O5 is 15.0% or less.
 
8. An optical glass according to any one of claims 1 to 7, wherein a sum of a content of an RO component (wherein R is one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn), in mass%, is more than 30.0% to 65.0%.
 
9. An optical glass according to any one of claims 1 to 8, wherein a sum of a content of an Rn2O component (wherein Rn is one or more selected from the group consisting of Li, Na, and K), in mass%, is 12.0% or less.
 
10. An optical glass according to any one of claims 1 to 9, having a refractive index (nd) of 1.70 or more, and an Abbe number (νd) of 20 to 50.
 
11. A preform material consisting of an optical glass according to any one of claims 1 to 10.
 
12. An optical element consisting of an optical glass according to any one of claims 1 to 10.
 
13. An optical device provided with an optical element according to claim 12.
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description