WO2008065937A1 - Verre optique - Google Patents

Verre optique Download PDF

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Publication number
WO2008065937A1
WO2008065937A1 PCT/JP2007/072498 JP2007072498W WO2008065937A1 WO 2008065937 A1 WO2008065937 A1 WO 2008065937A1 JP 2007072498 W JP2007072498 W JP 2007072498W WO 2008065937 A1 WO2008065937 A1 WO 2008065937A1
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WO
WIPO (PCT)
Prior art keywords
glass
weight
less
refractive index
optical glass
Prior art date
Application number
PCT/JP2007/072498
Other languages
English (en)
Japanese (ja)
Inventor
Umihiko Mori
Junichi Nakamura
Hitomi Matsumoto
Original Assignee
Nihon Yamamura Glass Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Yamamura Glass Co., Ltd. filed Critical Nihon Yamamura Glass Co., Ltd.
Publication of WO2008065937A1 publication Critical patent/WO2008065937A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium
    • 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
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors

Definitions

  • the present invention relates to an optical glass, and more particularly to an optical glass having a composition suitable for molding, having a high refractive index and a low Abbe number (high dispersion) and improved devitrification resistance during molding.
  • aspherical lenses are often used as optical devices are remarkably reduced in size and weight. This is because aspherical lenses can easily correct light aberrations, reduce the number of lenses, and make the device compact.
  • Aspherical lenses are manufactured by heating and softening a glass preform and precision molding press molding it into a desired shape.
  • One is a method of cutting glass pieces from glass blocks or rods into a spherical shape, and the other is dropping glass melt from the nozzle tip. To obtain a spherical glass preform.
  • glass used for aspherical lenses is required to have various optical characteristics depending on its application, and in particular, it has high refractive index and low Abbe number (high dispersion). There is a growing demand for those with characteristics.
  • SF type glass is a glass that satisfies such optical characteristics. If PbO is harmful to the human body, it is not preferable because metal lead precipitates on the surface of the product during precision press molding.
  • Na, K, Li Na, K, Li
  • This glass is preferred because it can have a refractive index of up to 1 ⁇ 905 (ie, in the region of 1 ⁇ 83 or more)! / (See the example in the same reference), but it is easy to color purple! / ⁇
  • the molding surface of the preform tends to become cloudy during molding.
  • the cloudiness of the molding surface that occurs during the molding of these glasses loses the transparency of the glass and gives defective products, making mass production impossible.
  • the degree of white turbidity depends on the preform preparation method and the surface roughness of the mold, but it has been confirmed that it is caused by surface devitrification due to pressurization during molding.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-58845
  • Patent Document 2 JP 2002-173336 A
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2003-238197
  • the present invention has a high refractive index (particularly preferably a refractive index of 1.83 or more), low Abbe number (high dispersion) optical characteristics, and does not contain lead oxide harmful to the human body.
  • An object of the present invention is to provide a low-cost optical glass that has a low glass transition temperature (Tg) and a glass yield point (At) and is less likely to cause white turbidity during precision mold press molding.
  • the present inventor has conducted research into glass production. By ensuring the stability of the glass by making the composition within a specific range, it has the desired high refractive index and low Abbe number optical characteristics, and has a glass transition temperature (Tg) and a glass yield point (At ) Has been found to be a low-cost glass for precision press-molded lenses, and the present invention has been completed.
  • Tg glass transition temperature
  • At glass yield point
  • the present invention provides the following.
  • MgO 0-5%
  • CaO 0-5%
  • SrO 0-5%
  • An optical glass comprising:
  • optical glass comprising MgO: 0 to 4%, CaO: 0 to 4%, SrO: 0 to 4%.
  • optical glass comprising MgO: 0 to 3%, CaO: 0 to 3%, SrO: 0 to 3%.
  • optical glass according to any one of 1 to 4 above, further comprising:
  • optical glass according to any one of 1 to 4 above, wherein the glass composition comprises Na 2 O in an amount of less than 3% by weight.
  • optical glass according to any one of 1 to 5 above, wherein the glass composition contains TeO in an amount of 10% or less by weight.
  • optical glass according to any one of 1 to 6 above, having a glass yield point (At) of 450 to 550 ° C at 10 to 510 ° C.
  • the refractive index (n) is 1.83 to; 1.88, Abbe number (v)
  • d d is in the range of 2;! to 26, and does not contain lead oxides that are toxic to the human body, and an optical glass can be obtained that is less prone to white turbidity on the molding surface during precision mold pressing.
  • the refractive index (nd) refers to the refractive index of helium with respect to the 587.6 nm emission line.
  • the refractive index is preferably in the range of 1.83-1.88, more preferably ⁇ is in the range of 1.83-1.87.
  • N are the refractive indices of the hydrogen at 486 ⁇ lnm and 656.3 nm, respectively.
  • the Abbe number is preferably in the range of 2;!-26, more preferably 2
  • the yield point (At) is the maximum point at which the expansion curve turns from rising to falling due to softening of the glass when the thermal expansion is measured with a thermomechanical analyzer (TMA).
  • PO is a glass network structure-forming component
  • the PO content is preferably 18% by weight or more in terms of% by weight, more preferably 20% by weight or more, and even more preferably 21% by weight or more.
  • the PO content is preferably 32% by weight or less, more preferably 30% by weight or less.
  • BO is not an essential component, but its content may be 0%, but it is a glass network structure-forming component like PO, and is an effective component for imparting stability to glass. Therefore, the content is more preferably 1% by weight or more, for example. However, in order to obtain a high refractive index as an optical glass, it is preferable to set it to 6% by weight or less, more preferably to 4% by weight or less.
  • GeO is also a glass network structure-forming component like P 2 O 3 and B 2 O, and is an effective component for imparting stability to the glass.
  • the GeO content is, for example, 0.1% by weight or more, preferably S, and more preferably 0.5% by weight or more. However, it is expensive, and from an economic point of view, it is preferably 5% by weight or less, more preferably 4% by weight or less.
  • Al 2 O is the most effective essential component for suppressing white turbidity during molding, which is an object of the present invention.
  • Al 2 O has an action as an intermediate oxide in borate and silicate systems, but has a glass former action in the composition range of the present invention.
  • the content is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and even more preferably 1% by weight or more.
  • excessive content raises the liquidus temperature of the glass and lowers the refractive index. Therefore, it is preferably 6% by weight or less, more preferably 5% by weight or less.
  • ZnO is an essential component for suppressing white turbidity at the time of molding, and is preferably 0.1% by weight or more, more preferably S, and more preferably 0.5% by weight or more. On the other hand, excessive content increases the liquidus temperature of the glass, so it is preferably 5% by weight or less.
  • the content of TiO which is not an essential component, may be 0%. However, TiO is effective for imparting high refractive index and high dispersion to glass. It is preferable to do. However, since excessive content tends to impair the stability of the glass, it is preferably 10% by weight or less, more preferably 8% by weight or less.
  • NbO is an essential component that contributes most to high refractive index and high dispersion in glass.
  • the content is preferably 50% by weight or less, more preferably 48% by weight or less.
  • WO is an effective component for imparting high refractive index and high dispersion to glass.
  • it is preferably 1% by weight or more, more preferably 2% by weight or more.
  • an excessive content impairs the stability of the glass, so that it is preferably 16% by weight or less, more preferably 14% by weight or less, and even more preferably 12% by weight or less.
  • BiO is an essential component that contributes to high refractive index and high dispersion in glass, and at the same time, contributes to lowering of glass transition point and yield point, and can suppress coloring to purple. It is more preferable to set it to 7% by weight or more, and more preferable to set it to 10% by weight or more. However, since excessive content impairs the stability of the glass, it is preferably 36% by weight or less, more preferably 30% by weight or less, and even more preferably 24% by weight or less. It is still more preferable to make it into the weight% or less.
  • the content of these components (the total when two or more are included) can be, for example, 2% by weight or more.
  • the content of these components is preferably 15% by weight or less, more preferably 12% by weight or less, and more preferably 10% by weight. More preferably, it is as follows.
  • Li 2 O is an effective component for lowering the glass transition point and maintaining the refractive index
  • it is preferable to contain, for example, 0.1% by weight or more.
  • excessive content lowers the viscosity of the glass and impairs the stability of the glass. Therefore, it is preferably 6% by weight or less, more preferably 5% by weight or less.
  • Na 2 O is an effective component for lowering the glass transition point and at the same time improving the stability of the glass.
  • 0.1% by weight or more is preferable to contain 0.5% by weight. % It is more preferable to make it contain above.
  • it is preferably 12% by weight or less, preferably 10% by weight or less, but more preferably 8% by weight or less, further preferably 3% by weight or less. Is still more preferred.
  • KO is an effective component for lowering the glass transition point and at the same time improving the stability of the glass.
  • 0.1% by weight or more is preferable. It is more preferable to make it contain above.
  • it is preferably 6% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less.
  • BaO is effective for increasing the stability of the glass and lowering the yield point and the liquidus temperature.
  • the content is preferably 0.1% by weight or more, for example, and more preferably 0.5% by weight or more. However, in order to maintain a high refractive index, it is preferably 8% by weight or less, more preferably 6% by weight or less, and even more preferably 4% by weight or less.
  • the glass of the present invention contains at least one selected from MgO, CaO and SrO.
  • MgO, CaO and SrO By adding these components together with BaO, any of them is effective for improving the stability of the glass and lowering the yield point and the liquidus temperature.
  • the sum of these contents is preferably 8% by weight or less, more preferably 6% by weight or less, and even more preferably 5% by weight or less.
  • the content of each of MgO, CaO and Sr 2 O is preferably 5% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less.
  • La O, Gd 2 O, Ga 2 O, ZrO, and Ta 2 O are components that can be added as appropriate because they all function to increase the refractive index.
  • La 2 O 3, Ta 2 O, and Ga 2 O also have a function of improving the stability of the glass. For this reason, the sum of the contents of these components is preferably 0.1% by weight or more, more preferably 0.5% by weight or more.
  • La 2 O 3, Gd 2 O 3, and ZrO work in the direction of increasing the glass Abbe number, and Ga 2 O 3 and Ta 2 O are expensive and are contrary to cost reduction.
  • the sum of the contents of these components is preferably 10% by weight or less, more preferably 8% by weight or less, and even more preferably 5% by weight or less.
  • Each content of La O, Gd O, Ga O, and ZrO is 4% by weight or more.
  • the content of Ta 2 O is preferable to be 6% by weight or less.
  • TeO is an optional component that functions to increase the stability of the glass and lower the yield point and the liquidus temperature. However, because it is harmful to the human body, it is preferable to set it to 10% by weight or less, more preferably 8% by weight or less!
  • B 2 O, etc., and other components can be used as raw materials such as various oxides and carbonates.
  • Ordinary optical glass materials such as nitrates can be used.
  • the raw materials for production are mixed at a rate that achieves the oxide composition in the predetermined range described above, and the mixture is melted at 1000 ° C to 1100 ° C and then homogenized through the steps of clarification (degassing) and stirring. After that, the temperature is lowered to 900-; 10 oo ° c, poured into a mold, and gradually cooled, so that it is colorless, has a high refractive index, a low Abbe number, is transparent, homogeneous, and has excellent processability. Glass can be obtained. A small amount of Sbo may be added for defoaming.
  • each glass plate was cut into a square shape to obtain a plurality of cut pieces having the same dimensions. Furthermore, the molding surface of a plurality of cut pieces was mirror-polished and the washed sample was used as a glass preform for press molding.
  • This press-molding glass preform is put into a press mold having an upper mold and a lower mold provided with a release film, and heated to N + atmosphere at + 5 ⁇ ; 10 ° C. After pressurizing with a press mold and sufficiently cooling, it was taken out as a press-molded product. The presence or absence of cloudiness on the molding surface of this press-molded product was confirmed visually.
  • Comparative Example 1 is special Patent Document 1 has the same composition as the glass described in Example 10 and Comparative Example 2 has the same composition as the glass described in Example 80 of Patent Document 2.
  • the refractive index (n) and the Abbe number) were measured using a refractometer (KPR-2, manufactured by Carneux).
  • the glass transition point (Tg) and yield point (At) are measured by heating and heating a rod-shaped sample with a length of 15 to 20 mm and a diameter of 3 to 4 mm at a constant rate of 5 ° C / min. was obtained from the thermal expansion curve obtained by measuring.
  • the glasses of the examples of the present invention all have a high refractive index (n) of 1.83 or more, while having a sufficient optical constant as an optical glass with a low Abbe number.
  • the optical glass of the present invention has properties suitable for enabling mass production. is doing.
  • any glass of the present invention has a glass transition point (Tg) force in the range of S410 to 510 ° C and At in a relatively low temperature range of 450 to 550 ° C, it can be easily molded. is there. From these facts, it is understood that the glass of the present invention is a glass suitable for precision mold press molding.
  • the glass of Comparative Example A produced white turbidity during molding
  • the glass of Comparative Example B exhibited a purple color in addition to white turbidity during molding.
  • the present invention has a high refractive index, a low Abbe number, a low glass transition temperature and a low glass yield point, is less susceptible to white turbidity during precision mold press molding, has excellent devitrification resistance, is particularly suitable for molding aspherical lenses, and is mass-produced.
  • An optical glass suitable for use is provided.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un verre optique peu coûteux qui présente un indice de réfraction élevé et un faible nombre d'Abbe, et qui ne contient pas d'oxyde de plomb. Ce verre optique présente une température de transition vitreuse et une température de déformation du verre basses, et ne cause quasiment pas de turbidité blanche pendant la formation par presse de moulage de précision. Le verre optique présente une composition de verre contenant, en pourcentage pondéral, 18-32 % de P2O5, 0-6 % de B2O3, 0,1-5 % de GeO2, 0,1-6 % d'Al2O3, 0,1-5 % de ZnO, 0-10 % de TiO2, 16-50 % de Nb2O5, 1-16 % de WO3, 3-36 % de Bi2O3, 2-15 % de Li2O + Na2O + K2O, la teneur en Li2O étant comprise entre 0,1 et 6 %, la teneur en Na2O étant comprise entre 0,1 et 12 % et la teneur en K2O étant comprise entre 0,1 et 6 %, 0,1-8 % de BaO, et 0,1-8 % de MgO + CaO + SrO, la teneur en MgO étant comprise entre 0 et 5 %, la teneur en CaO étant comprise entre 0 et 5 % et la teneur en SrO étant comprise entre 0 et 5 %.
PCT/JP2007/072498 2006-11-28 2007-11-21 Verre optique WO2008065937A1 (fr)

Applications Claiming Priority (2)

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JP2006319566A JP2008133148A (ja) 2006-11-28 2006-11-28 光学ガラス
JP2006-319566 2006-11-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101817638A (zh) * 2009-02-27 2010-09-01 株式会社小原 光学玻璃及光学元件
CN102249543A (zh) * 2009-02-27 2011-11-23 株式会社小原 光学玻璃及光学元件
US8389428B2 (en) 2009-01-26 2013-03-05 Asahi Glass Company, Limited Glass composition and member having the same on substrate
WO2020117651A1 (fr) * 2018-12-07 2020-06-11 Corning Incorporated Verre de phosphate à indice de réfraction élevé

Families Citing this family (11)

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JP5099890B2 (ja) * 2007-07-06 2012-12-19 独立行政法人産業技術総合研究所 光学ガラス
JP2009242208A (ja) * 2008-03-31 2009-10-22 Ohara Inc 光学ガラス、光学素子及び精密プレス成形用プリフォーム
JP2011219278A (ja) * 2008-08-22 2011-11-04 Asahi Glass Co Ltd 光学ガラス
WO2010074211A1 (fr) * 2008-12-26 2010-07-01 日本山村硝子株式会社 Verre optique
JP5589929B2 (ja) * 2011-03-30 2014-09-17 旭硝子株式会社 光学ガラス、精密プレス成型用プリフォーム、及び光学素子
JP6037501B2 (ja) * 2012-08-30 2016-12-07 株式会社オハラ 光学ガラス、光学素子、及びガラス成形体の製造方法
JP6893749B2 (ja) * 2014-02-28 2021-06-23 株式会社オハラ 光学ガラス、レンズプリフォーム及び光学素子
JP6639074B2 (ja) * 2014-03-03 2020-02-05 株式会社オハラ 光学ガラス、レンズプリフォーム及び光学素子
JP6309791B2 (ja) * 2014-03-11 2018-04-11 株式会社オハラ 光学ガラス、レンズプリフォーム及び光学素子
JP6656743B2 (ja) * 2014-03-20 2020-03-04 株式会社オハラ 光学ガラス、レンズプリフォーム及び光学素子
JP7440204B2 (ja) * 2018-04-03 2024-02-28 株式会社オハラ 光学ガラス、プリフォーム及び光学素子

Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH08104537A (ja) * 1994-09-30 1996-04-23 Hoya Corp 光学ガラス
JPH08157231A (ja) * 1994-12-02 1996-06-18 Hoya Corp 低融点光学ガラス
JP2002037644A (ja) * 2000-05-16 2002-02-06 Nippon Electric Glass Co Ltd 封着用ガラス及びそれを用いた封着材料
JP2005008518A (ja) * 2004-08-16 2005-01-13 Hoya Corp 低融点光学ガラス
JP2006131480A (ja) * 2004-11-09 2006-05-25 Konica Minolta Opto Inc 光学ガラス及び光学素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08104537A (ja) * 1994-09-30 1996-04-23 Hoya Corp 光学ガラス
JPH08157231A (ja) * 1994-12-02 1996-06-18 Hoya Corp 低融点光学ガラス
JP2002037644A (ja) * 2000-05-16 2002-02-06 Nippon Electric Glass Co Ltd 封着用ガラス及びそれを用いた封着材料
JP2005008518A (ja) * 2004-08-16 2005-01-13 Hoya Corp 低融点光学ガラス
JP2006131480A (ja) * 2004-11-09 2006-05-25 Konica Minolta Opto Inc 光学ガラス及び光学素子

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8389428B2 (en) 2009-01-26 2013-03-05 Asahi Glass Company, Limited Glass composition and member having the same on substrate
CN101817638A (zh) * 2009-02-27 2010-09-01 株式会社小原 光学玻璃及光学元件
CN102249543A (zh) * 2009-02-27 2011-11-23 株式会社小原 光学玻璃及光学元件
CN104129919A (zh) * 2009-02-27 2014-11-05 株式会社小原 光学玻璃及光学元件
CN102249543B (zh) * 2009-02-27 2016-03-23 株式会社小原 光学玻璃及光学元件
WO2020117651A1 (fr) * 2018-12-07 2020-06-11 Corning Incorporated Verre de phosphate à indice de réfraction élevé
CN113165952A (zh) * 2018-12-07 2021-07-23 康宁股份有限公司 高折射率磷酸盐玻璃
US11124445B2 (en) 2018-12-07 2021-09-21 Corning Incorporated High refractive index phosphate glass
US11919807B2 (en) 2018-12-07 2024-03-05 Corning Incorporated High refractive index phosphate glass

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