CN102344248A - Optical glass, perform, and optical element - Google Patents

Optical glass, perform, and optical element Download PDF

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Publication number
CN102344248A
CN102344248A CN2011102106793A CN201110210679A CN102344248A CN 102344248 A CN102344248 A CN 102344248A CN 2011102106793 A CN2011102106793 A CN 2011102106793A CN 201110210679 A CN201110210679 A CN 201110210679A CN 102344248 A CN102344248 A CN 102344248A
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composition
opticglass
glass
oxide compound
respect
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荻野道子
上原进
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Ohara Inc
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Ohara Inc
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Priority claimed from JP2010277385A external-priority patent/JP2012126586A/en
Application filed by Ohara Inc filed Critical Ohara Inc
Priority to CN201610284849.5A priority Critical patent/CN105948483B/en
Priority to CN201711179517.1A priority patent/CN107879619B/en
Publication of CN102344248A publication Critical patent/CN102344248A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
    • 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
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • 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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • 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
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials

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

Abstract

Provided are an optical glass having refractive index (nd) and abbe number (vd) within expected range and applicable to correcting chromatic aberration, a lens perform and an optical element using the same. The optical glass, containing B2O3 element, is provided with a refractive index (nd) over 1.70 and an abbe number (vd) over 39. Partial dispersion ratio (Theta g, F) and the abbe number (vd) satisfy the requirement indicated in the following formula: (Theta g, F) >= (-0.0170*vd+0.63750) or (Theta g, F)>=(-2.0*10-3*vd+0.6498).

Description

Opticglass, preform and optical element
Technical field
The present invention relates to opticglass, preform and optical element.
Background technology
Though its degree such as the optical system of digital camera, pick up camera etc. can be different, all contains the bleeding that is called as aberration.This aberration is categorized as monochromatic aberration and chromatic aberation, and especially chromatic aberation depends on the material behavior of the lens that use in the optical system strongly.
Convex lens and the concavees lens of high chromatic dispersion of general chromatic aberation through making up low chromatic dispersion are revised, but only can revise the aberration of red area and green area with this combination, and the aberration of blue region is understood residual.The aberration of the blue region that this can't be removed fully is called as secondary spectrum.Revise secondary spectrum and need consider the optical design of trend of the g line (435.835nm) of blue region.At this moment, as the index of the optical characteristics of in optical design, having in mind, use partial dispersion than (θ g, F).In aforesaid combination in the optical system of lens of lens and high chromatic dispersion of low chromatic dispersion; The lens of low chromatic dispersion side use partial dispersion than (lens of high chromatic dispersion side use partial dispersion than (θ g for θ g, F) big optical material; F) little optical material thus can be good with the secondary spectrum correction.
Partial dispersion is than (θ g F) representes with following formula (1).
θg，F＝(n g-n F)/(n F-n C)……(1)
(n gBe meant that glassy phase is that mercury and wavelength are the specific refractory power of the spectral line of 435.835nm for light source, n FBe meant that glassy phase is that hydrogen and wavelength are the specific refractory power of the spectral line of 486.13nm for light source, n CBe meant that glassy phase is that hydrogen and wavelength are the specific refractory power of the spectral line of 656.27nm for light source.)
In opticglass, the partial dispersion of the partial dispersion property in expression short wavelength territory is than (θ g is F) with Abbe number (v d) between roughly linear.About representing the straight line of this relation, adopting partial dispersion than (θ g F) is the longitudinal axis, employing Abbe number (v d) be on the rectangular coordinates of transverse axis, the partial dispersion of retouching out NSL7 and PBM2 with connection than and 2 straight line of Abbe number represent, be called standard lines (with reference to Fig. 1).According to each opticglass manufacturers and difference, but each company all defines with essentially identical slope and intercept as the normal glass of the benchmark of standard lines.(NSL7 and PBM2 are the opticglass that Kabushiki Kaisya Ohara makes, the Abbe number (v of PBM2 d) be 36.3, partial dispersion is than (θ g is 0.5828 F), the Abbe number (v of NSL7 d) be 60.5, partial dispersion is than (θ g is 0.5436 F).)
At this, as the high refractive index (n that has more than 1.73 d) and the glass of 45 above high Abbe numbers (low chromatic dispersion), for example known to the opticglass shown in the patent documentation 1～3.
In addition, as the high refractive index (n that has more than 1.70 d) and 39 above and less than the glass of 52 high Abbe number (low chromatic dispersion), for example known just like a large amount of La that contains shown in the patent documentation 4～6 2O 3Become the opticglass of the rare earth elements that grades.
In addition, as having more than 1.60 and high refractive index (the n below 1.70 d) and the high Abbe number (v more than 50 d) glass, for example known to the opticglass shown in the patent documentation 7～10.
In addition, as the high refractive index (n that has more than 1.57 d) and the high Abbe number (v more than 50 d) glass, for example known to a large amount of La that contains shown in the patent documentation 11～19 2O 3Become the opticglass of the rare earth elements that grades.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-261877 communique
Patent documentation 2: TOHKEMY 2009-084059 communique
Patent documentation 3: TOHKEMY 2009-242210 communique
Patent documentation 4: TOHKEMY 2005-170782 communique
Patent documentation 5: TOHKEMY 2006-016295 communique
Patent documentation 6: No. 2004/054937 pph of International Publication
Patent documentation 7: japanese kokai publication sho 56-096747 communique
Patent documentation 8: japanese kokai publication sho 62-087433 communique
Patent documentation 9: japanese kokai publication hei 11-157868 communique
Patent documentation 10: TOHKEMY 2006-117504 communique
Patent documentation 11: TOHKEMY 2007-261877 communique
Patent documentation 12: TOHKEMY 2009-084059 communique
Patent documentation 13: TOHKEMY 2009-242210 communique
Patent documentation 14: TOHKEMY 2006-117503 communique
Patent documentation 15: japanese kokai publication hei 11-139844 communique
Patent documentation 16: japanese kokai publication sho 62-100449 communique
Patent documentation 17: TOHKEMY 2005-170782 communique
Patent documentation 18: TOHKEMY 2006-016295 communique
Patent documentation 19: No. 2004/054937 pph of International Publication
Summary of the invention
The problem that invention will solve
Yet the partial dispersion of the opticglass of patent documentation 1～19 is more little than also, is not enough to use as the lens of revising aforementioned secondary spectrum.That is, need low chromatic dispersion (high Abbe number) and partial dispersion than (θ g, F) big opticglass.More specifically, need have high refractive index (n d) and high Abbe number (v d) and partial dispersion than (θ g, F) also big opticglass.
Especially, disclosed glass has the problem that when making glass, is easy to take place devitrification in the patent documentation 5～13.By in case the glass that devitrification taken place comes manufacturing optical elements, the such optical element of light of particularly controlling visibility region is difficult.
The present invention puts in view of the above problems and makes, and its purpose is to obtain specific refractory power (n d) and Abbe number (v d) in desired range and can be preferred for the lens preform revising the opticglass of chromatic aberation and use it.
The scheme that is used to deal with problems
The inventor etc. have carried out deep experimental study repeatedly in order to address the above problem, the result finds, uses B through combination 2O 3Composition and La 2O 3Composition can be realized the high refractive index and the low chromatic dispersionization of glass, and the partial dispersion of glass is than (θ g is F) with Abbe number (v d) between also have required relation, thereby accomplished the present invention.Especially also find, through containing the F composition, even contain the strong La of effect that reduces the partial dispersion ratio 2O 3The rare earth elements that becomes to grade, the partial dispersion that also can make glass is than (θ g is F) with Abbe number (v d)) between have required relation.
Also find in addition, use B through combination 2O 3Composition and F composition can be realized the low chromatic dispersionization of glass, and can improve partial dispersion than and obtain with Abbe number (v d) between required relation.
In addition, through with B 2O 3Composition and La 2O 3Composition and A1 2O 3The combination of composition and F composition is used, and can realize the high refractive index and the low chromatic dispersionization of glass, even and contain the strong La of effect that reduces the partial dispersion ratio 2O 3The rare earth elements that becomes to grade, also can improve partial dispersion than and obtain and Abbe number (v d) between required relation, and can improve the liquidus temperature of glass.
Particularly, the present invention provides following technical scheme.
(1) a kind of opticglass, it contains B 2O 3Composition has the specific refractory power (n more than 1.70 d) and the Abbe number (v more than 39 d), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) or (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.
(2) according to (1) described opticglass, it further contains La 2O 3Composition has the specific refractory power (n more than 1.73 d) and the Abbe number (v more than 45 d), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) relation.
(3) according to (1) described opticglass, it further contains La 2O 3Composition and F composition have more than 39 and less than 52 Abbe number (v d), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.
(4) according to (1) described opticglass, it further contains the F composition, with Abbe number (v d) be the x axle, with specific refractory power (n d) be in the xy rectangular coordinates of y axle, have by the Abbe number and the specific refractory power of the scope of A (50,1.70), B (60,1.60), C (63,1.60), 4 encirclements of D (63,1.70).
(5) according to each the described opticglass in (2)～(4), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, B 2O 3Composition is 5.0～50.0%, La 2O 3The content of composition is below 55.0%.
(6) according to (5) described opticglass, it contains the La more than 5.0% with respect to the glass total mass that oxide compound converts and forms 2O 3Composition.
(7) according to (5) or (6) described opticglass, it contains the La more than 10.0% with respect to the glass total mass that oxide compound converts and forms 2O 3Composition.
(8) according to each the described opticglass in (5)～(7), the glass total mass that it converts and form with respect to oxide compound, La 2O 3The content of composition is below 50.0%.
(9) according to each the described opticglass in (1)～(8), it further contains Al in oxide compound converts composition 2O 3Composition.
(10) according to each the described opticglass in (1)～(9), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Al 2O 3The content of composition is below 20.0%.
(11) according to (10) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, contains more than 0.1% and the Al below 20.0% 2O 3Composition.
(12) according to each the described opticglass in (1)～(11), wherein, in the increment quality % with respect to the glass total mass of oxide compound benchmark, the content of F composition is below 30.0%.
(13) according to (12) described opticglass, wherein, the increment quality % in respect to the glass total mass of oxide compound benchmark contains the F composition greater than 0%.
(14) according to (12) or (13) described opticglass, wherein, the increment quality % in respect to the glass total mass of oxide compound benchmark contains the F composition more than 0.1%.
(15) according to each the described opticglass in (1)～(14), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, SiO 2The content of composition is below 40.0%.
(16) according to (15) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, SiO 2The content of composition is below 25.0%.
(17) according to (15) or (16) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains SiO 2Composition and its content are below 25.0%.
(18) according to each the described opticglass in (1)～(17), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (SiO 2+ B 2O 3) be below 40.0%.
(19) according to each the described opticglass in (1)～(18), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %,
Gd 2O 3Composition be 0～40.0% and/or
Y 2O 3Composition be 0～20.0% and/or
Yb 2O 3Composition be 0～20.0% and/or
Lu 2O 3Composition is 0～20.0%.
(20) according to (19) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～40.0%Gd 2O 3Composition and/or
0～20.0%Y 2O 3Composition and/or
0～20.0%Yb 2O 3Composition and/or
0～10.0%Lu 2O 3Each composition of composition.
(21) according to (19) or (20) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～30.0%Gd 2O 3Composition and/or
0～20.0%Y 2O 3Composition and/or
0～20.0%Yb 2O 3Composition and/or
0～10.0%Lu 2O 3Each composition of composition.
(22) according to each the described opticglass in (1)～(21), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Gd 2O 3Content be below 29.5%.
(23) according to each the described opticglass in (1)～(22), wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) and be below 80.0%.
(24) according to (23) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) and be more than 20.0%.
(25) according to (23) or (24) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) and be more than 20.0% and below 80.0%.
(26) according to each the described opticglass in (1)～(25), wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) and greater than 43.0% and be below 80.0%.
(27) according to (26) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb more than one) and be below 63.5%.
(28) according to (26) or (27) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb more than one) and less than 53.0%.
(29) according to each the described opticglass in (1)～(28), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (Gd 2O 3+ Yb 2O 3) be below 26.0%.
(30) according to each the described opticglass in (1)～(29), wherein, the mass ratio Ln during the oxide compound conversion is formed 2O 3/ (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5) be more than 1.7 and below 25.0.
(31) according to each the described opticglass in (1)～(30), wherein, the mass ratio Ln that oxide compound converts and forms 2O 3/ (SiO 2+ B 2O 3) be (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) more than 1.00.
(32) according to each the described opticglass in (1)～(31), wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～10.0%Bi 2O 3Composition and/or
0～15.0%TiO 2Composition and/or
0～20.0%Nb 2O 5Each composition of composition.
(33) according to each the described opticglass in (1)～(32), wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～15.0%WO 3Composition and/or
0～10.0%K 2Each composition of O composition.
(34) according to each the described opticglass in (1)～(33), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be more than 0.1% and below 30.0%.
(35) according to (34) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be more than 1.0%.
(36) according to each the described opticglass in (1)～(35), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5) be below 20.0%.
(37) according to (36) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5) be below 10.0%.
(38) according to each the described opticglass in (1)～(37), wherein, the mass ratio F/ (F+Bi during the oxide compound conversion is formed 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be more than 0.36 and below 1.00.
(39) according to each the described opticglass in (1)～(38), wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～15.0%ZrO 2Composition and/or
0～25.0%Ta 2O 5Composition.
(40) according to (39) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～15.0%ZrO 2Composition and/or
0～15.0%Ta 2O 5Each composition of composition.
(41) according to each the described opticglass in (1)～(40), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (WO 3+ La 2O 3+ ZrO 2+ Ta 2O 5) be more than 10.0% and below 60.0%.
(42) according to each the described opticglass in (1)～(41), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5) greater than 0%.
(43) according to each the described opticglass in (1)～(42), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Li 2The content of O composition is below 15.0%.
(44) according to (43) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Li 2The content of O composition is below 10.0%.
(45) according to (44) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Li 2The content of O composition is below 5.0%.
(46) according to each the described opticglass in (1)～(45), wherein, the mass ratio (Ta during the oxide compound conversion is formed 2O 5+ ZrO 2+ Li 2O)/(F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be below 2.00.
(47) according to each the described opticglass in (1)～(46), wherein, the mass ratio (F+Bi that oxide compound converts and forms 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O)/(Ta 2O 5+ ZrO 2+ Li 2O) be more than 0.50.
(48) according to (47) described opticglass, wherein, the mass ratio (F+Bi that oxide compound converts and forms 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O)/(Ta 2O 5+ ZrO 2+ Li 2O) be more than 1.3.
(49) according to each the described opticglass in (1)～(48), wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～20.0%MgO composition and/or
0～40.0%CaO composition and/or
0～40.0%SrO composition and/or
Each composition of 0～55.0%BaO composition.
(50) according to (49) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～10.0%MgO composition and/or
0～25.0%CaO composition and/or
0～25.0%SrO composition and/or
Each composition of 0～55.0%BaO composition.
(51) according to (49) or (50) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %,
The MgO composition be 0～10.0% and/or
The CaO composition be 0～15.0% and/or
The SrO composition be 0～15.0% and/or
The BaO composition is 0～25.0%.
(52) according to each the described opticglass in (1)～(51), wherein, with respect to the glass total mass that oxide compound converts and forms, the quality of RO composition (in the formula, R is selected from the group of being made up of Mg, Ca, Sr, Ba more than one) and be below 55.0%.
(53) according to (52) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, the quality of RO composition (in the formula, R is selected from the group of being made up of Mg, Ca, Sr, Ba more than one) and be below 25.0%.
(54) according to (52) or (53) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, the quality of RO composition (in the formula, R is selected from the group of being made up of Mg, Ca, Sr, Ba more than one) and be below 20.0%.
(55) according to each the described opticglass in (1)～(54), wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Na 2The content of O composition is below 20.0%.
(56) according to (55) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Na 2The content of O composition is below 10.0%.
(57) according to each the described opticglass in (1)～(56), wherein, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition (in the formula, Rn is selected from the group of being made up of Li, Na, K more than one) and be below 25.0%.
(58) according to (57) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition (in the formula, Rn is selected from the group of being made up of Li, Na, K more than one) and be below 15.0%.
(59) according to each the described opticglass in (1)～(58), wherein, with respect to the glass total mass that oxide compound converts and forms, by quality %, the content of ZnO composition is below 30.0%.
(60) according to (59) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, by quality %, the content of ZnO composition is below 25.0%.
(61) according to (59) or (60) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, by quality %, the content of ZnO composition is below 15.0%.
(62) according to each the described opticglass in (1)～(61), wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～10.0%GeO 2Composition and/or
0～10.0%P 2O 5Composition and/or
0～10.0%Ga 2O 3Composition and/or
0～10.0%TeO 2Composition and/or
0～5.0%SnO 2Composition and/or
0～1.0%Sb 2O 3Each composition of composition.
(63) according to (62) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %,
GeO 2Composition be 0～10.0% and/or
P 2O 5Composition be 0～10.0% and/or
Ga 2O 3Composition be 0～10.0% and/or
TeO 2Composition be 0～10.0% and/or
SnO 2Composition be 0～1.0% and/or
Sb 2O 3Composition is 0～1.0%.
(64) according to each the described opticglass in (1)～(63), it has the specific refractory power (n more than 1.57 d) and the Abbe number (v more than 45 d).
(65) according to each the described opticglass in (1)～(64), wherein, Abbe number (v d) and specific refractory power (n d) between satisfy v d>=-100 * n d+ 220 relation.
(66) according to each the described opticglass in (1)～(65), wherein, Abbe number (v d) and specific refractory power (n d) between satisfy v d>=-125 * n d+ 265 relation.
(67) a kind of preform material, it is to be formed by each the described opticglass in (1)～(66).
(68) a kind of optical element, it makes the compression moulding of (67) said preform material.
(69) a kind of optical element, it is a mother metal with each the described opticglass in (1)～(66).
(70) a kind of optical device, it possesses each the described optical element in (68) or (69).
The effect of invention
According to the present invention, can access specific refractory power (n d) and Abbe number (v d) in desired range and can be preferred for preform and the optical element revising the opticglass of chromatic aberation and use it.
Description of drawings
Fig. 1 is illustrated in partial dispersion than (θ g F) is the longitudinal axis, Abbe number (v for illustrating d) be the figure of the standard lines in the rectangular coordinates of transverse axis.
Embodiment
Opticglass of the present invention contains B 2O 3Composition, partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) or (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.Through making partial dispersion than (θ g is F) with Abbe number (v d) between satisfy the relation of regulation, thereby the chromatic aberation of the optical element that reduces to form by opticglass.Therefore, can access specific refractory power (n d) and Abbe number (v d) in desired range and can be preferred for preform and the optical element revising the opticglass of chromatic aberation and use it.
Especially, the opticglass of first embodiment (below be called first opticglass.) contain B 2O 3Composition, La 2O 3Composition has the specific refractory power (n more than 1.73 d) and the Abbe number (v more than 45 d), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) relation.Especially, in first opticglass, through containing B 2O 3Composition and La 2O 3Composition can improve the specific refractory power of glass and reduce chromatic dispersion.In addition, through making partial dispersion than (θ g is F) with Abbe number (v d) between satisfy the relation of regulation, can reduce the chromatic aberation of the optical element that forms by opticglass.Therefore, can access specific refractory power (n d) and Abbe number (v d) in desired range and painted less, can be preferred for preform and the optical element revising the opticglass of chromatic aberation and use it.
In addition, the opticglass of second embodiment (below be called second opticglass.) contain B 2O 3Composition, La 2O 3Composition and F composition have the specific refractory power (n more than 1.70 d) and 39 above and less than 52 Abbe number (v d), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.Especially, in second opticglass, through containing B 2O 3Composition and La 2O 3Composition can improve the specific refractory power of glass and reduce chromatic dispersion, also can improve the transparency to visible light.In addition, through containing the F composition, even contain the strong La of effect that reduces the partial dispersion ratio 2O 3The rare earth elements that becomes to grade is through improving partial dispersion than (θ g F), also can reduce the chromatic aberation of the optical element that is formed by opticglass.Therefore, can access specific refractory power (n d) and Abbe number (v d) in desired range and painted less, can be preferred for revising the opticglass of chromatic aberation.
In addition, the opticglass of the 3rd embodiment (below be called the 3rd opticglass.) contain B 2O 3Composition and F composition are with Abbe number (v d) be the x axle, with specific refractory power (n d) be in the xy rectangular coordinates of y axle, have by the Abbe number and the specific refractory power of the scope of A (50,1.70), B (60,1.60), C (63,1.60), 4 encirclements of D (63,1.70), partial dispersion is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=-0.00170 * v d+ 0.6375 relation.Especially, in the 3rd opticglass, use B through combination 2O 3Composition and F composition can be realized the low chromatic dispersionization of glass, and can improve partial dispersion than and obtain with Abbe number (v d) between required relation.Therefore, can access specific refractory power (n d) and Abbe number (v d) in desired range and can be preferred for preform and the optical element revising the opticglass of chromatic aberation and use it.
In addition, the opticglass of the 4th embodiment (below be called the 4th opticglass.) contain 5.0～55.0% B by quality % 2O 3Composition, 10.0～55.0% La 2O 3Composition further contains Al 2O 3Composition and F composition.Especially, in the 4th opticglass, contain B through the scope of content with regulation 2O 3Composition and La 2O 3Composition can improve the specific refractory power of glass and reduce chromatic dispersion, and can improve the transparency to visible light.In addition, through with B 2O 3Composition and La 2O 3Composition and Al 2O 3Composition and the combination of F composition are used, even contain the strong La of effect that reduces the partial dispersion ratio 2O 3The rare earth elements that becomes to grade also can improve partial dispersion than (θ g F), and can improve the liquidus temperature of glass.Therefore, can access specific refractory power (n d) and Abbe number (v d) in desired range and can be preferred for revising chromatic aberation and the high opticglass of anti-increased devitrification resistance.
Below, the embodiment of opticglass of the present invention is elaborated, but the present invention does not receive any qualification of following embodiment, can be in the scope of the object of the invention in addition suitably change implement.In addition,, suitably omit explanation sometimes, but do not limit the aim of invention for the place of repeat specification.
Glass ingredient
Below explanation constitutes the compositing range of each composition of opticglass of the present invention.In this manual, do not having under the situation about specifying, the quality % of the glass total mass that the content of each composition is all formed to convert with respect to oxide compound representes.At this; " oxide compound converts and forms " is meant; The oxide compound that uses as the raw material of glass constituent of the present invention in supposition, composite salt, metal fluoride etc. all decompose during in fusion and become under the situation of oxide compound, the composition when being each composition that contains in the glass represented of 100 quality % with the total mass of this generation oxide compound.
About neccessary composition, optional member
B 2O 3Composition is at the inner composition that forms network structure, promotes stable glass formation of glass.Especially, through making B 2O 3The content of composition is more than 5.0%, can make glass be not easy devitrification, be easy to obtain stable glass.On the other hand, through making B 2O 3The content of composition is below 55.0%, can be easy to the specific refractory power and the dispersivity that obtain expecting.Therefore, with respect to the glass total mass that oxide compound converts and forms, B 2O 3The content of composition preferably with 5.0%, more preferably with 8.0%, further preferably with 10.0%, further preferably with 13.0%, most preferably be lower limit with 15.0%.On the other hand, this B 2O 3The content of composition preferably with 55.0%, more preferably with 50.0%, further preferably with 45.0%, further preferably with 40.0%, further be the upper limit preferably with 35.0%.Especially, in opticglass of the present invention, this B 2O 3The content of composition can be the upper limit with 30.0%.B 2O 3Composition for example can use H 3BO 3, Na 2B 4O 7, Na 2B 4O 710H 2O, BPO 4Deng containing in glass as raw material.
La 2O 3Composition is specific refractory power that improves glass and the composition that reduces chromatic dispersion.
Especially, through making La 2O 3The content of composition is below 55.0%, can suppress the glass phase-splitting, make that glass is not easy devitrification when making glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, La 2O 3The content of composition preferably with 55.0%, more preferably with 54.0%, further preferably with 53.0%, further preferably with 52.0%, further preferably with 50.0%, most preferably be the upper limit with 45.0%.In addition, La 2O 3The lower limit of the content of composition can suitably be set in the scope of the glass that can obtain having desired optical, through making La 2O 3The content of composition is more than 5.0%, can be easy to obtain expecting have high refractive index and high Abbe number and to the high glass of visible light transmittance.Therefore, this La 2O 3Component content preferably with 5.0%, more preferably be lower limit with 10.0%, further be preferably greater than 12.0%, further preferably with 13.0%, further be lower limit preferably with 15.0%.This La 2O 3The content of composition can be lower limit with 25.0% also 20.0% to be lower limit.La 2O 3Composition for example can use La 2O 3, La (NO 3) 3XH 2O (X is an arbitrary integer) etc. contains in glass as raw material.
The F composition is the composition of the partial dispersion ratio of raising glass, and for reducing the composition of second-order transition temperature (Tg).Especially, be below 30.0% through the content that makes the F composition, can improve the stability of glass and make it be not easy devitrification.Therefore, in increment quality % with respect to the glass total mass of oxide compound benchmark, the content of F composition preferably with 30.0%, more preferably with 25.0%, further preferably with 20.0%, most preferably be the upper limit with 15.0%.Especially, in the 3rd opticglass, the content that can make this F composition is below 10.0%.In addition, even opticglass of the present invention does not contain the opticglass that the F composition also can obtain having the high partial dispersion ratio of expectation, and through containing the F composition, can access have high partial dispersion than and the painted opticglass that lacks.Therefore, in the increment quality % with respect to the glass total mass of oxide compound benchmark, the content of F composition is preferably greater than 0%; Being lower limit with 0.1% more preferably, more preferably greater than 0.5%, is lower limit with 1.0% preferably further; Further be preferably greater than 1.0%; Further being preferably greater than 2.0%, is lower limit with 3.0% preferably further, most preferably greater than 3.0%.Especially, in the first and the 4th opticglass, in this increment quality % with respect to the glass total mass, the content of F composition can be 5.0% being lower limit, can be lower limit with 6.8% also 6.2% to be lower limit.In addition, in the 4th opticglass, the content of this F composition can be preferably with 6.0%, further preferably with 7.0%, most preferably be lower limit with 8.0%.The F composition for example can use ZrF 4, AlF 3, NaF, CaF 2, LaF 3Deng containing in glass as raw material.
In addition; Content for the F composition in this specification sheets; Suppose constitute glass cation constituent all by with electric charge just in time the oxide compound that combined of equilibrated oxygen form; With the overall quality of the glass that is formed by these oxide compounds is 100%, and the quality of F composition is represented (with respect to the increment quality % of the glass total mass of oxide compound benchmark) with quality %.
Al 2O 3Composition is the optional member in the opticglass of the present invention for making the composition that is easy to form stable glass.Especially, through making Al 2O 3The content of composition is below 20.0%, and the Abbe number that can suppress glass reduces.Therefore, with respect to the glass total mass that oxide compound converts and forms, Al 2O 3The content of composition preferably with 20.0%, more preferably with 15.0%, further be the upper limit preferably with 10.0%.This Al 2O 3The content of composition can be preferably with 8.0%, further preferably with 5.0%, most preferably be the upper limit with 2.0%.At this, can not contain Al 2O 3Composition, and especially in the 4th opticglass, through containing Al 2O 3Composition, the Abbe number that can suppress glass reduces.Therefore, with respect to the glass total mass that oxide compound converts and forms, Al 2O 3The content of composition is preferably greater than 0%, more preferably with 0.1%, further preferably with 0.5%, further be lower limit preferably with 1.0%, further be preferably greater than 3.0%, most preferably greater than 3.4%.Al 2O 3Composition for example can use Al 2O 3, Al (OH) 3, AlF 3Deng containing in glass as raw material.
Especially, in the 4th opticglass, preferably, Al 2O 3The content of composition with respect to the ratio of the content of F composition greater than 0 and be below 15.0.By making this ratio within the limits prescribed, can improve the stability of glass, therefore can access the higher glass of anti-increased devitrification resistance.Therefore, the mass ratio Al of oxide compound conversion composition 2O 3/ F is preferably greater than 0, more preferably with 0.1, most preferably be lower limit with 0.3.On the other hand, the upper limit of this ratio preferably with 15.0, more preferably with 10.0, further preferably with 5.0, further preferably with 4.0, most preferably be the upper limit with 3.2.In addition, in the ratio of this content, the content of F composition is meant in the content with respect to the increment quality % of the glass total mass of oxide compound benchmark, Al 2O 3The content of composition is meant the content of the glass total mass of forming with respect to the oxide compound conversion.
SiO 2Composition is the composition of the devitrification (generation crystallisate) when promoting stable glass formation and inhibition making glass, is the optional member in the opticglass of the present invention.Especially, through making SiO 2The content of composition is below 40.0%, can be easy to SiO 2Composition is dissolved in the melten glass, avoids at high temperature fusing.With respect to the glass total mass that oxide compound converts and forms, SiO 2The content of composition preferably with 40.0%, more preferably be the upper limit with 30.0%;, be the upper limit preferably further, further further preferably less than 25.0% with 25.0% preferably less than 28.0%; Further preferably with 24.0%, further be the upper limit preferably, most preferably less than 20.0% with 20.0%.Especially, first, second with the 4th opticglass in, this SiO 2The content of composition can be the upper limit with 10.0% also 15.0% to be the upper limit.In addition, even do not contain SiO 2Composition also can obtain having the glass of the high partial dispersion ratio of expectation, and through containing SiO 2Composition can improve the anti-increased devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, SiO 2The content of composition is preferably greater than 0%, preferably with 0.1%, more preferably with 0.5%, further be lower limit preferably with 1.0%.Especially, in the 3rd opticglass, this SiO 2The content of composition can be 4.0% to be lower limit, also can be greater than 5.0%.SiO 2Composition for example can use SiO 2, K 2SiF 6, Na 2SiF 6Deng containing in glass as raw material.
Especially, the preferred SiO of the 4th opticglass 2Composition and B 2O 3The quality of composition and be below 40.0%.Thus, the specific refractory power that can suppress glass reduces, and therefore can access the opticglass of the high refractive index with expectation.Therefore, with respect to the glass total mass that oxide compound converts and forms, quality and (SiO 2+ B 2O 3) preferably with 40.0%, more preferably with 35.0%, most preferably be the upper limit with 32.0%.In addition, consider this quality and (SiO from the viewpoint that obtains the high glass of stable height and anti-increased devitrification resistance 2+ B 2O 3) preferably with 5.0%, more preferably with 10.0%, most preferably be lower limit with 15.0%.
Gd 2O 3Composition is specific refractory power that improves glass and the composition that reduces chromatic dispersion.
Especially, through making Gd 2O 3The content of composition is below 40.0%, can suppress the glass phase-splitting and make that glass is not easy devitrification when making glass.
Therefore, with respect to the glass total mass that oxide compound converts and forms, Gd 2O 3The content of composition preferably with 40.0%, more preferably with 35.0%, further preferably with 30.0%, most preferably with 29.5%2 upper limits.
Especially, in the 3rd opticglass, this Gd 2O 3The content of composition can be more preferably less than 25.0% preferably less than 28.0%, most preferably less than 20.0%.
In addition, even do not contain Gd 2O 3Composition also can obtain having the glass of the high partial dispersion ratio of expectation, and through containing the Gd more than 0.1% 2O 3Composition can be easy to the specific refractory power and the dispersivity that obtain to expect.Therefore, with respect to the glass total mass that oxide compound converts and forms, Gd 2O 3The content of composition preferably with 0.1%, more preferably with 1.0%, further be lower limit preferably with 2.0%.Especially, in the first and the 4th opticglass, this Gd 2O 3The content of composition can be lower limit with 7.0% also 5.0% to be lower limit.Gd 2O 3Composition for example can use Gd 2O 3, GdF 3Deng containing in glass as raw material.
Y 2O 3Composition, Yb 2O 3Composition and Lu 2O 3Composition is specific refractory power that improves glass and the composition that reduces chromatic dispersion.At this, through making Y 2O 3Composition, Yb 2O 3Composition or Lu 2O 3The content of composition is below 20.0%, can make glass be not easy devitrification.Especially, through making Yb 2O 3The content of composition is below 10.0%, makes glass be not easy to produce near long wavelength side (wavelength 1000nm) and absorbs, and therefore can improve glass to ultrared patience.Therefore, with respect to the glass total mass that oxide compound converts and forms, Y 2O 3Composition and Yb 2O 3The content of composition preferably with 20.0%, more preferably with 15.0%, further preferably with 10.0%, further preferably with 8.0%, further preferably with 5.0%, most preferably be the upper limit with 4.0%.In addition, with respect to the glass total mass that oxide compound converts and forms, Lu 2O 3The content of composition preferably with 20.0%, more preferably with 15.0%, further preferably with 10.0%, further preferably with 8.0%, further preferably with 5.0%, most preferably be the upper limit with 3.0%.Especially, from improving glass the viewpoint of ultrared patience is considered, with respect to the glass total mass that oxide compound converts and forms, Yb 2O 3The content of composition is preferably less than 3.0%, most preferably less than 1.0%.Y 2O 3Composition, Yb 2O 3Composition and Lu 2O 3Composition for example can use Y 2O 3, YF 3, Yb 2O 3, Lu 2O 3Deng containing in glass as raw material.
The preferred Ln of opticglass of the present invention 2O 3The quality of the content of composition (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) and be below 80.0%.Thus, can alleviate the devitrification of glass when making glass.
Therefore, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of the content of composition and preferably with 80.0%, more preferably with 78.0%, most preferably be the upper limit with 75.0%.Especially, in the 3rd opticglass, this Ln 2O 3The quality of the content of composition with can be preferably with 63.5%, more preferably with 60.0%, further be the upper limit preferably, most preferably less than 50.0% with 55.0%.In addition, Ln 2O 3The lower limit of the total content of composition can suitably be selected in the scope of the opticglass that can obtain desired characteristics, and through making it for example greater than 10.0%, the high refractive index and the Abbe number that can be easy to obtain to expect, reduces painted and reduces photoelastic constant.Especially, in opticglass of the present invention, even contain a large amount of rare earth class, partial dispersion reduces than also being not easy, and therefore can be easy to have concurrently high partial dispersion ratio and the high refractive index and the Abbe number of expectation.Therefore, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of the content of composition be preferably greater than 10.0%, more preferably greater than 15.0%, further be preferably greater than 16.0%, be lower limit preferably further, most preferably greater than 20.0% with 20.0%.Especially, first, second with the 4th opticglass in, this Ln 2O 3The quality of the content of composition with can be preferably with 30.0%, more preferably be lower limit with 40.0%, further be preferably greater than 43.0%, further preferably with 45.0%, further preferably with 50.0%, most preferably be lower limit with 55.0%.
Especially, the preferred Gd of the 3rd opticglass 2O 3Composition and Yb 2O 3Composition and be below 26.0%.Thus, can control the strong Gd of effect that improves specific refractory power 2O 3Composition and Yb 2O 3The use of composition, therefore can improve partial dispersion than and be easy to the specific refractory power and the chromatic dispersion that obtain to expect.Therefore, with respect to the glass total mass that oxide compound converts and forms, quality and (Gd 2O 3+ Yb 2O 3) preferably with 26.0%, more preferably with 23.0%, further preferably with 20.0%, most preferably be the upper limit with 15.0%.
In addition, the preferred Ln of opticglass of the present invention 2O 3Content with respect to quality and (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5) mass ratio be more than 1.7 and below 25.0.Thus, with respect to the Bi that reduces Abbe number 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and Ta 2O 5The total content of composition, the feasible Ln that improves Abbe number 2O 3Total content in the scope of regulation, therefore can be easy to the Abbe number that obtains to expect, so can make partial dispersion than and Abbe number between have required relation.Therefore, the mass ratio Ln during the oxide compound conversion is formed 2O 3/ (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5) preferably with 1.7, more preferably with 3.0, further be lower limit preferably with 5.0, preferably with 25.0, more preferably with 20.0, most preferably be the upper limit with 16.8.
In addition, the 4th opticglass preferably, Ln 2O 3The content of (in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one) composition is with respect to S iO 2Composition and B 2O 3The quality of composition and ratio be more than 1.00.Through making this ratio is more than 1.00, even do not contain Al 2O 3Composition also can further improve specific refractory power, therefore can access the opticglass that has high partial dispersion ratio and have the stability and the high refractive index of glass concurrently.Therefore, the mass ratio Ln of oxide compound conversion composition 2O 3/ (SiO 2+ B 2O 3) preferably with 1.00, more preferably with 1.25, most preferably be lower limit with 1.40.On the other hand, as long as the upper limit of this ratio can obtain that stable glass is just not special to be limited, but infer for example might becoming and be easy to take place devitrification greater than 10.0 o'clock.Therefore, the mass ratio Ln of oxide compound conversion composition 2O 3/ (SiO 2+ B 2O 3) preferably with 10.00, more preferably with 8.00, most preferably be the upper limit with 5.00.At Ln 2O 3In the composition, La 2O 3Composition has the effect of the stability that further improves glass, therefore particularly considers from the viewpoint that obtains the high glass of anti-increased devitrification resistance, makes La 2O 3/ (SiO 2+ B 2O 3) ratio in above-mentioned scope, be preferred.In addition, consider the mass ratio La that oxide compound converts and forms from the viewpoint that obtains the high glass of more anti-increased devitrification resistance 2O 3/ B 2O 3Can be preferably with 10.00, more preferably with 5.00, further preferably with 3.50, further be the upper limit preferably, most preferably less than 2.00 with 2.30.
Bi 2O 3Composition is the composition of the partial dispersion ratio of raising glass, and for specific refractory power that improves glass and the composition that reduces second-order transition temperature, is the optional member in the opticglass of the present invention.Especially, through making Bi 2O 3The content of composition is below 10.0%, can make the light transmittance of visible short long (below the 500nm) be not easy variation.Therefore, with respect to the glass total mass that oxide compound converts and forms, Bi 2O 3The content of composition preferably with 10.0%, more preferably with 8.0%, most preferably be the upper limit with 5.0%.Bi 2O 3Composition for example can use Bi 2O 3Deng containing in glass as raw material.
TiO 2Composition is the composition of the partial dispersion ratio of raising glass, and for specific refractory power and chromatic dispersion that improves glass and the composition that improves the chemical durability of glass, is the optional member in the opticglass of the present invention.Especially, through making TiO 2The content of composition is below 15.0%, can be easy to the high Abbe number that obtains to expect and make the light transmittance of visible short long (below the 500nm) be not easy variation.Therefore, with respect to the glass total mass that oxide compound converts and forms, TiO 2The content of composition preferably with 15.0%, more preferably with 12.0%, further preferably with 10.0%, further preferably with 8.0%, further preferably with 7.0%, most preferably be the upper limit with 5.0%.TiO 2Composition for example can use TiO 2Deng containing in glass as raw material.
Nb 2O 5Composition is the composition of the partial dispersion ratio of raising glass, and for specific refractory power and chromatic dispersion that improves glass and the composition that improves the chemical durability of glass, is the optional member in the opticglass of the present invention.Especially, through making Nb 2O 5The content of composition is below 20.0%, can be easy to the high Abbe number that obtains to expect.Therefore, with respect to the glass total mass that oxide compound converts and forms, Nb 2O 5The content of composition preferably with 20.0%, more preferably with 15.0%, most preferably be the upper limit with 10.0%.Nb 2O 5Composition for example can use Nb 2O 5Deng containing in glass as raw material.
WO 3Composition is the composition of the partial dispersion ratio of raising glass, and for specific refractory power and chromatic dispersion that improves glass and the composition that improves the chemical durability of glass, is the optional member in the opticglass of the present invention.Especially, through making WO 3The content of composition is below 15.0%, can be easy to the high Abbe number that obtains to expect and make the light transmittance of visible short long (below the 500nm) be not easy variation.Therefore, with respect to the glass total mass that oxide compound converts and forms, WO 3The content of composition preferably with 15.0%, more preferably with 12.0%, further preferably with 10.0%, further preferably with 8.0%, most preferably be the upper limit with 5.0%.In addition, even do not contain WO 3Composition also can obtain having the opticglass of the high partial dispersion ratio of expectation, and through making WO 3Therefore the content of composition is more than 0.1%, can improve the partial dispersion ratio of glass, can be easy to obtain have the glass of the high partial dispersion ratio of expectation.Therefore, with respect to the glass total mass that oxide compound converts and forms, WO 3The content of composition preferably with 0.1%, more preferably with 0.3%, most preferably be lower limit with 0.5%.WO 3Composition for example can use WO 3Deng containing in glass as raw material.
K 2The O composition is the composition that further improves the partial dispersion ratio of glass, and for improving the composition of glass melting property, is the optional member in the opticglass of the present invention.Especially, through making K 2The content of O composition is below 10.0%, can make devitrification etc. be not easy to take place so that the specific refractory power of glass is not easy to reduce, improve the stability of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, K 2The content of O composition preferably with 10.0%, more preferably with 8.0%, most preferably be the upper limit with 5.0%.K 2The O composition for example can use K 2CO 3, KNO 3, KF, KHF 2, K 2SiF 6Deng containing in glass as raw material.
In opticglass of the present invention, be preferably selected from by F composition, Bi 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and K 2O become in the group be grouped into more than one content and be more than 0.1%.Through making this and being more than 0.1%, make it must contain the composition that improves the partial dispersion ratio, therefore can be easy to the high partial dispersion ratio that obtains to expect.In addition, can improve the partial dispersion ratio of glass, therefore can make between partial dispersion ratio and the Abbe number to have required relation.Therefore; With respect to the quality that oxide compound convert to be formed, the content of these compositions with preferably with 0.1%, more preferably with 1.0%, further preferably with 3.0%, further preferably with 4.0%, further preferably with 5.0%, further preferably with 6.2%, most preferably be lower limit with 8.0%.On the other hand, if the content of these compositions and the upper limit can obtain that stable glass is just not special to be limited, but infer for example might becoming and be easy to take place devitrification greater than 60.0% o'clock.Therefore, with respect to the quality that oxide compound convert to be formed, the content of these compositions with preferably with 60.0%, more preferably with 50.0%, further be the upper limit preferably with 40.0%.Especially, in the second and the 3rd opticglass, with respect to the quality that oxide compound convert to be formed, the content of these compositions with can be preferably with 30.0%, more preferably with 25.0%, more preferably with 20.0%, most preferably be the upper limit with 15.0%.In addition, this content with in, the content of F composition is meant in the content with respect to the increment quality % of the glass total mass of oxide compound benchmark, Bi 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and K 2The content of O composition is meant the content of the glass total mass of forming with respect to the oxide compound conversion.
In these compositions, K 2The O composition has the effect that reduces specific refractory power, therefore especially considers from the viewpoint that can access the high glass of specific refractory power, preferably contains to be selected from by F composition, Bi 2O 3Composition, TiO 2Composition, WO 3Composition and Nb 2O 5In the group that becomes to be grouped into more than one.In addition, Nb 2O 5It is strong that composition reduces the effect of Abbe number, therefore especially considers from the viewpoint that can access the high glass of Abbe number, preferably contains to be selected from by F composition, Bi 2O 3Composition, TiO 2Composition, WO 3Composition and K 2In the group that O becomes to be grouped into more than one.In addition, Bi 2O 3Composition, TiO 2Composition and WO 3Therefore composition is strong with the effect of glass coloring, especially considers from the viewpoint that can access painted few glass, preferably contains to be selected from by F composition, Nb 2O 5Composition and K 2In the group that O becomes to be grouped into more than one.Therefore, from can access have high partial dispersion than and specific refractory power and Abbe number are high and the viewpoint of the painted glass that lacks is considered, in these compositions, preferably make the content of F composition more.
Bi in preferred these compositions of opticglass of the present invention 2O 3Composition, TiO 2Composition, WO 3Composition and Nb 2O 5The content of composition and be below 20.0%.Thus, therefore the composition that can minimizing can cause chromatic dispersion to be increased can be easy to obtain have the glass of the chromatic dispersion of expectation.In addition, can suppress to reduce, therefore can further improve the anti-increased devitrification resistance of glass by the excessive stability that contains the glass that these compositions cause.Therefore, with respect to the glass total mass that oxide compound converts and forms, quality and (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5) preferably with 20.0%, more preferably with 15.0%, most preferably be the upper limit with 10.0%.Especially, this quality in the 3rd opticglass with can be the upper limit also 8.0% to be the upper limit with 5.0%.In addition, especially consider from the viewpoint that can access the little glass of chromatic dispersion, this quality with can be less than 0.5%.On the other hand; Even do not contain the opticglass that in these compositions any one also can obtain having the high partial dispersion ratio of expectation; And the quality through making these compositions and be more than 0.1%; Therefore the partial dispersion ratio of glass can be improved, the glass of the high partial dispersion ratio of expectation can be easy to obtain have.Therefore, consider this quality and (Bi from the viewpoint that obtains high partial dispersion ratio 2O 3+ TiO 2+ WO 3+ Nb 2O 5) can be preferably with 0.1%, more preferably with 0.5%, further be lower limit preferably with 0.8%.
Especially, the 3rd opticglass preferably, the content of F composition is with respect to F composition, Bi 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and K 2The content of O composition and ratio be more than 0.36.Especially, be more than 0.36 through making this ratio, can improve partial dispersion than and contain a large amount of painted compositions that lacks, therefore can access the transparent glass of partial dispersion ratio with expectation.Therefore, the mass ratio F/ (F+Bi during the oxide compound conversion is formed 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) preferably with 0.36, more preferably with 0.40, further be lower limit preferably with 0.50.In addition, this mass ratio most preferably is 1.00, considers from the viewpoint of wanting to obtain more stable glass, can be less than 1.00.
ZrO 2Composition is the optional member in the opticglass of the present invention for the specific refractory power that improves glass, the composition of anti-increased devitrification resistance the when improving making glass.Especially, through making ZrO 2The content of composition is below 15.0%, and the partial dispersion that can suppress glass is than reducing.In addition, through making ZrO 2The content of composition is below 15.0%, can suppress the Abbe number reduction of glass and avoid fusion, the power loss when reducing the glass manufacturing under the high temperature when the manufacturing of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, ZrO 2The content of composition preferably with 15.0%, more preferably with 10.0%, further preferably with 8.0%, further preferably with 7.0%, further be the upper limit preferably, most preferably less than 4.0% with 5.0%.In addition, even do not contain ZrO 2Composition also can obtain having the glass of desired optical, and through making ZrO 2The content of composition is more than 0.1%, can improve the anti-increased devitrification resistance of glass.Therefore, containing ZrO 2Under the situation of composition, with respect to the glass total mass that oxide compound converts and forms, ZrO 2The choosing of the content of composition with 0.1%, more preferably with 0.5%, further be lower limit preferably with 1.0%.ZrO 2Composition for example can use ZrO 2, ZrF 4Deng containing in glass as raw material.
Ta 2O 5Composition is the optional member in the opticglass of the present invention for make the composition of stabilizationization simultaneously in the specific refractory power that improves glass.Especially, through making Ta 2O 5The content of composition is below 25.0%, and the partial dispersion that can suppress glass is than reducing.In addition, through making Ta 2O 5The content of composition is below 25.0%, can reduce the material cost of glass and avoid fusion at high temperature and power loss when reducing glass and making.Therefore, with respect to the glass total mass that oxide compound converts and forms, Ta 2O 5The content of composition is the upper limit with 25.0% preferably, is more preferably less than 16.5%, further preferably with 15.0%, further preferably with 10.0%, most preferably be the upper limit with 5.0%.Ta 2O 5Composition for example can use Ta 2O 5Deng containing in glass as raw material.
In opticglass of the present invention, preferred WO 3Composition, La 2O 3Composition, ZrO 2Composition and Ta 2O 5Content and be more than 10.0%.Through making this and be more than 10.0%, can when alleviating glass painted, further improve specific refractory power.Therefore, with respect to the quality that oxide compound convert to be formed, the content of these compositions with preferably with 10.0%, more preferably with 20.0%, further preferably with 25.0%, most preferably be lower limit with 30.0%.On the other hand, if the content of these compositions and the upper limit can obtain that stable glass is just not special to be limited, but infer for example might becoming and be easy to take place devitrification greater than 65.0% o'clock.Therefore, with respect to the quality that oxide compound convert to be formed, the content of these compositions with preferably with 65.0%, more preferably with 60.0%, further preferably with 55.0%, most preferably be the upper limit with 50.0%.
Especially, in second opticglass, preferably, be selected from i by B 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and Ta 2O 5Become in the group be grouped into more than one content and greater than 0%.Therefore thus, make the Abbe number of glass diminish, can be easy to obtain have the opticglass of the Abbe number of desired range.Therefore, with respect to the quality that oxide compound convert to be formed, the content of these compositions be preferably greater than 0%, more preferably with 1.0%, most preferably be lower limit with 2.0%.On the other hand, if the content of these compositions and the upper limit can obtain that stable glass is just not special to be limited, but infer for example might becoming and be easy to take place devitrification greater than 25.0% o'clock.Therefore, with respect to the quality that oxide compound convert to be formed, the content of these compositions with preferably with 25.0%, more preferably with 15.0%, most preferably be the upper limit with 10.0%.
Li 2The O composition is the composition that improves glass melting property, is the optional member in the opticglass of the present invention.Especially, through making Li 2The content of O composition is below 15.0%, and the partial dispersion ratio that can suppress glass reduces, thereby can make partial dispersion than keeping required relation with Abbe number.In addition, through making Li 2The content of O composition is below 15.0%, can in the reduction of the specific refractory power that suppresses glass, make by the excessive Li that contains 2The devitrification that the O composition causes is not easy to take place.Therefore, with respect to the glass total mass that oxide compound converts and forms, Li 2The content of O composition preferably with 15.0%, more preferably with 10.0%, further preferably with 8.0%, further preferably with 5.0%, more preferably with 4.0%, further be the upper limit preferably with 3.0%;, be the upper limit preferably further further with 2.3% preferably less than 3.0%.Especially, consider this Li from the viewpoint that can be easy to obtain to have the opticglass of higher partial dispersion ratio 2The content of O composition can can can not contain less than 0.1% for below 0.4% for below 0.5% basically yet.Li 2The O composition for example can use Li 2CO 3, LiNO 3, LiF etc. contains in glass as raw material.
Opticglass of the present invention preferably, Ta 2O 5Composition, ZrO 2Composition and Li 2The content of O composition and with respect to F composition, Bi 2O 3Composition, TiO 2Composition, WO 3Composition, Nb 2O 5Composition and K 2The content of O composition and ratio be below 2.00.Thus, feasible content with composition of the effect that reduces the partial dispersion ratio is lower than the composition with the effect that improves the partial dispersion ratio, therefore can access the glass with higher partial dispersion ratio.Therefore, the mass ratio (Ta during the oxide compound conversion is formed 2O 5+ ZrO 2+ Li 2O)/(F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) preferably with 2.00, more preferably with 1.40, more preferably with 1.00, most preferably be the upper limit with 0.80.In addition, this mass ratio can be 0, and is more than 0.10 through making this mass ratio, can further improve the anti-increased devitrification resistance of glass.Therefore, the mass ratio (Ta during the oxide compound conversion is formed 2O 5+ ZrO 2+ Li 2O)/(F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) preferably with 0.10, more preferably with 0.20, most preferably be lower limit with 0.30.
In addition, in opticglass of the present invention, preferably, (F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) quality and with respect to (Ta 2O 5+ ZrO 2+ Li 2O) quality and be more than 0.50.Thus, the content of composition that make to improve the partial dispersion ratio is more than the content of the composition that significantly reduces the partial dispersion ratio, also can be easy to the high partial dispersion ratio that obtains expecting even therefore add more rare earth class.That is, can be easy to have concurrently high partial dispersion ratio and high Abbe number.Therefore, the mass ratio (F+Bi during the oxide compound conversion is formed 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O)/(Ta 2O 5+ ZrO 2+ Li 2O) preferably with 0.50, more preferably with 1.00, further preferably with 1.32, further be lower limit preferably with 1.70.Especially, in first opticglass, the ratio of this content can be preferably with 1.3, more preferably with 1.5, most preferably be lower limit with 2.0.On the other hand, not limiting the upper limit of the ratio of this content is special, can be that infinity (is Ta 2O 5+ ZrO 2+ Li 2O=0%), consider that from the viewpoint of the stability of further raising glass this ratio can be for below 100.0.
MgO composition, CaO composition, SrO composition and BaO composition are the composition that improves glass melting property and improve anti-increased devitrification resistance, are the optional members in the opticglass of the present invention.Especially, through the content that makes the MgO composition be below 20.0%, the content of CaO composition or SrO composition is below 40.0% or the content of BaO composition is below 55.0%, can be so that the specific refractory power of glass be not easy to reduce.Therefore, with respect to the glass total mass that oxide compound convert to be formed, the content of MgO composition preferably with 20.0%, more preferably with 15.0%, further preferably with 10.0%, further preferably with 8.0%, most preferably be the upper limit with 5.0%.In addition; Glass total mass with respect to oxide compound conversion composition; The content of CaO composition preferably with 40.0%, more preferably with 30.0%, further preferably with 25.0%, further preferably with 20.0%, further preferably with 15.0%, further preferably with 12.0%, further be the upper limit preferably, most preferably less than 10.0% with 10.0%.In addition; Glass total mass with respect to oxide compound conversion composition; The content of SrO composition preferably with 40.0%, more preferably with 30.0%, further preferably with 25.0%, further be the upper limit preferably with 20.0%, further preferably less than 16.0%, be the upper limit preferably further with 15.0%.In addition, the content of this SrO composition can be more preferably with 12.0%, further be the upper limit preferably with 10.0%.In addition, with respect to the glass total mass that oxide compound convert to be formed, the content of BaO composition preferably with 55.0%, more preferably with 45.0%, further preferably with 40.0%, further be the upper limit preferably, further preferably less than 30.0% with 35.0%.In addition, the content of this BaO composition can be preferably with 25.0%, more preferably with 20.0%, further be the upper limit preferably with 15.0%.Especially, in second opticglass, the content of this B aO composition can be 10.0% to be the upper limit, also can be less than 6.0%.MgO composition, CaO composition, SrO composition and B aO composition for example can use MgCO 3, MgF 2, CaCO 3, CaF 2, Sr (NO 3) 2, SrF 2, BaCO 3, Ba (NO 3) 2Deng containing in glass as raw material.
In opticglass of the present invention, preferably, the quality of the content of RO composition (in the formula, R is selected from the group of being made up of Mg, Ca, Sr, Ba more than one) and be below 55.0%.Thus, can alleviate glass devitrification that is caused by the excessive RO of containing composition and the specific refractory power that makes glass is not easy to reduce.Therefore, with respect to the glass total mass that oxide compound convert to be formed, the quality of the content of RO composition and preferably with 55.0%, more preferably with 45.0%, further preferably with 40.0%, most preferably be the upper limit with 35.0%.In addition, the quality of the content of this RO composition with can be preferably with 25.0%, more preferably with 20.0%, further preferably with 15.0%, most preferably be the upper limit with 10.0%.
Na 2The O composition is the composition that improves glass melting property, is the optional member in the opticglass of the present invention.Especially, through making Na 2The content of O composition is below 20.0%, and the specific refractory power that can make glass is not easy to reduce, improve the stability of glass and makes devitrification etc. be not easy to take place.Therefore, with respect to the glass total mass that oxide compound converts and forms, Na 2The content of O composition preferably with 20.0%, more preferably with 15.0%, further preferably with 10.0%, more preferably with 8.0%, most preferably be the upper limit with 5.0%.Na 2The O composition for example can use Na 2CO 3, NaNO 3, NaF, Na 2S iF 6Deng containing in glass as raw material.
Rn 2O composition (in the formula, Rn is selected from the group of being made up of Li, Na, K more than one) is for improving glass melting property and reducing second-order transition temperature, alleviate the composition of the devitrification of glass.At this, through making Rn 2The content of O composition is below 25.0%, and the specific refractory power that can make glass is not easy to reduce, improve the stability of glass and reduces the generation of devitrification etc.Therefore, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition and preferably with 25.0%, more preferably with 20.0%, most preferably be the upper limit with 15.0%.Especially, in the 4th opticglass, this quality with can be the upper limit also 10.0% to be the upper limit with 5.0%.
The ZnO composition is to improve glass melting property, reduction second-order transition temperature and the feasible composition that is easy to form stable glass, is the optional member in the opticglass of the present invention.
Especially, be below 30.0% through the content that makes the ZnO composition, can the photoelastic constant of opticglass be suppressed lower.Therefore, the polarized light property of the transmitted light of opticglass can be improved, and then the color rendering in projector, photographic camera can be improved.
Therefore; With respect to the glass total mass that oxide compound convert to be formed, the content of ZnO composition preferably with 30.0%, more preferably with 25.0%, further preferably with 20.0%, further preferably with 15.0%, further preferably with 12.0%, further preferably with 10.0%, further preferably with 8.7%, further be the upper limit preferably with 7.7%.Especially, in first opticglass, the content of this ZnO composition can be the upper limit with 5.0%.The ZnO composition for example can use ZnO, ZnF 2Deng containing in glass as raw material.
GeO 2Composition is to have the specific refractory power that improves glass, the composition that improves the effect of anti-increased devitrification resistance, is the optional member in the opticglass of the present invention.Yet, GeO 2The cost of material of composition is high, if therefore it measures at most that material cost can uprise, thereby gained glass can become impracticable.Therefore, with respect to the glass total mass that oxide compound converts and forms, GeO 2The content of composition preferably with 10.0%, more preferably with 8.0%, further preferably with 5.0%, further be the upper limit preferably, most preferably less than 2.0% with 2.0%.GeO 2Composition for example can use GeO 2Deng containing in glass as raw material.
P 2O 5Composition is to have liquidus temperature that reduces glass and the composition that improves the effect of anti-increased devitrification resistance, is the optional member in the opticglass of the present invention.Especially, through making P 2O 5The content of composition is below 10.0%, can suppress the chemical durability of glass, particularly water-proof reduction.Therefore, with respect to the glass total mass that oxide compound converts and forms, P 2O 5The content of composition preferably with 10.0%, more preferably with 8.0%, further preferably with 5.0%, most preferably be the upper limit with 2.0%.P 2O 5Composition for example can use Al (PO 3) 3, Ca (PO 3) 2, Ba (PO 3) 2, BPO 4, H 3PO 4Deng containing in glass as raw material.
Ga 2O 3Composition is the optional member in the opticglass of the present invention for making the composition that is easy to form stable glass.Especially, through making Ga 2O 3The content of composition is below 10.0%, and the Abbe number that can suppress glass reduces.Therefore, with respect to the glass total mass that oxide compound converts and forms, Ga 2O 3The content of composition each preferably with 10.0%, more preferably with 8.0%, further preferably with 5.0%, most preferably be the upper limit with 2.0%.Ga 2O 3Composition for example can use Ga 2O 3, Ga (OH) 3Deng containing in glass as raw material.
TeO 2Composition is the optional member in the opticglass of the present invention for improving the composition of specific refractory power, reduction second-order transition temperature (Tg).Yet, TeO 2Have following problems: in the part of the crucible of platinum system, contact melten glass is in the fusion tank that is formed by platinum during with the frit fusion, understands and platinum generation alloying.Therefore, with respect to the glass total mass that oxide compound converts and forms, TeO 2The containing ratio of composition preferably with 10.0%, more preferably with 8.0%, most preferably be the upper limit with 5.0%.TeO 2Composition for example can use TeO 2Deng containing in glass as raw material.
SnO 2Composition is to alleviate the oxidation of melten glass and make melten glass clarification and make glass be not easy the composition of variation to light-struck transsmissivity, is the optional member in the opticglass of the present invention.Especially, through making SnO 2The content of composition is below 5.0%, can be so that the glass coloring, the glass devitrification that are caused by the reduction of melten glass are not easy to take place.In addition, can alleviate SnO 2The alloying of composition and fusion equipment precious metals such as (particularly) Pt therefore can realize the long lifetime of the equipment that fuses.Therefore, with respect to the glass total mass that oxide compound converts and forms, SnO 2The content of composition preferably with 5.0%, more preferably with 3.0%, further preferably with 1.0%, more preferably with 0.7%, most preferably be the upper limit with 0.5%.SnO 2Composition for example can use SnO, SnO 2, SnF 2, SnF 4Deng containing in glass as raw material.
Sb 2O 3Composition is the composition with the melten glass deaeration, is the optional member in the opticglass of the present invention.Especially, through making Sb 2O 3The content of composition is below 1.0%, can be so that the excess foaming during glass melting be not easy to take place, and can make Sb 2O 3Composition is not easy with fusion equipment precious metals such as (particularly) Pt alloying to take place.Therefore, with respect to the glass total mass that oxide compound converts and forms, Sb 2O 3The content of composition preferably with 1.0%, more preferably with 0.8%, most preferably be the upper limit with 0.5%.Sb 2O 3Composition for example can use Sb 2O 3, Sb 2O 5, Na 2H 2Sb 2O 75H 2O etc. contain in glass as raw material.
In addition, make the composition of glass clarifying, deaeration be not limited to above-mentioned Sb 2O 3Composition can use known finings, deaerating agent or their combination in the glass manufacturing field.
About the composition that should not contain
Then, explain that the composition that should not contain in the opticglass of the present invention is not preferred composition with containing.
In opticglass of the present invention, can in the scope of the characteristic of the glass that does not damage the application invention, add other compositions as required.But, GeO 2Become branch to improve the dispersivity of glass, therefore preferably do not contain basically.
In addition; Even each transiting metal component such as the V except that Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo has also can make glass coloring under situation about containing on a small quantity with independent or compound form separately, the certain wavelengths of visibility region is taken place for the character that absorbs; Therefore; Particularly in the opticglass of the wavelength that uses visibility region, preferably do not contain basically.
And then, lead compound and As such as PbO 2O 3Deng each composition of arsenic compound and Th, Cd, Tl, Os, Be, Se in the tendency that exists control to use as harmful chemical in recent years; Not only in the manufacturing process of glass, even all need the measure in the environmental improvement in the processing after manufacturing procedure and commercialization.Therefore, under the situation of attention,, preferably do not contain these compositions basically except the situation of inevitably sneaking into to the influence of environment.Thus, make and do not contain the material that pollutes the environment basically in the opticglass.Therefore, even do not take the measure in the special environmental improvement, also can make, process and discard this opticglass.
The composition of glass composition of the present invention is that the quality % with the glass total mass of convert forming with respect to oxide compound representes; Therefore not directly to represent with the record of mole %; And the composition of representing in mole % of each composition that in satisfying the glass composition of various characteristics of the presently claimed invention, exists converts by oxide compound and forms, and is roughly following value.
10.0～75.0mol%B 2O 3Composition
With
0～25.0mol%La 2O 3Composition and/or
0～4.0mol%Bi 2O 3Composition and/or
0～30.0mol%TiO 2Composition and/or
0～10.0mol%WO 3Composition and/or
0～10.0mol%Nb 2O 5Composition and/or
0～15.0mol%K 2The O composition and/or
0～10.0mol%Ta 2O 5Composition and/or
0～25.0mol%ZrO 2Composition and/or
0～40.0mol%Li 2The O composition and/or
0～20.0mol%Gd 2O 3Composition and/or
0～15.0mol%Y 2O 3Composition and/or
0～10.0mol%Yb 2O 3Composition and/or
0～10.0mol%Lu 2O 3Composition and/or
0～50.0mol%MgO composition and/or
0～50.0mol%CaO composition and/or
0～50.0mol%SrO composition and/or
0～55.0mol%BaO composition and/or
0～70.0mol%SiO 2Composition and/or
0～30.0mol%ZnO composition and/or
0～20.0mol%GeO 2Composition and/or
0～10.0mol%P 2O 5Composition and/or
0～40.0mol%Al 2O 3Composition and/or
0～8.0mol%Ga 2O 3Composition and/or
0～25.0mol%Na 2The O composition and/or
0～8.0mol%TeO 2Composition and/or
0～5.0mol%SnO 2Composition and/or
0～1.0mol%SnO 2Composition and/or
0～0.5mol%Sb 2O 3Composition
With the conduct of 0～75.0mol% and in above-mentioned each metallic element one or more oxide compound a part or all carried out the total amount by F of metathetical fluorochemical.
Especially, the composition of representing in mole % of first opticglass converts by oxide compound and forms, and is preferably:
5.0～25.0mol%La 2O 3Composition
With
0～5.0mol%Ta 2O 5Composition and/or
0～25.0mol%Li 2The O composition and/or
0～35.0mol%MgO composition and/or
0～35.0mol%CaO composition and/or
0～25.0mol%SrO composition and/or
0～25.0mol%B aO composition and/or
0～60.0mol%SiO 2Composition and/or
0～20.0mol%Al 2O 3Composition and/or
0～1.0mol%SnO 2Composition.
In addition, the composition of representing in mole % of second opticglass converts by oxide compound and forms, and is preferably:
5.0～25.0mol%La 2O 3Composition
With
0～30.0mol%Li 2The O composition and/or
0～5.0mol%Lu 2O 3Composition and/or
0～35.0mol%MgO composition and/or
0～35.0mol%CaO composition and/or
0～25.0mol%SrO composition and/or
0～25.0mol%B aO composition and/or
0～60.0mol%SiO 2Composition and/or
0～20.0mol%Al 2O 3Composition and/or
0～1.0mol%SnO 2Composition.
Especially, the composition of representing in mole % of the 3rd opticglass converts by oxide compound and forms, and is preferably:
0～15.0mol%Gd 2O 3Composition and/or
0～3.0mol%Ta 2O 5Composition and/or
0～25.0mol%ZnO composition and/or
0～20.0mol%Al 2O 3Composition
With greater than 0mol% and for below the 75.0mol%, in conduct and above-mentioned each metallic element one or more oxide compound a part or all carried out the total amount by F of metathetical fluorochemical.
In addition, the composition of representing in mole % of the 4th opticglass converts by oxide compound and forms, and is preferably:
10.0～75.0mol%B 2O 3Composition,
10.0～25.0mol%La 2O 3Composition with
Greater than 0mol% and be the following Al of 40.0mol% 2O 3Composition
With
0～4.0mol%Ta 2O 5Composition and/or
0～15.0mol%Li 2The O composition and/or
0～35.0mol%MgO composition and/or
0～50.0mol%CaO composition and/or
0～35.0mol%SrO composition and/or
0～50.0mol%BaO composition and/or
0～25.0mol%ZnO composition
With greater than 0mol% and for below the 75.0mol%, in conduct and above-mentioned each metallic element one or more oxide compound a part or all carried out the total amount by F of metathetical fluorochemical.
Method of manufacture
Opticglass of the present invention for example can be made as follows.Promptly; The uniform mixing above-mentioned raw materials makes each composition in the scope of content of regulation, the mixture of made is dropped into platinum crucible, quartz crucible or alumina crucible carry out thick fusion, puts into golden crucible, platinum crucible, platinum alloy crucible or iridium crucible then 900～1400 ℃ TR fusion 1～5 hour; Stir homogenizing and carry out froth breaking etc.; After the temperature of reducing to below 1200 ℃, carry out then stirring end and remove brush line, use forming mould to come moulding, make thus.At this, as using forming mould to obtain the method for the glass of moulding, can enumerate out: the end at forming mould flows down melten glass, goes out the method for the glass of moulding simultaneously at the other end layback of forming mould; Form the method for glass forming body through so-called vertical compression (direct press); As so-called float glass process moulding with melten glass be cast into mould, annealing forms the method for glass forming body.
Rerum natura
Opticglass of the present invention preferably has the specific refractory power and the chromatic dispersion (Abbe number) of regulation.
At this, the specific refractory power (n of opticglass of the present invention d) preferably with 1.50, more preferably with 1.51, further be lower limit preferably with 1.52.Especially, the specific refractory power (n of first and second opticglass d) can be preferably with 1.70, more preferably with 1.73, further preferably with 1.75, most preferably be lower limit with 1.77.In addition, the specific refractory power (n of the 4th opticglass d) can be preferably with 1.57, more preferably with 1.60, most preferably be lower limit with 1.65.On the other hand, to the specific refractory power (n of opticglass of the present invention d) not special qualification of the upper limit, usually, be approximately below 2.20, more specifically be below 2.10, further to be specially below 2.00.Especially, the specific refractory power (n of the 3rd opticglass d) the upper limit can be the upper limit preferably with 1.70, be more preferably less than 1.70, be the upper limit most preferably with 1.69.
Abbe number (the v of opticglass of the present invention d) preferably with 39, more preferably with 40, further be lower limit preferably with 41.Especially, the Abbe number (v of the first and the 4th opticglass d) can be preferably with 45, more preferably with 47, most preferably be lower limit with 49.In addition, the Abbe number (v of the 3rd opticglass d) can be preferably with 50, more preferably with 52, most preferably be lower limit with 53.On the other hand, to the Abbe number (v of opticglass of the present invention d) not special qualification of the upper limit, usually, be approximately below 63, more specifically be below 61, further be specially below 60, further be specially below 58, further be specially below 57.Especially, the Abbe number (v of second opticglass of the present invention d) can be preferably with 52, more preferably with 51, most preferably be the upper limit with 50.
At this, the Abbe number (v of second opticglass of the present invention d) and specific refractory power (n d) between preferably satisfy (v d)>=(-125 * n d+ 265) relation more preferably satisfies (v d)>=(-125 * n d+ 266) relation most preferably satisfies (v d)>=(-125 * n d+ 267) relation.
In addition, the Abbe number (v of opticglass of the present invention d) and specific refractory power (n d) between preferably satisfy (v d)>=(-100 * n d+ 220) relation more preferably satisfies (v d)>=(-100 * n d+ 222) relation most preferably satisfies (v d)>=(-100 * n d+ 223) relation.Especially, in the 3rd opticglass, preferably, with Abbe number (v d) be the x axle, with specific refractory power (n d) be in the xy rectangular coordinates of y axle, have by the Abbe number and the specific refractory power of the scope of A (50,1.70), B (60,1.60), C (63,1.60), 4 encirclements of D (63,1.70).
Through these, make the degree of freedom of optical design increase, also can obtain big refraction of light amount even further seek the slimming of element.
In addition, opticglass of the present invention have high partial dispersion than (θ g, F).More specifically, the partial dispersion of opticglass of the present invention is than (θ g is F) with Abbe number (v d) between satisfy (θ g, F)>=(0.00170 * v d+ 0.6375) or (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.Even containing a large amount of rare earth elements, opticglass of the present invention also can obtain having than having the high partial dispersion of known glass now than (θ g, opticglass F).The chromatic aberation of the optical element that therefore, can in high refractive index that realizes glass and low chromatic dispersionization, reduce to form by this opticglass.
At this, the partial dispersion of first opticglass is than (θ g, lower limit F) is preferably (0.00170 * v d+ 0.63750), (0.00170 * v more preferably d+ 0.63950), most preferably is (0.00170 * v d+ 0.64150).On the other hand, to the partial dispersion of first opticglass than (θ g, upper limit F) is not special to be limited, and for example is (0.00170 * v usually d+ 0.65750), (0.00170 * v more preferably d+ 0.65550), most preferably is (0.00170 * v d+ 0.653750).
In addition, the partial dispersion of second opticglass is than (θ g, lower limit F) is preferably (2.0 * 10 -3* v d+ 0.6498), more preferably (2.0 * 10 -3* v d+ 0.6518), most preferably is (2.0 * 10 -3* v d+ 0.6558).On the other hand, to the partial dispersion of second opticglass than (θ g, upper limit F) is not special to be limited, and for example is (2.0 * 10 usually -3* v d+ 0.6950), more preferably (2.0 * 10 -3* v d+ 0.6930), most preferably is (2.0 * 10 -3* v d+ 0.6910).In addition, at partial dispersion ratio and Abbe number (v with second opticglass d) relation when defining with the straight line parallel with standard lines, partial dispersion is than (θ g for example is (1.7 * 10 usually F) -3* v d+ 0.63450) above, more specifically be (1.7 * 10 -3* v d+ 0.63750) above, further be specially (1.7 * 10 -3* v d+ 0.63950) above, further be specially (1.7 * 10 -3* v d+ 0.64150) more than, for example be (1.7 * 10 usually -3* v d+ 0.67750) below, more specifically be (1.7 * 10 -3* v d+ 0.67550) below, further be specially (1.7 * 10 -3* v d+ 0.67350) below.
In addition, the partial dispersion of the 3rd opticglass is than (θ g, lower limit F) is preferably (0.00170 * v d+ 0.6375), (0.00170 * v more preferably d+ 0.6395), most preferably is (0.00170 * v d+ 0.6415).On the other hand, to the partial dispersion of the 3rd opticglass than (θ g, upper limit F) is not special to be limited, and is typically about (0.00170 * v d+ 0.6575), more specifically is (0.00170 * v d+ 0.6555), further is specially (0.00170 * v d+ 0.6535).
In addition, the partial dispersion of the 4th opticglass is than (θ g, lower limit F) is preferably (0.00170 * v d+ 0.6375), (0.00170 * v more preferably d+ 0.6395), most preferably is (0.00170 * v d+ 0.6415).On the other hand, to the partial dispersion of the 4th opticglass than (θ g, upper limit F) is not special to be limited, and is typically about (0.00170 * v d+ 0.6800) below, more specifically be (0.00170 * v d+ 0.6790) below, further be specially (0.00170 * v d+ 0.6780) below.In addition, the preferable range of partial dispersion ratio of the present invention can change based on the Abbe number of optical glass, therefore uses the straight line parallel with normal line to represent.
The partial dispersion of opticglass of the present invention is than (θ g F) can measure by standard JOGIS01-2003 based on Japanese optics nitre industry.In addition, the used glass of this mensuration uses the glass that in lehre, carried out processing with-25 ℃/hour annealing cooling rate.
In addition, opticglass of the present invention preferably has the second-order transition temperature (Tg) below 650 ℃.Therefore thus, can under lower temperature, be pressed, can also alleviate the oxidation of the used mould of compression molding and seek the long lifetime of mould.Therefore, the second-order transition temperature of opticglass of the present invention (Tg) preferably with 650 ℃, more preferably with 620 ℃, most preferably be the upper limit with 600 ℃.In addition; Do not limit the lower limit of the second-order transition temperature (Tg) of opticglass of the present invention is special, the second-order transition temperature of the glass that obtains according to the present invention (Tg) is typically about more than 100 ℃, is specially more than 150 ℃, further is specially more than 200 ℃.
The second-order transition temperature of opticglass of the present invention (Tg) is obtained through the mensuration of using differential heat determination device (the STA 409CD that
Figure BSA00000545200300411
GmbH makes).At this, sample granularity is 425～600 μ m when measuring, and heat-up rate is 10 ℃/minute.
In addition, opticglass of the present invention is preferred painted few.When opticglass of the present invention was represented with the transsmissivity of glass, the sample of thickness 10mm showed the wavelength (λ of 70% spectral-transmission favtor 70) be below the 500nm, more preferably below the 480nm, most preferably be below the 450nm.Opticglass of the present invention particularly preferably is, and the sample of thickness 10mm shows the wavelength (λ of 80% spectral-transmission favtor 80) be below the 500nm, more preferably below the 480nm, most preferably be below the 450nm.In addition, the sample of the thickness 10mm of opticglass of the present invention shows the wavelength (λ of 5% spectral-transmission favtor 5) be below the 450nm, more preferably below the 430nm, most preferably be below the 410nm.Thus, make the absorption limit of glass be positioned at ultraviolet region near, can improve the transparency of the glass in the visibility region, therefore can use the material of this opticglass as optical elements such as lens.
The transsmissivity of opticglass of the present invention can be measured by standard JOGIS02 according to Japanese optics nitre industry.Particularly, measure the spectral-transmission favtor of 200～800nm of the parallel grinding object of opposite face of thickness 10 ± 0.1mm according to JI SZ8722, obtain λ 80(transsmissivity is 80% o'clock a wavelength), λ 70(transsmissivity is 70% o'clock a wavelength) and λ 5(transsmissivity is 5% o'clock a wavelength).
In addition, opticglass preferred light elastic constant of the present invention is little.Especially, the photoelastic constant (β) of opticglass of the present invention under wavelength 546.1nm is 2.0 * 10 -5Nmcm -1Pa -1Below, more preferably 1.5 * 10 -5Nmcm -1Pa -1Below, further be preferably 1.0 * 10 -5Nmcm -1Pa -1Below, most preferably be 0.7 * 10 -5Nmcm -1Pa -1Below.Thus; The partial dispersion that can improve opticglass compares and can improve the polarized light property of transmitted light; Therefore when opticglass being used for the optical system of projector, photographic camera (particularly possessing polarizing filter), can reducing chromatic aberation and can suppress the inner scattering of light of optical element.That is, can further improve the color rendering of these projector, photographic camera.
Photoelastic constant (β) about opticglass of the present invention; Use the sample of the disk shape of diameter 25mm that opposite face ground, thickness 8mm, when measuring the compression load along prescribed direction loading F [Pa] at the path difference δ [nm] of the light of the wavelength 546.1nm of center of glass generation.Then, the value of the value of use gained F and δ and the thickness d [cm] of glass is obtained photoelastic constant β [10 by the relational expression of δ=β * d * F -5Nmcm -1Pa -1].In addition, the mensuration light source of wavelength 546.1nm uses ultrahigh pressure mercury lamp.
In addition, the preferred anti-increased devitrification resistance of opticglass of the present invention is high.Especially, opticglass of the present invention preferably has the low liquidus temperature below 1200 ℃.More specifically, the liquidus temperature of opticglass of the present invention preferably with 1200 ℃, more preferably with 1180 ℃, most preferably be the upper limit with 1150 ℃.Thus, can improve the stability of glass and reduce crystallization, therefore can improve the anti-increased devitrification resistance when forming glass, can alleviate influence the optical characteristics of the optical element of use glass by molten state.On the other hand, do not limit the lower limit of the liquidus temperature of opticglass of the present invention is special, the liquidus temperature of the glass that obtains according to the present invention is typically about more than 500 ℃, is specially more than 550 ℃, further is specially more than 600 ℃.In addition; Whether " the insulation test " in this specification sheets be high for the anti-increased devitrification resistance of confirming glass, carries out as follows: frit is put into the crucible of the platinum system of 30cc, added a cover in 1200 ℃～1250 ℃ stove and fuse about 10～20 minutes; Stir after the homogenizing; Gained glass added a cover in being set at 1000～1150 ℃ stove kept 2 hours, the surface of sight glass with inner and with the crystal that the contact surface of the inwall of crucible is separated out, carry out thus.
Preform and optical element
The opticglass that can use for example hot repressing to process the method cause made of compression moldings such as type, precision press molding is made glass forming body.That is, can make preform that compression molding uses, carry out attrition process after processing type and make glass forming body this preform being carried out hot repressing by opticglass; Perhaps, the preform that can make for example carrying out attrition process carries out precision press molding and makes glass forming body.In addition, the method for making glass forming body is not limited to these methods.
The glass forming body of making like this can be used for various optical elements, wherein, is particularly preferred for the purposes of optical elements such as lens, prism.Thus, can alleviate the bleeding that causes by chromatic aberation of the transmitted light of the optical system that is provided with optical element.Therefore, when this optical element is used for photographic camera, can more correctly show the reference object thing, when this optical element is used for projector, can be with the picture of higher color projection expectation.
Embodiment
Embodiments of the invention (No.A1～No.A13, No.B1～No.B23, No.C1～No.C6, No.D1～No.D36) and the composition of comparative example (No.a1, No.c1, No.d1) and the specific refractory power (n of their glass d) and Abbe number (v d), partial dispersion is 80% o'clock wavelength (λ than (θ g, F), second-order transition temperature (Tg), transsmissivity 80), transsmissivity is 5% o'clock wavelength (λ 5) and the value of liquidus temperature be shown in table 1～table 11.In addition, only to be illustrated as purpose, the present invention is only for scheduling these embodiment for following examples.
Embodiments of the invention (all make as follows: as the raw material of each composition by No.A1～No.A13, No.B1～No.B23, No.C1～No.C6, No.D1～opticglass No.D36) and the glass of comparative example (No.a1, No.c1, No.d1); The high-purity raw that selected respectively corresponding oxide compound, oxyhydroxide, carbonate, nitrate salt, fluorochemical, oxyhydroxide, metaphosphoric acid compound etc. use in common opticglass; Ratio in the composition of each embodiment shown in table 1～table 11 and comparative example is carried out weighing and uniform mixing; Drop into platinum crucible then; Fusion difficulty according to glass is formed was fused in 1000～1400 ℃ TR 1～6 hour with electric furnace; Stir homogenizing and carry out froth breaking etc., after reducing to 1200 ℃ temperature and stirring homogenizing, be poured in the mould then, glass is made in annealing.
At this, embodiment (No.A1～No.A13, No.B1～No.B23, No.C1～No.C6, No.D1～No.D36) and the specific refractory power (n of the glass of comparative example (No.a1, No.c1, No.d1) d) and Abbe number (v d) and partial dispersion than (θ g F) can measure by standard JOGIS01-2003 based on the industry of Japanese optics nitre.Then, for the Abbe number (v that is obtained d) and partial dispersion than (θ g, value F), obtain relational expression (θ g, F)=-a * v dSlope a among the+b is 0.0017 and 0.0020 o'clock intercept b.In addition, for the specific refractory power (n that is obtained d) value, obtain relational expression-100 * n d+ 220 value.In addition, the used glass of this mensuration uses the glass that in lehre, carried out processing with-25 ℃/hour annealing cooling rate.
In addition, embodiment (obtain through the mensuration of using differential heat determination device ( GmbH makes STA 409CD) by the No.D1～No.D36) and the second-order transition temperature (Tg) of the glass of comparative example (No.d1).At this, sample granularity is 425～600 μ m when measuring, and heat-up rate is 10 ℃/minute.
In addition, (No.D1～No.D36) and the transsmissivity of the glass of comparative example (No.d1) are understood standard JOGIS02 according to Japanese optics nitre industry and are measured about embodiment.In addition, in the present invention, obtain painted the having or not and degree of glass through the transsmissivity of measuring glass.Particularly, according to the spectral-transmission favtor that JI SZ8722 comes the parallel grinding object of the opposite face of thickness 10 ± 0.1mm is measured 200～800nm, obtain λ 80(transsmissivity is 80% o'clock a wavelength) and λ 5(transsmissivity is 5% o'clock a wavelength).
In addition; Embodiment (measure as follows: chippy glass specimen is carried with 10mm at interval place on the platinum plate by the No.D1～No.D36) and the liquidus temperature of the glass of comparative example (No.d1); Take out it is kept 3 minutes in having 800 ℃～1200 ℃ the stove of thermograde after; The crystalline of cooling back in the microscopically sight glass sample of 80 times of multiplying powers has or not, thereby measures.At this moment, opticglass is ground into granular as sample about diameter 2mm.
Table 1
Figure BSA00000545200300461
Table 2
Figure BSA00000545200300471
Table 3
Figure BSA00000545200300481
Table 4
Figure BSA00000545200300491
Table 5
Figure BSA00000545200300501
Table 6
Figure BSA00000545200300511
Table 7
Figure BSA00000545200300521
Table 8
Figure BSA00000545200300531
Table 9
Figure BSA00000545200300541
Table 10
Figure BSA00000545200300551
Table 11
Figure BSA00000545200300561
The partial dispersion of the opticglass of embodiments of the invention is than (θ g F) is (0.00170 * v d+ 0.6375) more than, more specifically be (0.00170 * v d+ 0.6420) more than.Especially, (partial dispersion of the opticglass of No.C1～No.C6) is than (θ g F) is (0.00170 * v for embodiment d+ 0.64486) more than.In addition, the partial dispersion of the opticglass of embodiments of the invention (No.A 1～No.A 13) is than (θ g F) also is (0.00170 * v d+ 0.63750) more than, infers that it has the high partial dispersion ratio of expectation.On the other hand, (partial dispersion of the opticglass of No.B1～No.B23) is than (θ g F) is (0.00200 * v for embodiments of the invention d+ 0.64982) more than.Therefore clear and definite, the opticglass of embodiments of the invention with Abbe number (v d) relational expression in partial dispersion than (θ g, F) chromatic aberation big, when forming optical element is little.
Specific refractory power (the n of the opticglass of embodiments of the invention d) be more than 1.57, be more than 1.65 more in detail, and this specific refractory power (n d) be below 2.20, be below 1.85 more in detail, all in desired range.Especially, the embodiments of the invention (specific refractory power (n of the opticglass of No.A1～No.A13) d) be more than 1.73, and this specific refractory power (n d) be below 1.78.In addition, the embodiments of the invention (specific refractory power (n of the opticglass of No.B1～No.B23) d) be more than 1.70, more specifically be more than 1.75.In addition, the embodiment (specific refractory power (n of the opticglass of No.C1～No.C6) d) be more than 1.60, be more than 1.65 more in detail, and this specific refractory power (n d) be below 1.70.In addition, the embodiment (specific refractory power (n of the opticglass of No.D1～No.D36) d) be more than 1.69, and this specific refractory power (n d) be below 1.81.
In addition, the Abbe number (v of the opticglass of embodiments of the invention d) be more than 39, be more than 40.7 more in detail, and this Abbe number (v d) be below 63, be below 61 more in detail, all in desired range.Especially, the embodiments of the invention (Abbe number (v of the opticglass of No.A1～No.A13) d) be more than 45, be more than 49 more in detail, and this Abbe number (v d) be below 60, be below 54 more in detail.In addition, the embodiments of the invention (Abbe number (v of the opticglass of No.B1～No.B23) d) be more than 39, be more than 40.7 more in detail, and this Abbe number (v d) all less than 52, be below 51.3 more in detail.In addition, the embodiments of the invention (Abbe number (v of the opticglass of No.C1～No.C6) d) be more than 50, more specifically be more than 54, and this Abbe number (v d) be below 57.In addition, the embodiments of the invention (Abbe number (v of the opticglass of No.D1～No.D36) d) be more than 45, and this Abbe number (v d) be below 63, be below 61 more in detail.
At this, (No.C1～opticglass No.C6) satisfies the Abbe number (v of opticglass of the present invention to embodiments of the invention d) and specific refractory power (n d) between (v d)>=(-100 * n d+ 220) relation.
In addition, embodiments of the invention (second-order transition temperature (Tg) of the opticglass of No.D1～No.D36) is below 650 ℃, be below 620 ℃, in desired range more in detail.In addition, the second-order transition temperature (Tg) that can infer the opticglass of other embodiment of the present invention also is below 650 ℃.
In addition, the embodiments of the invention (λ of the opticglass of No.D1～No.D36) 80(transsmissivity is 80% o'clock a wavelength) is below the 500nm, is below the 410nm more in detail.In addition, the embodiments of the invention (λ of the opticglass of No.D1～No.D36) 5(transsmissivity is 5% o'clock a wavelength) is below the 450nm, is below the 350nm, all in desired range more in detail.In addition, can infer that the opticglass of other embodiment of the present invention is also similar, λ 70(transsmissivity is 70% o'clock a wavelength) is for 500nm is following, λ 5(transsmissivity is 5% o'clock a wavelength) is for below the 450nm.
In addition, embodiments of the invention (liquidus temperature of the opticglass of No.D1～No.D36) is below 1200 ℃, be below 1100 ℃ more in detail, and this liquidus temperature is more than 500 ℃.On the other hand, the liquidus temperature of the glass of comparative example (No.d1) is more than 1200 ℃.Therefore clear and definite, the opticglass of embodiments of the invention and the glassy phase of comparative example are lower and be not easy devitrification than liquidus temperature.
In addition, can infer that (photoelastic constant (β) of opticglass under wavelength 546.1nm of No.A1～No.A13) is 2.0 * 10 to embodiments of the invention -5Nmcm -1Pa -1Below.
Therefore clear and definite, the specific refractory power (n of the opticglass of embodiments of the invention d) and Abbe number (v d) in desired range and chromatic aberation little, be easy to carry out compression molding, high to the transparency of the light of the wavelength of visibility region.Especially clear and definite, (the anti-increased devitrification resistance of the opticglass of No.D1～No.D36) is high for embodiments of the invention.(opticglass of No.A1～No.A13) is also little in the inner scattering of opticglass can to think embodiment in addition.
And then, use the opticglass that obtains in the embodiments of the invention to carry out hot repressing and process type, grind then and cut and grind, be processed into lens and prismatical shape.In addition, use the opticglass formation precision press molding of embodiments of the invention to use preform, precision press molding is carried out precision press molding processing with preform.In either event, all do not produce problems such as opacification and devitrification in the glass after the thermoplastic, can stably be processed into various lens and prismatical shape.
More than, to be illustrated as purpose the present invention is specified, but present embodiment is hoped to understand those skilled in the art and can carried out multiple change with not breaking away from thought of the present invention and scope only to be illustrated as purpose.

Claims (40)

1. opticglass, it contains B 2O 3Composition has the refractive index n more than 1.70 dWith the Abbe number v more than 39 d, partial dispersion is than (θ g is F) with Abbe number v dBetween satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) or (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.
2. opticglass according to claim 1, it further contains La 2O 3Composition has the refractive index n more than 1.73 dWith the Abbe number v more than 45 d, partial dispersion is than (θ g is F) with Abbe number v dBetween satisfy (θ g, F)>=(0.00170 * v d+ 0.63750) relation.
3. opticglass according to claim 1, it further contains La 2O 3Composition and F composition have more than 39 and less than 52 Abbe number v d, partial dispersion is than (θ g is F) with Abbe number v dBetween satisfy (θ g, F)>=(2.0 * 10 -3* v d+ 0.6498) relation.
4. opticglass according to claim 1, it further contains the F composition, with Abbe number v dFor the x axle, with refractive index n dIn the xy rectangular coordinates for the y axle, have by the Abbe number and the specific refractory power of the scope of A (50,1.70), B (60,1.60), C (63,1.60), 4 encirclements of D (63,1.70).
5. according to each the described opticglass in the claim 2～4, wherein, the glass total mass that converts and form with respect to oxide compound is by quality %, B 2O 3Composition is 5.0～50.0%, La 2O 3The content of composition is below 55.0%.
6. opticglass according to claim 5, it contains the La more than 5.0% with respect to the glass total mass that oxide compound converts and forms 2O 3Composition.
7. opticglass according to claim 1, it further contains Al in oxide compound converts composition 2O 3Composition.
8. opticglass according to claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Al 2O 3The content of composition is below 20.0%.
9. opticglass according to claim 1, wherein, in the increment quality % with respect to the glass total mass of oxide compound benchmark, the content of F composition is below 30.0%.
10. opticglass according to claim 9, wherein, the increment quality % in respect to the glass total mass of oxide compound benchmark contains the F composition greater than 0%.
11. opticglass according to claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, SiO 2The content of composition is below 40.0%.
12. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and SiO 2+ B 2O 3Be below 40.0%.
13. opticglass according to claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %,
Gd 2O 3Composition be 0～40.0% and/or
Y 2O 3Composition be 0～20.0% and/or
Yb 2O 3Composition be 0～20.0% and/or
Lu 2O 3Composition is 0～20.0%.
14. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition and be below 80.0%, in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one.
15. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Gd 2O 3+ Yb 2O 3Be below 26.0%.
16. opticglass according to claim 1, wherein, the mass ratio Ln during the oxide compound conversion is formed 2O 3/ (Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5) be more than 1.7 and below 25.0.
17. opticglass according to claim 1, wherein, the mass ratio Ln that oxide compound converts and forms 2O 3/ (SiO 2+ B 2O 3) be more than 1.00, in the formula, Ln is selected from the group of being made up of La, Gd, Y, Yb, Lu more than one.
18. opticglass according to claim 1, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～10.0%Bi 2O 3Composition and/or
0～15.0%TiO 2Composition and/or
0～20.0%Nb 2O 5Composition and/or
0～15.0%WO 3Composition and/or
0～10.0%K 2Each composition of O composition.
19. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O is more than 0.1% and below 30.0%.
20. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5Be below 20.0%.
21. opticglass according to claim 1, wherein, the mass ratio F/ (F+Bi during the oxide compound conversion is formed 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be more than 0.36 and below 1.00.
22. opticglass according to claim 1, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～15.0%ZrO 2Composition and/or
0～25.0%Ta 2O 5Composition.
23. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and WO 3+ La 2O 3+ ZrO 2+ Ta 2O 5Be more than 10.0% and below 60.0%.
24. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ Ta 2O 5Greater than 0%.
25. opticglass according to claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Li 2The content of O composition is below 15.0%.
26. opticglass according to claim 1, wherein, the mass ratio (Ta during the oxide compound conversion is formed 2O 5+ ZrO 2+ Li 2O)/(F+Bi 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O) be below 2.00.
27. opticglass according to claim 1, wherein, the mass ratio (F+Bi that oxide compound converts and forms 2O 3+ TiO 2+ WO 3+ Nb 2O 5+ K 2O)/(Ta 2O 5+ ZrO 2+ Li 2O) be more than 0.50.
28. opticglass according to claim 1, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～20.0%MgO composition and/or
0～40.0%CaO composition and/or
0～40.0%SrO composition and/or
Each composition of 0～55.0%BaO composition.
29. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound convert to be formed, the quality of RO composition and be below 55.0%, in the formula, R is selected from the group of being made up of Mg, C a, Sr, Ba more than one.
30. opticglass according to claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, by quality %, Na 2The content of O composition is below 20.0%.
31. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition and be below 25.0%, in the formula, Rn is selected from the group of being made up of Li, Na, K more than one.
32. opticglass according to claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, by quality %, the content of ZnO composition is below 30.0%.
33. opticglass according to claim 1, wherein, the glass total mass with respect to oxide compound converts and forms by quality %, further contains
0～10.0%GeO 2Composition and/or
0～10.0%P 2O 5Composition and/or
0～10.0%Ga 2O 3Composition and/or
0～10.0%TeO 2Composition and/or
0～5.0%SnO 2Composition and/or
0～1.0%Sb 2O 3Each composition of composition.
34. opticglass according to claim 1, it has the refractive index n more than 1.57 dWith the Abbe number v more than 45 d
35. opticglass according to claim 1, wherein, Abbe number v dWith refractive index n dBetween satisfy v d>=-100 * n d+ 220 relation.
36. opticglass according to claim 1, wherein, Abbe number v dWith refractive index n dBetween satisfy v d>=-125 * n d+ 265 relation.
37. a preform material, it is formed by the described opticglass of claim 1.
38. an optical element, it makes the compression moulding of the described preform material of claim 37.
39. an optical element, it is a mother metal with the described opticglass of claim 1.
40. an optical device, it possesses each the described optical element in claim 38 or 39.
CN2011102106793A 2010-07-26 2011-07-26 Optical glass, perform, and optical element Pending CN102344248A (en)

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