CN104098267A - Optical Glass, Preforming Material And Optical Element - Google Patents

Optical Glass, Preforming Material And Optical Element Download PDF

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Publication number
CN104098267A
CN104098267A CN201410133778.XA CN201410133778A CN104098267A CN 104098267 A CN104098267 A CN 104098267A CN 201410133778 A CN201410133778 A CN 201410133778A CN 104098267 A CN104098267 A CN 104098267A
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China
Prior art keywords
composition
opticglass
glass
content
mol
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CN201410133778.XA
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Chinese (zh)
Inventor
桃野净行
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Ohara Inc
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Ohara Inc
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Publication date
Priority claimed from JP2013239213A external-priority patent/JP5875572B2/en
Priority claimed from JP2013241228A external-priority patent/JP6014573B2/en
Application filed by Ohara Inc filed Critical Ohara Inc
Priority to CN202111072851.3A priority Critical patent/CN113788614A/en
Priority to CN201711008789.5A priority patent/CN107721160A/en
Publication of CN104098267A publication Critical patent/CN104098267A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—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
    • C03C3/04—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
    • C03C3/12—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
    • C03C4/00—Compositions for glass with special properties
    • 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

Abstract

The object of the present invention is to provide an optical glass which is made of a preforming material, can be obtained at a lower cost, is high in devitrification resistance and is easy to carry out the precise compression moulding forming and of which the refractive index (nd) and the abbe number (vd) are within a desired range, the preforming material and an optical element. The optical glass of the present invention, by moore%, contains more than 10.0% and less than 50.0% of a B2O3 component and more than 5.0% and less than 30.0% of an La2O3 component, has the refractive index (nd) more than 1.80 and has the abbe number (vd) more than 30 and less than 45.

Description

Opticglass, preforming material and optical element
Technical field
The present invention relates to opticglass, preforming material and optical element.
Background technology
In recent years, use digitizing and the high-precision densification of the equipment of optical system to develop rapidly, in the various optical devices fields such as the image players such as the photographic equipments such as digital camera, pick up camera, projector, projection TV (projection) equipment, number to optical elements such as the lens that use in minimizing optical system, prisms, makes the requirement of optical system integral light and miniaturization increasingly strong.
In making the opticglass of optical element, particularly, can realize the more than 1.80 specific refractory power (n that has of the lighting of optical system integral body and miniaturization d) and there is the more than 30 Abbe number (ν below 45 d) can precise compression molding the demand of the low dispersion glass of high refractive index very high.As the low dispersion glass of such high refractive index, known have take patent documentation 1～4 as the such glass composition of representative.
[patent documentation 1] Japanese kokai publication hei 06-305769 communique
[patent documentation 2] TOHKEMY 2006-137662 communique
[patent documentation 3] TOHKEMY 2006-240889 communique
[patent documentation 4] TOHKEMY 2008-201661 communique
Summary of the invention
The lens that use in optical system have spherical lens and non-spherical lens, if utilize non-spherical lens, can reduce the number of optical element.In addition, for the various optical elements beyond lens, the also known element with the face that has formed complicated shape.Yet, at the grinding, the grinding step that utilize in the past, when wanting to obtain aspheric surface or having formed the face of complicated shape, need expensive and complicated flow chart.Therefore, use and by the finished mould of ultraprecise, the preforming material direct weighting moulding being obtained by material piece (gob) or glass block (glass block) is obtained to the method for the shape of optical element, the method for precise compression molding is main flow at present.
In addition, except by the method for preforming material precise compression molding, known following method also: the material piece being formed by glass material or glass block are reheated and by its moulding (hot repressing moulding), thereby obtain glass forming body, this glass forming body is carried out to grinding and grinding.
As the manufacture method of the preforming material using in such precise compression molding, hot repressing moulding, the method for have the method for utilizing the method for dripping directly to be manufactured by melten glass, the processed goods that glass block hot repressing or ground finish balling-up shape are obtained being carried out to grinding grinding.For either method, for being molded into desired shape, melten glass obtains optical element, all require easily to carry out precise compression molding, and the glass forming is difficult for occurring devitrification.
In addition, in order to reduce the material cost of opticglass, the expense of raw materials of each composition of expectation formation opticglass is cheap as far as possible.In addition, in order to reduce the manufacturing cost of opticglass, the meltbility of expectation raw material is high, i.e. melting at a lower temperature.But the glass composition of recording in patent documentation 1～4 fully meets above-mentioned each requirement hardly.
The present invention completes in view of the above problems, and object is to obtain more at an easy rate specific refractory power (n d) and Abbe number (ν d) in desired scope, and easily carry out precise compression molding, and the high preforming material of devitrification resistance.
The inventor etc. have carried out experimental study repeatedly in order to solve above-mentioned problem, found that, for containing B 2o 3composition and La 2o 3the glass of composition, can obtain specific refractory power (n d) and Abbe number (ν d) in desired scope, and easily carry out the opticglass of precise compression molding, thus completed the present invention.
Especially, the discoveries such as the inventor, can obtain specific refractory power (n d) and Abbe number (ν d) in desired scope, and reduce the high Gd of material cost 2o 3composition and Ta 2o 5the content of composition, and easily carry out the opticglass of precise compression molding.
In addition, the discoveries such as the inventor, can obtain specific refractory power (n d) and Abbe number (ν d) in desired scope, and the Y that contains lower cost for material in the composition that contributes to high refractive index high dispersive 2o 3composition, and easily carry out the opticglass of precise compression molding.
Particularly, the invention provides following such scheme.
(1) opticglass, in mol%, contains more than 10.0% B below 50.0% 2o 3composition, the La more than 5.0% below 30.0% 2o 3composition, has more than 1.80 specific refractory power (n d), there is the more than 30 Abbe number (ν below 45 d).
(2) (1) described opticglass, in mol%, Y 2o 3the content of composition is below 20.0%.
(3) (1) or (2) described opticglass, in mol%, contains and is greater than 0% and be the Y below 20.0% 2o 3composition.
(4) opticglass in (1)～(3) described in any one, in mol%, Y 2o 3the content of composition is below 10.0%.
(5) opticglass in (1)～(4) described in any one, in mol%,
Gd 2o 3composition is 0～10.0%,
Yb 2o 3composition is 0～10.0%,
Lu 2o 3composition is 0～10.0%.
(6) opticglass in (1)～(5) described in any one, in mol%, Ta 2o 5the content of composition is below 10.0%.
(7) opticglass in (1)～(6) described in any one, mole and (Gd 2o 3+ Yb 2o 3+ Ta 2o 5) be below 10.0%.
(8) opticglass in (1)～(7) described in any one, mole and (Gd 2o 3+ Ta 2o 5) be less than 5.0%.
(9) opticglass in (1)～(8) described in any one, in mol%, Ta 2o 5the content of composition is less than 1.0%.
(10) opticglass in (1)～(9) described in any one, in mol%, Gd 2o 3the content of composition is less than 1.0%.
(11) opticglass in (1)～(10) described in any one, Ln 2o 3composition (in formula, Ln is selected from more than one in La, Gd, Y, Yb, Lu) mole and be more than 10.0% below 40.0%.
(12) opticglass in (1)～(11) described in any one, contains above-mentioned Ln 2o 3two or more composition in composition.
(13) opticglass in (1)～(12) described in any one, in mol%,
TiO 2composition is 0～20.0%,
Nb 2o 5composition is 0～10.0%.
(14) opticglass in (1)～(13) described in any one, in mol%, WO 3the content of composition is below 20.0%.
(15) opticglass in (1)～(14) described in any one, in mol%, contains more than 1.0% WO below 20.0% 3composition.
(16) opticglass in (1)～(15) described in any one, mole and (TiO 2+ WO 3+ Nb 2o 5) be 1.0～30.0%.
(17) opticglass in (1)～(16) described in any one, in mol%, contains the more than 10.0% ZnO composition below 38.0%.
(18) opticglass in (1)～(17) described in any one, in mol%, ZrO 2the content of composition is below 10.0%.
(19) opticglass in (1)～(18) described in any one, in mol%, SiO 2the content of composition is below 15.0%.
(20) opticglass in (1)～(19) described in any one, in mol%, Li 2the content of O composition is below 8.0%.
(21) opticglass in (1)～(20) described in any one, in mol%,
Na 2o composition is 0～15.0%,
K 2o composition is 0～10.0%,
Cs 2o composition is 0～10.0%.
(22) opticglass in (1)～(21) described in any one, Rn 2o composition (in formula, Rn is selected from more than one in Li, Na, K, Cs) mole and be below 20.0%.
(23) opticglass in (1)～(22) described in any one, in mol%,
MgO composition is 0～10.0%,
CaO composition is 0～10.0%,
SrO composition is 0～10.0%,
BaO composition is 0～10.0%.
(24) opticglass in (1)～(23) described in any one, RO composition (in formula, R is selected from more than one in Mg, Ca, Sr, Ba) mole and be below 11.0%.
(25) opticglass in (1)～(24) described in any one, in mol%,
GeO 2composition is 0～10.0%,
P 2o 5composition is 0～10.0%,
Bi 2o 3composition is 0～15.0%,
TeO 2composition is 0～15.0%,
Al 2o 3composition is 0～15.0%,
Ga 2o 3composition is 0～15.0%,
Sb 2o 3composition is 0～1.0%,
Replace above-mentioned each element one or more oxide compound part or all and the content of the fluorine atom that the fluorochemical that contains has is 0～15.0 % by mole.
(26) opticglass in (1)～(25) described in any one, has the more than 1.80 specific refractory power (n below 1.95 d), there is the more than 30 Abbe number (ν below 45 d).
(27) opticglass in (1)～(26) described in any one, second-order transition temperature (Tg) is greater than 580 ℃ and be below 630 ℃.
(28) opticglass in (1)～(27) described in any one, has 1100 ℃ of following liquidus temperatures.
(29) preforming material is that the opticglass described in any one forms in (1)～(28).
(30) optical element, makes the preforming material extrusion forming (29) Suo Shu.
(31) optical element, take (1)～(28) in opticglass described in any one be main raw.
(32) optical device, possesses (30) described optical element.
(33) optical device, possesses (31) described optical element.
By the present invention, can obtain more at an easy rate specific refractory power (n d) and Abbe number (ν d) in desired scope, and easily carry out precise compression molding, and the high preforming material of devitrification resistance.
Embodiment
Opticglass of the present invention, in mol%, contains more than 10.0% B below 50.0% 2o 3composition, the La more than 5.0% below 30.0% 2o 3composition, has more than 1.80 specific refractory power (n d) and there is the more than 30 Abbe number (ν below 45 d).
Especially, the 1st opticglass, in mol%, contains more than 10.0% B below 50.0% 2o 3composition, the La more than 5.0% below 30.0% 2o 3composition, mole and (Gd 2o 3+ Ta 2o 5) be less than 5.0%, there is more than 1.80 specific refractory power (n d) and there is the more than 30 Abbe number (ν below 45 d).
In addition, the 2nd opticglass, in mol%, contains more than 10.0% B below 50.0% 2o 3composition, the La more than 5.0% below 30.0% 2o 3composition, is greater than 0% and be the Y below 20.0% 2o 3composition, has more than 1.80 specific refractory power (n d) and there is the more than 30 Abbe number (ν below 45 d).
Especially, in the 1st opticglass, by reducing Gd 2o 3composition and Ta 2o 5the content of composition, can reduce the material cost of glass.On the other hand, especially, in the 2nd opticglass, by containing Y 2o 3composition, can reduce the material cost of glass.And, by with B 2o 3composition and La 2o 3composition is basis, thereby has the more than 1.80 specific refractory power (n below 1.95 d) and 30 above Abbe number (ν below 45 d) time, liquidus temperature is easy step-down also.
Present inventor finds, by having the more than 1.80 specific refractory power (n below 1.95 d) and 30 above Abbe number (ν below 45 d) glass in, reduce the high Gd of material cost 2o 3composition and Ta 2o 5the content of composition also contains the Y of the lower cost for material in the composition that contributes to high refractive index high dispersive simultaneously 2o 3composition, and regulate the content of each composition, thus, the opticglass low with second-order transition temperature is compared, and the devitrification in the time of can reducing glass and make, thus, can obtain more easily carrying out the glass of extrusion forming.
By foregoing, can obtain at an easy rate following opticglass, described opticglass can obtain specific refractory power (n d) and Abbe number (ν d) in desired scope, and easily carry out precise compression molding, and the high preforming material of devitrification resistance.
Below describe the embodiment of opticglass of the present invention in detail.The present invention is not subject to any restriction of following embodiment, in the scope of object of the present invention, can carry out appropriate change and implement.It should be noted that, for repeat specification part, suitably description thereof is omitted sometimes, but do not limit the purport of invention.
[glass ingredient]
The compositing range of each composition that forms opticglass of the present invention is as described below.In this specification sheets, about the content of each composition, unless otherwise specified, be the content of % by mole expression of the total amount of glass forming to convert with respect to oxide compound.Herein, " oxide compound converts and forms " refers to, suppose as the raw material of glass constituent of the present invention and the oxide compound using, double salt, metal fluoride etc. are all decomposed and are converted into oxide compound when melting, now, the total amount of this generation oxide compound of take is 100 % by mole, represents the composition of each composition of containing in glass.
< is about essential composition, optional member >
B 2o 3composition, in containing in a large number the opticglass of the present invention of rare-earth oxide, is the essential composition as network former.Especially, by making B 2o 3the content of composition is more than 10.0%, can improve the devitrification resistance of glass, and can improve the Abbe number of glass.Therefore, B 2o 3the lower limit of the content of composition is preferably 10.0%, and more preferably 15.0%, more preferably 20.0%, more preferably 25.0%.
On the other hand, by making B 2o 3the content of composition is below 50.0%, can easily obtain larger specific refractory power, and can suppress the deterioration of chemical durability.Therefore, B 2o 3the upper limit of the content of composition is preferably 50.0%, and more preferably 45.0%, more preferably 40.0%.
For B 2o 3composition, can be used H as raw material 3bO 3, Na 2b 4o 7, Na 2b 4o 710H 2o, BPO 4deng.
La 2o 3composition is the essential composition that improves the specific refractory power of glass and improve the Abbe number of glass.Therefore, La 2o 3the lower limit of the content of composition is preferably 5.0%, and more preferably 10.0%, more preferably 13.0%.
On the other hand, by making La 2o 3the content of composition is below 30.0%, can reduce devitrification by improving the stability of glass.The La of the total amount of glass therefore, forming with respect to oxide compound conversion 2o 3the upper limit of the content of composition is preferably 30.0%, and more preferably 25.0%, more preferably 20.0%, more preferably 17.0%.
For La 2o 3composition, can be used La as raw material 2o 3, La(NO 3) 3xH 2o(X is integer arbitrarily) etc.
Y 2o 3composition is to contain while being greater than 0%, can, when maintaining high refractive index and high Abbe number, suppress the material cost of glass, and compare the optional member that can reduce specific gravity of glass with other rare earth class composition.Especially, in the 2nd opticglass, Y 2o 3composition is essential composition.Therefore, Y 2o 3the content of composition is preferably greater than 0%, lower limit more preferably 0.5%, more preferably 1.0%, more preferably 2.0%, more preferably 3.0%.
On the other hand, by making Y 2o 3the content of composition is below 20.0%, can suppress the reduction of the specific refractory power of glass, and can improve the devitrification resistance of glass.Therefore, Y 2o 3the upper content limit of composition is preferably 20.0%, and more preferably 10.0%, more preferably 8.0%, more preferably 6.0%.
For Y 2o 3composition, can be used Y as raw material 2o 3, YF 3deng.
Gd 2o 3composition is to contain the specific refractory power that can improve glass while being greater than 0%, and can improve the optional member of Abbe number.
On the other hand, in rare earth element, especially by making expensive Gd 2o 3composition is less than 10.0%, can reduce the material cost of glass, therefore, can make more at an easy rate opticglass.In addition, can suppress thus glass Abbe number exceed necessary rising.Therefore, Gd 2o 3the content of composition is preferably less than 10.0% respectively, is more preferably less than 5.0%, is further preferably less than 1.0%, is further preferably less than 0.5%, is further preferably less than 0.3%, is further preferably less than 0.1%.
For Gd 2o 3composition, can be used Gd as raw material 2o 3, GdF 3deng.
Yb 2o 3composition and Lu 2o 3composition is to contain while being greater than 0%, can improve the specific refractory power of glass, and can improve the optional member of Abbe number.
On the other hand, by making Yb 2o 3composition and Lu 2o 3the content of composition is respectively below 10.0%, can reduce the material cost of glass, therefore can make more at an easy rate opticglass.In addition, can improve thus the devitrification resistance of glass.Therefore, Yb 2o 3composition and Lu 2o 3the upper limit of the content of composition is preferably respectively 10.0%, and more preferably 5.0%, more preferably 3.0%, more preferably 1.0%, more preferably 0.1%.From reducing the viewpoint of material cost, consider, also can not contain Yb 2o 3composition and Lu 2o 3composition.
For Yb 2o 3composition and Lu 2o 3composition, can be used Yb as raw material 2o 3, Lu 2o 3deng.
Ta 2o 5composition is to contain while being greater than 0%, can improve the specific refractory power of glass, and can improve the optional member of devitrification resistance.
On the other hand, by making expensive Ta 2o 5composition is less than 10.0%, can reduce the material cost of glass, therefore can make more at an easy rate opticglass.In addition, the melt temperature step-down of raw material thus, the needed energy of melting of raw material reduces, and therefore also can reduce the manufacturing cost of opticglass.Therefore, Ta 2o 5the content of composition is preferably less than 10.0%, is more preferably less than 5.0%, is further preferably less than 1.0%, more preferably, below 0.7%, more preferably, below 0.4%, be further preferably less than 0.3%, more preferably below 0.2%, more preferably below 0.1%.
For Ta 2o 5composition, can be used Ta as raw material 2o 5deng.
Gd 2o 3composition, Yb 2o 3composition and Ta 2o 5the content of composition and be preferably below 10.0%.Can reduce the content of these expensive compositions thus, therefore can suppress the material cost of glass., mole and (Gd therefore 2o 3+ Yb 2o 3+ Ta 2o 5) the upper limit be preferably 10.0%, more preferably 7.0%, more preferably 5.0%, more preferably 3.5%, more preferably 2.0%, more preferably 1.0%, be further preferably less than 0.5%.
Gd 2o 3composition and Ta 2o 5the total amount of composition is preferably less than 5.0%.Can reduce the content of these expensive compositions thus, therefore can suppress the material cost of glass., mole and (Gd therefore 2o 3+ Ta 2o 5) be preferably less than 5.0%, more preferably, below 3.5%, be further preferably less than 1.0%, be further preferably less than 0.5%.
Ln 2o 3the content of composition (in formula, Ln is selected from more than one in La, Gd, Y, Yb, Lu) and (mole and) be preferably more than 10.0% below 40.0%.
Especially, by making this and being more than 10.0%, can improve the specific refractory power of glass and Abbe number both, therefore can easily obtain thering is desired specific refractory power and the glass of Abbe number.Therefore, Ln 2o 3composition mole and lower limit be preferably 10.0%, more preferably 15.0%, more preferably 16.0%, more preferably 17.0%, more preferably 18.0%.
Therefore on the other hand, by making this and being below 40.0%, the liquidus temperature step-down of glass, can reduce the devitrification of glass.Therefore, Ln 2o 3composition mole and the upper limit be preferably 40.0%, more preferably 30.0%, more preferably 25.0%, more preferably 22.0%.
Opticglass of the present invention preferably contains above-mentioned Ln 2o 3two or more composition in composition.Thus, the further step-down of the liquidus temperature of glass, therefore can obtain the glass that devitrification resistance is higher.Especially, as Ln 2o 3composition, considers from can easily reducing the aspect of liquidus temperature of glass and the aspect that can make cheap opticglass, preferably contains and comprises La 2o 3composition and Y 2o 3the two or more composition of composition.
TiO 2composition is to contain while being greater than 0%, can improve specific refractory power and the Abbe number of glass, and by reducing the liquidus temperature of glass, can improve the optional member of devitrification resistance.
On the other hand, by making TiO 2the content of composition is below 20.0%, can reduce by TiO 2excessive containing of composition and the devitrification that causes can suppress glassy phase for the reduction of the transmissivity of visible ray (especially wavelength 500nm is following).Therefore, TiO 2the upper limit of the content of composition is preferably 20.0%, and more preferably 15.0%, more preferably 12.0%, more preferably 10.0%.
For TiO 2composition, can be used TiO as raw material 2deng.
Nb 2o 5composition is to contain while being greater than 0%, and the specific refractory power that can improve glass reduces Abbe number, and by reducing the liquidus temperature of glass, can improve the optional member of devitrification resistance.
On the other hand, by making Nb 2o 5the content of composition is below 10.0%, can reduce Nb 2o 5excessive the containing of composition and the devitrification that causes, and, glassy phase can be suppressed for the reduction of the transmissivity of visible ray (especially wavelength 500nm is following).Therefore, Nb 2o 5the upper limit of the content of composition is preferably 10.0%, and more preferably 8.0%, more preferably 6.0%, more preferably 5.0%.
For Nb 2o 5composition, can be used Nb as raw material 2o 5deng.
WO 3composition is to contain while being greater than 0%, can reduce the painted of glass that other high refractive index composition causes, and can improve specific refractory power, can reduce second-order transition temperature, and can improve the optional member of the devitrification resistance of glass.Therefore, WO 3the content of composition is preferably greater than 0%, more preferably greater than 0.3%, is further preferably greater than 0.5%, is further preferably greater than 1.0%.
On the other hand, by making WO 3the content of composition is below 20.0%, can reduce WO 3the glass that composition causes painted, improves transmission of visible light.Therefore, WO 3the upper limit of the content of composition is preferably below 20.0%, more preferably, below 17.0%, is more preferably less than 15.0%, more preferably below 13.0%.
For WO 3composition, can be used WO as raw material 3deng.
TiO 2composition, WO 3composition and Nb 2o 5composition mole and be preferably more than 1.0% below 30.0%.
Especially, by making this mole and being more than 1.0%, even if reduce Ta 2o 5one-tenth grades, and also can obtain desired optical constant, therefore can make more at an easy rate the opticglass with desired optical characteristics., mole and (TiO therefore 2+ WO 3+ Nb 2o 5) lower limit be preferably 1.0%, more preferably 2.5%, more preferably 5.0%.
On the other hand, by making this mole and being below 30.0%, the excessive rising that contains the liquidus temperature causing due to these compositions can be suppressed, therefore, the devitrification of opticglass can be reduced., mole and (TiO therefore 2+ WO 3+ Nb 2o 5) the upper limit be preferably 30.0%, more preferably 25.0%, more preferably 20.0%.
ZnO composition is to contain while being greater than 0%, can reduce second-order transition temperature, and can improve the optional member of chemical durability.Therefore, the content of ZnO composition can be preferably greater than 0%, and lower limit can be more preferably 10.0%, and more preferably 12.0%, more preferably 15.0%, more preferably 20.0%, more preferably 24.0%.
On the other hand, by making the content of ZnO composition, be below 38.0%, can reduce liquidus temperature, and, can reduce the necessary reduction of exceeding of second-order transition temperature and the devitrification that causes.Therefore, the upper limit of the content of ZnO composition is preferably 38.0%, and more preferably 36.0%, more preferably 35.0%.
For ZnO composition, as raw material, can use ZnO, ZnF 2deng.
ZrO 2composition is to contain while being greater than 0%, can improve specific refractory power and the Abbe number of glass, and can improve the optional member of devitrification resistance.Therefore, ZrO 2the content of composition can be preferably greater than 0%, more preferably greater than 0.5%, is further preferably greater than 0.8%.
On the other hand, by making ZrO 2the content of composition is below 10.0%, can reduce ZrO 2excessive the containing of composition and the devitrification that causes.Therefore, ZrO 2the upper limit of the content of composition is preferably 10.0%, and more preferably 8.0%, more preferably 5.0%.
For ZrO 2composition, can be used ZrO as raw material 2, ZrF 4deng.
SiO 2composition is to contain while being greater than 0%, can improve the viscosity of melten glass, can reduce the painted of glass, and can improve the optional member of devitrification resistance.Therefore, SiO 2the content of composition is preferably greater than 0%, and lower limit can be more preferably 1.0%, and more preferably 3.0%, more preferably 4.0%.
On the other hand, by making SiO 2the content of composition is below 15.0%, can suppress the rising of second-order transition temperature, and can suppress the reduction of specific refractory power.Therefore, SiO 2the upper limit of the content of composition is preferably 15.0%, and more preferably 12.0%, more preferably 10.0%, more preferably 9.0%.
For SiO 2composition, can be used SiO as raw material 2, K 2siF 6, Na 2siF 6deng.
Li 2o composition is to contain while being greater than 0%, can reduce the optional member of second-order transition temperature.
On the other hand, by making Li 2the content of O composition is below 8.0%, can reduce the liquidus temperature of glass, reduces devitrification, can improve chemical durability.Therefore, Li 2the content of O composition is preferably below 8.0%, is more preferably less than 4.0%, is further preferably less than 2.0%, is further preferably less than 1.0%.
For Li 2o composition, can be used Li as raw material 2cO 3, LiNO 3, Li 2cO 3deng.
Na 2o composition, K 2o composition and Cs 2o composition is to contain while being greater than 0%, can improve the meltbility of glass, can reduce second-order transition temperature, and can improve the optional member of devitrification resistance.
On the other hand, by making Na 2the content of O composition is below 15.0%, and/or makes K 2o composition and Cs 2o composition content is separately below 10.0%, can make to be difficult to reduce the specific refractory power of glass, and can reduce the devitrification of glass.Therefore, Na 2the upper limit of the content of O composition is preferably 15.0%, and more preferably 10.0%, more preferably 5.0%, more preferably 3.0%.In addition, K 2o composition and Cs 2the upper limit of the content of O composition is preferably respectively 10.0%, and more preferably 5.0%, more preferably 3.0%.
For Na 2o composition, K 2o composition and Cs 2o composition, can be used Na as raw material 2cO 3, NaNO 3, NaF, Na 2siF 6, K 2cO 3, KNO 3, KF, KHF 2, K 2siF 6, Cs 2cO 3, CsNO 3deng.
Rn 2the content of O composition (in formula, Rn is selected from more than one in Li, Na, K) and (mole and) be preferably below 20.0%.Thus, the specific refractory power of glass can be made to be difficult to reduce, and the devitrification of glass can be reduced.Therefore, Rn 2o composition mole and the upper limit be preferably 20.0%, more preferably 10.0%, more preferably 5.0%, more preferably 3.5%, more preferably 1.7%.
MgO composition, CaO composition, SrO composition and BaO composition are to contain while being greater than 0%, the optional member of the specific refractory power of adjustable glass, meltbility, devitrification resistance.
On the other hand, by making MgO composition, CaO composition, SrO composition and BaO composition content separately, be below 10.0%, can make to be easy to obtain desired specific refractory power, and can suppress the excessive devitrification that contains the glass causing of these compositions.Therefore, the upper limit of MgO composition, CaO composition, SrO composition and BaO composition content is separately preferably 10.0%, and more preferably 5.0%, more preferably 3.0%.
For MgO composition, CaO composition, SrO composition and BaO composition, as raw material, can use MgCO 3, MgF 2, CaCO 3, CaF 2, Sr(NO 3) 2, SrF 2, BaCO 3, Ba(NO 3) 2, BaF 2deng.
The content of RO composition (in formula, R is selected from more than one in Mg, Ca, Sr, Ba) and (mole and) be preferably below 11.0%.Thus, can easily obtain desired high refractive index.Therefore, RO composition mole and the upper limit be preferably 11.0%, more preferably 5.0%, more preferably 3.0%.
GeO 2composition is to contain while being greater than 0%, can improve the specific refractory power of glass, and can improve the optional member of devitrification resistance.
Yet, GeO 2because cost of material is high, if therefore its content at most production cost uprise, therefore, by reducing Gd 2o 3composition, Ta 2o 5the effect that becomes to grade and obtain reduces.Therefore, GeO 2the upper limit of the content of composition is preferably 10.0%, and more preferably 5.0%, more preferably 3.0%, more preferably 1.0%, more preferably 0.1%.From reducing the viewpoint of material cost, consider, also can not contain GeO 2composition.
For GeO 2composition, can be used GeO as raw material 2deng.
P 2o 5composition is to contain while being greater than 0%, can reduce the liquidus temperature of glass, improves the optional member of devitrification resistance.
On the other hand, by making P 2o 5the content of composition is below 10.0%, can suppress the especially reduction of water tolerance of chemical durability of glass.Therefore, P 2o 5the upper limit of the content of composition is preferably 10.0%, and more preferably 5.0%, more preferably 3.0%.
For P 2o 5composition, can be used Al(PO as raw material 3) 3, Ca(PO 3) 2, Ba(PO 3) 2, BPO 4, H 3pO 4deng.
Bi 2o 3composition is to contain while being greater than 0%, can improve specific refractory power, and can reduce the optional member of second-order transition temperature.
On the other hand, by making Bi 2o 3the content of composition is below 15.0%, can reduce the liquidus temperature of glass, improves devitrification resistance.Therefore, Bi 2o 3the content of composition is preferably below 15.0%, is more preferably less than 10.0%, is further preferably less than 5.0%, is further preferably less than 3.0%.
For Bi 2o 3composition, can be used Bi as raw material 2o 3deng.
TeO 2composition is to contain while being greater than 0%, can improve specific refractory power, and can reduce the optional member of second-order transition temperature.
On the other hand, with regard to TeO 2, in the crucible by platinum system or the part that contacts with melten glass, be the fusion tank that formed by platinum while carrying out molten raw, existence can with the problem of platinum alloy.Therefore, TeO 2the content of composition is preferably below 15.0%, is more preferably less than 10.0%, is further preferably less than 5.0%, is further preferably less than 3.0%.
For TeO 2composition, can be used TeO as raw material 2deng.
Al 2o 3composition and Ga 2o 3composition is to contain while being greater than 0%, can improve the chemical durability of glass, and can improve the optional member of the devitrification resistance of melten glass.
On the other hand, by making Al 2o 3composition and Ga 2o 3composition content is separately below 15.0%, can reduce the liquidus temperature of glass, improves devitrification resistance.Therefore, Al 2o 3composition and Ga 2o 3the upper limit of composition content is separately preferably 15.0%, and more preferably 10.0%, more preferably 5.0%, more preferably 3.0%.
For Al 2o 3composition and Ga 2o 3composition, can be used Al as raw material 2o 3, Al(OH) 3, AlF 3, Ga 2o 3, Ga(OH) 3deng.
SnO 2composition is to contain while being greater than 0%, reduces the oxidation of melten glass, makes its clarification, and can improve the optional member of the transmission of visible light of glass.
On the other hand, by making SnO 2the content of composition is below 1.0%, can reduce the devitrification of the painted and glass of the glass that the reduction of melten glass causes.In addition, due to SnO 2the alloying of composition and fusion apparatus precious metals such as (especially) Pt is reduced, and therefore can seek the long lifetime of fusion apparatus.Therefore, SnO 2the content of composition is preferably below 1.0%, more preferably, below 0.5%, is further preferably less than 0.1%.
For SnO 2composition, can be used SnO, SnO as raw material 2, SnF 2, SnF 4deng.
Sb 2o 3composition is to contain while being greater than 0%, can be by the optional member of melten glass deaeration.
On the other hand, Sb 2o 3measure when too much transmissivity variation in the short wavelength region of visible region.Therefore, Sb 2o 3the upper limit of the content of composition is preferably 1.0%, and more preferably 0.7%, more preferably 0.5%.
For Sb 2o 3composition, can be used Sb as raw material 2o 3, Sb 2o 5, Na 2h 2sb 2o 75H 2o etc.
It should be noted that, the composition that makes glass clarifying and carry out deaeration is not limited to above-mentioned Sb 2o 3composition, can be used known finings, deaerating agent or their combination in glass manufacturing area.
F composition is to contain while being greater than 0%, can improve the Abbe number of glass, and can reduce second-order transition temperature, and can improve the optional member of devitrification resistance.
Yet, when the content of F composition replace one or more part or all and the total amount in F of the fluorochemical that contains of oxide compound of above-mentioned each element to be greater than 15.0%, because the volatilization quantitative change of F composition is many, therefore be difficult to obtain stable optical constant, be difficult to obtain the glass of homogeneous.
Therefore, the upper limit of the content of F composition is preferably 15.0%, and more preferably 10.0%, most preferably be 5.0%.
By using for example ZrF 4, AlF 3, NaF, CaF 2deng as raw material, can contain F composition at glass.
The composition > of < about not containing
The composition that next, should not contain in opticglass of the present invention if illustrate and contain undesirable composition.
As required, in the scope of characteristic of glass of not damaging the present application, can add other compositions.Wherein, except Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, each transiting metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo have character as follows, therefore, especially, in the opticglass of wavelength that uses visibility region, preferably do not contain in fact, described character is, even if containing separately respectively a small amount of or compound containing when a small amount of, glass also can occur painted, at the specific wavelength place of visible region, produces and absorbs.
In addition, lead compound and the As such as PbO 2o 3deng arsenic compound, be the composition that carrying capacity of environment is large, therefore, expectation does not contain in fact, that is, except inevitably sneaking into, do not contain completely.
And then each composition of Th, Cd, Tl, Os, Be and Se, as harmful chemical substance, has the tendency of controlling its use in recent years.Not only in the manufacturing process of glass, and in manufacturing procedure and until the punishment after commercialization needs the measure in environmental cure.Therefore,, during affecting on paying attention to environment, preferably do not contain in fact these.
With regard to glass composition of the present invention, it forms % by mole expression of the total amount of glass forming to convert with respect to oxide compound, therefore, directly with the record of quality %, do not represent, but the composition representing based on quality % of each composition existing in the glass composition of each characteristic requiring in meeting the present invention, in oxide compound, convert and form, conventionally get following value.
B 2o 3composition is 5.0～30.0 quality %,
La 2o 3composition is 10.0～60.0 quality %, and
And,
Y 2o 3composition is 0～40.0 quality %,
Gd 2o 3composition is 0～30.0 quality %,
Yb 2o 3composition is 0～20.0 quality %,
Lu 2o 3composition is 0～20.0 quality %,
Ta 2o 5composition is 0～30.0 quality %,
TiO 2composition is 0～15.0 quality %,
Nb 2o 5composition is 0～20.0 quality %,
WO 3composition is 0～40.0 quality %,
ZnO composition is 0～25.0 quality %,
ZrO 2composition is 0～10.0 quality %,
SiO 2composition is 0～8.0 quality %,
Li 2o composition is 0～2.0 quality %,
Na 2o composition is 0～10.0 quality %,
K 2o composition is 0～8.0 quality %,
Cs 2o composition is 0～15.0 quality %,
MgO composition is 0～3.0 quality %,
CaO composition is 0～5.0 quality %,
SrO composition is 0～8.0 quality %,
BaO composition is 0～10.0 quality %,
GeO 2composition is 0～12.0 quality %,
P 2o 5composition is 0～10.0 quality %,
Bi 2o 3composition is 0～40.0 quality %,
TeO 2composition is 0～15.0 quality %,
Al 2o 3composition is 0～12.0 quality %,
Ga 2o 3composition is 0～20.0 quality %,
Sb 2o 3composition is 0～3.0 quality %,
And, replace above-mentioned each element one or more oxide compound part or all and the total amount of F of take in the fluorochemical that contains is 0～3.0 quality %.
Especially, the composition representing based on quality % of each composition existing in the 1st opticglass, converts and forms in oxide compound, conventionally gets following value.
B 2o 3composition is 5.0～30.0 quality %, and
La 2o 3composition is 10.0～60.0 quality %,
And,
Y 2o 3composition is 0～20.0 quality %,
Gd 2o 3composition is 0～3.0 quality %,
Yb 2o 3composition is 0～20.0 quality %,
Lu 2o 3composition is 0～20.0 quality %,
Ta 2o 5composition is 0～4.0 quality %,
TiO 2composition is 0～15.0 quality %,
Nb 2o 5composition is 0～20.0 quality %,
WO 3composition is 0～40.0 quality %,
ZnO composition is 0～25.0 quality %,
ZrO 2composition is 0～10.0 quality %,
SiO 2composition is 0～8.0 quality %,
Li 2o composition is 0～2.0 quality %,
Na 2o composition is 0～10.0 quality %,
K 2o composition is 0～8.0 quality %,
Cs 2o composition is 0～15.0 quality %,
MgO composition is 0～3.0 quality %,
CaO composition is 0～5.0 quality %,
SrO composition is 0～8.0 quality %,
BaO composition is 0～10.0 quality %,
GeO 2composition is 0～12.0 quality %,
P 2o 5composition is 0～10.0 quality %,
Bi 2o 3composition is 0～40.0 quality %,
TeO 2composition is 0～15.0 quality %,
Al 2o 3composition is 0～12.0 quality %,
Ga 2o 3composition is 0～20.0 quality %,
Sb 2o 3composition is 0～3.0 quality %,
And, replace above-mentioned each element one or more oxide compound part or all and the total amount of F of take in the fluorochemical that contains is 0～3.0 quality %.
On the other hand, the composition representing based on quality % of each composition existing in the 2nd opticglass, converts and forms in oxide compound, conventionally gets following value.
B 2o 3composition is 5.0～30.0 quality %,
La 2o 3composition is 10.0～60.0 quality %, and
Y 2o 3composition is for being greater than 0 quality %～40.0 quality %,
And,
Gd 2o 3composition is 0～30.0 quality %,
Yb 2o 3composition is 0～20.0 quality %,
Lu 2o 3composition is 0～20.0 quality %,
Ta 2o 5composition is 0～30.0 quality %,
TiO 2composition is 0～15.0 quality %,
Nb 2o 5composition is 0～20.0 quality %,
WO 3composition is 0～40.0 quality %,
ZnO composition is 0～25.0 quality %,
ZrO 2composition is 0～10.0 quality %,
SiO 2composition is 0～8.0 quality %,
Li 2o composition is 0～2.0 quality %,
Na 2o composition is 0～10.0 quality %,
K 2o composition is 0～8.0 quality %,
Cs 2o composition is 0～15.0 quality %,
MgO composition is 0～3.0 quality %,
CaO composition is 0～5.0 quality %,
SrO composition is 0～8.0 quality %,
BaO composition is 0～10.0 quality %,
GeO 2composition is 0～12.0 quality %,
P 2o 5composition is 0～10.0 quality %,
Bi 2o 3composition is 0～40.0 quality %,
TeO 2composition is 0～15.0 quality %,
Al 2o 3composition is 0～12.0 quality %,
Ga 2o 3composition is 0～20.0 quality %,
Sb 2o 3composition is 0～3.0 quality %,
And, replace above-mentioned each element one or more oxide compound part or all and the total amount of F of take in the fluorochemical that contains is 0～3.0 quality %.
[manufacture method]
Opticglass of the present invention is for example made in the following way.; according to the mode that makes each composition in the scope of the content of regulation, evenly mix above-mentioned raw materials; the mixture of making is put in platinum crucible; the melting difficulty forming according to glass; in electric furnace, in the temperature range of 1100～1500 ℃, carry out melting in 2～5 hours, and stir and to homogenize, be then reduced to suitable temperature; then be poured in mould Slow cooling.Make thus.
[physical property]
Opticglass of the present invention preferably has high refractive index and high Abbe number (low dispersion).Especially, the specific refractory power (n of opticglass of the present invention d) lower limit be preferably 1.80, more preferably 1.81, more preferably 1.82.This specific refractory power (n d) the upper limit be preferably 1.95, more preferably 1.93, more preferably 1.92.In addition, the Abbe number (ν of opticglass of the present invention d) lower limit be preferably 30, more preferably 32, more preferably 33.This Abbe number (ν d) the upper limit be preferably 45, more preferably 43, more preferably 41.
By thering is such high refractive index, thereby even if seek the slimming of optical element, also can obtain the amount of refraction of large light.In addition, by thering is so low dispersion, thereby even simple lens, because the different focus deviations (aberration) that cause of light wavelength also diminish.And, by thering is so low dispersion, for example, when thering is the optical element combination of high dispersive (low Abbe number), can seek high imaging characteristic etc.
Therefore, opticglass of the present invention is useful in optical design, especially, not only can realize high imaging characteristic etc., but also can realize the miniaturization of optical system, can expansion optical the degree of freedom of design.
For opticglass of the present invention, preferably especially the optical transmission rate of the short-and-medium wavelength side of visible ray is high for transmission of visible light, painted few by its generation.
Especially, use the sample of the thick 10mm in opticglass of the present invention, the minimal wave length (λ of the spectral-transmission favtor of demonstration 70% 70) the upper limit be preferably 450nm, more preferably 420nm, more preferably 400nm.
In addition, use the sample of the thick 10mm in opticglass of the present invention, the minimal wave length (λ of the spectral-transmission favtor of demonstration 5% 5) the upper limit be preferably 400nm, more preferably 380nm, more preferably 360nm.
Thus, the absorption limit of glass is near ultraviolet region, and glassy phase improves for the transparency of visible ray, therefore, can preferably this opticglass be used for to the optical element that lens etc. make light transmission.
The devitrification resistance of opticglass of the present invention is high, more specifically, preferably has low liquidus temperature.That is, the upper limit of the liquidus temperature of opticglass of the present invention is preferably 1100 ℃, and more preferably 1080 ℃, more preferably 1060 ℃.Thus, even if flow out at a lower temperature melten glass, the crystallization of the glass of making is also lowered, and therefore, can reduce the devitrification while forming glass from molten state, can reduce having used the impact of optical characteristics of the optical element of glass.In addition, the scope of temperature that can stably manufactured preforming material broadens, and therefore, even if reduce the melt temperature of glass, also can form preforming material, the energy consuming in the time of can suppressing to form preforming material.On the other hand, the lower limit of the liquidus temperature of opticglass of the present invention is not particularly limited, the liquidus temperature of the glass obtaining by the present invention, conventionally more than 800 ℃, is specially more than 850 ℃, is more specifically more than 900 ℃, and such situation is more.It should be noted that, " liquidus temperature " in this specification sheets refers to following temperature: to the glass specimen that packs the glass cullet shape of 30cc in the platinum crucible processed of the capacity of 50ml into, put into platinum crucible and at 1250 ℃, make complete molten state, be cooled to the temperature of regulation, keep 12 hours, be taken out to outside stove, it is cooling, then in sight glass surface and glass, have or not crystallization immediately, using the minimum temperature of not finding crystallization now as " liquidus temperature ".Herein, the temperature of regulation during cooling is the temperature of every 10 ℃ between 1180 ℃～800 ℃.
Opticglass of the present invention preferably has and is greater than 580 ℃ and be 630 ℃ of following second-order transition temperatures (Tg).
Especially, by opticglass is had, be greater than the second-order transition temperature of 580 ℃, thereby even there is the more than 1.80 specific refractory power (n below 1.95 d) and 30 above Abbe number (ν below 45 d) the opticglass of the low dispersion of high refractive index, be also difficult for occurring the crystallization of glass, therefore, the devitrification in the time of can reducing glass and make, thus, can obtain easily carrying out the glass of extrusion forming.Especially, the large glass of specific refractory power high Abbe number, just more has the tendency of the crystallization of easy generation glass, therefore, and by the obvious technical effects that second-order transition temperature is obtained in being greater than the temperature range of 580 ℃.Therefore, the second-order transition temperature of opticglass of the present invention is preferably greater than 580 ℃, more preferably greater than 590 ℃, is further preferably greater than 600 ℃.
On the other hand, by making opticglass there are 630 ℃ of following second-order transition temperatures, can make glass softening at lower temperature, therefore, can easily to glass, carry out extrusion forming at a lower temperature.In addition, the oxidation for the mould of extrusion forming can also be reduced, the long lifetime of mould can be realized.Therefore, the upper limit of the second-order transition temperature of opticglass of the present invention is preferably 630 ℃, and more preferably 625 ℃, more preferably 620 ℃.
It should be noted that, even if second-order transition temperature is greater than 580 ℃, by using forming machine such shown in TOHKEMY 2007-186384 communique and mould etc., also can reduce the surperficial damage with mould to pressurization, can improve the weather resistance of moulding stock, what therefore, conventionally carry out is the precision press formation with the opticglass of the second-order transition temperature that is greater than 580 ℃.
Opticglass preferred specific gravity of the present invention is little.More specifically, the proportion of opticglass of the present invention is 5.50[g/cm 3] below.Thus, can reduce optical element and use the quality of its optical device, therefore, can contribute to the lighting of optical device.Therefore, the upper limit of the proportion of opticglass of the present invention is preferably 5.50, and more preferably 5.40, be preferably 5.30.It should be noted that, the proportion of opticglass of the present invention, conventionally more than 3.00, in more detail, how more than 3.50, is said, more than 4.00 in further detail.
The proportion of opticglass of the present invention can be measured by standard JOGIS05-1975 " measuring method of the proportion of opticglass " based on Japanese optics nitre industry.
[preforming material and optical element]
By the opticglass of making, use compression-moulding methods such as hot repressing moulding, precision press formation, can make glass forming body.; by opticglass, make the preform that compression molding is used; this preform is carried out to hot repressing moulding; then carry out attrition process; can make glass forming body; or the preform of making carrying out attrition process, utilize the preform of the moulding such as known floating moulding to carry out precision press formation, can make glass forming body.It should be noted that, the means of making glass forming body are not limited to these means.
Like this, opticglass of the present invention is useful for multiple optical element and optical design.Wherein, particularly preferably be, by opticglass of the present invention, form preform, use this preform to carry out hot repressing moulding, precision press formation etc., make the optical elements such as lens, prism.Thus, the preform that diameter is large can be formed, therefore, the maximization of optical element can be realized, and, when for optical devices such as photographic camera, projectors, can realize fine and high-precision imaging characteristic and projection property.
[embodiment]
Embodiments of the invention (No.A1～No.A75, No.B1～No.B71) and the composition of comparative example (No.a) and the specific refractory power (n of these glass d), Abbe number (ν d), second-order transition temperature (Tg), liquidus temperature, spectral-transmission favtor be shown as 5%, 70% wavelength (λ 5, λ 70) and proportion the results are shown in table 1～table 20.Herein, embodiment (No.A1～No.A75) is the example of the 1st opticglass, and embodiment (No.B1～No.B71) is the example of the 2nd opticglass.It should be noted that, following embodiment is only illustration object, is not limited in these embodiment.
The glass of embodiments of the invention and comparative example is all made in the following manner: select the suitable oxide compound of raw material difference as each composition, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the high-purity raw using in the common opticglass such as metaphosphoric acid compound, the ratio of composition with each embodiment shown in table weighs and evenly mixing, then put in platinum crucible, the melting difficulty forming according to glass, use electric furnace in the temperature range of 1100～1500 ℃, to carry out melting in 2～5 hours, then stir and homogenize, then be poured in mould etc., Slow cooling, make thus.
Herein, the specific refractory power (n of the glass of embodiment and comparative example d) and Abbe number (ν d) based on Japanese optics nitre industry, can measure by standard JOGIS01-2003.Herein, specific refractory power (n d), Abbe number (ν d) by the glass that Slow cooling cooling rate is obtained for-25 ℃/hr is measured and is obtained.
In addition, the second-order transition temperature of the glass of embodiment and comparative example (Tg) is by having been used the mensuration of horizontal type dilatometer (Japanese: horizontal type Peng Zhang Measuring determines device) to obtain.Sample while herein, measuring is used the sample of long 50～55mm, making heat-up rate is 4 ℃/min.
In addition, the transmissivity of the glass of embodiment and comparative example can be measured by standard JOGIS02 according to Japanese optics nitre industry.It should be noted that, in the present invention, by measuring the transmissivity of glass, thereby obtained paneless painted and degree.Particularly, for the parallel grinding object in opposite of thick 10 ± 0.1mm, according to JISZ8722, measure the spectral-transmission favtor of 200～800nm, obtain λ 5(wavelength during transmissivity 5%), λ 70(wavelength during transmissivity 70%).
In addition, the liquidus temperature of the glass of embodiment and comparative example is obtained as follows: to the glass specimen that packs the glass cullet shape of 30cc in the platinum crucible processed of the capacity of 50ml into, pack into and in platinum crucible and at 1250 ℃, make complete molten state, be cooled to certain temperature of setting every 10 ℃ of ground of 1180 ℃ to 800 ℃, keep 12 hours, be taken out to outside stove, it is cooling, then in sight glass surface and glass, have or not crystallization immediately, obtain the minimum temperature of not finding crystallization.
In addition, the proportion of the glass of embodiment and comparative example can be measured by standard JOGIS05-1975 " measuring method of the proportion of opticglass " based on Japanese optics nitre industry.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
[table 11]
[table 12]
[table 13]
[table 14]
[table 15]
[table 16]
[table 17]
[table 18]
[table 19]
[table 20]
As seen from table, with regard to the opticglass of embodiments of the invention, can reduce the Gd that material cost is high 2o 3composition, Ta 2o 5the content of composition, therefore, can obtain more at an easy rate.
Especially, with regard to the opticglass of embodiments of the invention (No.A1～No.A75), mole and (Gd 2o 3+ Ta 2o 5) be less than 5.0%, in more detail, be less than 0.3%, therefore, can obtain more at an easy rate.
In addition, especially, with regard to the opticglass of embodiments of the invention (No.B1～No.B71), by containing, be greater than 0%, say in more detail the Y of more than 3.0% lower cost for material 2o 3composition, can reduce the Gd that material cost is high 2o 3composition and Ta 2o 5the content of composition.In more detail, due to can by mole and (Gd 2o 3+ Ta 2o 5) be reduced to and be less than 5.0%, in more detail, be reduced to and be less than 0.3%, therefore, can obtain more at an easy rate having the opticglass of desired optical constant.
On the other hand, the glass of comparative example does not contain the Y of lower cost for material 2o 3composition, mole and (Gd 2o 3+ Ta 2o 5) be 16.455%, more contain Gd 2o 3or Ta 2o 5, therefore, material cost uprises.
The second-order transition temperature of the opticglass of embodiments of the invention (Tg) is all greater than 580 ℃ and be below 630 ℃, in more detail, be 583 ℃ above below 630 ℃, in desired scope.On the other hand, the second-order transition temperature of the glass of comparative example (Tg) is greater than 630 ℃.
In addition, the liquidus temperature of the opticglass of embodiments of the invention is below 1100 ℃, in desired scope.On the other hand, the liquidus temperature of the glass of comparative example is greater than 1100 ℃.
Therefore known, with regard to the opticglass of embodiments of the invention, even in contributing to the composition of high refractive index high dispersive, the Y that contains lower cost for material 2o 3during composition, do not use Gd 2o 3composition, Ta 2o 5while becoming the high composition of the material cost of grading, even be in a ratio of with the glass of comparative example the opticglass that second-order transition temperature is low, the devitrification in the time of also can reducing glass and make.
In addition, the λ of the opticglass of embodiments of the invention 70(wavelength during transmissivity 70%) is below 450nm, in more detail, and below 440nm.In addition, the λ of the opticglass of embodiments of the invention 5(wavelength during transmissivity 5%) is below 400nm, in more detail, and below 370nm.Therefore known, the opticglass of embodiments of the invention, the transmissivity under visible ray short wavelength is high, is difficult to painted.
In addition, the specific refractory power (n of the opticglass of embodiments of the invention d) be more than 1.80, in more detail, be more than 1.81, and this specific refractory power (n d) be below 1.95, in more detail, be below 1.92, in desired scope.
In addition, the Abbe number (ν of the opticglass of embodiments of the invention d) be more than 30, in more detail, be more than 33, and this Abbe number (ν d) be below 45, in more detail, be below 43, in desired scope.
In addition, the proportion of the opticglass of embodiments of the invention is below 5.50, in more detail, is below 5.21.Therefore known, the proportion of the opticglass of embodiments of the invention is little.
Therefore known, the specific refractory power (n of the opticglass of embodiments of the invention d) and Abbe number (ν d) in desired scope, and the transmissivity under visible ray short wavelength is high, and devitrification resistance is high, easily carry out based on thermoplastic extrusion forming, and proportion is little.
And then the opticglass of use embodiments of the invention, after carrying out hot repressing moulding, carries out grinding and grinding, is processed into the shape of lens and prism.In addition, use the opticglass of embodiments of the invention, form precision press formation preform, precision press formation is processed into the shape of lens and prism with preform precision press formation.In all cases, in the glass after thermoplastic, all there is not the problems such as opacification and devitrification, can stably be processed into the shape of multiple lens and prism.
Be above the clear the present invention in detail of illustration object, but the present embodiment is only illustration object, should be appreciated that in the situation that not exceeding thought of the present invention and scope, those skilled in the art can carry out multiple change.

Claims (33)

1. an opticglass, in mol%, contains more than 10.0% B below 50.0% 2o 3composition, the La more than 5.0% below 30.0% 2o 3composition, and there is more than 1.80 refractive index ns d, there is the more than 30 Abbe number ν below 45 d.
2. opticglass as claimed in claim 1, in mol%, Y 2o 3the content of composition is below 20.0%.
3. opticglass as claimed in claim 1, in mol%, contains and is greater than 0% and be the Y below 20.0% 2o 3composition.
4. opticglass as claimed in claim 1, in mol%, Y 2o 3the content of composition is below 10.0%.
5. opticglass as claimed in claim 1, in mol%,
Gd 2o 3composition is 0～10.0%,
Yb 2o 3composition is 0～10.0%,
Lu 2o 3composition is 0～10.0%.
6. opticglass as claimed in claim 1, in mol%, Ta 2o 5the content of composition is below 10.0%.
7. opticglass as claimed in claim 1, Gd 2o 3+ Yb 2o 3+ Ta 2o 5mole and be below 10.0%.
8. opticglass as claimed in claim 1, Gd 2o 3+ Ta 2o 5mole and be less than 5.0%.
9. opticglass as claimed in claim 1, in mol%, Ta 2o 5the content of composition is less than 1.0%.
10. opticglass as claimed in claim 1, in mol%, Gd 2o 3the content of composition is less than 1.0%.
11. opticglass as claimed in claim 1, Ln 2o 3composition mole and be more than 10.0% below 40.0%, Ln 2o 3in, Ln is selected from more than one in La, Gd, Y, Yb, Lu.
12. opticglass as claimed in claim 1, contain above-mentioned Ln 2o 3two or more composition in composition.
13. opticglass as claimed in claim 1, in mol%,
TiO 2composition is 0～20.0%,
Nb 2o 5composition is 0～10.0%.
14. opticglass as claimed in claim 1, in mol%, WO 3the content of composition is below 20.0%.
15. opticglass as claimed in claim 1, in mol%, contain more than 1.0% WO below 20.0% 3composition.
16. opticglass as claimed in claim 1, TiO 2+ WO 3+ Nb 2o 5mole and be 1.0～30.0%.
17. opticglass as claimed in claim 1, in mol%, contain the more than 10.0% ZnO composition below 38.0%.
18. opticglass as claimed in claim 1, in mol%, ZrO 2the content of composition is below 10.0%.
19. opticglass as claimed in claim 1, in mol%, SiO 2the content of composition is below 15.0%.
20. opticglass as claimed in claim 1, in mol%, Li 2the content of O composition is below 8.0%.
21. opticglass as claimed in claim 1, in mol%,
Na 2o composition is 0～15.0%,
K 2o composition is 0～10.0%,
Cs 2o composition is 0～10.0%.
22. opticglass as claimed in claim 1, Rn 2o composition mole and be below 20.0%, Rn 2in O, Rn is selected from more than one in Li, Na, K, Cs.
23. opticglass as claimed in claim 1, in mol%,
MgO composition is 0～10.0%,
CaO composition is 0～10.0%,
SrO composition is 0～10.0%,
BaO composition is 0～10.0%.
24. opticglass as claimed in claim 1, RO composition mole and be below 11.0%, in RO, R is selected from more than one in Mg, Ca, Sr, Ba.
25. opticglass as claimed in claim 1, in mol%,
GeO 2composition is 0～10.0%,
P 2o 5composition is 0～10.0%,
Bi 2o 3composition is 0～15.0%,
TeO 2composition is 0～15.0%,
Al 2o 3composition is 0～15.0%,
Ga 2o 3composition is 0～15.0%,
Sb 2o 3composition is 0～1.0%,
Replace above-mentioned each element one or more oxide compound part or all and the content of the fluorine atom that the fluorochemical that contains has is 0～15.0 % by mole.
26. opticglass as claimed in claim 1, have more than 1.80 refractive index n below 1.95 d, there is the more than 30 Abbe number ν below 45 d.
27. opticglass as claimed in claim 1, glass transition temperature Tg is greater than 580 ℃ and be below 630 ℃.
28. opticglass as claimed in claim 1, have 1100 ℃ of following liquidus temperatures.
29. 1 kinds of preforming materials, are formed by opticglass claimed in claim 1.
30. 1 kinds of optical elements, make the preforming material extrusion forming described in claim 29.
31. 1 kinds of optical elements, the opticglass described in any one in claim 1～28 of take is main raw.
32. 1 kinds of optical devices, possess the optical element described in claim 30.
33. 1 kinds of optical devices, possess the optical element described in claim 31.
CN201410133778.XA 2013-04-05 2014-04-03 Optical Glass, Preforming Material And Optical Element Pending CN104098267A (en)

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