CN106630595A - Optical glass, preform material, and optical element - Google Patents
Optical glass, preform material, and optical element Download PDFInfo
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- CN106630595A CN106630595A CN201611249628.0A CN201611249628A CN106630595A CN 106630595 A CN106630595 A CN 106630595A CN 201611249628 A CN201611249628 A CN 201611249628A CN 106630595 A CN106630595 A CN 106630595A
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- glass
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- optical glass
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
-
- 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
-
- 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 invention provides an optical glass with which it is possible to inexpensively obtain a preform material having a high devitrification resistance and which has a refractive index (nd) and an Abbe number ([nu]d) within a predetermined range; a preform material; and an optical element. An optical glass containing 10.0 to 50.0 mol % of a B2O3 component and 5.0 to 30.0 mol % of a La2O3 component relative to the total amount of the glass composition in terms of oxides, wherein the sum of (TiO2+WO3+Nb2O5) is 0.1 to 30.0 mol % relative to the total amount of the glass composition in terms of oxides.
Description
It is October 7, Application No. 201180048593.3, entitled " optics in 2011 applying date that the application is
The divisional application of the application of glass, preform material and optical element ".
Technical field
The present invention relates to optical glass, preform material and optical element.
Background technology
In recent years, using optics system equipment digitlization and High precision develop rapidly, in digital camera or shooting
In the fields of various optical devices such as image regeneration (projection) equipment such as the photographic equipments such as machine and projecting apparatus or projection TV, by force
The strong piece number of optical element such as lens, prism required to reduce used in optics system, make optics system integral light and little
Type.
In the optical glass for making optical element, particularly to the demand of the low dispersing glass of following highs index of refraction very
Height, the low dispersing glass of the high index of refraction can realize the overall lighting of optics system and miniaturization, with more than 1.75
Refractive index (nd), with less than more than 30 50 Abbe number (νd) and precision die extrusion forming can be carried out.As above-mentioned height
The low dispersing glass of refractive index, it is known to the glass composition with patent document 1～2 as representative.
Patent document 1：Japanese Unexamined Patent Publication 2001-348244 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-001551 publications
The content of the invention
Lens used in optics system include spherical lens and non-spherical lens, if using non-spherical lens, can
To reduce the piece number of optical element.Additionally, it is known that also having the shape for defining complexity in the various optical elements beyond lens
The face of shape.But, it is desirable to when obtaining face that is aspherical or defining complicated shape using existing grinding, grinding step, cost
Operational sequence that is high and needing complexity.Therefore, precision die extrusion forming method is current main flow, and methods described utilizes Jing
Having crossed preform material of the mould of Ultra-precision Turning to being obtained by gob or glass blocks carries out direct weighting shaping, obtains
The shape of optical element.
In addition, in addition to preform material to be carried out the method for precision die extrusion forming, it is also known that there is following sides
Method：The gob formed by glass material or glass blocks are reheated and be molded (reheat extrusion forming), will be obtained
Glass forming body be ground and ground.
The manufacturer of the preform material used in extrusion forming is press-formed and reheated as above-mentioned precision die
Method, including following methods：The method directly manufactured by melten glass using drop-method；Add with carrying out reheating glass blocks
Pressure, or grinding glomeration, the method that gained processed goods is carried out being ground grinding.Above-mentioned all methods are in order to by melten glass
It is shaped to desired shape and obtains optical element, is required to the devitrification of the glass that reduction is formed.
In addition, the material cost in order to reduce optical glass, the raw material cost of the various composition for expecting to make composition optical glass
With as far as possible inexpensively.In addition, the manufacturing cost in order to reduce optical glass, expect that the meltability of raw material is high, i.e. in lower temperature
It is lower to melt.However, for the glass composition disclosed in patent document 1～2, it is difficult to which saying can fully meet above-mentioned various
Require.
The present invention is completed in view of the above problems, it is an object of the invention to it is high more inexpensively to obtain devitrification resistance
Preform material and refractive index (nd) and Abbe number (νd) in desired scope.
Deep experimental study is repeated in order to solve above-mentioned problem, the present inventor etc., has as a result been found：By containing
There is B2O3Composition and La2O3Contain TiO in the glass of composition2Composition, WO3Composition and Nb2O5At least one in composition is used as required
Composition, even if reducing the Ta of expensive and fusibility difference2O5Composition can also obtain desired optical constant, so as to complete this
It is bright.Specifically, the present invention provides invention below.
(1) a kind of optical glass, relative to the glass total material amount for being scaled oxide composition, in terms of mole %, contains
10.0～50.0%B2O3Composition and 5.0～30.0%La2O3Composition, relative to the glass total material for being scaled oxide composition
Amount, mole and (TiO2+WO3+Nb2O5) it is 0.1～30.0%.
(2) optical glass as described in (1), wherein, relative to the glass total material amount for being scaled oxide composition, to rub
Your % is counted, WO3The content of composition is less than 20.0%.
(3) optical glass as described in (1), wherein, relative to the glass total material amount for being scaled oxide composition, to rub
Your % is counted, WO3The content of composition is less than 7.0%.
(4) optical glass as any one of (1) to (3), wherein, also containing following each compositions：Relative to conversion
For oxide composition glass total material amount, in terms of mole %,
TiO2The content of composition is 0～20.0%, and/or
Nb2O5The content of composition is 0～20.0%.
(5) optical glass as described in (4), wherein, relative to the glass total material amount for being scaled oxide composition, mole
(TiO2+Nb2O5) it is less than more than 2.0% 30.0%.
(6) optical glass as any one of (1) to (5), wherein, it is scaled mol ratio WO of oxide composition3/
(TiO2+Nb2O5+WO3) it is less than 0.600.
(7) optical glass as any one of (1) to (6), wherein, relative to the glass for being scaled oxide composition
Total material amount, in terms of mole %, Li2The content of O compositions is less than 20.0%.
(8) optical glass as described in (7), wherein, relative to the glass total material amount for being scaled oxide composition, to rub
Your % is counted, Li2The content of O compositions is more than 0.1%.
(9) optical glass as any one of (1) to (8), wherein, also containing following each compositions：Relative to conversion
For oxide composition glass total material amount, in terms of mole %,
Gd2O3The content of composition is 0～30.0%, and/or
Y2O3The content of composition is 0～10.0%, and/or
Yb2O3The content of composition is 0～10.0%, and/or
Lu2O3The content of composition is 0～10.0%.
(10) optical glass as any one of (1) to (9), wherein, relative to the glass for being scaled oxide composition
Glass total material amount, Ln2O3Composition (in formula, Ln is more than a kind in La, Gd, Y, Yb, Lu) mole and for 10.0% with
Upper less than 40.0%.
(11) optical glass as any one of (1) to (10), wherein, the Ln2O3Contain two or more in composition
Composition.
(12) optical glass as any one of (1) to (11), wherein, relative to the glass for being scaled oxide composition
Glass total material amount, in terms of mole %, Ta2O5The content of composition is less than 20.0%.
(13) optical glass as described in (12), wherein, it is scaled mol ratio Ta of oxide composition2O5/WO3For 1.0 with
Upper less than 10.0.
(14) optical glass as any one of (1) to (13), wherein, relative to the glass for being scaled oxide composition
Glass total material amount, in terms of mole %, SiO2The content of composition is less than 25.0%.
(15) optical glass as described in (14), wherein, relative to be scaled oxide composition glass total material amount, with
Mole % meter, SiO2The content of composition is less than 19.0%.
(16) optical glass as any one of (1) to (15), wherein, also containing following each compositions：Relative to changing
The glass total material amount constituted for oxide is calculated, in terms of mole %,
Na2The content of O compositions is 0～15.0%, and/or
K2The content of O compositions is 0～10.0%.
(17) optical glass as described in (16), wherein, relative to the glass total material amount for being scaled oxide composition,
Rn2O compositions (in formula, Rn is more than a kind in Li, Na, K) mole and for less than 20.0%.
(18) optical glass as any one of (1) to (17), wherein, also containing following each compositions：Relative to changing
The glass total material amount constituted for oxide is calculated, in terms of mole %,
The content of MgO compositions is 0～10.0%, and/or
The content of CaO compositions is 0～10.0%, and/or
The content of SrO compositions is 0～10.0%, and/or
The content of BaO compositions is 0～10.0%.
(19) optical glass as described in (18), wherein, relative to the glass total material amount for being scaled oxide composition, RO
Composition (in formula, R is more than a kind in Mg, Ca, Sr, Ba) mole and for less than 11.0%.
(20) optical glass as any one of (1) to (19), wherein, also containing following each compositions：Relative to changing
The glass total material amount constituted for oxide is calculated, in terms of mole %,
GeO2The content of composition is 0～10.0%, and/or
P2O5The content of composition is 0～10.0%, and/or
ZrO2The content of composition is 0～15.0%, and/or
The content of ZnO component is 0～50.0%, and/or
Bi2O3The content of composition is 0～15.0%, and/or
TeO2The content of composition is 0～15.0%, and/or
Al2O3The content of composition is 0～15.0%, and/or
Ga2O3The content of composition is 0～15.0%, and/or
Sb2O3The content of composition is 0～1.0%,
The fluoride obtained with part or all of displacement of the one kind or two or more oxide of each metallic element
It is 0～6.0% as the content of F.
(21) optical glass as any one of (1) to (20), wherein, with the refraction below more than 1.75 1.95
Rate (nd), less than more than 30 50 Abbe number (νd)。
(22) optical glass as any one of (1) to (21), wherein, with the vitrification point below 680 DEG C
(Tg)。
(23) optical glass as any one of (1) to (22), wherein, with the liquidus temperature below 1250 DEG C.
(24) a kind of preform material, is that the optical glass by any one of (1) to (23) is formed.
(25) a kind of optical element, is to be press-formed the preform material described in (24) and made.
(26) a kind of optical element, using the optical glass any one of (1) to (23) as mother metal.
(27) a kind of optical device, with the optical element described in (25) or (26).
According to the present invention, by containing B2O3Composition and La2O3Containing selected from TiO in the glass of composition2Composition, WO3Into
Divide and Nb2O5The composition of more than a kind in composition, can obtain desired optical constant with more cheap composition.Therefore, may be used
Inexpensively to obtain optical glass, the refractive index (n of the optical glassd) and Abbe number (νd) in desired scope, and energy
Access the high preform material of devitrification resistance.
Specific embodiment
For the optical glass of the present invention, relative to the glass total material amount for being scaled oxide composition, in terms of mole %,
Containing 10.0～50.0%B2O3Composition and 5.0～30.0%La2O3Composition, it is total relative to the glass for being scaled oxide composition
Amount of substance, mole and (TiO2+WO3+Nb2O5) it is 0.1～30.0%.By containing selected from TiO2Composition, WO3Composition and Nb2O5Into
More than a kind in point, even if reducing the Ta of expensive and fusibility difference2O5Composition, it is also possible to obtain desired optical constant.And
And, by by B2O3Composition and La2O3Based on composition, with less than more than 1.75 1.95 refractive index (nd) and more than 30 50
Following Abbe number (νd), and the easy step-down of liquidus temperature.Therefore, it can inexpensively obtain following optical glass, the optics glass
Refractive index (the n of glassd) and Abbe number (νd) in desired scope, and the high preform material of devitrification resistance can be obtained.
The optical glass of the present invention contains selected from TiO2Composition, WO3Composition and Nb2O5More than a kind in composition is used as required
Composition.By above-mentioned TiO2Composition, WO3Composition and Nb2O5At least contain TiO in composition2Composition and/or Nb2O5The glass of composition is made
Illustrate for the 1st optical glass.In addition, by TiO2Composition, WO3Composition and Nb2O5At least contain WO in composition3The glass of composition
Illustrate as the 2nd optical glass.It should be noted that the optical glass of the present invention can also contain TiO2Composition and/or
Nb2O5Composition and WO3Both compositions.
The embodiment of the optical glass of the present invention is described in detail below.The present invention is not limited to following embodiment party
Formula, in the range of the object of the invention, can suitably change to carry out.It should be noted that for repeat specification part, sometimes
Appropriate explanation is omitted, but does not limit the purport of invention.
[glass ingredient]
The compositing range for constituting each composition of the optical glass of the present invention is as described below.In this manual, each composition
When content is not particularly illustrated, all table is carried out with mole % relative to the glass total material amount for being scaled oxide composition
Show.Herein " be scaled oxide composition ", refer to assume to be used as the raw material of the glass constituent of the present invention oxide,
Complex salt, metal fluoride etc. are all decomposed when being changed into oxide in melting, with the total material amount of the generation oxide
For 100 moles of % to represent glass in the composition of each composition that contains.
＜ is with regard to required composition, any condition ＞
B2O3Composition is as the oxidation for forming glass in the optical glass of the invention containing more rare-earth oxide
Composition necessary to thing.Especially by making B2O3The content of composition is more than 10.0%, can improve the devitrification resistance of glass,
And the dispersion of reduction glass.Accordingly, with respect to the glass total material amount for being scaled oxide composition, B2O3Component content lower limit is excellent
Elect 10.0% as, be more preferably 15.0%, most preferably 20.0%.On the other hand, by making B2O3The content of composition is 50.0%
Hereinafter, may be easy to obtain bigger refractive index, and suppress chemical durability to deteriorate.Accordingly, with respect to being scaled oxide group
Into glass total material amount, B2O3The upper content limit of composition is preferably 50.0%, is more preferably 48.0%, and most preferably 46.0%.
B2O3Composition can use such as H3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4Deng being contained in glass as raw material.
La2O3Composition is to improve the refractive index of glass and reduce glass dispersible, improve the composition of glass Abbe number.Particularly
By making La2O3The content of composition is more than 5.0%, can improve the refractive index of glass.Accordingly, with respect to being scaled oxide
The glass total material amount of composition, La2O3The content lower limit of composition is preferably 5.0%, is more preferably 8.0%, most preferably
10.0%.On the other hand, by making La2O3The content of composition is less than 30.0%, can improve the stability of glass, thus, it is possible to
Enough reduce devitrification.Accordingly, with respect to the glass total material amount for being scaled oxide composition, La2O3The upper content limit of composition is preferably
30.0%, it is more preferably 25.0%, more preferably 20.0%, most preferably 18.0%.La2O3Composition can be using for example
La2O3、La(NO3)3·XH2O (X is arbitrary integer) etc. is contained in glass as raw material.
In the optical glass of the present invention, selected from TiO2Composition, WO3Composition and Nb2O5More than a kind in composition mole and
Preferably less than more than 0.1% 30.0%.Especially by making above-mentioned mole and for more than 0.1%, even if reducing Ta2O5Composition
Desired optical constant can also be obtained, therefore, it can more inexpensively make the optics glass with desired optical characteristics
Glass.On the other hand, by making above-mentioned mole and for less than 30.0%, the liquid caused containing mentioned component by excess can be suppressed
Phase temperature is raised, it is possible to more stably make optical glass.Accordingly, with respect to the total thing of glass for being scaled oxide composition
Quality, the lower limit of mole sum of mentioned component is preferably 0.1%, is more preferably 1.0%, and most preferably 1.5%.On the other hand,
Relative to the glass total material amount for being scaled oxide composition, the upper limit of mole sum of mentioned component is preferably 30.0%, more excellent
Elect 28.0%, more preferably 26.0%, more preferably less than 11.0% as.Particularly in the 2nd optical glass, from further raising
From the viewpoint of refractive index and devitrification resistance, the upper limit that can make mole sum of mentioned component is preferably 20.0%, more preferably for
18.0%, more preferably 15.0%.
WO3Composition is the composition for improving the refractive index of glass and improving the devitrification resistance of glass.On the other hand, by making
WO3The content of composition is less than 20.0%, can suppress enhancement of dispersion, and forms the glass for having high index of refraction and devitrification resistance concurrently
Glass.In addition, by making WO3The content of composition is less than 20.0%, can particularly be difficult to the visible-short wavelength region of reduction (little
In 500nm) in transmissivity.Accordingly, with respect to the glass total material amount for being scaled oxide composition, WO3In the content of composition
Limit is preferably 20.0%, is more preferably 15.0%, and more preferably 10.0%, more preferably less than 7.0%.Particularly in the 1st optics
In glass, from WO3Composition is to be difficult to from the viewpoint of the composition of the refractive index of raising glass, can make WO3The content of composition it is upper
Limit is preferably 4.0%, is more preferably 3.0%, and more preferably less than 1.0%.Even if it should be noted that the optical glass of the present invention
WO is not contained3Composition, it is also possible to obtain the glass with desired optical constant and devitrification resistance, but by containing WO3Into
Point, high index of refraction can be obtained, and can further reduce vitrification point.Therefore, particularly in the 2nd optical glass,
Relative to the glass total material amount for being scaled oxide composition, WO3The content lower limit of composition is preferably 0.1%, more preferably for
0.5%, more preferably 1.0%, most preferably 1.5%.WO3Composition can use such as WO3Deng being contained in glass as raw material.
TiO2It is composition that is higher and improving devitrification resistance that composition is the refractive index and Abbe number of regulation glass, is this
Any condition in bright optical glass.But, TiO2When excessive, devitrification resistance is deteriorated on the contrary, it is seen that short wavelength (500nm with
Under) transmissivity of the glass at place also deteriorates.Accordingly, with respect to the glass total material amount for being scaled oxide composition, TiO2Composition
Upper content limit be preferably 20.0%, be more preferably 15.0%, most preferably 12.0%.Even if it should be noted that not containing
TiO2Composition, it is also possible to obtain the glass with desired characteristic, but by containing TiO2Composition, can not reduce glass
Stability in the case of obtain high index of refraction.Alternatively, it is also possible to reduce the liquidus temperature of glass, stability is improved.Therefore, it is special
It is not the TiO in the 1st optical glass2Composition is excellent relative to the content lower limit of the glass total material amount for being scaled oxide composition
Elect 0.1% as, be more preferably 3.0%, more preferably 5.0%, most preferably greater than 8.0%.TiO2Composition can use such as TiO2
Deng being contained in glass as raw material.
Nb2O5Composition is to adjust the refractive index of glass and be separated into higher composition, is appointing in optical glass of the invention
Meaning composition.Especially by making Nb2O5The content of composition is less than 20.0%, can be suppressed by excessively containing Nb2O5Composition and lead
The devitrification resistance of the glass of cause deteriorates, and suppresses reduction of the glass to the transmissivity of visible ray.Accordingly, with respect to being scaled oxidation
The glass total material amount of thing composition, Nb2O5The upper content limit of composition is preferably 20.0%, is more preferably 15.0%, more preferably
10.0%, most preferably 7.0%.Even if it should be noted that not containing Nb2O5Composition, it is also possible to obtain with desired spy
The glass of property, but by containing Nb2O5Composition, can obtain high index of refraction in the case where the stability of glass is not reduced.Separately
Outward, it is also possible to reduce the liquidus temperature of glass, stability is improved.Therefore, particularly in the 1st optical glass, relative to conversion
For the glass total material amount of oxide composition, Nb2O5The content lower limit of composition is preferably 0.1%, more preferably greater than 2.0%, more excellent
Lower limit is selected for 5.0%, most preferably greater than 8.0%.Nb2O5Composition can use such as Nb2O5Deng being contained in glass as raw material.
In 1st optical glass of the present invention, TiO2Composition and Nb2O5The content sum of composition is preferably more than 2.0%
Less than 30.0%.Especially by making above-mentioned content sum be more than 2.0%, the liquidus temperature of glass can be reduced, while
To high index of refraction.Therefore, in the 1st optical glass, be scaled oxide composition mole and (TiO2+Nb2O5) lower limit be preferably
2.0%, it is more preferably 5.0%, more preferably 8.0%.On the other hand, by making above-mentioned content sum be less than 30.0%, can
To suppress the devitrification resistance by excess caused glass containing these compositions to deteriorate.Accordingly, with respect to being scaled oxide group
Into glass total material amount, mole and (TiO2+Nb2O5) the upper limit be preferably 30.0%, be more preferably 25.0%, most preferably
20.0%.
In addition, in the 1st optical glass of the present invention, relative to TiO2Composition, Nb2O5Composition and WO3Composition sum, WO3Into
The content ratio divided is preferably less than 0.600.By reducing above-mentioned ratio, it can be ensured that the desired Abbe number of glass, together
When be easy to improve refractive index, therefore, it can be easily obtained the glass with desired refractive index and Abbe number.Further, since
The TiO of the effect with the refractive index and dispersion these two aspects for improving glass2Composition, Nb2O5Composition and WO3Composition it is overall
Aequum is reduced, it is possible to reduced by excessively containing mentioned component, caused liquidus temperature is raised, can reduce devitrification.
Therefore, in the 1st optical glass, it is scaled mol ratio WO of oxide composition3/(TiO2+Nb2O5+WO3) the upper limit be preferably
0.600, it is more preferably 0.500, most preferably 0.370.On the other hand, it is scaled mol ratio WO of oxide composition3/(TiO2+
Nb2O5+WO3) lower limit can also be 0.
Li2O compositions are the composition for reducing vitrification point.Especially by making Li2The content of O compositions is less than 20.0%,
The liquidus temperature of glass can be reduced, devitrification is reduced.Accordingly, with respect to the glass total material amount for being scaled oxide composition,
Li2The upper content limit of O compositions is preferably 20.0%, is more preferably 15.0%, and most preferably 10.0%.It should be noted that i.e.
Make not containing Li2O compositions can also obtain the glass with desired characteristic, but by containing Li2O compositions, reduce vitrifying
The effect of temperature becomes big, therefore, it can be easily obtained the optical glass being easily press-formed.Accordingly, with respect to being scaled oxygen
The glass total material amount of compound composition, Li2The content lower limit of O compositions is preferably 0.1%, is more preferably 0.3%, most preferably
0.5%.
Gd2O3Composition is the refractive index for improving glass and the composition for improving Abbe number, in being optical glass of the invention
Any condition.Especially by making Gd2O3The content of composition is less than 30.0%, may be easy to obtain with desired optics
The glass of constant, can suppress by excessively containing Gd2O3Composition and caused vitrification point (Tg) are raised, and can improve glass
The devitrification resistance of glass.Accordingly, with respect to the glass total material amount for being scaled oxide composition, Gd2O3The upper content limit of composition is preferred
It is more preferably 20.0% for 30.0%, most preferably 10.0%.Even if it should be noted that not containing Gd2O3Composition, in technology
Aspect will not also produce disadvantage, but by by La2O3A part for composition is replaced into Gd2O3Composition, and does not contain Gd2O3Into
Situation about dividing is compared, and sometimes the liquidus temperature step-down of glass, can further improve devitrification resistance sometimes.Accordingly, with respect to changing
Calculate as the glass total material amount of oxide composition, Gd2O3The content of composition is preferably greater than 0%, and more preferably lower limit is 2.0%, more excellent
Choosing is more than 5.0%.Gd2O3Composition can use such as Gd2O3、GdF3Deng being contained in glass as raw material.
Y2O3Composition, Yb2O3Composition and Lu2O3Composition is to improve the refractive index of glass and reduce scattered composition, is this
Any condition in the optical glass of invention.Especially by making Y2O3Composition, Yb2O3Composition and/or Lu2O3The content of composition point
Not Wei less than 10.0%, may be easy to obtain the desired optical constant of glass, and improve the devitrification resistance of glass.Therefore,
Relative to the glass total material amount for being scaled oxide composition, Y2O3、Yb2O3And Lu2O3Each composition upper content limit difference it is excellent
Elect 10.0% as, be more preferably 8.0%, most preferably 5.0%.Particularly from the low glass of vitrification point (Tg) can be obtained
From the viewpoint of, may also be makes Y2O3Content be less than 1.3%.Y2O3、Yb2O3And Lu2O3Each composition can be using for example
Y2O3、YF3、Yb2O3、Lu2O3Deng being contained in glass as raw material.
In the optical glass of the present invention, Ln2O3Composition (in formula, Ln is more than a kind in La, Gd, Y, Yb, Lu)
Mole and preferably less than more than 10.0% 40.0%.Especially by making Ln2O3Composition mole and for more than 10.0%, glass
The refractive index and Abbe number of glass is improved, it is possible to can be easily obtained the glass with desired refractive index and Abbe number
Glass.Accordingly, with respect to the glass total material amount for being scaled oxide composition, Ln2O3The lower limit of mole sum of composition is preferably
10.0%, it is more preferably 12.0%, most preferably 15.0%.On the other hand, by making Ln2O3Composition mole and for 40.0%
Hereinafter, the liquidus temperature step-down of glass, therefore, it can reduce the devitrification of glass.Accordingly, with respect to be scaled oxide composition
Glass total material amount, Ln2O3The upper limit of mole sum of composition is preferably 40.0%, is more preferably 35.0%, more preferably
30.0%, most preferably 27.0%.
For the optical glass of the present invention, above-mentioned Ln is preferably comprised2O3Composition of more than two kinds in composition.Thus, glass
The further step-down of liquidus temperature, therefore, it can to form the higher glass of devitrification resistance.From the liquidus temperature for being easy to reduction glass
From the aspect of, particularly preferably contain La2O3Composition and Gd2O3The composition of more than two kinds of composition is used as Ln2O3Composition.
Ta2O5Composition is the composition for improving the refractive index of glass and improving the devitrification resistance of glass, is the optics of the present invention
Any condition in glass.Especially by making Ta2O5The content of composition is less than 20.0%, can be reduced by excessively containing
Ta2O5Composition and caused devitrification.In addition, by reducing Ta2O5The content of composition, expensive Ta2O5The content of composition is reduced, and
The temperature for melting raw material can be reduced, it is possible to reduce the raw material and the cost that manufacture is required of optical glass.Therefore, relatively
In the glass total material amount for being scaled oxide composition, Ta2O5The upper content limit of composition is preferably 20.0%, more preferably for
10.0%, most preferably 8.0%.Particularly in the 1st optical glass, Ta2O5The content of composition can also be less than 4.5%.Need
Even if it is noted that not containing Ta2O5Composition can also obtain the glass with desired characteristic, but particularly in the 2nd light
In learning glass, by containing Ta2O5Composition, can improve the refractive index of glass, and the liquidus temperature of reduction glass, such that it is able to
Improve devitrification resistance.Therefore, in the 2nd optical glass, relative to the glass total material amount for being scaled oxide composition, Ta2O5Composition
Content be preferably greater than 0%, more preferably lower limit is 1.0%, most preferably 2.0%.Ta2O5Composition can use such as Ta2O5Deng
It is contained in glass as raw material.
In 2nd optical glass of the present invention, Ta2O5The content of composition is relative to WO3The ratio of the content of composition is preferably
1.0 more than.Especially by making above-mentioned ratio be more than 1.0, the visible light transmission of glass can be maintained, and improve refraction
Rate, and suppress the dispersion of glass to raise.In addition, the liquidus temperature by lowering glass, can improve the devitrification resistance of glass.
Therefore, in the 2nd optical glass, it is scaled mol ratio Ta of oxide composition2O5/WO3Lower limit be preferably 1.0, more preferably for
2.0, more preferably 2.1, most preferably 2.5.On the other hand, the upper limit of above-mentioned ratio is not particularly limited, or and it is unlimited
(WO is not contained greatly3Composition).But, it is less than 10.0 by making above-mentioned ratio, the Ta of costliness can be reduced2O5Composition contains
Amount, therefore, it can reduce the raw material of optical glass and the cost needed for manufacture.Therefore, in the 2nd optical glass, it is scaled oxidation
Mol ratio Ta of thing composition2O5/WO3The upper limit be preferably 10.0, be more preferably 7.0, most preferably 4.0.
SiO2Composition is to improve the viscosity of melten glass and promote form stable glass, thus reduce as optical glass
The composition of undesirable devitrification (generation crystal), is any condition in optical glass of the invention.Especially by making
SiO2The content of composition is less than 25.0%, can suppress the rising of vitrification point (Tg), and be can be easily obtained as the present invention
Purpose high index of refraction.Accordingly, with respect to the glass total material amount for being scaled oxide composition, SiO2The upper content limit of composition
Preferably 25.0%, it is more preferably 19.0%, more preferably 17.5%, most preferably 13.0%.Even if it should be noted that not
Containing SiO2Composition can also obtain the glass with desired characteristic, but particularly in the 2nd optical glass, by containing
There is SiO2Composition, can make the liquidus temperature step-down of glass, reduce the devitrification of glass.In addition, dissolving the viscous of glass by improving
Property, it is readily able to carry out the shaping of glass.Accordingly, with respect to the glass total material amount for being scaled oxide composition, SiO2Composition
Content be preferably greater than 0%, more preferably greater than 1.0%, most preferably greater than 4.0%.SiO2Composition can use such as SiO2、
K2SiF6、Na2SiF6Deng being contained in glass as raw material.
Na2O compositions and K2O compositions are to improve the meltbility of glass, reduce vitrification point and improve the devitrification of glass
Property composition, be the present invention optical glass in any condition.Especially by making Na2The content of O compositions be 15.0% with
Under and/or make K2The content of O compositions is less than 10.0%, can be difficult to reduce the refractive index of glass, and improves stablizing for glass
Property, reduce producing devitrification etc..Accordingly, with respect to the glass total material amount for being scaled oxide composition, Na2In the content of O compositions
Limit is preferably 15.0%, is more preferably 10.0%, and most preferably 5.0%.In addition, relative to the glass for being scaled oxide composition
Total material amount, K2The upper content limit of O compositions is preferably 10.0%, is more preferably 8.0%, and most preferably 5.0%.Na2O compositions and
K2O compositions can use such as Na2CO3、NaNO3、NaF、Na2SiF6、K2CO3、KNO3、KF、KHF2、K2SiF6Deng containing as raw material
In glass.
Rn2O compositions (in formula, Rn is more than a kind in Li, Na, K) are the meltbility for improving glass, and reduce glass
The composition of the devitrification of glass.Herein, by making Rn2The content of O compositions is less than 20.0%, can be difficult to reduce the refraction of glass
Rate, and the stability of glass is improved, reduce the generation of devitrification etc..Accordingly, with respect to the total thing of glass for being scaled oxide composition
Quality, Rn2O compositions mole and the upper limit be preferably 20.0%, be more preferably 15.0%, most preferably 10.0%.
MgO compositions, CaO compositions, SrO compositions and BaO compositions be adjust the refractive index of glass, meltbility and increased devitrification resistance into
Point, it is any condition in optical glass of the invention.Especially by make MgO compositions, CaO compositions, SrO compositions and BaO into
The content divided is respectively less than 10.0%, may be easy to obtain desired refractive index and can reduce by excessively containing above-mentioned
The generation of composition and the devitrification of caused glass.Accordingly, with respect to be scaled oxide composition glass total material amount, MgO into
Point, the upper content limit of CaO compositions, SrO compositions and BaO compositions is respectively preferably 10.0%, is more preferably 8.0%, most preferably
5.0%.MgO compositions can use such as MgCO3、MgF2、CaCO3、CaF2、Sr(NO3)2、SrF2、BaCO3、Ba(NO3)2、BaF2
Deng being contained in glass as raw material.
In the optical glass of the present invention, the total content of RO compositions (in formula, R is more than a kind in Mg, Ca, Sr, Ba)
Preferably less than 11.0%.Thus, it is possible to can be easily obtained desired refractive index.Constitute accordingly, with respect to oxide is scaled
Glass total material amount, RO compositions mole and the upper limit be preferably 11.0%, be more preferably 8.0%, more preferably 5.0%.
GeO2Composition is the composition of the effect with the refractive index and raising devitrification resistance for improving glass, is the light of the present invention
Learn any condition in glass.But, due to GeO2Cost of material it is high, so when its amount is more, production cost is uprised, by reducing
Ta2O5Effect produced by composition is cut down.Accordingly, with respect to the glass total material amount for being scaled oxide composition, GeO2Composition
Upper content limit be preferably 10.0%, be more preferably 5.0%, most preferably 1.0%.GeO2Composition can use such as GeO2Deng
It is contained in glass as raw material.
P2O5Composition is the composition with the liquidus temperature for reducing glass, the effect for improving devitrification resistance, is the light of the present invention
Learn any condition in glass.Especially by making P2O5The content of composition is less than 10.0%, can suppress the chemical resistance to of glass
Long property, can particularly suppress resistance to water to reduce.Accordingly, with respect to the glass total material amount for being scaled oxide composition, P2O5Into
The upper limit of the content divided is preferably 10.0%, is more preferably 8.0%, and most preferably 5.0%.P2O5Composition can use such as Al
(PO3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4Deng being contained in glass as raw material.
ZrO2Composition is the composition of high index of refraction and low dispersion and the raising devitrification resistance for being conducive to glass, is the present invention
Optical glass in any condition.But, ZrO2When measuring excessive, devitrification resistance deteriorates on the contrary.Accordingly, with respect to being scaled oxygen
The glass total material amount of compound composition, ZrO2The upper content limit of composition is preferably 15.0%, is more preferably 12.0%, more preferably
10.0%.Even if it should be noted that not containing ZrO2Composition can also obtain the glass with desired characteristic, but pass through
Containing ZrO2Composition, may be easy to obtain the low scattered performance of high index of refraction, and may be easy to be improved the effect of devitrification resistance
Really.Therefore, particularly in the 2nd optical glass, relative to the glass total material amount for being scaled oxide composition, ZrO2Composition
Content lower limit is preferably greater than 0%, relatively elects 1.0%, most preferably 3.0% as.ZrO2Composition can use such as ZrO2、ZrF4
Deng being contained in glass as raw material.
ZnO component is the composition for reducing vitrification point (Tg) and improving chemical durability, is the optical glass of the present invention
In any condition.But, during containing more ZnO component, the devitrification resistance of glass easily deteriorates.Accordingly, with respect to being scaled
The glass total material amount of oxide composition, the upper content limit of ZnO component is preferably 50.0%, is more preferably 45.0%, more preferably
For 40.0%.Particularly from can improve the stability of glass, reduce from the viewpoint of liquidus temperature, relative to being scaled oxidation
The glass total material amount of thing composition, the content of ZnO component can be less than 27.0%, it is also possible to less than 24.0%.Need explanation
Even if not containing ZnO component can also obtain the glass with desired characteristic, but by containing ZnO component, glass
Change temperature step-down, therefore, it can be easily obtained the optical glass for being more easy to be press-formed.Accordingly, with respect to being scaled oxidation
The glass total material amount of thing composition, the content lower limit of ZnO component is preferably greater than 0%, is more preferably 5.0%, most preferably
10.0%.ZnO component can use such as ZnO, ZnF2Deng being contained in glass as raw material.
Bi2O3Composition is raising refractive index and the composition of reduction vitrification point (Tg), in being optical glass of the invention
Any condition.Especially by making Bi2O3The content of composition is less than 15.0%, can suppress the rising of liquidus temperature, so
The devitrification resistance of glass can be suppressed to be reduced.Accordingly, with respect to the glass total material amount for being scaled oxide composition, Bi2O3Composition
Upper content limit be preferably 15.0%, preferably less than 10.0%, more preferably less than 5.0%.Bi2O3Composition can be using for example
Bi2O3Deng being contained in glass as raw material.
TeO2Composition is raising refractive index and the composition of reduction vitrification point (Tg), in being optical glass of the invention
Any condition.But, TeO2There are following problems：Formed by platinum in platinum crucible or the part contacted with melten glass
In fusion tank, when melting frit, alloying can occur with platinum.Accordingly, with respect to the glass for being scaled oxide composition
Total material amount, TeO2The upper content limit of composition is preferably 15.0%, preferably less than 10.0%, more preferably less than 5.0%.TeO2
Composition can use such as TeO2Deng being contained in glass as raw material.
Al2O3Composition and Ga2O3Composition is the chemical durability for improving glass and the devitrification resistance for improving melten glass
Composition, is any condition in optical glass of the invention.Especially by making Al2O3Composition and Ga2O3The content difference of composition
For less than 15.0%, the stability of glass can be improved, and weaken the tendency towards devitrification of glass.Accordingly, with respect to being scaled oxidation
The glass total material amount of thing composition, Al2O3Composition and Ga2O3The upper content limit of composition is respectively preferably 15.0%, more preferably for
10.0%, most preferably 5.0%.Al2O3Composition and Ga2O3Composition can use such as Al2O3、Al(OH)3、AlF3、Ga2O3、Ga
(OH)3Deng being contained in glass as raw material.
Sb2O3Composition is the composition for making melten glass deaeration, is any condition in optical glass of the invention.Sb2O3Amount
When excessive, it is seen that the transmissivity in the short wavelength region in light region is deteriorated.Accordingly, with respect to the glass for being scaled oxide composition
Total material amount, Sb2O3The upper content limit of composition is preferably 1.0%, is more preferably 0.7%, and most preferably 0.5%.Sb2O3Composition
Such as Sb can be used2O3、Sb2O5、Na2H2Sb2O7·5H2O etc. is contained in glass as raw material.
It should be noted that making glass clarifying and the composition of deaeration is not limited to above-mentioned Sb2O3Composition, it is possible to use in glass
Known fining agent, deaeration agent or combinations thereof in the field of glass manufacture.
F compositions be reduce glass dispersion, while reduce vitrification point (Tg) and improve devitrification resistance composition, be
Any condition in the optical glass of the present invention.But, the content of F compositions, i.e. with a kind or 2 kinds of above-mentioned each metallic element with
When the total amount as F of the fluoride that part or all of displacement of upper oxide is obtained is more than 6.0%, the volatile quantity of F compositions
Become many, therefore it is difficult to obtain stable optical constant, it is difficult to obtain the glass of homogeneous.Accordingly, with respect to being scaled oxide group
Into glass total material amount, the upper content limit of F compositions is preferably 6.0%, is more preferably 5.0%, most preferably 3.0%.F compositions
Such as ZrF can be used4、AlF3、NaF、CaF2Deng being contained in glass as raw material.
＜ is with regard to the composition ＞ that should not contain
Then, the composition that should not contain in the optical glass of the present invention and the composition not preferably comprised are illustrated.
As needed, in the range of the glass performance of without prejudice to the present application other compositions can be added.Its
In, in addition to Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo,
Even if individually or it is compound containing also have in the case of a small amount of make glass coloration, certain wave strong point is produced in visibility region
The raw property for absorbing, so particularly preferably containing substantially no above-mentioned in the optical glass using the wavelength of visibility region
Composition.
In addition, the lead compound such as PbO and As2O3It is the high composition of carrying capacity of environment Deng arsenic compound, it is therefore preferable that substantially
Do not contain, i.e. in addition to being inevitably mixed into, preferably completely do not contain.
Further, each composition of Th, Cd, Tl, Os, Be and Se, exists used by control as harmful chemical in recent years
Tendency, not only in the manufacturing process of glass, or even environmentally friendly ring side is also required in the process after manufacturing procedure and product
The measure in face.Therefore, in the case of the impact in terms of environment is paid attention to, mentioned component is preferably contained substantially no.
The glass composition of the present invention, because its composition is with relative to the glass total material amount for being scaled oxide composition
A mole % be indicated, so be not directly to be expressed as quality %, in the glass for meeting required each characteristic in the present invention
The composition represented with quality % of each composition present in composition, in terms of being scaled oxide composition values below is probably taken.
And, the fluorine obtained with part or all of displacement of the one kind or two or more oxide of above-mentioned each metallic element
Mass % of total amount 0～3.0 as F of compound
[manufacture method]
The optical glass of the present invention for example can make as described below.That is, by above-mentioned raw materials mix to uniformly make it is each into
Divide in the range of the content of regulation, the mixture for making is put in platinum crucible, according to the melting complexity of glass composition,
In electric furnace, melt 2～5 hours within the temperature range of 1100～1500 DEG C, after stirring homogenizes, be reduced to suitable temperature
Afterwards, it is cast in mould, Slow cooling, thus makes optical glass.
[physical property]
The optical glass of the present invention has high index of refraction (nd) and low dispersion.The refraction of optical glass particularly of the invention
Rate (nd) lower limit be preferably 1.75, be more preferably 1.77, most preferably 1.80, its upper limit is preferably 1.95, more preferably for
1.92, most preferably 1.91.In addition, Abbe number (the ν of the optical glass of the present inventiond) lower limit be preferably 30, be more preferably 31,
Most preferably 32, its upper limit is preferably 50, is more preferably 45, and most preferably 40.Thus, the free degree of optical design increases, and
Even and if realize the slimming of element, it is also possible to obtain larger anaclasis amount.
In addition, the preferred coloring of the optical glass of the present invention is few.The transmissivity of optical glass glass particularly of the invention
During expression, the wavelength (λ that spectral transmission is 70% is represented in the sample of thick 10mm70) it is below 450nm, it is more preferably 430nm
Hereinafter, most preferably below 420nm.In addition, representing the wavelength (λ of spectral transmission 5%5) be below 400nm, more preferably for
Below 380nm, most preferably below 370nm.In addition, representing the wavelength (λ of spectral transmission 80%80) it is below 550nm, it is more excellent
Elect below 520nm, most preferably more preferably below 500nm, below 480nm as.Thus, the absorption edge of glass is made positioned at ultraviolet
The position of areas adjacent, it is seen that the transparency raising of the glass in region, therefore preferably the optical glass can be used as into lens
Deng the material of optical element.
In addition, the preferred devitrification resistance of the optical glass of the present invention is high.Optical glass particularly of the invention preferably has
Less than 1200 DEG C of low liquidus temperature.More specifically, the upper limit of the liquidus temperature of optical glass of the invention is preferably
1200 DEG C, be more preferably 1180 DEG C, most preferably 1160 DEG C.Thus, even if at lower temperatures flowing out melten glass,
The crystallization of made glass can be reduced, it is thus possible to improve devitrification resistance when glass is formed by molten condition, can be with
Reduce the impact of the optical characteristics to the optical element using glass.Further, since stably producing the temperature of preform material
The scope of degree broadens, even if so reducing the melting temperature of glass, it is also possible to form preform material, can suppress preforming
The energy that body material is consumed when being formed.On the other hand, the lower limit of the liquidus temperature of optical glass of the invention is without especially limit
It is fixed, but the liquidus temperature of the glass obtained according to the present invention is about more than 500 DEG C, in most cases, in particular 550 DEG C
More than, more specifically more than 600 DEG C.It should be noted that so-called " liquidus temperature " in this specification, refers to following temperature
Degree：The cullet shape glass specimen of 30cc is added in the platinum crucible of capacity 50ml, is at fully at 1250 DEG C
Molten condition, is reduced to the temperature of regulation, is kept for 12 hours, is fetched into outside stove, sight glass surface and glass immediately after cooling
In have nodeless mesh, will not confirm the minimum temperature of crystallization as liquidus temperature.The temperature for specifying herein, refers to from 1180 DEG C
To 500 DEG C of temperature set with 10 DEG C of pitch scales.
In addition, the optical glass of the present invention has less than 680 DEG C of vitrification point (Tg).Thus, glass is lower
At a temperature of soften, therefore may be easy at lower temperatures be press-formed glass.Alternatively, it is also possible to reduce
The oxidation of the mould used in extrusion forming, realizes the long lifetime of mould.Therefore, the vitrification point of optical glass of the invention
(Tg) the upper limit is preferably 680 DEG C, is more preferably 650 DEG C, most preferably 630 DEG C.It should be noted that the optics glass of the present invention
The lower limit of the vitrification point (Tg) of glass is not particularly limited, and the vitrification point (Tg) of the glass obtained according to the present invention is probably
For more than 100 DEG C, in most cases in particular more than 150 DEG C, more specifically more than 200 DEG C.
In addition, the optical glass of the present invention preferably has less than 720 DEG C of yield point (At).Yield point (At) and vitrifying
Temperature (Tg) is similarly one of index of the property of softening of expression glass, is the finger of the temperature for representing close with extrusion forming temperature
Mark.Therefore, by using the glass that yield point (At) is less than 720 DEG C, can be press-formed at lower temperatures, because
This can be more easily press-formed.Therefore, the upper limit of the yield point (At) of optical glass of the invention is preferably 720
DEG C, it is more preferably 700 DEG C, most preferably 680 DEG C.It should be noted that under the yield point (At) of the optical glass of the present invention
Limit is not particularly limited, and the yield point (At) of the glass obtained according to the present invention is about more than 150 DEG C, in most cases has
Body ground is more than 200 DEG C, more specifically more than 250 DEG C.
In addition, the optical glass of the present invention preferably has low part dispersion ratio (θ g, F).More specifically, it is of the invention
The part dispersion ratio (θ g, F) of optical glass and Abbe number (νd) between meet (- 2.50 × 10- 3×νd+ 0.6571)≤(θ g,
F)≤(- 2.50 × 10- 3×νd+ 0.6971) relation.Thus, it is possible to the little optical glass of part dispersion ratio (θ g, F) is obtained,
Therefore the aberration of the optical element that can reduce being formed by above-mentioned optical glass.Part dispersion ratio (the θ of the optical glass of the present invention
G, F) lower limit be preferably (- 2.50 × 10- 3×νd+ 0.6571) it is more preferably, (- 2.50 × 10- 3×νd+ 0.6591), most
Preferably (- 2.50 × 10- 3×νd+0.6611).On the other hand, the part dispersion ratio (θ g, F) of optical glass of the invention
The upper limit is preferably (- 2.50 × 10- 3×νd+ 0.6971) it is more preferably, (- 2.50 × 10- 3×νd+ 0.6921), most preferably
(- 2.50 × 10- 3×νd+0.6871)。
[preform material and optical element]
Method using the shaping of the mould pressurizings such as extrusion forming or precision press formation is for example reheated, by the optics for making
Glass makes glass forming body.I.e., it is possible to mould pressurizing preform for molding is made by optical glass, to above-mentioned preform
After carrying out reheating extrusion forming, processing is ground, makes glass forming body, or to being ground the preformation of processing and fabricating
Type body or the preform for being molded shapings such as (float forming) using known float glass process carry out precision press formation making
Glass forming body.It should be noted that the method for making glass forming body is not limited to these methods.
As described above, the optical glass of the present invention is useful to various optical elements and optical design.Wherein, particularly preferably by
The optical glass of the present invention forms preform material, carries out reheating extrusion forming using the preform material or precision adds
It is molded etc., make the optical element such as lens or prism.Thus, the preform material big due to diameter can be formed, so
The maximization of optical element can be realized, and during for optical devices such as camera or projecting apparatus, it is possible to achieve fine, height
The imaging characteristic of precision and projection property.
Embodiment
The refractive index of the composition and above-mentioned glass of embodiments of the invention (No.1～No.105) and comparative example (No.A)
(nd), Abbe number (νd), part dispersion ratio (θ g, F), vitrification point (Tg), yield point (At), liquidus temperature, represent light splitting it is saturating
The rate of penetrating is 5%, 70% and 80% wavelength (λ5、λ70And λ80) result be shown in 1～table of table 14.It should be noted that embodiment
(No.1～No.12) is the embodiment for being related to the 1st optical glass, and embodiment (No.1～No.2, No.13～No.105) is to be related to
The embodiment of the 2nd optical glass.In addition, following examples are all the time for exemplary purposes, however it is not limited to these embodiments.
The glass of embodiments of the invention (No.1～No.105) and comparative example (No.A) makes as follows：As each composition
Raw material selects respectively corresponding oxide, hydroxide, carbonate, nitrate, fluoride, hydroxide, metaphosphoric acid compound
Etc. the high-purity raw used in common optical glass, carry out weighing the group for being each embodiment shown in 1～table of table 14
Into ratio, after being well mixed, in input platinum crucible, according to the melting complexity of glass composition, in electric furnace 1100～
Melting 2～5 hours is carried out within the temperature range of 1500 DEG C, after stirring makes it homogenize, in being cast to mould etc., Slow cooling.
Herein, glass, the refractive index (n of embodiment (No.1～No.105) and comparative example (No.A)d), Abbe number (νd)
And part dispersion ratio (θ g, F) is determined based on Japanese Optical nitre industry meeting regulations JOGIS01-2003.With regard to what is obtained
Abbe number (νd) and part dispersion ratio (θ g, F) value, obtain relational expression (θ g, F)=- a × νdSlope a in+b is 0.0025
When intercept b.Herein, refractive index (nd), Abbe number (νd) and part dispersion ratio (θ g, F) be by by Slow cooling cooling speed
Degree is set to glass of -25 DEG C/hr to obtaining and is measured what is obtained.
In addition, the vitrification point (Tg) and yield point of the glass of embodiment (No.1～No.105) and comparative example (No.A)
(At) it is that measure by carrying out using horizontal expander analyzer is obtained.Herein, sample when being measured is usedThe sample of long 50～55mm, will heat up speed and is set to 4 DEG C/min.
In addition, the transmissivity of the glass of embodiment (No.1～No.105) and comparative example (No.A) is based on Japanese Optical nitre
What sub- industry meeting regulations JOGIS02 were determined.It should be noted that in the present invention, by the transmissivity for determining glass, obtaining glass
There are non-coloring and degree.Specifically, according to JISZ8722, determine 10 ± 0.1mm of thickness the parallel grinding object in opposite 200～
The spectral transmission of 800nm, obtains λ5(wavelength during transmissivity 5%), λ70(wavelength during transmissivity 70%) and λ80(transmissivity
Wavelength when 80%).
In addition, the liquidus temperature of the glass of embodiment (No.1～No.105) and comparative example (No.A) is in capacity 50ml
The cullet shape glass specimen of 30cc is added in platinum crucible, fully molten condition is at 1250 DEG C, be cooled to
The arbitrary temp set with 10 DEG C of pitch scales from 1180 DEG C to 1000 DEG C, is kept for 12 hours, is fetched into outside stove, is cooled down
Afterwards, there is nodeless mesh in sight glass surface and glass immediately, obtain the minimum temperature for not confirming crystallization.
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
As shown in 1～table of table 14, the liquidus temperature of the optical glass of embodiments of the invention is less than 1200 DEG C, more in detail
It it is less than 1160 DEG C for thin, in desired scope.On the other hand, the liquidus temperature of the glass of comparative example (No.A) is higher than
1200℃.As described above, as liquidus temperature it is different the reasons why, following aspects can be enumerated：The optics of embodiments of the invention
Glass is different from comparative example (No.A), at least contains TiO2Composition, WO3Composition and Nb2O5Any one in composition.Therefore, it is known that
The liquidus temperature of the optical glass of embodiments of the invention is less than comparative example (No.A).
In addition, the λ of the optical glass of embodiments of the invention70(wavelength during transmissivity 70%) is below 450nm, more
It is in detail below 413nm.In addition, the λ of the optical glass of embodiments of the invention5(wavelength during transmissivity 5%) is
Below 400nm, is in more detail below 361nm.In addition, the λ of the optical glass of embodiments of the invention80(during transmissivity 80%
Wavelength) be below 550nm, be in more detail below 530nm.Therefore, it is known that the optical glass of embodiments of the invention exists
The transmissivity of visible short strong point is high, be difficult to colour.
In addition, the vitrification point (Tg) of the optical glass of embodiments of the invention is less than 680 DEG C, in more detail for
Less than 630 DEG C, in desired scope.In addition, the yield point (At) of the optical glass of embodiments of the invention (No.8) is
Less than 720 DEG C, be in more detail less than 680 DEG C, in desired scope.
In addition, refractive index (the n of the optical glass of embodiments of the inventiond) more than 1.75 are, it is in more detail 1.85
More than, and the refractive index (nd) it is less than 1.95, it is in more detail less than 1.91, in desired scope.
In addition, Abbe number (the ν of the optical glass of embodiments of the inventiond) more than 30 are, it is in more detail more than 31,
And the Abbe number (νd) it is less than 50, it is in more detail less than 41, in desired scope.
In addition, the part dispersion ratio (θ g, F) of the optical glass of embodiments of the invention is (- 2.50 × 10- 3×νd+
0.6571) it is in more detail (- 2.50 × 10 more than- 3×νd+ 0.6672) more than.Its reverse side, the light of embodiments of the invention
The part dispersion ratio for learning glass is (- 2.50 × 10- 3×νd+ 0.6971) it is in more detail below, (- 2.50 × 10- 3×νd+
0.6725) below.Therefore, it is known that above-mentioned part dispersion ratio (θ g, F) is in desired scope.
Therefore, it is known that the refractive index (n of the optical glass of embodiments of the inventiond) and Abbe number (νd) in desired model
In enclosing, and the transmissivity in visible short length is high, devitrification resistance is high and is easy to be press-formed using heating and softening.
Further, using the optical glass of embodiments of the invention, carry out being ground and being ground after reheating extrusion forming,
It is processed into the shape of lens and prism.In addition, using the optical glass of embodiments of the invention, forming precision press formation with advance
Formed body, by performing body for precision pressurizing precision press formation lens and prism shape are processed into.Any of the above-described kind of feelings
Under condition, the problems such as will not produce opalization and devitrification in the glass after heating and softening, can stably be processed into various
The shape of mirror and prism.
Below the present invention, but the present embodiment are described in detail by for exemplary purposes all the time simply for the mesh of example
, it can be understood as can carry out in the case of the design without departing from the present invention and scope to those skilled in the art
Various changes.
Claims (27)
1. a kind of optical glass, relative to the glass total material amount for being scaled oxide composition, in terms of mole %, containing 10.0～
50.0%B2O3Composition and 5.0～30.0%La2O3Composition, relative to the glass total material amount for being scaled oxide composition, TiO2+
WO3+Nb2O5Mole and for 0.1～30.0%.
2. optical glass as claimed in claim 1, wherein, relative to the glass total material amount for being scaled oxide composition, with
Mole % meter, WO3The content of composition is less than 20.0%.
3. optical glass as claimed in claim 1, wherein, relative to the glass total material amount for being scaled oxide composition, with
Mole % meter, WO3The content of composition is less than 7.0%.
4. optical glass as claimed any one in claims 1 to 3, wherein, also containing following each compositions：Relative to being scaled
The glass total material amount of oxide composition, in terms of mole %,
TiO2The content of composition is 0～20.0%, and/or
Nb2O5The content of composition is 0～20.0%.
5. optical glass as claimed in claim 4, wherein, relative to the glass total material amount for being scaled oxide composition, TiO2
+Nb2O5Mole and for less than more than 2.0% 30.0%.
6. the optical glass as any one of claim 1 to 5, wherein, it is scaled mol ratio WO of oxide composition3/
(TiO2+Nb2O5+WO3) it is less than 0.600.
7. the optical glass as any one of claim 1 to 6, wherein, relative to the glass for being scaled oxide composition
Total material amount, in terms of mole %, Li2The content of O compositions is less than 20.0%.
8. optical glass as claimed in claim 7, wherein, relative to the glass total material amount for being scaled oxide composition, with
Mole % meter, Li2The content of O compositions is more than 0.1%.
9. the optical glass as any one of claim 1 to 8, wherein, also containing following each compositions：Relative to being scaled
The glass total material amount of oxide composition, in terms of mole %,
Gd2O3The content of composition is 0～30.0%, and/or
Y2O3The content of composition is 0～10.0%, and/or
Yb2O3The content of composition is 0～10.0%, and/or
Lu2O3The content of composition is 0～10.0%.
10. optical glass as claimed in any one of claims 1-9 wherein, wherein, relative to the glass for being scaled oxide composition
Total material amount, Ln2O3Composition mole and for less than more than 10.0% 40.0%, in formula, Ln is in La, Gd, Y, Yb, Lu
More than a kind.
11. optical glass as any one of claim 1 to 10, wherein, the Ln2O3Containing of more than two kinds in composition
Composition.
12. optical glass as any one of claim 1 to 11, wherein, relative to the glass for being scaled oxide composition
Glass total material amount, in terms of mole %, Ta2O5The content of composition is less than 20.0%.
13. optical glass as claimed in claim 12, wherein, it is scaled mol ratio Ta of oxide composition2O5/WO3For 1.0
Below the above 10.0.
14. optical glass as any one of claim 1 to 13, wherein, relative to the glass for being scaled oxide composition
Glass total material amount, in terms of mole %, SiO2The content of composition is less than 25.0%.
15. optical glass as claimed in claim 14, wherein, relative to the glass total material amount for being scaled oxide composition,
In terms of mole %, SiO2The content of composition is less than 19.0%.
16. optical glass as any one of claim 1 to 15, wherein, also containing following each compositions：Relative to conversion
For oxide composition glass total material amount, in terms of mole %,
Na2The content of O compositions is 0～15.0%, and/or
K2The content of O compositions is 0～10.0%.
17. optical glass as claimed in claim 16, wherein, relative to the glass total material amount for being scaled oxide composition,
Rn2O compositions mole and for less than 20.0%, in formula, Rn is more than a kind in Li, Na, K.
18. optical glass as any one of claim 1 to 17, wherein, also containing following each compositions：Relative to conversion
For oxide composition glass total material amount, in terms of mole %,
The content of MgO compositions is 0～10.0%, and/or
The content of CaO compositions is 0～10.0%, and/or
The content of SrO compositions is 0～10.0%, and/or
The content of BaO compositions is 0～10.0%.
19. optical glass as claimed in claim 18, wherein, relative to the glass total material amount for being scaled oxide composition,
RO compositions mole and for less than 11.0%, in formula, R is more than a kind in Mg, Ca, Sr, Ba.
20. optical glass as any one of claim 1 to 19, wherein, also containing following each compositions：Relative to conversion
For oxide composition glass total material amount, in terms of mole %,
GeO2The content of composition is 0～10.0%, and/or
P2O5The content of composition is 0～10.0%, and/or
ZrO2The content of composition is 0～15.0%, and/or
The content of ZnO component is 0～50.0%, and/or
Bi2O3The content of composition is 0～15.0%, and/or
TeO2The content of composition is 0～15.0%, and/or
Al2O3The content of composition is 0～15.0%, and/or
Ga2O3The content of composition is 0～15.0%, and/or
Sb2O3The content of composition is 0～1.0%,
With the one kind or two or more oxide of each metallic element part or all displacement obtain fluoride as F
Content be 0～6.0%.
21. optical glass as any one of claim 1 to 20, wherein, refractive index (nd) for more than 1.75 1.95 with
Under, Abbe number (νd) it is less than more than 30 50.
22. optical glass as any one of claim 1 to 21, wherein, vitrification point (Tg) is less than 680 DEG C.
23. optical glass as any one of claim 1 to 22, wherein, liquidus temperature is less than 1250 DEG C.
A kind of 24. preform materials, are formed by the optical glass any one of claim 1 to 23.
A kind of 25. optical elements, are to be press-formed the preform material described in claim 24 and made.
26. a kind of optical elements, using the optical glass any one of claim 1 to 23 as mother metal.
27. a kind of optical devices, with the optical element described in claim 25 or 26.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010229077 | 2010-10-08 | ||
| JP2010-229077 | 2010-10-08 | ||
| JP2011107572 | 2011-05-12 | ||
| JP2011-107572 | 2011-05-12 | ||
| CN2011800485933A CN103168013A (en) | 2010-10-08 | 2011-10-07 | Optical glass, preform material, and optical element |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800485933A Division CN103168013A (en) | 2010-10-08 | 2011-10-07 | Optical glass, preform material, and optical element |
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| CN106630595A true CN106630595A (en) | 2017-05-10 |
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| CN201611249628.0A Pending CN106630595A (en) | 2010-10-08 | 2011-10-07 | Optical glass, preform material, and optical element |
| CN2011800485933A Pending CN103168013A (en) | 2010-10-08 | 2011-10-07 | Optical glass, preform material, and optical element |
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| CN2011800485933A Pending CN103168013A (en) | 2010-10-08 | 2011-10-07 | Optical glass, preform material, and optical element |
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| Country | Link |
|---|---|
| JP (3) | JP2012250900A (en) |
| CN (2) | CN106630595A (en) |
| TW (1) | TWI594966B (en) |
| WO (1) | WO2012046833A1 (en) |
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| CN112714753A (en) * | 2019-08-26 | 2021-04-27 | Ａｇｃ株式会社 | Optical glass |
| CN115536267A (en) * | 2017-07-21 | 2022-12-30 | 株式会社小原 | Optical glass, preform and optical element |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2012046833A1 (en) | 2012-04-12 |
| TWI594966B (en) | 2017-08-11 |
| CN103168013A (en) | 2013-06-19 |
| JP6033486B2 (en) | 2016-11-30 |
| JP2012250900A (en) | 2012-12-20 |
| JP2016188173A (en) | 2016-11-04 |
| JP2016193828A (en) | 2016-11-17 |
| TW201223907A (en) | 2012-06-16 |
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