CN102320739B - Optical glass - Google Patents

Optical glass Download PDF

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CN102320739B
CN102320739B CN201110201285.1A CN201110201285A CN102320739B CN 102320739 B CN102320739 B CN 102320739B CN 201110201285 A CN201110201285 A CN 201110201285A CN 102320739 B CN102320739 B CN 102320739B
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opticglass
glass
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CN102320739A (en
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铃木顺子
荻野道子
小野泽雅浩
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Ohara Inc
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Ohara Inc
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Abstract

The invention provides high-refraction-index and low-dispersion optical glass which has refraction index (nd) of more than 1.75 and Abbe number (nu d) of more than 35, and the imaging characteristic of the optical glass is not susceptible to the temperature change of use environment. By using SiO2, B2O3 and La2O3 as essential components and adjusting the component ratio, the optical glass is obtained, and the optical glass has the characteristic that the product of average linear expansion coefficient alpha at (-30)-(+70) DEG C and photoelastic constant beta at wavelength of 546.1 nm is less than 130*10<-12> DEG C<-1>*nm*cm<-1>*Pa<-1>.

Description

Opticglass
The divisional application that the application is the applying date is on September 29th, 2007, application number is 200710151795.6, denomination of invention is the application of " opticglass ".
Technical field
The present invention relates to specific refractory power (nd) and be more than 1.75 and Abbe number (ν d) is the low dispersed optical glass of high refractive index of more than 35 and the optical element such as lens, prism that utilizes this opticglass to obtain, particularly relate to require high-precision imaging characteristic with the low dispersed optical glass of high refractive index be suitable in the projecting lens of photographic camera or pick up camera, the projector optical apparatus that is representative, prism with by its obtained optical element and optical apparatus.
Background technology
The low dispersing glass of high refractive index is very high as the demand of the materials used for optical elements such as various lens, be more than 1.75 as specific refractory power (nd) and Abbe number (ν d) be more than 35 opticglass, there will be a known various glass compositions such representated by patent documentation 1 ~ 3.
In recent years, the digitizing of optical apparatus, high-precision refinement, in development, require that the optical element be used in the cameras such as digital camera, pick up camera and the image regeneration such as projector, projection TV (projection) machine has high-performance.Its performance be not only specific refractory power, Abbe number, degree of staining these from the past just to the characteristic of opticglass requirement, to be also included in practical service environment characteristic variation less, that opticglass manufacture, optical element add man-hour carrying capacity of environment is little.
The reason that imaging characteristic changes in practical service environment, being presumably the optical element such as lens, prism is fixed in optical apparatus by fixture etc., along with the temperature variation temperature variation of the enclosure interior (, at high temperature used) of environment for use, produce the hot exapnsion of optical element, due to different from the coefficient of expansion of stationary fixture, in optical element, produce stress, result, in optical element, produce double refraction, imaging characteristic changes.
As mentioned above, when cannot realize in practical service environment with the imaging characteristic of the optical constant such as specific refractory power, Abbe number obtained based on certain temperature (mainly room temperature degree) design, have a negative impact, namely, must suppose environment for use when optical design, and the characteristic variation of prediction complexity designs.
Man-hour is added at opticglass manufacture, optical element, if comprise the composition that the carrying capacity of environment such as lead (Pb) compound, arsenic (As) compound is high, then can produce in order to preventing pollution material needs the disadvantageous effects such as special measure to the diffusion of air, water quality.In addition, use in a large number the representative rare mineral resource such as tantalum (Ta) not only production cost uprise but also need for the cost of resource reclaim, labor force.
For the low dispersed optical glass of high refractive index not containing the high composition of carrying capacity of environment in glass composition, as representated by patent gazette 1 ~ 3, disclose various glass composition, but do not consider about the variation of imaging characteristic in practical service environment.
Patent documentation 1: Japanese Unexamined Patent Publication 2005-306732 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-284542 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2004-161506 publication
Patent documentation 4: Japanese Laid-Open Patent Publication 56-160340 publication
Patent documentation 5: Japanese Laid-Open Patent Publication 52-14607 publication
Summary of the invention
problem to be solved by this invention
The present invention is based on such fact, the imaging characteristic impact that is not vulnerable to be caused by the temperature variation of environment for use is provided and specific refractory power (nd) is more than 1.75 and Abbe number (ν d) be more than 35 the low dispersed optical glass of high refractive index, and without the need to the high composition of a large amount of environment for use load and rare mineral resource.
for the method for dealing with problems
The present inventors furthers investigate repeatedly in order to reach preceding aim, found that by containing SiO 2, B 2o 3, La 2o 3as essential component, and adjust the ratio of moiety, the product α × β that can manufacture photoelastic constant β when realizing the average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 130 × 10 -12dEG C -1× nm × cm -1× Pa -1following high refractive index low dispersed optical glass and without the need to the high composition of a large amount of environment for use load and rare mineral resource, and reach aforementioned object, thus complete the present invention.Shown in it is composed as follows.
composition 1
A kind of opticglass, it is characterized in that, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C of this opticglass and wavelength 546.1nm is 130 × 10 -12dEG C -1× nm × cm -1× Pa -1below, wherein, take oxide compound as benchmark, containing being greater than 1.0 quality % and less than the SiO of 12.0 quality % 2, the B containing 8.0 ~ 35.0 quality % 2o 3, and the ratio SiO of quality % 2/ B 2o 3be greater than 0 and less than 0.6, the La containing 25.0 ~ 50.0 quality % 2o 3.
composition 2
Opticglass according to composition 1, is characterized in that, the optical constant that it has, and specific refractory power (nd) is 1.75 ~ 2.00, Abbe number (ν d) is the scope of 35 ~ 55.
composition 3
Opticglass according to composition 1 or 2, is characterized in that, take oxide compound as benchmark, also containing 0.0 ~ 40.0 quality %Gd 2o 3, 0.0 ~ 15.0 quality %Y 2o 3, 0.0 ~ 15.0 quality %ZrO 2, 0.0 ~ 25.0 quality %Ta 2o 5, 0.0 ~ 18.0 quality %Nb 2o 5, 0.0 ~ 10.0 quality %WO 3.
composition 4
According to the opticglass according to any one of composition 1 ~ 3, it is characterized in that, be benchmark with oxide compound, contain
0.0 ~ 0.1 quality %GeO 2and/or
0.0 ~ 1.0 quality %Yb 2o 3and/or
0.0 ~ 1.0 quality %Ga 2o 3and/or
0.0 ~ 1.0 quality %Bi 2o 3,
Not containing lead compound and As such as PbO 2o 3deng arsenic compound.
composition 5
According to the opticglass according to any one of composition 1 ~ 4, it is characterized in that, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 100 × 10 -12dEG C -1× nm × cm -1× Pa -1below.
composition 6
According to the opticglass according to any one of composition 1 ~ 5, it is characterized in that, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 90 × 10 -12dEG C -1× nm × cm -1× Pa -1below.
composition 7
According to the opticglass according to any one of composition 1 ~ 6, it is characterized in that, take oxide compound as the ratio (Ta of the quality % of benchmark 2o 5+ Nb 2o 5+ WO 3)/(Gd 2o 3+ Y 2o 3) be greater than 0.05 and less than 1.30.
composition 8
According to the opticglass according to any one of composition 1 ~ 7, it is characterized in that, represent with the quality % based on oxide compound, contain
0 ~ 5.0%Li 2o and/or
0 ~ 5.0%Na 2o and/or
0 ~ 5.0%K 2o and/or
0 ~ 5.0%Cs 2o and/or
0 ~ 5.0%MgO and/or
0 ~ 5.0%CaO and/or
0 ~ 5.0%SrO and/or
0 ~ 5.0%BaO and/or
0 ~ 3.0%TiO 2and/or
0 ~ 3.0%SnO 2and/or
0 ~ 3.0%Al 2o 3and/or
0 ~ 5.0%P 2o 5and/or
0 ~ 10.0%ZnO and/or
0 ~ 5.0%Lu 2o 3and/or
0 ~ 3.0%TeO 2and/or
0 ~ 2.0%Sb 2o 3and/or
0～3.0％F。
composition 9
According to the opticglass according to any one of composition 1 ~ 8, it is characterized in that, take oxide compound as benchmark, containing the ZnO less than 2.0 quality %.
composition 10
According to the opticglass according to any one of composition 1 ~ 9, it is characterized in that, take oxide compound as benchmark, containing the Y less than 3.5 quality % 2o 3.
composition 11
According to the opticglass according to any one of composition 1 ~ 10, it is characterized in that, take oxide compound as benchmark, the ratio (ZrO of quality % 2+ Ta 2o 5+ Nb 2o 5)/(SiO 2+ B 2o 3) less than 1.00.
composition 12
According to the opticglass according to any one of composition 1 ~ 11, it is characterized in that, take oxide compound as benchmark, containing the Y less than 3.5 quality % 2o 3, the ratio (ZnO+Y of quality % 2o 3)/La 2o 3be greater than 0 and less than 0.5, quality % sum ZrO 2+ Nb 2o 5be greater than 5.0% and less than 13.0%.
composition 13
A kind of opticglass, it is characterized in that, take oxide compound as benchmark, this glass contains
Be greater than 1.0 quality % and less than the SiO of 10.0 quality % 2,
15.0 ~ 28.0 quality %B 2o 3,
28.0 ~ 35.0 quality %La 2o 3,
25.0 ~ 35.0 quality %Gd 2o 3,
5.0 ~ 9.0 quality %ZrO 2with
0.1 ~ less than 2.0 quality % ZnO and
0.0 ~ 6.0 quality %Ta 2o 5and/or
0.0 ~ 5.0 quality %Nb 2o 5and/or
0.0 ~ 1.0 quality %Sb 2o 3and/or
0.0 ~ less than the Al of 1.0 quality % 2o 3,
Further, ZrO 2+ Nb 2o 5total be greater than 5.0 quality % and less than 13.0 quality %, this opticglass has the optical constant that specific refractory power (nd) is 1.78 ~ 1.83, Abbe number (ν d) is the scope of 44 ~ 48, and the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 90 × 10 -12dEG C -1× nm × cm -1× Pa -1below.
composition 14
The optical element such as lens, prism, its using the glass of composition 1 ~ 13 as starting material.
composition 15
The optical element such as lens, prism, it is made by carrying out reheating press process to the glass of composition 1 ~ 14.
composition 16
Photographic camera or the optical apparatus such as pick up camera, projector, it uses the optical element and Optical substrate materials made with the glass forming 1 ~ 15.
invention effect
By adopting above-mentioned form, can provide be not vulnerable to be caused by the temperature variation of environment for use imaging characteristic impact, specific refractory power (nd) is more than 1.75 and Abbe number (ν d) be more than 35 the low dispersed optical glass of high refractive index.
Embodiment
Opticglass of the present invention is described.
The opticglass of aforementioned component 1, is characterized in that, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 130 × 10 -12dEG C × nm × cm -1× Pa -1below, the variable quantity of imaging characteristic under the index expression environment for use of this α × β.Further illustrate, average coefficient of linear expansion α is larger, means the temperature variation relative to environment for use, and the exapnsion rate (volume change) of optical element is larger, thus, mean and can produce larger thermal stresses in the optical element fixing with fixture etc.In addition, photoelastic constant β is larger, and mean that the double refraction produced by the thermal stresses produced is larger, therefore namely enlighten out, α × β is less, then the change of the imaging characteristic under environment for use is fewer.
In addition, be 130 × 10 by α × β -12dEG C -1× nm × cm -1× Pa -1below, there is following advantage: even if imaging characteristic desired when also easily realizing optical design when producing temperature variation in practical service environment.
In order to the product α × β realizing the low dispersed optical glass of high refractive index is 130 × 10 -12dEG C -1× nm × cm -1× Pa -1below, in composition 1, it is characterized in that, containing being greater than 1.0 quality % and less than the SiO of 12.0 quality % 2, containing 8.0 ~ 35.0 quality %B 2o 3, and, the ratio SiO of quality % 2/ B 2o 3be greater than 0 and less than 0.6, containing 25.0 ~ 50.0 quality %La 2o 3.
If be described each composition, then SiO 2composition has the glass promoting that formation is stable, and suppresses the effect of the preferred devitrification (appearance of crystallisate) of opticglass, arteries and veins reason (ununiformity of inside glass), but superfluous containing SiO 2during composition, then there is the tendency that specific refractory power (nd) easily diminishes, photoelastic constant β enlarges markedly, consequently be difficult to obtain desired characteristic, thus, its upper limit is less than 12.0 quality %, is more preferably 11.5 quality %, most preferably is 11.0 quality %, and its lower limit is preferably greater than 1.0 quality %, is more preferably more than 1.2 quality %, most preferably is more than 1.4 quality %.SiO 2composition can contain, preferably with oxide compound (SiO with arbitrary raw material form 2), K 2siF 6, Na 2siF 6form import.
B 2o 3composition and SiO 2composition is form stable glass to promote and realize the little indispensable composition of average coefficient of linear expansion equally.But, if its amount is very few, then there is the tendency being difficult to obtain stable glass, if its amount is too much, then there is the tendency that specific refractory power (nd) easily diminishes, photoelastic constant β enlarges markedly, be consequently difficult to obtain desired characteristic.Its upper limit is preferably 35 quality %, is more preferably 34 quality %, most preferably is 33 quality %, and lower limit is preferably 8.0 quality %, is more preferably 8.5 quality %, most preferably is 9.0 quality %.B 2o 3composition can H 3bO 3, Na 2b 4o 7, Na 2b 4o 710H 2o, BPO 4contain Deng raw material form, preferably with H 3bO 3form import.
In addition, by making the ratio SiO of quality % 2/ B 2o 3be greater than 0 and less than 0.6, not only can obtain the effect of the meltbility of raw material and the stability increase of glass, but also the effect that the average coefficient of linear expansion α that can be inhibited increases.When exceeding in limited time, not only average coefficient of linear expansion α increases, and can produce slag during glass melting and (mainly comprise SiO 2difficult meltbility crystallization), productivity be deteriorated, to inside quality produce detrimentally affect.The scope of the ratio of preferred quality % is 0.03 ~ 0.59, most preferably is the scope of 0.05 ~ 0.58.
La 2o 3composition improving specific refractory power except having, reducing to disperse, except (Abbe number becomes large) effect, to make the effect that photoelastic constant β reduces in addition.But, when surplus contains, the significantly unstable and easy devitrification of glass.Therefore, the upper limit is preferably 50 quality %, is more preferably 49.5 quality %, most preferably is 49.0 quality %, and lower limit is preferably 25 quality %, is more preferably 25.5 quality %, most preferably is 26 quality %.La 2o 3composition can contain with arbitrary raw material form, but preferably with oxide compound (La 2o 3), nitrate and nitrate hydrate (La (NO 3) 3xH 2o (X is arbitrary integer)) form import.
The opticglass of aforementioned component 2, is characterized in that, the optical constant that it has, and specific refractory power (nd) is 1.75 ~ 2.00, Abbe number (ν d) is the scope of 35 ~ 55, this opticglass to various optical element and optical design useful.
Above-mentioned optical constant particularly from optics system Miniaturizable (even if the characteristic that specific refractory power is the high refractive index of more than 1.75 makes thin sheet lens also can obtain the amount of refraction of larger light.Even if departing from (aberration) of the focus that the wavelength that the low dispersing characteristic that Abbe number is more than 35 makes simple lens also can reduce light causes.) reason set out, useful in optical design.
In the opticglass of aforementioned component 1 and 2, Gd 2o 3composition and La 2o 3composition have equally improve specific refractory power, reduce dispersion effect, if but surplus contain, then with La 2o 3composition is same, easily devitrification occurs.Therefore, its higher limit is preferably 40 quality %, is more preferably 39 quality %, most preferably is 38 quality %.Gd 2o 3composition can import with arbitrary raw material form, but preferably with oxide compound (Gd 2o 3) or fluorochemical (GdF 3) form import.
Y 2o 3composition has the effect regulating specific refractory power and dispersion, when surplus contains, may can not get desired optical constant.Its higher limit is preferably 15 quality %, is more preferably 14.5 quality %, most preferably is 14.0 quality %.Y 2o 3composition can import with arbitrary raw material form, but preferably with oxide compound (Y 2o 3) or fluorochemical (YF 3) form import.
In addition, if in aforementioned range, technically without special detrimentally affect, but due to Y 2o 3be the rarest mineral wealth in the composition that can realize the low dispersing characteristic of high refractive index, when thus considering manufacturing cost, preferred less than 3.5 quality %.
ZrO 2composition can be improved specific refractory power (nd), improve the effect of devitrification resistance, but due to ZrO 2composition is difficult molten component, and thus when surplus contains, must at high temperature melt when manufacturing glass, energy loss easily becomes problem.On the other hand, by containing with specified amount, the effect of the devitrification that also can be inhibited.Therefore, the upper limit is preferably 15 quality %, is more preferably 13 quality %, most preferably is 12 quality %, and lower limit is preferably 1 quality %, is more preferably 2 quality %, most preferably is 3 quality %.In addition, even if do not adding ZrO 2when composition also can not produce devitrification in glass, ZrO can not be contained 2composition.ZrO 2composition can import with arbitrary raw material form, but preferably with oxide compound (ZrO 2) and fluorochemical (ZrF 4) form import.
Ta 2o 5composition can be improved specific refractory power make the effect of stabilization, therefore can contain arbitrarily.But, Ta 2o 5composition is rare mineral resource, and cost of material is high, be difficult molten component, must high-temperature digestion when manufacturing glass, thus not only production cost increases but also has the characteristic that photoelastic constant β is increased, and thus, the upper limit of its content is preferably 25 quality %.Preferred higher limit is 22 quality %, most preferred higher limit is 19 quality %.Ta 2o 5composition can import with arbitrary raw material form, but preferably with oxide compound (Ta 2o 5) form import.
Nb 2o 5composition and Ta 2o 5composition is same, and the specific refractory power that can be improved also makes the effect of stabilization, therefore can contain arbitrarily with the scope of 0 ~ 18 quality %.But, due to Nb 2o 5composition is difficult molten component, and necessary high-temperature digestion during manufacture glass, thus not only production cost increases, but also has the characteristic that photoelastic constant β is increased, and therefore, the upper limit of its content is preferably 18 quality %.Preferred higher limit is 16 quality %, most preferred higher limit is 14 quality %.Nb 2o 5composition can import with arbitrary raw material form, but preferably with oxide compound (Nb 2o 5) form import.
WO 3composition has and regulates specific refractory power and dispersion and the effect improving the devitrification resistance of glass.But if surplus contains, then the painted of glass becomes remarkable, the transmitance step-down of particularly as seen-short wavelength region (less than 500nm), thus not preferred.Therefore, the upper limit is preferably 10 quality %, is more preferably 8 quality %, most preferably is 6 quality %.WO 3composition can import with arbitrary raw material form, but preferably with oxide compound (WO 3) form import.
In the opticglass of aforementioned component 4, in order to regulate the viscosity of specific refractory power and adjustment melten glass, GeO 2composition can add arbitrarily in the scope of 0.0 ~ 0.1 quality %, but is rare mineral resource and price is high due to it, does not therefore preferably contain completely.Yb can be added arbitrarily to regulate specific refractory power 2o 3, Ga 2o 3, Bi 2o 3each composition, but due to it, there is the character that photoelastic constant β is increased, therefore its upper limit is 1.0 quality %.But because these compositions are also rare mineral resources, thus preferred higher limit is 0.5 quality %, most preferably is and does not contain completely.GeO 2, Yb 2o 3, Ga 2o 3, Bi 2o 3each composition can raw material form import arbitrarily, but preferably with oxide compound (GeO 2, Yb 2o 3, Ga 2o 3, Bi 2o 3) form import.
Due to the lead compounds such as PbO and As 2o 3be the composition that carrying capacity of environment is high Deng arsenic compound, thus except being inevitably mixed into, expect not contain completely.
In the opticglass of aforementioned component 5 and composition 6, in order to for more high precision and the optical element of fine purposes, product α × β is preferably 100 × 10 -12dEG C -1× nm × cm -1× Pa -1below, 90 × 10 most preferably are -12dEG C -1× nm × cm -1× Pa -1below.
The value of this α × β is less, then the more faithful to optical design value calculated based on the optics physics value of near room temperature of the imaging characteristic under practical service environment, thus has the advantage not needing to implement complicated optical analogy on the basis of the various environment for use of supposition.
In the opticglass of composition 7, by the strong Ta of effect of dispersion will be improved 2o 5, Nb 2o 5, WO 3total amount with can obtain the Gd reducing the effect of disperseing 2o 3, Y 2o 3the ratio (Ta of quality % of total amount 2o 5+ Nb 2o 5+ WO 3)/(Gd 2o 3+ Y 2o 3) control be greater than 0.05 and scope less than 1.30, the Abbe number (35 ~ 55) desired by easily realizing, thus preferred aforesaid scope.Be more preferably 0.055 ~ 1.29, most preferably be the scope of 0.06 ~ 1.28.
In the opticglass of aforementioned component 8, by the composition containing described scope, realize the characteristic described in composition 1 ~ 7 Absorbable organic halogens.Restriction reason for each composition is described.
Alkali metal oxide components (Li 2o, Na 2o, K 2o, Cs 2o) can be improved the effect of meltbility of glass, thus can contain arbitrarily, if but contain in a large number, then easily produce evenly heat coefficient of expansion α increase, specific refractory power easily reduces, glass is unstable and the preferred phenomenons such as devitrification occur, thus, represent with quality %, respectively preferred 0.0 ~ 5.0% scope.Preferred higher limit is Li 2o composition and Na 2o composition and K 2o composition is 4.5%, Cs 2o composition is 4.0%.The most preferred upper limit is Li 2o composition is 2.0%, Na 2o, K 2o, Cs 2o composition does not contain completely.Alkali metal oxide components can with carbonate (Li 2cO 3, Na 2cO 3, K 2cO 3, Cs 2cO 3), nitrate (LiNO 3, NaNO 3, KNO 3, CsNO 3), fluorochemical (LiF, NaF, KF, KHF 2), composite salt (Na 2siF 6, K 2siF 6) etc. various form import, but preferably to import with carbonate and/or nitrate.
Alkaline earth metal oxide composition (MgO, CaO, SrO, BaO) can the specific refractory power of adjusted glass and the effect of photoelastic constant, thus can contain arbitrarily, if but contain in a large number, then be difficult to the optical constant (particularly specific refractory power) desired by realizing, thus represent with quality %, respectively the preferred scope at 0.0 ~ 5.0 quality %.Preferred higher limit is that MgO composition and CaO composition are 4.0%, SrO composition and BaO composition are 4.5%.Most preferred higher limit be completely not containing MgO composition, CaO composition be 3.0%, SrO composition and BaO composition be 4.0%.Alkaline earth metal oxide composition can with carbonate (MgCO 3, CaCO 3, BaCO 3), nitrate (Sr (NO 3) 2, Ba (NO 3) 2), fluorochemical (MgF 2, CaF 2, SrF 2, BaF 2) etc. various form import, but preferably to import with the form of carbonate and/or nitrate and/or fluorochemical.
In order to regulate specific refractory power and Abbe number, TiO can be contained arbitrarily 2composition, if but surplus contain, then the painted of glass easily becomes remarkable, the tendency that the transmitance that there is especially visible short long (below 500nm) is deteriorated.Therefore, preferred higher limit is 3.0 quality %, preferred higher limit is 2.5 quality %, most preferred higher limit is 2.0 quality %.TiO 2composition can raw material form import arbitrarily, but preferably with oxide compound (TiO 2) form import.
SnO 2composition can be inhibited the oxidation of melten glass, clarifying effect, prevent effect that light-struck transmitance is deteriorated, therefore can contain arbitrarily, if but surplus contains, then likely due to the reduction of melten glass cause glass coloring, with the melting equipment alloying such as (particularly Pt precious metal).The upper limit is preferably 3.0 quality %, is more preferably 2.0 quality %, most preferably is 1.0 quality %.SnO 2composition can import with arbitrary raw material form, but preferably with oxide compound (SnO, SnO 2), fluorochemical (SnF 2, SnF 4) form import.
Al 2o 3composition can be improved opticglass and optical element chemical durability, improve the effect of devitrification resistance of melten glass, therefore can contain arbitrarily, if but surplus contain, then specific refractory power significantly reduces, photoelastic constant easily becomes large.Therefore, the upper limit is preferably 3.0 quality %, is more preferably 2.0 quality %, most preferably is 1.0 quality %.Al 2o 3composition can import with arbitrary raw material form, but preferably with oxide compound (Al 2o 3), oxyhydroxide (Al (OH) 3), fluorochemical (AlF 3) form import.
P 2o 5composition can be improved the effect of meltbility of glass, therefore can contain arbitrarily, if but surplus contain, then the devitrification resistance of glass is easily significantly deteriorated, and is difficult to obtain the opticglass without devitrification.Therefore, the upper limit is preferably 5.0 quality %, is more preferably 1.0 quality %, does not most preferably contain completely.P 2o 5composition can import with arbitrary raw material form, but preferably with Al (PO 3) 3, Ca (PO 3) 2, Ba (PO 3) 2, BPO 4, H 3pO 4form import.
ZnO component improves the meltbility of glass, on the other hand, can obtain the effect reducing evenly heat coefficient of expansion α, thus can contain arbitrarily in the scope of 0 ~ 10.0 quality %, owing to having the character making photoelastic constant β enlarge markedly, thus, if surplus contains, be then difficult to the characteristic desired by realizing.The preferred scope of the upper limit is 5.0 quality %, most preferably less than 2.0 quality %, lower limit is preferably 0.1 quality %.ZnO component can import with arbitrary raw material form, but preferably with oxide compound (ZnO) and/or fluorochemical (ZnF 2) form import.
Lu 2o 3composition and La 2o 3, Gd 2o 3, Y 2o 3composition is same, can the effect of accomplished high refractive index and low dispersion, and thus can contain arbitrarily in the scope of 0 ~ 5.0 quality %, but be rare mineral resource due to it, thus preferably surplus contains.Preferred higher limit is 3.0 quality %, does not most preferably contain completely.Lu 2o 3composition can import with arbitrary raw material form, but preferably with oxide compound (Lu 2o 3) import.
TeO 2the effect of clarification when composition can be promoted glass melting, thus can contain arbitrarily in the scope of 0 ~ 3.0 quality %, if but surplus contain, then glass painted is become significantly, transmitance is easily deteriorated.Preferred higher limit is 1.5 quality %, does not most preferably contain completely.TeO 2composition can import with arbitrary raw material form, but preferably with oxide compound (TeO 2) import.
Sb 2o 3composition can obtain the effect of the deaeration material as glass, thus can contain arbitrarily in the scope of 0 ~ 2.0 quality %, if but containing exceeding its upper limit, then easily produce during glass melting excessive foaming, may with melting equipment (particularly the precious metal such as Pt) alloying, thus preferred containing being no more than its upper limit.Sb 2o 3composition can import with arbitrary raw material form, but preferably with oxide compound (Sb 2o 3, Sb 2o 5) or Na 2h 2sb 2o 75H 2the form of O imports.
F composition can obtain the effect making Abbe number become large, the effect that photoelastic constant β is reduced, and thus, can contain arbitrarily in the scope of 0 ~ 3.0 quality %, if but containing exceeding its upper limit, then the easy step-down of possibility specific refractory power, average coefficient of linear expansion α increase.Preferred higher limit is 2.8 quality %, most preferably is 2.5 quality %.In the importing of above-mentioned various oxide compound, when importing raw material form with fluorochemical, F composition is directed in glass.
In addition, the content of each composition used in this manual with oxide compound for the statement of benchmark be represent when the oxide compound, composite salt, metal fluoride etc. that suppose to use as the raw material of glass moiety of the present invention in melting time be decomposed completely and become oxide compound, this generation oxide compound of each composition is relative to the quality % of total composition, in the case of fluoride, the F atom quality contained with reality represents relative to the mass percent generating oxide mass.
Each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo etc. except Ti all carries out painted when individually containing or compound contains on a small quantity, the specific wavelength of visible region is produced and absorbs, thus, use visible region wavelength opticglass in be preferably substantially devoid of.In addition, for each composition of Pb, Th, Cd, Tl, As, Os, Be, Se, trend in recent years controls it as harmful chemical substance to use, not only in the manufacturing process of glass, the process also needed in manufacturing procedure and the process after making product in environmental cure, be preferably substantially devoid of when paying attention to affecting environmentally.
In the opticglass of aforementioned component 11, by using the ZrO as difficult molten component 2, Ta 2o 5, Nb 2o 5total amount with as the SiO of glass forming constituents 2, B 2o 3the ratio of total amount control at quality % ratio (ZrO 2+ Ta 2o 5+ Nb 2o 5)/(SiO 2+ B 2o 3) less than 1.00, can energy expenditure is reduced and not need to make glass melting temperature become the effect of very high temperature.When the ratio of above-mentioned quality % is greater than 1.00, due to Ta 2o 5, Nb 2o 5each composition be rare mineral resource, thus this ratio is larger, then cost of raw and processed materials is higher, and the content of glass forming constituents relatively tails off, not only likely glass destabilization, and the ZrO owing to making photoelastic constant increase 2, Ta 2o 5, Nb 2o 5relative content become large, that there is the effect that average coefficient of linear expansion α is reduced B 2o 3relative content tail off, thus likely product α × β increases, the opticglass desired by producing from the viewpoint of cheapness, not preferably.
In the opticglass of aforementioned component 12, by the composition that can realize the low dispersing characteristic of high refractive index, make most rare mineral resource Y 2o 3composition, less than 3.5 quality %, can be reduced manufacturing cost, Absorbable organic halogens and manufacture the effect of glass constantly, and by making the ratio (ZnO+Y of quality % 2o 3)/La 2o 3be greater than 0 and less than 0.5, stably can be formed the effect of the opticglass of the product α × β desired by realization, in addition, by quality % sum ZrO 2+ Nb 2o 5be greater than 5.0 quality % and less than 13.0 quality %, the content limiting difficult molten component, the effect suppressing energy expenditure, realize the opticglass of devitrification resistance excellence simultaneously can be obtained.
In the opticglass of aforementioned component 13, write the scope of the moiety ratio of optimal opticglass in the opticglass of above-mentioned composition 1 ~ 12 exactly.Specifically, by glass composition is remained on
SiO 2for be greater than 1.0 quality % and less than 10.0 quality %,
B 2o 3be 15.0 ~ 28.0 quality %,
La 2o 3be 28.0 ~ 35.0 quality %,
Gd 2o 3be 25.0 ~ 35.0 quality %,
ZrO 2be 5.0 ~ 9.0 quality % and
ZnO is 0.1 ~ less than 2.0 quality % and
Ta 2o 5be 0.0 ~ 6.0 quality % and/or
Nb 2o 5be 0.0 ~ 5.0 quality % and/or
Sb 2o 3be 0.0 ~ 1.0 quality % and/or
Al 2o 3be 0.0 ~ less than 1.0 quality %, tool has the following advantages: particularly had the optical constant that specific refractory power (nd) is 1.78 ~ 1.83, Abbe number (ν d) is the scope of 44 ~ 48, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 90 × 10 Absorbable organic halogens -12dEG C -1× nm × cm -1× Pa -1following opticglass.As mentioned above, by making moiety and its content be the ratio of specialized range, the use of difficult molten component, rare mineral resource can be suppressed to inferior limit and the high composition of non-environment for use load, just can produce the optical element with low uncertainty, high precision/fine purposes of imaging characteristic under environment for use.
As formed as described in 14 ~ 16, opticglass described in aforementioned component 1 ~ 13 is useful as the starting material for the manufacture of the optical element such as lens, prism, by this optical element is used for photographic camera or pick up camera, projector, fine can be realized and high-precision imaging and projection property.
Glass composition of the present invention, its composition represents with quality %, because of instead of be directly expressed as the record of mol%, the composition represented with mol% meeting in the glass composition of each characteristic of the presently claimed invention each composition existed probably gets following value.
The scope of composition 1 is SiO 22.0 ~ 25.0mol%, B 2o 3the ratio SiO of 25 ~ 65mol%, mol% 2/ B 2o 3be greater than 0 and less than 0.7, La 2o 310 ~ 30mol%;
The scope of composition 3 is Gd 2o 30 ~ 18mol%, Y 2o 30 ~ 10mol%, ZrO 20 ~ 10mol%, Ta 2o 50 ~ 10mol%, Nb 2o 50 ~ 10mol%, WO 30 ~ 5mol%;
The scope of composition 4 is GeO 20.0 ~ 0.1mol%, Yb 2o 30.0 ~ 1.0mol%, Ga 2o 30.0 ~ 1.0mol%, Bi 2o 30.0 ~ 1.0mol%;
The scope of composition 7 is ratio (Ta of mol% 2o 5+ Nb 2o 5+ WO 3)/(Gd 2o 3+ Y 2o 3) be greater than 0.03 and less than 1.25;
The scope of composition 8 is expressed as Li with Mol% 2o 0 ~ 7.0%, Na 2o 0 ~ 5.0%, K 2o 0 ~ 5.0%, Cs 2o 0 ~ 3.0%, MgO 0 ~ 5.0%, CaO 0 ~ 5.0%, SrO 0 ~ 5.0%, BaO 0 ~ 5.0%, TiO 20 ~ 5.0%, SnO 20 ~ 3.0%, Al 2o 30 ~ 3.0%, P 2o 50 ~ 3.0%, ZnO 0 ~ 7.0%, Lu 2o 30 ~ 2.0%, TeO 20 ~ 1.0%, Sb 2o 30 ~ 1.0%, F 0 ~ 10%;
The scope of composition 9 is that ZnO is less than 5.0mol%;
The scope of composition 10 is Y 2o 3less than 4.0mol%;
The scope of composition 11 is ratio (ZrO of mol% 2+ Ta 2o 5+ Nb 2o 5)/(SiO 2+ B 2o 3) less than 0.8;
The scope of composition 12 is Y 2o 3less than the ratio (ZnO+Y of 4.0mol%, mol% 2o 3)/La 2o 3be greater than 0 and less than 1.0, mol% sum ZrO 2+ Nb 2o 5be greater than 5.0% and less than 13.0%;
The scope of composition 13 is SiO 23 ~ 22mol%, B 2o 327 ~ 63mol%, La 2o 310 ~ 25mol%, Gd 2o 36 ~ 15mol%, ZrO 24 ~ 10mol%, ZnO0.1 ~ 2.0mol%, Ta 2o 50 ~ 5.0mol%, Nb 2o 50 ~ 3mol%, Sb 2o 30 ~ 0.5mol%, Al 2o 30 ~ less than 1.0mol%.
embodiment
Then, by embodiment, the present invention is described in more detail, but the present invention is not limited to this example.
The imaging characteristic caused for the temperature variation not being vulnerable to environment for use shown in table 1 ~ table 8 affects, specific refractory power (nd) is more than 1.75, and Abbe number (ν d) is the glass composition of the suitable embodiment (No.1 ~ 38) of the high refractive index low dispersed optical glass of more than 35, specific refractory power (nd), Abbe number (ν d), the average coefficient of linear expansion α of-30 ~+70 DEG C, photoelastic constant β during wavelength 546.1nm, product α × β, the ratio of various composition containing ratio and containing ratio sum.
In addition, the glass of the comparative example (No.A ~ C) of known opticglass shown in table 9 forms and various physics value.At this, the embodiment 1 that the embodiment 6 that Comparative examples A is Japanese Unexamined Patent Publication 2005-306732 publication, comparative example B are Japanese Unexamined Patent Publication 2002-284542 publications, comparative example C are the embodiments 7 of Japanese Unexamined Patent Publication 2004-161506 publication.Specific refractory power (nd) in table, Abbe number (ν d) are the values recorded in each publication.
For the opticglass of gained, measure the photoelastic constant (β) when specific refractory power (nd), Abbe number (ν d), average coefficient of linear expansion (α), the wavelength 546.1nm of-30 ~+70 DEG C as described below.
(1) specific refractory power (nd) and Abbe number (ν d)
For Slow cooling cooling rate being set to-25 DEG C/h and the opticglass obtained measures.
The average coefficient of linear expansion (α) of (2)-30 ~+70 DEG C
Can standard JOGIS16-based on the industry of Japanese Optical nitre 2003method described in (measuring method of the average coefficient of linear expansion near the normal temperature of opticglass), measures.The sample of long 50mm, diameter 4mm is used as test film.
(3) photoelastic constant β during wavelength 546.1nm
Photoelastic constant (β) be make specimen shape be relatively grind the diameter 25mm obtained, thick 8mm discoideus, to prescribed direction apply compression load, be determined at glass center produce path difference, tried to achieve by δ=β dF relational expression.546.1nm measures light source and uses ultrahigh pressure mercury lamp.In above-mentioned formula, path difference is designated as δ (nm),
The thickness of glass is designated as d (cm), stress is designated as F (Pa).
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
The glass of the embodiments of the invention described in table 1 ~ 8 is following acquisitions, namely, all use oxide compound corresponding respectively, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the common Optical Glass Materials such as metaphosphoric acid compound are as the raw material of each composition, weigh with the ratio of regulation, after mixing, put in platinum crucible, according to the melting difficulty of glass composition in electric furnace in the temperature range melting 3 ~ 4 hours of 1200 ~ 1400 DEG C, after stirring, cool to proper temperature, then be cast in mould etc., Slow cooling, obtain the glass of the embodiment of the present invention thus.
As shown in table 1 ~ 8, in known the preferred embodiments of the present invention, all can realize desired optical constant, product α × β.On the other hand, in the comparative example shown in table 9, Comparative examples A can realize less α × β, if but compared with the embodiment 36 ~ 34 close with optical constant, then the ratio SiO of quality % 2/ B 2o 3than being greater than 0.6, therefore, average coefficient of linear expansion α becomes large, product α × β is greater than 90 × 10 -12dEG C -1× nm × cm -1× Pa -1.In addition, in comparative example B, if compared with the embodiment 30 ~ 32 close with optical constant, then owing to containing ZnO in a large number, therefore photoelastic constant β becomes large, and product α × β is greater than 100 × 10 -12dEG C -1× nm × cm -1× Pa -1.In addition, due to SiO 2content is few, the ratio SiO of quality % 2/ B 2o 3than less than 0.05, therefore the devitrification resistance of glass insufficient, when watering cast glass, almost create crystallization in glass surface entirety.In addition, in comparative example C, the content of ZnO significantly becomes many, the ratio (ZnO+Y of quality % 2o 3)/La 2o 3being 0.733, is large value, and thus photoelastic constant β increase, product α × β are greater than 130 × 10 -12dEG C -1× nm × cm -1× Pa -1.
In addition, the glass of the embodiment described in his-and-hers watches 1 ~ 8 carries out cold working or reheating compacting (reheat press) processing, found that to stablize with can not producing the problems such as devitrification and is processed into various lens, prism shape.
Lens obtained as described above, prism are contained on photographic camera or pick up camera, projector, confirm imaging characteristic, also can reproduce when high temperature (about 50 ~ 70 DEG C) works at the imaging characteristic desired by the optical design that the optical constant that room temperature obtains is carried out even if found that to utilize.
Above, for illustrative purposes, to invention has been detailed description, but the present embodiment is only for illustrating eventually, is appreciated that those skilled in the art can carry out more changes in thought of the present invention and scope and complete not departing from.
utilizability in industry
According to the present invention, the temperature variation not being vulnerable to environment for use can be provided to cause imaging characteristic impact, specific refractory power (nd) is more than 1.75 and Abbe number (ν d) be more than 35 the low dispersed optical glass of high refractive index, use this opticglass, Absorbable organic halogens ground manufactures lens, the prism of the image projection such as cameras and projector (regeneration) machine such as high-precision photographic camera or pick up camera.

Claims (14)

1. an opticglass, is characterized in that, the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C of this opticglass and wavelength 546.1nm is 90 × 10 -12dEG C -1× nm × cm -1× Pa -1below, wherein, take oxide compound as benchmark, containing being greater than 1.0 quality % and less than the SiO of 12.0 quality % 2, the B containing 8.0 ~ 35.0 quality % 2o 3, 3.00 ~ 15 quality % Y 2o 3, and the ratio SiO of quality % 2/ B 2o 3be greater than 0 and less than 0.6, the La containing 43.00 ~ 50.0 quality % 2o 3, also containing 0.0 ~ 8.17 quality %Gd 2o 3, 0.0 ~ 5.85 quality %Ta 2o 5.
2. opticglass according to claim 1, is characterized in that, the optical constant that it has, and specific refractory power (nd) is 1.75 ~ 2.00, Abbe number (ν d) is the scope of 35 ~ 55.
3. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, also containing 0.0 ~ 15.0 quality %ZrO 2, 0.0 ~ 18.0 quality %Nb 2o 5, 0.0 ~ 10.0 quality %WO 3.
4. opticglass according to claim 1, is characterized in that, is benchmark, contains with oxide compound
0.0 ~ 0.1 quality %GeO 2and/or
0.0 ~ 1.0 quality %Yb 2o 3and/or
0.0 ~ 1.0 quality %Ga 2o 3and/or
0.0 ~ 1.0 quality %Bi 2o 3,
Not containing lead compound and arsenic compound.
5. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, the ratio (Ta of quality % 2o 5+ Nb 2o 5+ WO 3)/(Gd 2o 3+ Y 2o 3) be greater than 0.05 and less than 1.30.
6. opticglass according to claim 1, is characterized in that, represents, contain with the quality % based on oxide compound
0 ~ 5.0%Li 2o and/or
0 ~ 5.0%Na 2o and/or
0 ~ 5.0%K 2o and/or
0 ~ 5.0%Cs 2o and/or
0 ~ 5.0%MgO and/or
0 ~ 5.0%CaO and/or
0 ~ 5.0%SrO and/or
0 ~ 5.0%BaO and/or
0 ~ 3.0%TiO 2and/or
0 ~ 3.0%SnO 2and/or
0 ~ 3.0%Al 2o 3and/or
0 ~ 5.0%P 2o 5and/or
0 ~ 10.0%ZnO and/or
0 ~ 5.0%Lu 2o 3and/or
0 ~ 3.0%TeO 2and/or
0 ~ 2.0%Sb 2o 3and/or
0～3.0％F。
7. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, containing the ZnO less than 2.0 quality %.
8. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, containing the Y less than 3.5 quality % 2o 3.
9. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, the ratio (ZrO of quality % 2+ Ta 2o 5+ Nb 2o 5)/(SiO 2+ B 2o 3) less than 1.00.
10. opticglass according to claim 1, is characterized in that, take oxide compound as benchmark, containing the Y less than 3.5 quality % 2o 3, the ratio (ZnO+Y of quality % 2o 3)/La 2o 3be greater than 0 and less than 0.5, quality % sum ZrO 2+ Nb 2o 5be greater than 5.0% and less than 13.0%.
11. 1 kinds of opticglass, is characterized in that, take oxide compound as benchmark, and this glass contains
Be greater than 1.0 quality % and less than the SiO of 10.0 quality % 2,
15.0 ~ 28.0 quality %B 2o 3,
28.0 ~ 35.0 quality %La 2o 3,
25.0 ~ 35.0 quality %Gd 2o 3,
The Y of 3.00 ~ 15 quality % 2o 3,
5.0 ~ 9.0 quality %ZrO 2with
0.1 ~ less than 2.0 quality % ZnO and
0.0 ~ 6.0 quality %Ta 2o 5and/or
0.0 ~ 5.0 quality %Nb 2o 5and/or
0.0 ~ 1.0 quality %Sb 2o 3and/or
0.0 ~ less than the Al of 1.0 quality % 2o 3,
Further, not containing Li 2o, ZrO 2+ Nb 2o 5total be greater than 5.0 quality % and less than 13.0 quality %, this opticglass has the optical constant that specific refractory power (nd) is 1.78 ~ 1.83, Abbe number (ν d) is the scope of 44 ~ 48, and the product α × β of the photoelastic constant β during average coefficient of linear expansion α of-30 ~+70 DEG C and wavelength 546.1nm is 90 × 10 -12dEG C -1× nm × cm -1× Pa -1below.
12. optical elements, its using the glass of claim 1 as starting material.
13. optical elements, it is processed into by carrying out reheating compacting to the glass of claim 1.
14. optical apparatus, it uses the optical element and Optical substrate materials made with the glass of claim 1.
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