CN103339075A - Optical glass and optical element produced therefrom - Google Patents

Optical glass and optical element produced therefrom Download PDF

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Publication number
CN103339075A
CN103339075A CN2011800618668A CN201180061866A CN103339075A CN 103339075 A CN103339075 A CN 103339075A CN 2011800618668 A CN2011800618668 A CN 2011800618668A CN 201180061866 A CN201180061866 A CN 201180061866A CN 103339075 A CN103339075 A CN 103339075A
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Prior art keywords
zero
opticglass
glass
content
optical element
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CN2011800618668A
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Chinese (zh)
Inventor
大垣昭男
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum

Abstract

Provided is an optical glass comprising glass components, in mass%, of P2O5: 35%-50%, B2O3: 3%-25%, Al2O3: 1%-12%, Li2O: 0%-10% (including 0), Na2O: 0%-10% (including 0), K2O: 0%-12% (including 0), wherein Li2O+Na2O+K2O: 5%-15%, MgO: 0%-30% (including 0), CaO: 0%-30% (including 0), wherein MgO+CaO: 18%-32%, Nb2O5: 5%-20%, and ZnO: 0%-10% (including 0).

Description

Opticglass and the optical element of being made by this opticglass
Technical field
The optical element that the present invention relates to opticglass and made by this opticglass.
Background technology
In recent years, as the lens of the image pickup optical system of digital camera (also comprising the digital camera that is equipped on mobile phone), employed collimating lens, the object lens such as optical take-up apparatus of BD (Blu-ray Disc) recording/reproducing apparatus, for miniaturization, lighting, use non-spherical lens mostly.Making under the situation of above-mentioned non-spherical lens by cutting, grinding step, needing the technology of high performance manufacturing installation and height, production cost increases.Therefore, as the method for the glass forming body of making the such unmanageable shape of non-spherical lens simply, adopt precise punch forming method (compression molding method).Above-mentioned precise punch forming method is carried out impact briquetting with press tool to the glass after heating.
Under with the situation of this precise punch forming method with glass ware forming, the high temperature that press tool need be set at more than the second-order transition temperature carries out moulding.Particularly, making under the situation of non-spherical lens, for from above-mentioned the press tool complicated and exquisite shape of transfer printing reliably, preferred mold temperature is higher.On the other hand, when the moulding temperature raise, the temperature of above-mentioned press tool also raise, and the surface will oxidation, or metal forms and change, and deterioration swashs acute, and descend to die life.Thus, in order to suppress the decline of die life, preferred its mold temperature (particularly, second-order transition temperature) of the employed glass of above-mentioned precise punch forming method is lower.
The multiple opticglass that is fit to this precise punch forming method has been proposed at present.Wherein, as have the specific refractory power that optical constant useful in the optical design is the d ray (nd) be 1.57～1.65 and Abbe number (ν d) be 40～61 or have opticglass with the suitable precise punch forming method of its optical constant that approaches, the opticglass of putting down in writing in following each patent documentation is arranged.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-53749 communique
Patent documentation 2: Japanese kokai publication hei 11-139845 communique
Patent documentation 3: Japanese kokai publication hei 9-301735 communique
Patent documentation 4: TOHKEMY 2007-119329 communique
Summary of the invention
The problem that invention will solve
In recent years, the more and more miniaturization of above-mentioned digital camera, lighting are requiring further energy-conservationization.In addition, the BD recording/reproducing apparatus has also proposed pocket or has been equipped on the vehicle-mounted type of automobile, also requiring the raising (except suppressing vibration and impacting, also will suppress between the optical device or the contacting of optical device and miscellaneous part) of anti-vibration performance, impact resistance.In order to respond the requirement of this energy-conservationization and anti-vibration performance, impact resistance raising, need be with own lightings of optical element such as lens, prism, speculums.In addition, these optical devices mostly in outdoor, automobile Working environments such as equitemperature, the humidity place harsher than existing installation use, also require to have excellent weathering resistance.
Therefore, the opticglass of the formation optical element that above-mentioned optical device uses also needs proportion little (below 3.0) and has excellent weathering resistance except possessing above-mentioned optical constant.But the opticglass of patent documentation 1 and patent documentation 2 records is than great, is not suitable as to be formed on the optical device that uses under the above-mentioned harsh envrionment conditions with the opticglass of optical element.In addition, the opticglass proportion of patent documentation 3 and patent documentation 4 records is little, but weathering resistance is low, is not suitable as the opticglass that is formed on employed above-mentioned optical element in the optical device that uses under the above-mentioned harsh envrionment conditions.
Therefore, the present invention finishes in view of such problem, its purpose is to provide a kind of opticglass, its specific refractory power (nd) with d ray be 1.57～1.65 and Abbe number (ν d) be 40～61 optical constant, it is below 520 ℃ that proportion reaches second-order transition temperature (Tg) below 3.0, and have excellent weathering resistance, be fit to the precise punch forming method.
The method of dealing with problems
The inventor has carried out continuous further investigation to achieve these goals, and its result finds experimentally, by with P 2O 5, B 2O 3, Al 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, Nb 2O 5, each composition of ZnO is main component, can obtain following opticglass, namely, specific refractory power (nd) with d ray be 1.57～1.65 and Abbe number (ν d) be 40～61 optical constant, it is below 520 ℃ that proportion reaches second-order transition temperature (Tg) below 3.0, and have excellent weathering resistance, be fit to the precise punch forming method, thereby finished the present invention.
That is, opticglass of the present invention is characterised in that, in quality %, contains following glass ingredient:
P 2O 5 35%～50%、
B 2O 3 3%～25%、
Al 2O 3 1%～12%、
Li 2O 0%～10% (comprising zero),
Na 2O 0%～10% (comprising zero),
K 2O 0%～12% (comprising zero),
Wherein, Li 2O+Na 2O+K 2O5%～15%,
M gO 0%～30% (comprising zero),
CaO 0%～30% (comprising zero),
Wherein MgO+CaO 18%～32%,
Nb 2O 5 5%～20%、
ZnO 0%～10% (comprising zero),
And do not contain SiO in fact 2, ZrO 2These two kinds of glass ingredients,
Its specific refractory power (nd) with d ray be 1.57～1.65 and Abbe number (ν d) be 40～61 optical constant, proportion is below 3.0, and second-order transition temperature (Tg) is below 520 ℃.
In addition, opticglass of the present invention is characterised in that, in quality %, also contains in the following glass ingredient one or more:
SrO 0%～5% (comprising zero),
BaO 0%～5% (comprising zero),
TiO 20%～10% (comprising zero),
WO 30%～5% (comprising zero),
Bi 2O 30%～3% (comprising zero),
La 2O 30%～3% (comprising zero),
Y 2O 30%～3% (comprising zero),
Gd 2O 30%～3% (comprising zero),
Ta 2O 50%～3% (comprising zero),
Sb 2O 30%～0.5% (comprising zero).
In addition, the P of opticglass of the present invention 2O 5, B 2O 3, Al 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, Nb 2O 5, ZnO total content surpass 95%.
In addition, according to the present invention, can provide a kind of by described opticglass is carried out the optical element that precise punch forming is made.As this optical element, can enumerate: the object lens of imaging lens, laser optical system, prism and speculum etc.
The effect of invention
In opticglass of the present invention, by with P 2O 5, B 2O 3, Al 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, Nb 2O 5, ZnO is main component, can access following opticglass, namely, specific refractory power (nd) with d ray be 1.57～1.65 and Abbe number (ν d) be 40～61 optical constant, it is below 520 ℃ that proportion reaches second-order transition temperature (Tg) below 3.0, and have excellent weathering resistance, be fit to the precise punch forming method.
Embodiment
Below, the reason of each composition of limiting opticglass of the present invention is as described above described.In addition, in the following description, abbreviating as under the situation of %, refer to mass percent.
P 2O 5Be the main component that forms glass, and be essential composition.At P 2O 5Content be lower than at 35% o'clock, the glass instability.In addition, when surpassing 50%, the weathering resistance variation.Therefore, with P 2O 5Content be set in 35%～50% the scope.Preferred range is 38%～47%.
B 2O 3Be the composition that forms glass, effective aspect the stabilization of glass, be essential composition.At B 2O 3Content be lower than at 3% o'clock, its effect deficiency in addition, is surpassing at 25% o'clock, glass is volatile, is prone to texture.Therefore, with B 2O 3Content be set in 3%～25% the scope.Preferred range is 8%～21%.
MgO, CaO are for improving weathering resistance and reducing the very effective composition of proportion.When the content of MgO, CaO surpasses 30% respectively, the easy devitrification of glass.Therefore, each content with MgO, CaO is set in below 30%.Preferred range is respectively below 25%.
In addition, when the total content of MgO and CaO is 18% when above, weathering resistance is good, and when surpassing 32%, anti-cleaning is poor.Therefore, the total content (content of MgO+CaO) of MgO and CaO is set in 18%～32% the scope.Preferred range is 20%～30%.Preferred scope is 21～28%.
Al 2O 3Be for the very effective composition of weathering resistance that improves glass, be essential composition.At Al 2O 3Content be lower than at 1% o'clock, its effect is insufficient, when surpassing 12%, the easy devitrification of glass.And under the content of MgO+CaO was situation more than 20%, tendency towards devitrification was strong, so Al 2O 3Content be preferably 1%～7% scope.Preferred scope is 1%～5%.
Li 2O, Na 2O, K 2O makes that vitrifying is easy, and this external stabilization aspect is effective.Work as Li 2O, Na 2O, K 2The content of O surpasses at 10%, 10%, 12% o'clock respectively, and glass is volatile, is prone to texture.Therefore, with Li 2The content of O is set in 0%～10% the scope, with Na 2The content of O is set in 0%～10% the scope, with K 2The content of O is set in 0%～12% the scope.In addition, at Li 2O, Na 2O, K 2Total content (the Li of O 2O+Na 2O+K 2The content of O) be lower than at 5% o'clock, the sense of stability effect of glass is less, when surpassing 15%, and the easy variation of weathering resistance.Therefore, with Li 2O+Na 2O+K 2The content of O is set in 5%～15% the scope.Preferred range is 6%～12%.
Nb 2O 5Be to the effective composition of weathering resistance.Only be MgO, CaO, Al 2O 3The time, be difficult to keep well weathering resistance, but by using Nb simultaneously 2O 5, it is significantly good that weathering resistance can become.In addition, by using Nb 2O 5, also have the effect of the anti-cleaning variation that inhibition causes by MgO, CaO.In addition, under the situation of a large amount of use MgO or CaO, by using the Nb of specified quantitative 2O 5Make glass become stable, have the effect that is difficult for devitrification.Further, also has proportion than SrO, BaO, ZnO is little and specific refractory power is improved effect.At Nb 2O 5Content be lower than at 5% o'clock, can not fully obtain these effects, when surpassing 20%, easy devitrification.Therefore, with Nb 2O 5Content be set in 5%～20% the scope.Preferred range is 6%～15%.
ZnO has the effect that makes stabilizationization.In addition, comparing with SrO, BaO, is the composition that does not increase proportion, but when content is big, the weathering resistance variation.Therefore, the content with ZnO is set in below 10%.Be preferably below 5%, more preferably below 3%.
Work as SiO 2And ZrO 2The content that is used for MgO+CaO is above-mentioned scope and Nb 2O 5Content when being the glass of above-mentioned scope, the stability of glass is rapid variation just, and easy devitrification.Therefore, in fact preferably do not use SiO 2And ZrO 2
BaO, SrO have the effect that makes stabilizationization and be difficult for devitrification.But, when BaO, SrO content separately is big, the just rapid variation of weathering resistance.Therefore, BaO, SrO content separately is set in 0%～5% the scope.Preferred range is 0%～2%.But BaO is toxic substance, does not just preferably use if do not need especially.
TiO 2, WO 3, Bi 2O 3Be the composition that improves specific refractory power, still, work as TiO 2Content surpass 10%, WO 3Content surpass 5% and Bi 2O 3Content surpass at 3% o'clock, the glass easy coloring.Therefore, TiO 2Content be set at below 10% WO 3Content be set at below 5% Bi 2O 3Content be set at below 3%.If do not need just preferably not use TiO 2, WO 3, Bi 2O 3
La 2O 3, Y 2O 3, Gd 2O 3, Ta 2O 5Be to improve specific refractory power and do not produce painted composition, still, in the glass that the present invention forms, it is insoluble easily residual composition.Therefore, La 2O 3, Y 2O 3, Gd 2O 3, Ta 2O 5Content separately is preferably below 3%, more preferably La 2O 3, Y 2O 3, Gd 2O 3, Ta 2O 5Content separately is below 1%.Just preferably do not use if do not need especially.
Sb 2O 3Can when glass melting, use as finings or as depigmenting agent.Sb 2O 3Content be 0%～0.5% o'clock namely fully.Because Sb 2O 3Therefore be toxic substance, if do not need just not to use into well.
From considering that the viewpoint of the influence of environment is not in fact preferably used PbO, As 2O 3, F.
Glass of the present invention is preferably basically by P 2O 5, B 2O 3, Al 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, Nb 2O 5, ZnO constitutes.The total content of mentioned component preferably is made as and surpasses 95% in the glass of the present invention, more preferably is made as to surpass 99%.
In addition, can certainly in the scope of not damaging effect of the present invention, add existing known glass ingredient and additive as required.
Optical element of the present invention is made by the opticglass that contains mentioned component is carried out precise punch forming.Representational method as this precise punch forming method, comprise direct precise punch forming method and the reheat method of forming, described direct precise punch forming method is to utilize nozzle to the glass of the press tool instillation fusion that is heated to specified temperature in advance, carries out stamping forming method under the state that keeps specified temperature; The described reheat method of forming is that the preform that will contain mentioned component is positioned in the mould, and the above temperature of glass softening point that is heated to each mould is carried out impact briquetting.By utilizing above-mentioned precise punch forming method, though make (for example, non-spherical lens) such as object lens or collimating lenses such have the optical element of complicated shape the time, do not need cutting, grinding step yet, productivity is improved.In addition, in the forming method shown in above, as the manufacture method of optical element of the present invention, direct precise punch forming method more preferably.Hereinafter, optical element of the present invention describes to use direct precise punch forming method to make.
As condition of molding, can enumerate: die temperature, punching press time, stamping pressure, glass viscosity etc.Usually, die temperature is preferably near the high temperature of second-order transition temperature (Tg: be below 520 ℃ in the present invention).The punching press time be preferably the several seconds～tens of seconds scope, the punching press time is more long, more can realize high-precision moulding.In addition, stamping pressure is preferably 50kgf/cm 2～800kgf/cm 2(scope of 4.903MPa～78.45MPa) with the high pressure punching press, more can realize high-precision moulding.Glass viscosity during as moulding is preferably 10 2Poise～10 12The scope of poise.Need to prove that this condition of molding is because of glass ingredient or want the shape of the optical element of moulding to carry out slight change.
As optical element of the present invention, can enumerate: digital camera, be equipped on the lens, collimating lens, speculum etc. of image pickup optical system of the digital camera of mobile phone etc., perhaps the object lens of the employed optical take-up apparatus of BD device used of vehicle mounted or PC, collimating lens, speculum etc.
Embodiment
Below, utilize the present invention of embodiment to be described more specifically.Need to prove that embodiment only is an example, does not limit the present invention.
(embodiment 1～47)
Composition and the feature of each composition of embodiment 1～47 are as shown in table 1.The sample of each embodiment is made by following order (method).Come common frits such as weighing oxide compound, oxyhydroxide, carbonate, phosphoric acid salt and nitrate in the mode that becomes the target composition shown in the table 1, fully mix with powder then, make the blending material.Should concoct material and drop in the platinum crucible, and utilize electric furnace, fusion is 1 hour～3 hours under 1000 ℃～1300 ℃ temperature, after stirring, casts in the mold of the iron or carbon system through having preheated, and slowly cools off, and is made into sample thus.
To each sample of making by above sequential system, the specific refractory power (nd) of mensuration d ray and Abbe number (ν d), proportion, second-order transition temperature (Tg).Said determination carries out based on the test method of Japanese opticglass TIA's standard (JOGIS).In addition, about the evaluation of weathering resistance, mirror ultrafinish is carried out on the surface of the sample of each embodiment, in the constant temperature and humidity machine of the cleaning of 60 ℃ of temperature, humidity 95%, kept 168 hours, use the surface after microscope (40 times) is observed mirror ultrafinish then.Need to prove, about the evaluation result of weathering resistance, with zero or * be illustrated in the table.Zero mark in the table represents not see and changes and in the sample of practicality, in the table * mark represents to note abnormalities (bluring, separate out foreign matter etc.) and can not be used for practical sample.In addition, in table 1, for the ease of comparative studies, both represent to contain components in proportions with mass percent (wt%) and molecular fraction (mol%).
Comparative example 1～4
On the other hand, as a comparative example 1～4, adopt and form and feature examples approximate with opticglass of the present invention all, with the composition of each composition and character representation in table 2.Comparative example 1 is the embodiment 10 (comparative example 1) of TOHKEMY 2005-53749 communique, comparative example 2 is embodiment 42 of Japanese kokai publication hei 11-139845 communique, comparative example 3 is that the embodiment 8 of Japanese kokai publication hei 9-301735 communique is (about the composition of composition, be scaled mass percent), comparative example 4 is embodiment 7 of TOHKEMY 2007-119329 communique.Produce the sample of above-mentioned comparative example with the method for putting down in writing in each communique, use the method identical with embodiment, carried out the evaluation of atmospheric exposure test.The method for expressing of evaluation result is identical with embodiment.Need to prove that the optical constant of each comparative example is utilized the numeral of each communique record, about comparative example 1～comparative example 3, has expressed yield temperature (At), replaces second-order transition temperature (Tg).
[table 1]
Figure BDA00003385692800081
Figure BDA00003385692800082
Figure BDA00003385692800091
Figure BDA00003385692800092
Figure BDA00003385692800101
Figure BDA00003385692800102
Figure BDA00003385692800111
Figure BDA00003385692800121
[table 2]
Figure BDA00003385692800141
As shown in Table 1, the opticglass of embodiment 1～48 is specific refractory power (nd) with d ray at the scope of 1.57280～1.64983 (target values 1.57～1.65) and Abbe number (ν d) opticglass in the optical constant of the scope of 42.6～58.8 (target values 40～61), and it is that second-order transition temperature (Tg) is 439 ℃～512 ℃ (target value is below 520 ℃), the opticglass that is fit to direct precise punch forming.In addition, its proportion is 2.7～2.9 (target value is below 3.0), and all embodiment has excellent weathering resistance.By The above results as can be known, has the opticglass that glass that the one-tenth of embodiment 1～48 is grouped into is suitable as the optical element that is configured for above-mentioned optical device.
In contrast to this, as shown in table 2, the proportion of the opticglass of comparative example 1 and comparative example 2 has all surpassed the proportion 3.0 that requires in the design.In addition, the Abbe number of the opticglass of comparative example 3 and comparative example 4 (ν d) is the value of departing from objectives all, and weathering resistance is poor.By The above results as can be known, the glass that is grouped into of the one-tenth of comparative example all is not suitable as the opticglass of the optical element that constitutes above-mentioned optical device.

Claims (6)

1. opticglass, it contains following glass ingredient in quality %:
P 2O 5 35%～50%、
B 2O 3 3%～25%、
Al 2O 3 1%～12%、
Li 2O 0%～10% (comprising zero),
Na 2O 0%～10% (comprising zero),
K 2O 0%～12% (comprising zero),
Wherein, Li 2O+Na 2O+K 2O 5%～15%,
MgO 0%～30% (comprising zero),
CaO 0%～30% (comprising zero),
Wherein, MgO+CaO 18%～32%,
Nb 2O 5 5%～20%、
ZnO 0%～10% (comprising zero),
Specific refractory power (nd) with d ray be 1.57～1.65 and Abbe number (ν d) be 40～61 optical constant, proportion is below 3.0, and second-order transition temperature (Tg) is below 520 ℃.
2. opticglass according to claim 1, wherein, in quality %, also contain in the following glass ingredient one or more:
SrO 0%～5% (comprising zero),
BaO 0%～5% (comprising zero),
TiO 20%～10% (comprising zero),
WO 30%～5% (comprising zero),
Bi 2O 30%～3% (comprising zero),
La 2O 30%～3% (comprising zero),
Y 2O 30%～3% (comprising zero),
Gd 2O 30%～3% (comprising zero),
Ta 2O 50%～3% (comprising zero),
Sb 2O 30%～0.5% (comprising zero).
3. opticglass according to claim 1 and 2, wherein,
P 2O 5, B 2O 3, Al 2O 3, Li 2O, Na 2O, K 2O, MgO, CaO, Nb 2O 5, ZnO total content surpass 95%.
4. according to each described opticglass in the claim 1～3, it does not contain glass ingredient SiO in fact 2, ZrO 2
5. optical element, it is made by each described opticglass in the claim 1～4 is carried out precise punch forming.
6. optical element according to claim 5, wherein, described optical element is any in lens, prism and the speculum.
CN2011800618668A 2010-12-22 2011-12-16 Optical glass and optical element produced therefrom Pending CN103339075A (en)

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