CN103663961A - Optical glass, optical element and manufacturing method of glass formed member - Google Patents
Optical glass, optical element and manufacturing method of glass formed member Download PDFInfo
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- CN103663961A CN103663961A CN201310389532.4A CN201310389532A CN103663961A CN 103663961 A CN103663961 A CN 103663961A CN 201310389532 A CN201310389532 A CN 201310389532A CN 103663961 A CN103663961 A CN 103663961A
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Abstract
The present invention provides optical glass with anticipated high stability and high chromatic dispersion (low abbe number), an optical element and a manufacturing method of a glass formed member. Relative to the amount of total matter of glass with composition that is converted by oxide, the optical glass comprises the following components in mol%: more than 20% and less than 45% of P2O5, more than 15% and less than 60% of Nb2O5, more than 5% and less than 50% of ZnO and MgO, wherein the refraction index of the optical glass is more than 1.75, and the abbe number is above 10 and less than 35. Preferably, the optical glass comprises one or more components selected from more than 0.1% and less than 20% of SiO2 and Al2O3 in mol%.
Description
Technical field
The present invention relates to the manufacture method of opticglass, optical element and glass forming body.
Background technology
In recent years, use digitizing and the high-definition of the instrument of optical system to develop rapidly, for to take the requirement of high precision int, light weight and miniaturization of the optical elements such as lens that use in the various opticinstruments that the photographic instruments such as digital camera and pick up camera are representative strong all the more.
In making the opticglass of optical element, especially can realize the lightweight of optical element and miniaturization, there is high refractive index (n
d) and low Abbe number (ν
d) the demand of glass of high refractive index very high.As such glass of high refractive index, for example, the opticglass of recording in patent documentation 1 has more than 21 and lower than 31 Abbe number, and in patent documentation 2, the opticglass of record has more than 22 and lower than 25 Abbe number.
prior art document
patent documentation
Patent documentation 1: Japanese kokai publication hei 8-157231 communique
Patent documentation 2: TOHKEMY 2001-58845 communique
Patent documentation 3: TOHKEMY 2003-238197 communique
Patent documentation 4: TOHKEMY 2003-321245 communique
Patent documentation 5: TOHKEMY 2003-335549 communique
Patent documentation 6: TOHKEMY 2005-154248 communique
Patent documentation 7: TOHKEMY 2009-143801 communique
Patent documentation 8: TOHKEMY 2010-83701 communique
Patent documentation 9: TOHKEMY 2011-57509 communique
Patent documentation 10: Chinese patent discloses communique No. 101134641
Summary of the invention
the problem that invention will solve
Yet, the opticglass that patent documentation 1～patent documentation 10 is recorded, although Abbe number is low, stability is difficult to be referred to as height, and devitrification etc. likely occurs.
Therefore, the present invention completes in view of the above problems, and its object is, the manufacture method with the high stability of expectation and opticglass, optical element and the glass forming body of high dispersion (low Abbe number) is provided.
for the scheme of dealing with problems
The inventor has carried out deep experimental study in order to address the above problem, and found that, is kept and contained the P of specified amount by the balance with regulation
2o
5composition, Nb
2o
5composition, ZnO composition and MgO composition, can improve stability, improve dispersion, thereby complete the present invention.Particularly, the invention provides following technical scheme.
(1) opticglass, wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the P more than 20% and below 45%
2o
5composition, the Nb more than 15% and below 60%
2o
5composition, total amount are ZnO composition and the MgO composition more than 5% and below 50%, and the specific refractory power of described opticglass is more than 1.75, and Abbe number is more than 10 and below 35.
(2) opticglass according to (1), wherein, with respect to total amount of substance of the glass of the composition converting with oxide compound, in mol%, containing total amount is the SiO more than 0.1% and below 20%
2composition and Al
2o
3one or both compositions in composition.
(3) opticglass according to (1) or (2), wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the TiO more than 0% and below 40%
2composition.
(4), according to the opticglass described in any one in (1)～(3), wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the R more than 0% and below 25%
2o composition, R
2o/(ZnO+MgO) be below 2.0.
Wherein, R is more than one elements that select in the group that free Li, Na and K form.
(5), according to the opticglass described in any one in (1)～(4), wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the MO composition more than 0% and below 25%, is MO/(ZnO+MgO) below 0.5.
Wherein, M is more than one elements that select in the group that free Ca, Sr and Ba form.
(6) optical element, the opticglass described in its any one in (1)～(5) forms.
(7) manufacture method for glass forming body, the opticglass that it uses described in any one in (1)～(6) is pressed to the aforementioned opticglass softening in mould.
the effect of invention
According to the present invention, can provide the P that keeps and contain specified amount by the balance with regulation
2o
5composition, Nb
2o
5composition, ZnO composition and MgO composition and there is the manufacture method of the high stability of expectation and the opticglass of high dispersion, optical element and glass forming body.
Accompanying drawing explanation
Fig. 1 is the graphic representation of the transmission characteristics of the opticglass of expression embodiment 1.
Embodiment
Opticglass of the present invention, with respect to total amount of substance of the glass of the composition converting with oxide compound, contains the P more than 20% and below 45% in mol%
2o
5composition, the Nb more than 15% and below 60%
2o
5composition, total amount are ZnO composition and the MgO composition more than 5% and below 50%, and the specific refractory power of described opticglass is more than 1.75, and Abbe number is more than 10 and below 35.By containing the P of specified amount
2o
5composition, Nb
2o
5composition and TiO
2composition, the reduction to the transmissivity of visible ray of opticglass is suppressed, dispersion is improved.In addition, by reducing the Sb containing in opticglass
2o
3composition, alleviates, in the concavo-convex and blushing of glass surface, reduces the impact of environment.Therefore, can provide the manufacture method that there is high-transmission rate and the high dispersion of expectation and can reduce opticglass, optical element and the glass forming body of surperficial concavo-convex and blushing.
Below, the embodiment of opticglass of the present invention is described in detail, but the present invention is not subject to any restriction of following embodiment, can within the scope of object of the present invention, suitably changes and implement.It should be noted that, the place of repeating about explanation, suitably description thereof is omitted sometimes, but and the purport of non-limiting invention.
glass ingredient
Below narration forms the compositing range of each composition of opticglass of the present invention.In this manual, in the situation that being not particularly limited, the containing ratio of each composition is all used % by mole representing with respect to total amount of substance of the glass of the composition converting with oxide compound.Herein, " oxide compound of usining convert composition " refers to: oxide compound, composite salt and the metal fluoride etc. that supposition is used as the raw material of glass constituent of the present invention all decompose and change to oxide compound in the situation that when melting, usings total amount of substance of this generation oxide compound as 100 % by mole of compositions that represent each composition contained in glass.
about essential composition, any composition
Then, to as opticglass of the present invention and preferably essential composition that use, glass and any composition describe.
P
2o
5composition is glass forming component, and is the essential composition that reduces the melting temperature (Tm) of glass.Particularly, by making P
2o
5the containing ratio of composition is more than 20%, and devitrification resistance rises, and can easily obtain the glass that stability is high.On the other hand, by making P
2o
5the containing ratio of composition is below 45%, can obtain high refractive index.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, P
2o
5the containing ratio of composition preferably be take 20% as lower limit, more preferably be take 22% as lower limit, most preferably take 24% as lower limit, preferably take 45% as the upper limit, more preferably take 35% as the upper limit, most preferably take 32% as the upper limit.P
2o
5composition can be by being used for example Al(PO
3)
3, Ca(PO
3)
2, Ba(PO
3)
2, BPO
4, H
3pO
4deng being contained in glass as raw material.
Nb
2o
5composition is to improve the specific refractory power of glass and the essential composition of dispersion.Particularly, by making Nb
2o
5the containing ratio of composition is more than 15%, can obtain high refractive index, and can obtain the high dispersion of expectation.On the other hand, by making Nb
2o
5the containing ratio of composition is below 60%, can improve glass stability, can improve devitrification resistance.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Nb
2o
5the containing ratio of composition preferably be take 15% as lower limit, more preferably be take 20% as lower limit, most preferably take 23% as lower limit, preferably take 60% as the upper limit, more preferably take 50% as the upper limit, most preferably take 40% as the upper limit.Nb
2o
5composition can be by being used for example Nb
2o
5deng being contained in glass as raw material.
SiO
2composition is effectively in the raising of meltbility, stability and the chemical durability of glass, is therefore the composition that can add arbitrarily.By making its content, particularly SiO
2the containing ratio of composition is greater than 0%, can improve the devitrification resistance of glass.On the other hand, by making SiO
2the containing ratio of composition is below 15%, by SiO
2the reduction of the stability that composition causes is suppressed, can easily obtain high refractive index.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, SiO
2the containing ratio of composition preferably be take 15% as the upper limit, more preferably be take 12% as the upper limit, most preferably take 10% as the upper limit.SiO
2composition can be by being used for example SiO
2, K
2siF
6, Na
2siF
6deng being contained in glass as raw material.
GeO
2composition has and above-mentioned SiO
2therefore the effect that composition is same is the composition that can add arbitrarily.By making GeO
2the containing ratio of composition is below 10%, can reduce material cost.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, GeO
2the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 5% as the upper limit, most preferably take 1% as the upper limit.GeO
2composition can be by being used for example GeO
2deng being contained in glass as raw material.
Al
2o
3composition is effectively in the raising of meltbility, stability and the chemical durability of glass, therefore can add arbitrarily.Particularly, by making Al
2o
3the containing ratio of composition is below 15%, can improve the meltbility of glass and weaken the tendency towards devitrification of glass.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Al
2o
3the containing ratio of composition preferably surpasses 0%, preferably take 15% as the upper limit, more preferably take 10% as the upper limit, most preferably take 8% as the upper limit.Al
2o
3composition can be by being used for example Al
2o
3, Al(OH)
3, AlF
3deng being contained in glass as raw material.
Ga
2o
3composition has and above-mentioned Al
2o
3therefore the effect that composition is same is the composition that can add arbitrarily.By making Ga
2o
3the containing ratio of composition is below 10%, can improve the devitrification resistance of glass and reduce material cost.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Ga
2o
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.Ga
2o
3composition can be by being used for example Ga
2o
3, GaF
3deng being contained in glass as raw material.
B
2o
3composition is to improve the meltbility of glass and the composition of devitrification resistance, is any composition in glass.Particularly, by making B
2o
3the containing ratio of composition, lower than 10%, can suppress by B
2o
3the reduction of the stability, glass that composition causes.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, B
2o
3the containing ratio of composition is preferably made as lower than 10%, more preferably take 5% as the upper limit, most preferably take 1% as the upper limit.B
2o
3composition can be by being used for example H
3bO
3, Na
2b
4o
7, Na
2b
4o
710H
2o, BPO
4deng being contained in glass as raw material.
ZnO composition is any composition that reduces the liquidus temperature of glass and improve the devitrification resistance of glass, and is to make the transmissivity of visible ray be difficult to the composition reducing, and is any composition in glass.Particularly, by making the containing ratio of ZnO composition, be below 50%, can easily obtain high refractive index and high dispersion.Therefore,, with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of ZnO composition preferably be take 50 as upper limit %, more preferably be take 45% as the upper limit, most preferably take 40% as the upper limit.ZnO composition can be by being used for example ZnO, ZnF
2deng being contained in glass as raw material.
MgO composition is any composition that reduces the liquidus temperature of glass and improve the devitrification resistance of glass, and is to make the transmissivity of visible ray be difficult to the composition reducing, and is any composition in glass.Particularly, by making the containing ratio of MgO composition, be below 45%, can easily obtain high refractive index and high dispersion.Therefore,, with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of MgO composition preferably be take 50% as the upper limit, more preferably be take 45% as the upper limit, most preferably take 40% as the upper limit.MgO composition can be by being used for example MgCO
3, MgF
2deng being contained in glass as raw material.
CaO composition is any composition that reduces the liquidus temperature of glass and improve the devitrification resistance of glass, and is to make the transmissivity of visible ray be difficult to the composition reducing, and is any composition in glass.Particularly, by making the containing ratio of CaO composition, be below 25%, high refractive index and high dispersion can be easily obtained, and the devitrification resistance of glass and the reduction of chemical durability can be suppressed.Therefore,, with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of CaO composition preferably be take 25% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.CaO composition can be by being used for example CaCO
3, CaF
2deng being contained in glass as raw material.
SrO composition is the liquidus temperature that reduces glass, any composition that improves the devitrification resistance of glass, is any composition in glass.Particularly, by making the containing ratio of SrO composition, be below 25%, high refractive index and high dispersion can be easily obtained, and the devitrification resistance of glass and the reduction of chemical durability can be suppressed.Therefore,, with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of SrO composition preferably be take 25% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.SrO composition can be by being used for example Sr(NO
3)
2, SrF
2deng being contained in glass as raw material.
BaO composition is any composition that improves the specific refractory power of glass and improve the devitrification resistance of glass, and is to make the transmissivity of visible ray be difficult to the composition reducing, and is any composition in glass.Particularly, by making the containing ratio of BaO composition, be below 25%, high refractive index and high dispersion can be easily obtained, and the reduction of devitrification resistance and chemical durability can be suppressed.Therefore,, with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of BaO composition preferably be take 25% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.Herein, particularly from accessing the viewpoint of the glass of dispersion large (Abbe number is little), with respect to total amount of substance of the glass of the composition converting with oxide compound, the containing ratio of BaO composition is preferably below 12.0%.BaO composition can be by being used for example BaCO
3, Ba(NO
3)
2, BaF
2deng being contained in glass as raw material.
Li
2o composition is any composition that improves stability and the transparency of glass and reduce second-order transition temperature (Tg), is any composition in glass.Particularly, by making Li
2the containing ratio of O composition is below 25%, can easily obtain high refractive index, and can improve glass stability, reduce the generation of devitrification etc.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Li
2the containing ratio of O composition preferably be take 25% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.Li
2o composition can be by being used for example Li
2cO
3, LiNO
3, LiF etc. is contained in glass as raw material.
Na
2o composition is any composition that improves stability and the transparency of glass and reduce second-order transition temperature (Tg), is any composition in glass.Particularly, by making Na
2the containing ratio of O composition, lower than 25%, can easily obtain high refractive index, and can improve glass stability, reduce the generation of devitrification etc.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Na
2the containing ratio of O composition is preferably made as lower than 25%, more preferably take 20% as the upper limit, most preferably take 15% as the upper limit.Na
2o composition can be by being used for example Na
2cO
3, NaNO
3, NaF, Na
2siF
6deng being contained in glass as raw material.
K
2o composition is any composition that improves stability and the transparency of glass and reduce second-order transition temperature (Tg), is any composition in glass.Particularly, by making K
2the containing ratio of O composition is below 25%, can easily obtain high refractive index, and can improve glass stability, reduce the generation of devitrification etc.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, K
2the containing ratio of O composition preferably be take 25% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.K
2o composition can be by being used for example K
2cO
3, KNO
3, KF, KHF
2, K
2siF
6deng being contained in glass as raw material.
TiO
2composition is any composition that improves specific refractory power and the dispersion of glass and improve the chemical durability of glass.Particularly, by making TiO
2the containing ratio of composition is more than 0%, can obtain high refractive index, and can obtain the high dispersion of expectation.On the other hand, by making TiO
2the containing ratio of composition is below 40%, can improve stability and the transparency of glass.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, TiO
2the containing ratio of composition preferably be take 0% as lower limit, more preferably be take 1% as lower limit, further preferably take 3% as lower limit.On the other hand, with respect to total amount of substance of the glass of the composition converting with oxide compound, TiO
2the containing ratio of composition preferably be take 40% as the upper limit, more preferably be take 35% as the upper limit, most preferably take 30% as the upper limit.TiO
2composition can be by being used for example TiO
2deng being contained in glass as raw material.
ZrO
2composition be reduce glass painted, improve the transmissivity of short wavelength's visible ray and promote stable glass to form, improve any composition of the devitrification resistance of glass, be any composition in glass.Particularly, by making ZrO
2the containing ratio of composition is below 10%, due to by ZrO
2the reduction of the specific refractory power that composition causes is suppressed, therefore can easily obtain the high refractive index of expectation.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, ZrO
2the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.ZrO
2composition can be by being used for example ZrO
2, ZrF
4deng being contained in glass as raw material.
Ta
2o
5composition is the composition that improves the specific refractory power of glass, is any composition in glass.Particularly, by making Ta
2o
5the containing ratio of composition is below 10%, can make glass be difficult to devitrification.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Ta
2o
5the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.Ta
2o
5composition can be by being used for example Ta
2o
5deng being contained in glass as raw material.
WO
3composition is the specific refractory power that improves glass, any composition that improves the dispersion of glass, is any composition in glass.Particularly, by making WO
3the containing ratio of composition is below 10%, can improve the devitrification resistance of glass and suppress the reduction to the transmissivity of the glass of short wavelength's visible ray.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, WO
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 5% as the upper limit, most preferably take 1% as the upper limit.WO
3composition can be by being used for example WO
3deng being contained in glass as raw material.
Y
2o
3composition is the specific refractory power that improves glass, the composition adjustment of dispersion to huge effect, is any composition in opticglass of the present invention.Particularly, by making Y
2o
3the containing ratio of composition is below 10%, can suppress glass devitrification resistance reduction and suppress the rising of glass transition point (Tg).Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Y
2o
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.Y
2o
3composition can be by being used for example Y
2o
3, YF
3deng being contained in glass as raw material.
La
2o
3composition is the composition that improves the specific refractory power of glass and the adjustment of dispersion is had to huge effect, is any composition in glass.Particularly, by making La
2o
3the containing ratio of composition is below 10%, can increase the dispersion of glass, and can improve the devitrification resistance of glass.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, La
2o
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.La
2o
3composition can be by being used for example La
2o
3, La (NO
3)
3xH
2o(X is arbitrary integer) etc. as raw material, be contained in glass.
Gd
2o
3composition is the composition that improves the specific refractory power of glass and the adjustment of dispersion is had to huge effect, is any composition in glass.Particularly, by making Gd
2o
3the containing ratio of composition is below 10%, can increase the dispersion of glass and can improve the devitrification resistance of glass.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Gd
2o
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 8% as the upper limit, most preferably take 5% as the upper limit.Gd
2o
3composition can be by being used for example Gd
2o
3, GdF
3deng being contained in glass as raw material.
Bi
2o
3composition is the raising specific refractory power of glass and the composition of dispersion, is any composition in opticglass of the present invention.Particularly, by making Bi
2o
3the containing ratio of composition is below 10%, and the stability of glass is improved, and therefore can suppress the reduction of devitrification resistance, and can suppress the reduction of the transmissivity of glass.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, Bi
2o
3the containing ratio of composition preferably be take 10% as the upper limit, more preferably be take 5% as the upper limit, is most preferably made as lower than 1%.
TeO
2composition is glass forming component, is any composition that improves specific refractory power and the dispersion of glass and improve transmissivity.Particularly, by making TeO
2the containing ratio of composition surpasses 0%, and dispersion and the specific refractory power of glass are improved, and therefore can obtain the Abbe number (ν of expectation
d) and specific refractory power.On the other hand, by making TeO
2the containing ratio of composition is below 30.0%, can reduce the liquidus temperature of glass, the devitrification resistance when improving glass and forming.In addition, if contain in a large number, can make antifriction consumption worsen.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, TeO
2the containing ratio of composition preferably be take 0% as lower limit, more preferably be take 0.5% as lower limit, most preferably take 1% as lower limit.In addition this TeO,
2the containing ratio of composition preferably be take 30% as the upper limit, more preferably be take 20% as the upper limit, most preferably take lower than 5% is the upper limit.TeO
2composition can be by being used for example TeO
2deng being contained in glass as raw material.
SnO
2composition is to reduce the oxidation of melten glass and make melten glass clarification and make light-struck transmissivity of glass is difficult to the composition worsening, and is any composition in opticglass of the present invention.Particularly, by making SnO
2the content of composition is below 6%, can make the devitrification painted, glass of the glass that the reduction by melten glass causes be difficult to produce.In addition, due to SnO
2the alloying of composition and melting equipment precious metals such as (particularly) Pt reduces, and therefore can realize the long lifetime of melting equipment.Therefore, with respect to total amount of substance of the glass of the composition converting with oxide compound, SnO
2the content of composition preferably be take 6% as the upper limit, more preferably be take 5% as the upper limit, most preferably take 4% as the upper limit.SnO
2composition can be by being used for example SnO, SnO
2, SnF
2, SnF
4deng being contained in glass as raw material.
Sb
2o
3composition is the composition improving the transmissivity of the glass of short wavelength's visible ray, and is when melten glass, to have the composition of deaeration effect, is any composition in opticglass of the present invention.Herein, by making Sb
2o
3the content of composition is below 1.0%, and excessive foaming during glass melting is difficult to produce, and therefore can make Sb
2o
3composition is difficult to, with melting equipment precious metals such as (particularly) Pt, alloying occurs.Therefore, Sb
2o
3the content of composition preferably be take 1.0% as the upper limit, more preferably be take 0.9% as the upper limit, further preferably take 0.8% as the upper limit.Particularly, even if containing on a small quantity Sb
2o
3in the situation of composition, Sb
2o
3composition also can be from melten glass volatilization and be attached to mould with the form of impurity, therefore can become the reason that produces concavo-convex and blushing on the surface of glass forming body.So, by making Sb
2o
3the content of composition is below 0.7%, as the Sb composition of the main component of impurity, from glass, is removed, and the impurity that is attached to thus mould reduces, and therefore can reduce the concavo-convex and blushing forming on the surface of glass forming body.Therefore, Sb
2o
3the content of composition preferably be take 0.7% as the upper limit, more preferably be take 0.6% as the upper limit, further preferably take 0.5% as the upper limit.For the purpose of the present invention, especially use is not most preferred containing the glass of Sb composition in fact.When improving compression moulding temperature, the formation of the impurity on mould becomes significantly, and the effect of therefore not bringing containing Sb composition in fact becomes remarkable.
In opticglass of the present invention, preferably containing total amount is ZnO composition and the MgO composition more than 5% and below 50%.
Meltbility, stability and the transparent effect that rises significantly and easily obtain the optical constant of expectation thus, with glass.Therefore, ZnO composition and MgO composition preferably be take 5% as lower limit, more preferably be take 7% as lower limit, most preferably take 9% as lower limit, preferably take 50% as the upper limit, more preferably take 45% as the upper limit, most preferably take 40% as the upper limit in total amount.
In opticglass of the present invention, preferably containing total amount is the SiO more than 0.1% and below 20%
2composition and Al
2o
3one or both compositions in composition.
Thus, there is the effect that meltbility, stability and the chemical durability of glass significantly improve.Therefore, SiO
2composition and Al
2o
3one or both compositions in composition preferably be take 0.5% as lower limit, more preferably be take 1% as lower limit, most preferably take 3% as lower limit in total amount, preferably take 20% as the upper limit, more preferably take 15% as the upper limit, most preferably take 10% as the upper limit.
In opticglass of the present invention, preferably contain the R more than 0% and below 30%
2o composition.Herein, R is more than one elements that select in the group that free Li, Na and K form.
Meltbility, stability and the transparent effect that rises and easily obtain having the glass of lower Tg thus, with glass.Therefore, R
2o composition preferably be take 30% as the upper limit, more preferably be take 25% as the upper limit, most preferably take 20% as the upper limit in total amount.
In opticglass of the present invention, R
2o/(ZnO+MgO) be preferably below 2.0.Herein, R is more than one elements that select in the group that free Li, Na and K form.
Thus, can manufacture the opticglass that stability is higher.Therefore, R
2o/(ZnO+MgO) preferably take 2.0% as the upper limit, more preferably take 1.5% as the upper limit, most preferably take 0.8% as the upper limit.
In opticglass of the present invention, preferably contain the MO composition more than 0% and below 30%.Herein, M is more than one elements that select in the group that free Ca, Sr and Ba form.
Thus, can manufacture the opticglass that stability is higher.Therefore, MO composition preferably be take 30% as the upper limit, more preferably be take 20% as the upper limit, most preferably take 15% as the upper limit.
In opticglass of the present invention, MO/(ZnO+MgO) be preferably below 0.5.Herein, M is more than one elements that select in the group that free Ca, Sr and Ba form.
Thus, can manufacture the opticglass that stability is higher.Therefore, MO/(ZnO+MgO) preferably take 0.5% as the upper limit, more preferably take 0.45% as the upper limit, most preferably take 0.4% as the upper limit.
In opticglass of the present invention, preferably: (1) contains the P more than 20% and below 45%
2o
5composition, the Nb more than 15% and below 60%
2o
5composition, total amount are ZnO composition and the MgO composition more than 5% and below 50%, the specific refractory power of described opticglass is more than 1.75, Abbe number is more than 10 and below 35, (2) with respect to total amount of substance of the glass of the composition converting with oxide compound, in mol%, SiO
2composition and Al
2o
3the total amount of the composition of one or both in composition is more than 0.1% and below 20%.
Thus, can manufacture stability and the high opticglass of the transparency.
about the composition that should not contain
Then, the composition that should not contain in opticglass of the present invention and the composition that preferably do not contain are described.
In opticglass of the present invention, can in the scope of characteristic of glass of not damaging the present application, add as required other composition.
But, for each transiting metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if independent or compound contain on a small quantity in the situation that respectively, also there is the glass coloring of making, at the specific wavelength place of visible region, produce the character absorbing, therefore particularly in the opticglass of wavelength that uses visible region, preferably do not contain in fact.
And then, the lead compounds such as PbO and As
2o
3each composition Deng arsenic compound and Th, Cd, Tl, Os, Be and Se has the tendency of controlling use as harmful chemical substance in recent years, not only, in the manufacturing process of glass, in the processing after manufacturing procedure and even commercialization, all need handling in environmental cure.Therefore,, in the situation that pay attention to the impact on environment, except inevitably sneaking into, preferably do not contain in fact these compositions.Thus, the material that does not contain in fact contaminate environment in opticglass.Therefore, even if do not seek handling in the environmental cure of Te Do, yet can this opticglass not manufactured, be processed and discarded.
the physical property of opticglass
Opticglass of the present invention has high refractive index (n
d) and there is the dispersion of regulation.Particularly, the specific refractory power (n of opticglass of the present invention
d) preferably take 1.75 as lower limit, more preferably take 1.80 as lower limit, most preferably take 1.84 as lower limit, preferably take 2.20 as the upper limit, more preferably take 2.10 as the upper limit, most preferably take 2.02 as the upper limit.In addition Abbe number (the ν of opticglass of the present invention,
d) preferably take 10 as lower limit, more preferably take 13 as lower limit, most preferably take 17 as lower limit, preferably take 35 as the upper limit, more preferably take 30 as the upper limit, most preferably take 24 as the upper limit.Thus, even if expand optical design degree of freedom, further seek the slimming of element, also can obtain the amount of refraction of large light.
In addition,, although need during for opticglass painted less, there is painted situation in glass of the present invention while there is moulding due to composition.Yet thereafter by carry out more than 4 hours thermal treatment near temperature glass transition point, this painted can disappearance, can be met the transparent glass of application.Particularly, for opticglass of the present invention, when the transmissivity with glass represents, with the sample of thickness 10mm, show the wavelength (λ of spectral transmission 70%
70) for 500nm is following, more preferably 480nm following, most preferably be below 450nm.Thus, the transparency of the glass in visible region is improved, materials'use that therefore can be using this opticglass as optical elements such as lens.It should be noted that, in the present invention, although the glass of heat-treating after glass material melting, Slow cooling and obtaining is had to above-mentioned transmissivity, but the painted viewpoint that never needs to heat-treat to suppress glass is set out, and it is preferred that the transmissivity of the glass before heat-treating has above-mentioned transmissivity.
the manufacture method of glass forming body
Opticglass of the present invention is for example made in the following way.; mode with each composition in the scope of the containing ratio of regulation is mixed above-mentioned raw materials equably; after the mixture of making is put in quartz crucible or alumina crucible, is carried out thick melting; put in golden crucible, platinum crucible, platinum alloy crucible or iridium crucible, the temperature range melting of 1250～1500 ℃, stir homogenizing and carry out froth breaking etc.; then be reduced to suitable temperature; then be poured in mould, carry out Slow cooling, make thus.
About made the means of optical element by the opticglass of making like this, can use the method for carrying out grinding and grinding after carry out hot repressing system, or the method for making preform, carrying out mold pressing.
Particularly, when carrying out mold pressing, by the preform being formed by opticglass of the present invention is heated in the mould for example consisting of the mold component that comprises upper die and lower die, cover die, thereby make it soften, be pressed.Herein, about the material of the quality of parent material of mould and the protective membrane that forms in the molding surface of mould, as long as for the material not melting is just not particularly limited, can use known material in softening preform.Wherein, the material of the mother metal of mould is preferably the known moulding stock such as wolfram varbide (WC), silicon carbide (SiC) or Stainless Steel Alloy, the material that the preferred most surface layer of material of protective membrane comprises at least one the above element in the element set of selecting free Pt, Au, Ir, Ni, Cr, Mo, Rh, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Re and C composition.By the material by such, make the mother metal of mould, the mother metal of mould becomes and is difficult to distortion, therefore can realize the long lifetime of mould.Wherein, from the easiness of processing, can in the mother metal of mould, use the metals such as Stainless Steel Alloy.In addition; by utilization, select at least one above element in the element set that free Pt, Au, Ir, Ni, Cr, Mo, Rh, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Re and C form to make the most surface layer of protective membrane; softening glass is suppressed with reacting of protective membrane, therefore can further reduce impurity adhering to protective membrane.In addition the softening mode that is not limited to utilize the heating in mould and carries out of preform.
Compression moulding is for example carried out according to following step.After the center configuration preform of the molding surface of the counterdie inserting, in the communicating pores of cover die, insert patrix in the communicating pores of cover die.Now, the molding surface of counterdie and the molding surface of patrix arrange in relative mode.Then, by preform is heated together with mould, the glass that forms preform is softening, and result is by pressurizeing to suppress to preform with upper die and lower die.Thus, the inside of the die cavity that preform surrounds at the upper die and lower die by matched moulds and cover die is extruded extension, therefore can be by glass filled the inside to die cavity.That is, can be by the shape transferred thereon of the internal surface of die cavity on glass.
Herein, the mode that mould becomes the shape of regulation with die cavity critically forms upper die and lower die in matched moulds state and the relative position of each molding surface and the angle that normal was of molding surface of cover die.In addition, till completing to the compacting that utilizes mould to carry out, in the mutual consistent mode of central shaft relative and patrix and counterdie of being oriented of patrix and counterdie, accurately maintain.Thus, can make the glass forming body that optical function face and determining positions reference plane form with high-precision position relationship and angle mutually.
the making of optical element
Opticglass of the present invention is all useful in various optical elements and optical design, wherein, particularly preferably opticglass of the present invention is pressed to make the optical elements such as lens, prism and mirror.Thus, by resulting optical element for as photographic camera and projector etc. make opticinstrument that visible ray sees through time, can realize high-resolution and high-precision imaging characteristic, and can realize the miniaturization of the optical system in these opticinstruments.
embodiment
The composition of embodiments of the invention shown in table 1～table 3 (No.1～No.32) (% by mole), specific refractory power (n
d), Abbe number (ν
d), second-order transition temperature (℃), deformation point (At, ℃) and linear expansivity (10
-7/ K) measurement result.It should be noted that, following embodiment is only for illustration, and the present invention is not limited in these embodiment.
The opticglass of embodiments of the invention (No.1～No.32) has all been chosen corresponding oxide compound separately as the raw material of each composition, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the high-purity raw that the common opticglass such as metaphosphoric acid compound are used, after carrying out weighing and mix equably according to the ratio of the composition of each embodiment shown in table 1～table 3, put in quartz crucible or platinum crucible, the melting difficulty forming according to glass is carried out melting with electric furnace in the temperature range of 1300～1450 ℃, after stirring homogenizing, be poured in mould, make test film.
About the opticglass of comparative example, it has adopted the composition that with respect to embodiments of the invention (No.1～No.32), ZnO composition and MgO is become to be divided into 0%, but not vitrifying.
Herein, the specific refractory power (n of the glass of embodiment (No.1～No.32)
d) and Abbe number (ν
d) according to Japanese optics nitre industry, can measure by standard JOGIS01-2003.It should be noted that, as the glass using in this mensuration, used annealing conditions for Slow cooling cooling rate is set as to-25 ℃/h and the glass obtaining processed in Slow cooling stove.
In addition, second-order transition temperature (℃), deformation point (At, ℃) utilizes thermal expansion curve to obtain, described thermal expansion curve according to Japanese optics nitre industry can standard JOGIS08-2003 " measuring method of the thermal expansion of opticglass ", the elongation of measuring above-mentioned temperature and sample obtains.
About linear expansivity (10
-7/ K), the average coefficient of linear expansion at can standard JOGIS08-2003 " measuring method of the thermal expansion of opticglass " having obtained 100～300 ℃ according to the industry of Japanese optics nitre.
table 1
table 2
table 3
As shown in Table 1 to Table 3, the Abbe number (ν of the opticglass of embodiments of the invention
d) be more than 10, be more specifically more than 17, and this Abbe number (ν
d) be below 35, be more specifically below 24.On the other hand, not vitrifying of the glass of comparative example.
In addition specific refractory power (the n of the opticglass of embodiments of the invention,
d) be more than 1.75, be more specifically more than 1.84, and this specific refractory power (n
d) be below 2.20, be more specifically below 2.02, in desired scope.On the other hand, not vitrifying of the glass of comparative example.
Moreover all there is not devitrification etc. in the opticglass of embodiments of the invention.On the other hand, not vitrifying of the opticglass of comparative example.Therefore, obviously can find out, opticglass of the present invention has high devitrification resistance.
In addition, use the optical element of the glass making of the composition of recording in embodiment 1～31 on surface, not produce concavo-convex and blushing.Therefore, obviously can find out, surperficial concavo-convex and blushing and stably compression moulding that opticglass of the present invention has reduced at glass forming body are various optical elements, are the shape of lens and prism.
Fig. 1 is the graphic representation of the transmission characteristics of the opticglass of expression embodiment 1.The thickness of measuring the opticglass using is 10mm.As shown in Figure 1, from about 430nm, start transmissivity and surpass 70%, realized more than 80% high-transmission rate.
Herein, the transmissivity of glass is measured according to Japanese optics nitre industry meeting standard JOGIS02.
Therefore, obviously can find out, the opticglass of embodiments of the invention has high stability and the high dispersion of expectation and can reduce the concavo-convex and blushing on surface.
Above, for illustrative purposes the present invention is had been described in detail, yet the present embodiment is eventually only for illustration, should be appreciated that those skilled in the art can not depart from thought of the present invention and scope and carry out multiple change.
Claims (7)
1. an opticglass, wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the P more than 20% and below 45%
2o
5composition, the Nb more than 15% and below 60%
2o
5composition, total amount are ZnO composition and the MgO composition more than 5% and below 50%, and the specific refractory power of described opticglass is more than 1.75, and Abbe number is more than 10 and below 35.
2. opticglass according to claim 1, wherein, with respect to total amount of substance of the glass of the composition converting with oxide compound, in mol%, containing total amount is the SiO more than 0.1% and below 20%
2composition and Al
2o
3one or both compositions in composition.
3. according to claim 1 or opticglass claimed in claim 2, wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the TiO more than 0% and below 40%
2composition.
4. according to the opticglass described in any one in claim 1～claim 3, wherein, the total amount of substance with respect to the glass of the composition converting with oxide compound, in mol%, contains the R more than 0% and below 25%
2o composition, R
2o/(ZnO+MgO) be below 2.0,
Wherein, R is more than one elements that select in the group that free Li, Na and K form.
5. according to the opticglass described in any one in claim 1～claim 4, wherein, with respect to total amount of substance of the glass of the composition converting with oxide compound, in mol%, containing the MO composition more than 0% and below 25%, is MO/(ZnO+MgO) below 0.5
Wherein, M is more than one elements that select in the group that free Ca, Sr and Ba form.
6. an optical element, the opticglass described in its any one in claim 1～claim 5 forms.
7. a manufacture method for glass forming body, its right to use requires the opticglass described in any one in 1～claim 6, in mould, softening described opticglass is pressed.
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| JP2012-190501 | 2012-08-30 | ||
| JP2012190501A JP6037501B2 (en) | 2012-08-30 | 2012-08-30 | Optical glass, optical element, and method for producing glass molded body |
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| CN103663961B CN103663961B (en) | 2018-12-07 |
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Cited By (4)
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| CN105481244A (en) * | 2014-10-07 | 2016-04-13 | 株式会社小原 | Optical glass, lens preforming and optical element |
| CN106915901A (en) * | 2015-12-25 | 2017-07-04 | 株式会社小原 | A kind of optical glass, prefabricated component and optical element |
| CN111556855A (en) * | 2018-02-01 | 2020-08-18 | Hoya株式会社 | Colored glass and method for producing same |
| CN113645873A (en) * | 2019-04-05 | 2021-11-12 | 日本电气硝子株式会社 | Glass article for decoration |
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| JP2015163564A (en) * | 2014-02-28 | 2015-09-10 | 株式会社オハラ | optical glass, lens preform and optical element |
| JP6692570B2 (en) * | 2014-10-07 | 2020-05-13 | 株式会社オハラ | Optical glass, lens preform and optical element |
| JP6635667B2 (en) * | 2015-03-24 | 2020-01-29 | 株式会社オハラ | Optical glass, lens preform and optical element |
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| CN105481244A (en) * | 2014-10-07 | 2016-04-13 | 株式会社小原 | Optical glass, lens preforming and optical element |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103663961B (en) | 2018-12-07 |
| JP2014047095A (en) | 2014-03-17 |
| JP6037501B2 (en) | 2016-12-07 |
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