CN104936916A - Optical glass - Google Patents
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- CN104936916A CN104936916A CN201480005367.0A CN201480005367A CN104936916A CN 104936916 A CN104936916 A CN 104936916A CN 201480005367 A CN201480005367 A CN 201480005367A CN 104936916 A CN104936916 A CN 104936916A
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Abstract
Provided is an optical glass which exhibits excellent weather resistance, chemical durability, and transmittance with respect to the visible range and the near ultraviolet range, and which is capable of easily achieving a low glass transition point without including components unfavourable to the environment. This optical glass is characterized by including, in mol%, 43.5-80% of SnO, and a total of 0.1-29.9% of P2O5, B2O3, and SiO2. The optical glass is further characterized by substantially not including lead components and arsenic components. It is preferable that the P2O5 content be 0.1-29.5%.
Description
Technical field
The present invention relates to opticglass.Specifically, the opticglass of the light pick up tube lens, pick up camera, general camera shooting lens etc. that are suitable for various optical disk system is related to.
Background technology
Usually, the photography lens of the light pick up tube lens of CD, MD, DVD, other various optical disk systems, pick up camera, general photographic camera are made by following operation.
First, the raw material powder melting of desired composition will be adjusted to.Then, to drip melten glass from spray nozzle front end, make droplet-like glass (drop is shaping), as required, grinding, grinding, to clean, make modular glass.Or by melten glass quenching cast, glass ingot of producing once, grinding, grinding, clean, make modular glass.Then, thermoplastic modular glass, carries out extrusion forming by being applied with precision machined mould, by the transferring surface shape of mould on glass, makes lens.Such forming method is commonly called compression molding method (or precision pressure method of forming).
When adopting compression molding method, worsen to suppress mould and by lens critically compression molding, require to have the glass of alap yield-point or second-order transition temperature, the various glass of motion.
Usually, in order to make the low opticglass of yield-point, must many compositions becoming the reason that specific refractory power and weathering resistance or chemical durability decline containing alkali composition etc.Therefore, even if the content of alkali composition etc. is few, as the glass that can reach low Tg, also motion bismuth glass, phosphate-based glass (for example, referring to patent documentation 1 and 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-106625 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-297936 publication
Summary of the invention
Invent problem to be solved
The Bi of the low Tg with about 400 DEG C is described in patent documentation 1
2o
3-B
2o
3-SiO
2be glass, but containing many Bi
2o
3glass be difficult to easily to be colored as yellow high-transmission rate.In addition, in patent documentation 2, as the glass of low Tg with less than 300 DEG C, describe SnO-PbO-P
2o
5be glass, but because this glass contains lead composition as essential component, so environmentally not preferred.
Therefore, problem of the present invention is: provide not containing environmentally preferred composition, easily can reach low Tg, the also excellent and opticglass of the transmissivity excellence of visibility region or near ultraviolet region of weathering resistance and chemical durability.
For solving the method for problem
< the 1st aspect > of the present invention
The opticglass of the 1st aspect of the present invention, is characterized in that: in mol%, containing the SnO of 43.5 ~ the 80% and P of 0.1 ~ 29.9%
2o
5+ B
2o
3+ SiO
2, and in fact not containing lead composition and arsenic composition.
The opticglass of the 1st aspect of the present invention, because a large amount of containing SnO in glass composition, so easily reach high refractive index characteristic and weathering resistance and chemical durability are also excellent.In addition, when compression molding, be difficult to generate the devitrification thing hindering the transparency.
The opticglass of the 1st aspect of the present invention, because except SnO, also containing P
2o
5, B
2o
3or SiO
2as essential component, so it is painted to be difficult to generation, the transmissivity of visibility region or near ultraviolet region is excellent.In addition, the opticglass of the 1st aspect of the present invention, because the lead composition do not contained in fact as objectionable constituent and arsenic composition, so be one environmentally preferred glass.
In addition, in the of the present invention 1st, so-called " in fact not containing lead composition and arsenic composition ", referring to it is not the meaning containing these compositions wittingly in glass, is not the meaning that inevitable impurity is got rid of all completely.Say objectively, refer to that the content of these compositions comprising impurity is less than the meaning of 0.1% in mol% respectively.
P
2o
5content be preferably 0.1 ~ 29.5%.
According to this formation, easily obtain the glass with low Tg.
With molar ratio computing, SnO/ (P
2o
5+ B
2o
3+ SiO
2) be preferably more than 1.5.
According to this formation, easily obtain there is high refractive index characteristic and the glass of weathering resistance and chemical durability excellence.
In mol%, the CaO+SrO+BaO+MgO+ZnO of 0 ~ 25% is preferably also contained.
According to this formation, easily obtain the glass of devitrification resistance excellence.
In mol%, the Al of 0 ~ 10% is preferably also contained
2o
3+ Zr
2o.
According to this formation, easily obtain the glass of weathering resistance and chemical durability excellence.
Yield-point is preferably less than 500 DEG C.
According to this formation, the compression molding under low temperature can be carried out, can suppress to be oxidized by mould, glass ingredient volatilizees the mold fouling caused, the problems such as the fusion of glass and mould can also be suppressed.
Water tolerance based on JOGIS is preferably more than 2 grades.
Specific refractory power (nd) is preferably more than 1.6, and Abbe number (ν d) is preferably less than 40.
Abbe number (ν d) and partial dispersion ratio (θ g, F) preferably meet the relation of (θ g, F)≤-0.0047 × (ν d)+0.76.
In opticinstrument, generally by combinationally using by low dispersion and the optical lens that forms than large glass of partial dispersion and by high dispersive and the optical lens that forms than little glass of partial dispersion, revise chromatic aberation.The opticglass of the 1st aspect of the present invention, meets above-mentioned relation by Abbe number and partial dispersion ratio, easily reach high dispersive and partial dispersion than little optical characteristics, easily can make the opticinstrument of chromatic aberation excellence.
Preferred degree of staining λ
70be less than 500nm.
By glass coloring degree λ
70meet above-mentioned scope, the transmissivity that can obtain visibility region or near ultraviolet region is excellent, is suitable for the glass of the optical element of various optical lenses etc.In addition, in the of the present invention 1st, so-called " degree of staining λ
70", refer in transmittance graph, transmissivity becomes the wavelength of 70%.
Be preferred for optical lens.
Be preferred for compression molding.
The feature of the optical element of the 1st aspect of the present invention is, employs above-mentioned arbitrary opticglass.
< the 2nd aspect > of the present invention
The feature of the opticglass of the 2nd aspect of the present invention is, in mol%, containing the SnO of 23.5 ~ 85%, the P of 0.1 ~ 49.9%
2o
5, 0 ~ 2% ZrO
2, 0.1 ~ 20% La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2with 0 ~ 1% MgO+CaO+SrO+BaO, and in fact not containing lead composition and arsenic composition.
The opticglass of the 2nd aspect of the present invention, because a large amount of containing SnO in glass composition, so easily reach high refractive index characteristic and weathering resistance and chemical durability are also excellent.In addition, when compression molding, be difficult to generate the devitrification thing hindering the transparency.In addition, the opticglass of the 2nd aspect of the present invention, because except SnO, also containing P
2o
5as essential component, so the transmittance of visibility region or near ultraviolet region is excellent.The opticglass of the 2nd aspect of the present invention, because containing La
2o
3, Gd
2o
3, Ta
2o
5, WO
3, Nb
2o
5, TiO
2, Y
2o
3, Yb
2o
3and GeO
2in at least a kind as essential component, so easily reach high refractive index and the optical characteristics of high dispersive.
In addition, the opticglass of the 2nd aspect of the present invention, because in fact containing as the lead composition of objectionable constituent and arsenic composition, so be environmentally preferred glass.In in the of the present invention 2nd, so-called " in fact not containing lead composition and arsenic composition ", referring to it is not the meaning containing these compositions wittingly in glass, is not the meaning that inevitable impurity is got rid of all completely.Say objectively, refer to that the content of these compositions comprising impurity is less than the meaning of 0.1% in mol% respectively.
The opticglass of the 2nd aspect of the present invention, preferably in mol%, containing the Li of 0 ~ 10%
2o+Na
2o+K
2o.
The opticglass of the 2nd aspect of the present invention, preferably in mol%, containing the B of 0 ~ 10%
2o
3+ ZnO.
The opticglass of the 2nd aspect of the present invention, in mol%, can containing the Cl+S+Br of 0.01 ~ 1%.
The opticglass of the 2nd aspect of the present invention, preferred yield-point is less than 500 DEG C.
The opticglass of the 2nd aspect of the present invention, the water tolerance based on JOGIS is preferably more than 3 grades.
The opticglass of the 2nd aspect of the present invention, preferred index is more than 1.6, and Abbe number is less than 40.
By meeting above-mentioned optical characteristics, look dispersion tails off, so be applicable as the optical lens of high function, small-sized opticinstrument.
The opticglass of the 2nd aspect of the present invention, preferred Abbe number (ν d) and partial dispersion ratio (θ g, F) meet the relation of (θ g, F)≤-0.0047 × (ν d)+0.76.
In opticinstrument, generally by combinationally using by low dispersion and the optical lens that forms than large glass of partial dispersion and by high dispersive and the optical lens that forms than little glass of partial dispersion, revise chromatic aberation.The opticglass of the 2nd aspect of the present invention, meets above-mentioned relation by Abbe number and partial dispersion ratio, easily reach high dispersive and partial dispersion than little optical characteristics, easily can make the opticinstrument of chromatic aberation excellence.
The opticglass of the 2nd aspect of the present invention, preferred degree of staining λ
70be less than 500nm.In addition, in the of the present invention 2nd, so-called " degree of staining λ
70", refer in light transmittance curve, transmittance becomes the minimal wave length of 70%.
The opticglass of the 2nd aspect of the present invention, is preferred for optical lens.
The opticglass of the 2nd aspect of the present invention, is preferred for compression molding.
The feature of the optical element of the 2nd aspect of the present invention is, uses above-mentioned opticglass.
The effect of invention
According to the present invention, can provide not containing environmentally preferred composition, easily can reach the also excellent and opticglass of the transmissivity excellence of visibility region or near ultraviolet region of low Tg, weathering resistance and chemical durability.
Embodiment
< the 1st aspect > of the present invention
The feature of the opticglass of the 1st aspect of the present invention is, in mol%, containing the SnO of 43.5 ~ the 80% and P of 0.1 ~ 29.9%
2o
5+ B
2o
3+ SiO
2and in fact not containing lead composition and arsenic composition.Below, illustrate each component content is carried out specific reason as described above.In addition, when not illustrating, in the explanation about following component content, " % " means " % by mole ".
SnO is for reaching high refractive index and the optical characteristics of high dispersive, the essential component that makes chemical durability improve, also has and makes partial dispersion than the effect declined.The content of SnO is 43.5 ~ 80%, is preferably 43.5 ~ 70%, is more preferably 45 ~ 69%, is more preferably 50 ~ 68%, is particularly preferably 55 ~ 67%, most preferably is 60 ~ 66%.When the content of SnO is very few, has and be difficult to reach high refractive index characteristic, in addition, the tendency that weathering resistance and chemical durability reduce.On the other hand, when the content of SnO is too much, there is the tendency being difficult to vitrifying or devitrification resistance reduction.
P
2o
5, B
2o
3and SiO
2it is the constituent of glass skeleton.In addition, these compositions have the effect improving transmissivity, and the effect particularly suppressing the transmissivity near ultraviolet region to decline is high.Special in the glass of high refractive index, the effect that the transmissivity easily obtaining being produced by these compositions improves.In addition, also there is the effect suppressing devitrification.P
2o
5, B
2o
3and SiO
2content, count 0.1 ~ 29.9% with total amount, be preferably 10 ~ 29.5%, be more preferably 12.5 ~ 29%, be more preferably 15 ~ 28.5%, be particularly preferably 20 ~ 27%.When the content of these compositions is too small, be difficult to obtain above-mentioned effect, on the other hand, when the content of these compositions is too much, the content of SnO tails off relatively, and specific refractory power easily declines.
In addition, P
2o
5, B
2o
3and SiO
2the preferable range of each component content as follows.
P
2o
5content be preferably 0 ~ 29.5%, be more preferably 0.1 ~ 29%, be more preferably 3 ~ 27.5%, be particularly preferably 5 ~ 26%, most preferably be 10 ~ 25%.P
2o
5content too much time, specific refractory power easily reduces.In addition, weathering resistance and chemical durability easily reduce.In addition, by adding P energetically
2o
5, easily obtain the low glass of yield-point and the few glass of devitrification, also easily obtain the little glass of Young's modulus.
Compared to SiO
2and Al
2o
3, B
2o
3suppress the effect of devitrification high.B
2o
3content be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%, be more preferably 1 ~ 10%, be particularly preferably 3 ~ 7.5%, most preferably be 4 ~ 7%.B
2o
3content too much time, specific refractory power easily reduces.In addition, weathering resistance and chemical durability easily reduce.
SiO
2content be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%, be more preferably 1 ~ 10%, be particularly preferably 3 ~ 7.5%, most preferably be 4 ~ 7%.SiO
2content too much time, specific refractory power easily reduces.In addition, residual in glass by the striped and bubble not dissolving generation, there is the possibility that can not meet as the required grade such as optical lens glass.
In in the of the present invention 1st, in order to obtain the glass of weathering resistance and chemical durability excellence, with molar ratio computing, SnO/ (P
2o
5+ B
2o
3+ SiO
2) be preferably more than 1.5, be more preferably more than 1.7, be more preferably more than 1.9, be particularly preferably more than 2, most preferably be more than 2.4.In addition, the upper limit is not particularly limited, but when this ratio is excessive, separates out because SnO easily becomes pit, so be preferably less than 9, be more preferably less than 7, be more preferably less than 5.
In in the of the present invention 1st, in order to be had excellent weather resistance and be there is the glass of high refractive index, B
2o
3+ SiO
2content be preferably 0 ~ 30%, be more preferably 0 ~ 20%, be more preferably 0 ~ 10%.
In addition, by containing P
2o
5as essential component, and containing being selected from B
2o
3and SiO
2at least a kind as essential component, easily obtain the glass of devitrification resistance excellence.Now, even if in a large number containing SnO, excellent devitrification resistance and weathering resistance is also easily reached.Therefore, it is possible to realize higher refraction.As now concrete glass compositing range, in mol%, can enumerate and (wherein not comprise 70% containing 70 ~ 80%, preferably 70.1 ~ 79%, more preferably 70.5 ~ 78%, be more preferably 71 ~ 77%) SnO, the P of 0.1 ~ 29.9% (wherein, do not comprise 29.9%, preferably 10 ~ 29.5%, more preferably 15 ~ 29%, be more preferably 20 ~ 28%)
2o
5, and the B of more than 0.1% (preferably more than 0.15%, more preferably more than 0.2%)
2o
3+ SiO
2glass.In addition, in above-mentioned compositing range, B
2o
3+ SiO
2content too much time because be difficult to vitrifying or be difficult to obtain desired high refractive index characteristic, thus be preferably less than 0.9%, be more preferably less than 0.8%.
The opticglass of the 1st aspect of the present invention, except mentioned component, can also containing following composition.
The alkaline earth metal oxide (RO) of CaO, SrO and BaO and so on, MgO and ZnO are the compositions played a role as melting agent.In addition, have and weathering resistance is improved, suppress glass ingredient to stripping in the various clean solution such as grinding washing water or the rotten effect suppressing the glass surface under high temperature and humidity state.But, when the content of these compositions is too much, there is liquidus temperature to rise (liquid phase viscosity decline), in melting or molding procedure, the tendency that devitrification thing is easily separated out.Its result, has the tendency that batch production becomes difficulty.In addition, these compositions have and do not make specific refractory power and the very large feature of Abbe number variation.In view of more than, the content of CaO, SrO, BaO, MgO and ZnO is to add up to gauge to be preferably 0 ~ 25%, be more preferably 0 ~ 20%, be more preferably 0 ~ 10%, be particularly preferably 0.1 ~ 10%.
In addition, the preferred content of each composition is as follows.
CaO is to the effective composition of raising weathering resistance, and the effect particularly making water tolerance and alkali resistance improve is high.But, when its content is too much, become easily painted.Therefore, the content of CaO is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
SrO is the composition improving specific refractory power.In addition, compared to CaO, the effect that the weathering resistance of water tolerance and alkali resistance etc. is improved is high.Therefore, by energetically containing SrO, the glass had excellent weather resistance can easily be obtained.But, when its content is too much, become easily painted.Therefore, the content of SrO is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
With regard to BaO, compared to CaO, the rising of liquidus temperature is little, and in addition, the effect that water tolerance and alkali resistance are improved is high.But, when its content is too much, become easily painted.Therefore, the content of BaO is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
MgO is the composition improving specific refractory power.In addition, compared to CaO, the effect that the weathering resistance of water tolerance and alkali resistance etc. is improved is high.Therefore, by energetically containing MgO, the glass had excellent weather resistance can easily be obtained.But, when its content is too much, become easily painted.Therefore, the content of MgO is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
ZnO is the composition making specific refractory power decline hardly, can make viscosity degradation.Therefore, can obtain yield-point is reduced, be difficult to the glass fused with mould.In addition, also there is the effect that weathering resistance is improved.In addition, compared to CaO, SrO, BaO and MgO, tendency towards devitrification is not strong, even if therefore contain more, can obtain the glass of homogeneous yet.In addition, ZnO is also the composition being difficult to make glass coloring.The content of ZnO is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.When the content of ZnO is too much, there is tendency that weathering resistance reduces on the contrary.In addition, be difficult to obtain high refractive index and the optical characteristics of high dispersive.
In in the of the present invention 1st, in order to be had excellent weather resistance and be there is the glass of high refractive index, B
2o
3the content of+ZnO is preferably 0 ~ 20%, is more preferably 0 ~ 10%, is more preferably 0.1 ~ 5%.
Li
2the O composition that to be that the effect making softening temperature decline in alkalimetal oxide is maximum, liquidus temperature rises few.In addition, there is the effect making partial dispersion than decline.Furthermore, by with B
2o
3, SiO
2or Al
2o
3displacement, can make specific refractory power improve.But, because Li
2point phasic property of O is strong, so when its content is too much, has the tendency that liquidus temperature rises, devitrification thing becomes easy precipitation, workability reduces.In addition, Li
2o easily makes chemical durability decline, also easily make transmissivity decline.Therefore, Li
2the content of O is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
Na
2o and Li
2o has the effect that softening temperature is declined equally.In addition, by with B
2o
3, SiO
2or Al
2o
3displacement, can make specific refractory power improve.In addition, there is the effect making partial dispersion than decline.But, when its content is too much, have specific refractory power significantly to decline or encourage striped generate tendency.In addition, liquidus temperature rises, and in glass, devitrification thing is easily separated out.Therefore, Na
2the content of O is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
K
2o also and Li
2o has the effect that softening temperature is declined equally.In addition, by with B
2o
3, SiO
2or Al
2o
3displacement, can make specific refractory power improve.In addition, also there is the effect making partial dispersion than decline.But, when its content is too much, have specific refractory power significantly to decline or weathering resistance reduce tendency.In addition, liquidus temperature rises, and in glass, devitrification thing is easily separated out.Therefore, K
2the content of O is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.
In addition, Li
2o, Na
2o and K
2the total amount of O is preferably 0 ~ 25%, is more preferably 0 ~ 20%, is more preferably 0.1 ~ 10%.When the total amount of these compositions is too much, have become easy devitrification, tendency that chemical durability also reduces.In addition, be difficult to obtain desired optical characteristics.Also has loss of transmission tendency.
Al
2o
3be can with SiO
2, B
2o
3form the composition of glass skeleton together.In addition, there is the effect that weathering resistance is improved, particularly suppress the P in glass
2o
5, B
2o
3or the composition such as alkalimetal oxide is large to the effect of selectivity stripping in water.Also there is effect in addition that improve Young's modulus, thermal expansivity is declined.Al
2o
3content be preferably 0 ~ 10%, be more preferably 0.1 ~ 5%.Al
2o
3content too much time, become easy devitrification.In addition, melt temperature uprises, easily residual by the striped and the bubble that do not dissolve generation in glass.Its result, has the possibility that can not meet as the required grade such as optical lens glass.In addition, the tendency having transmissivity to decline.
In in the of the present invention 1st, in order to be had excellent weather resistance and be there is the glass of high refractive index, SiO
2+ Al
2o
3content be preferably 0 ~ 20%, be more preferably 0 ~ 10%, be more preferably 0.1 ~ 5%.
ZrO
2as intermidate oxide, form glass skeleton, there is the effect that weathering resistance is improved.Particularly suppress the P in glass
2o
5, B
2o
3or the composition such as alkalimetal oxide is large to the effect of selectivity stripping in water.ZrO
2content be preferably 0 ~ 10%, be more preferably 0.1 ~ 5%.ZrO
2content too much time, become easy devitrification.In addition, melt temperature uprises, easily residual by the striped and the bubble that do not dissolve generation in glass.Its result, has the possibility that can not meet as the required grade such as optical lens glass.In addition, the tendency having transmissivity to decline.
In addition, in order to obtain the glass of weathering resistance and chemical durability excellence, Al
2o
3+ ZrO
2content be preferably 0 ~ 10%, be more preferably 0.1 ~ 5%.
La
2o
3and Gd
2o
3it is the composition making transmissivity decline, specific refractory power is improved hardly.But, when its content is too much, while devitrification resistance declines, be difficult to the glass obtaining high dispersive.Therefore, the content of these compositions is preferably 0 ~ 25% respectively, is more preferably 0.1 ~ 20%, is more preferably 1 ~ 10%.
Ta
2o
5, WO
3and Nb
2o
5there is the effect making transmissivity decline hardly, improve specific refractory power and dispersion.But when its content is too much, devitrification resistance easily declines.Therefore, the content of these compositions is preferably 0 ~ 25% respectively, is more preferably 0.1 ~ 20%, is more preferably 1 ~ 10%.
TiO
2it is the composition with the effect improving specific refractory power and dispersion.In addition, compared to Nb
2o
5and WO
3, be to the effective composition of raising devitrification resistance.But, when its content is too much, have the tendency that transmissivity declines.Particularly as impurity, Fe composition in a large number containing sometimes (such as more than 20ppm), has the significantly reduced tendency of transmissivity in glass.In addition, devitrification resistance easily declines.Therefore, TiO
2content be preferably 0 ~ 25%, be more preferably 0.1 ~ 20%, be more preferably 1 ~ 10%.
Y
2o
3, Yb
2o
3, GeO
2and Bi
2o
3, with Ta
2o
5make transmissivity decline hardly, improve the effect of specific refractory power and dispersion Deng having equally.But when its content is too much, devitrification resistance easily declines.Therefore, the content of these compositions is preferably 0 ~ 25% respectively, is more preferably 0.1 ~ 20%, is more preferably 1 ~ 10%.
TeO
2there is the effect making transmissivity decline hardly, improve specific refractory power and dispersion.In addition, there is the effect making partial dispersion than decline.But when its content is too much, devitrification resistance easily declines.Therefore, TeO
2content be preferably 0 ~ 25%, be more preferably 0.1 ~ 20%, be more preferably 1 ~ 10%.
In addition, there is desired specific refractory power and the glass of Abbe number, La to obtain
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2+ Bi
2o
3+ TeO
2content be preferably more than 0.1%, be more preferably more than 1%.But, when the content of these compositions is too much, because devitrification resistance easily declines, so be preferably less than 25%, be more preferably less than 20%, be more preferably less than 10%.
Fluorine composition is the composition that chemical durability and devitrification resistance are improved.But when its content is too much, specific refractory power easily reduces.The content of fluorine composition (is scaled F
2) be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%, be more preferably 1 ~ 10%.In addition, as fluorine raw material, SnF can be used
2, ZnF
2, AlF
3, MgF
3, SrF
3or CaF
3deng.
In order to obtain there is desired specific refractory power and the glass of Abbe number, SnO+SnF
2content be preferably more than 45%, be more preferably more than 55%.But, when its content is too much, because devitrification resistance easily declines, so SnO+SnF
2content be preferably less than 80%, be more preferably less than 70%, be more preferably less than 69%, be particularly preferably less than 67.5%.
Fe
2o
3, NiO and CoO be the composition that transmissivity is declined.Thus, the content of these compositions is preferably respectively less than 0.1%.
In addition, because the rare earth composition of Ce, Pr, Nd, Eu, Tb and Er etc. also has the danger making transmissivity decline, so the content of these compositions, to be scaled oxide basis, be preferably respectively less than 0.1%.
In addition, In, Ga and Ge have the danger that transmissivity is declined, in addition, because high price, so preferably its content is few.Specifically, the content of these compositions, to be scaled oxide basis, to be preferably respectively less than 0.1%, more preferably not contain.
From reason environmentally, the opticglass of the 1st aspect of the present invention, in fact not containing (being less than 0.1% respectively particularly) lead composition (such as PbO) and arsenic composition (such as As
2o
3).
The specific refractory power (nd) of the opticglass of the 1st aspect of the present invention is preferably more than 1.6, is more preferably more than 1.65, is more preferably more than 1.7, is particularly preferably more than 1.72.In addition, about the upper limit, be not particularly limited, but, when specific refractory power is too high, because there is the tendency that glass becomes unstable, so be preferably less than 1.95, be more preferably less than 1.9.
The Abbe number (ν d) of the opticglass of the 1st aspect of the present invention is preferably less than 40, is more preferably less than 35, is more preferably less than 30, is particularly preferably less than 28, most preferably is less than 25.When Abbe number is too low, because there is the tendency that glass becomes unstable, so be preferably more than 15, be more preferably more than 16.
Because by meeting these optical characteristics, look dispersion tails off, so be suitable for the optical lens of high function, small-sized opticinstrument.
In addition, the opticglass of the 1st aspect of the present invention, Abbe number (ν d) and partial dispersion ratio (θ g, F) preferably meet the relation of (θ g, F)≤-0.0047 × ν d+0.76.Meet this relation by Abbe number and partial dispersion ratio, easily reach high dispersive and the optical characteristics of lower part dispersion ratio.
The opticglass of the 1st aspect of the present invention, preferred degree of staining λ
70be less than 500nm, be more preferably below 470nm, be more preferably below 460nm.Degree of staining λ
70time excessive, there is the transmissivity of visibility region or near ultraviolet region to be deteriorated, be difficult to use in the tendency of various optical lenses etc.
The opticglass of the 1st aspect of the present invention, yield-point is preferably less than 500 DEG C, is more preferably less than 450 DEG C, is more preferably less than 425 DEG C, is particularly preferably less than 420 DEG C.When yield-point is too high, compression molding at low temperatures becomes difficulty, and the problem of the mold fouling produced by the volatilization of the oxidation of mould, glass ingredient easily occurs, and the problems such as the fusion of glass and mould also easily occur.
The opticglass of the 1st aspect of the present invention, the water tolerance based on JOGIS is preferably more than 2 grades.If water tolerance is this scope, be difficult to after by attrition process clean and hot and humid under use and produce surface deterioration.
The opticglass of the 1st aspect of the present invention, preferably 30 ~ 200 DEG C time thermal expansivity be 100 × 10
-7~ 200 × 10
-7/ DEG C, be more preferably 120 × 10
-7~ 180 × 10
-7/ DEG C.When thermal expansivity is too small, when compression molding, glass easily declines from the release property of compression molding die.On the other hand, when thermal expansivity is excessive, when compression molding, glass is easily broken.
The opticglass of the 1st aspect of the present invention, Young's modulus is preferably 15 ~ 50GPa, is more preferably 20 ~ 40GPa.When Young's modulus is too low, physical strength declines, and becomes easy fragmentation when processing.On the other hand, when Young's modulus is too high, when compression molding, glass easily declines from the release property of compression molding die.
Then, the method that the opticglass manufacturing the 1st aspect of the present invention is described and the opticglass using the 1st aspect of the present invention manufacture the method for the optical element such as light pick up tube lens and photography lens.
First, after coordinating raw material in the mode becoming desired composition, in melting furnace, melting is carried out.Here, after melting making glass cullet, use these glass cullet to carry out second melting, the adjustment of specific refractory power and homogenizing of composition can be realized thus.Homogenized by composition, the glass that transmissivity is high can be obtained.In addition, during second melting, by using the high glass cullet of specific refractory power and the low glass cullet of specific refractory power, the precise hard_drawn tuhes of specific refractory power can be carried out.Melting atmosphere is torpescence atmosphere or reducing atmosphere particularly preferably.Such as, by melting in the torpescence such as nitrogen and argon gas atmosphere, the glass of homogeneous easily can be obtained.As glass melting container, the metal, refractory body, silica glass, vitreous carbon etc. of platinum and gold etc. can be used.Particularly gold plate, because be difficult to cause and the alloy reaction of SnO and preferably.In addition, as metal container, preferably use the strengthening material being dispersed with the oxide compounds such as ZrO.
Then, to drip melten glass from spray nozzle front end, edge forming cooling (drop is shaping), obtains the modular glass be made up of the opticglass of the 1st aspect of the present invention thus.Or melten glass quenching is cast, glass block of producing once, carry out grinding, grinding, clean, obtain modular glass.
As the material for the shaping nozzle of drop, the material same with glass melting container can be used.In addition, during the wettability height of the glass of relative nozzle, easily there is shaping striped.With regard to gold nozzle, because the wettability of glass is low, the generation of shaping striped can be suppressed, so preferably.
Then, drop into modular glass implementing in precision machined mould, be heated to soft state extrusion forming, make the transferring surface shape of mould (compression molding) on modular glass.In order to suppress the oxidation of mould, the torpescence atmosphere such as atmosphere preferred nitrogen atmosphere during extrusion forming.Operate in this wise, the optical element of light pick up tube lens and photography lens etc. can be obtained.
< the 2nd aspect > of the present invention
The feature of the opticglass of the 2nd aspect of the present invention is, in mol%, containing the SnO of 23.5 ~ 85%, the P of 0.1 ~ 49.9%
2o
5, 0 ~ 2% ZrO
2, 0.1 ~ 20% La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2with 0 ~ 1% MgO+CaO+SrO+BaO, and in fact not containing lead composition and arsenic composition.Below, illustrate each component content specific reason as described above.In addition, when not illustrating, in the explanation about following component content, " % " means " % by mole ".
SnO is for reaching high refractive index and the optical characteristics of high dispersive, the essential component that makes chemical durability improve, also has and makes partial dispersion than the effect declined.The content of SnO is 23.5 ~ 85%, is preferably 27.5 ~ 82.5%, is more preferably 30 ~ 80%, is more preferably 32.5 ~ 77.5%, is particularly preferably 35 ~ 75%.When the content of SnO is very few, be difficult to reach high refractive index characteristic, in addition, also there is the tendency of weathering resistance and chemical durability reduction.On the other hand, when the content of SnO is too much, be difficult to vitrifying or devitrification resistance easily reduces.In addition, in the of the present invention 2nd, SnO component content refers to Sn composition (metal Sn, SnO beyond SnO
2deng) be also scaled the content of SnO joint account.
P
2o
5it is the constituent of glass skeleton.In addition, there is the effect of raising transmittance (transmittance particularly near ultraviolet region).Special in the glass of high refractive index, easily obtain by P
2o
5the effect that the transmittance produced improves.In addition, also there is the effect suppressing devitrification.P
2o
5content be 0.1 ~ 49.9%, be preferably 1 ~ 45%, be more preferably 5 ~ 40%, be more preferably 7.5 ~ 35%, be particularly preferably 10 ~ 30%.P
2o
5content very few time, be difficult to obtain above-mentioned effect.On the other hand, P
2o
5content too much time, the content of SnO tails off relatively, and specific refractory power just easily reduces.In addition, weathering resistance easily declines.
ZrO
2it is the composition that weathering resistance is improved.But when its content is too much, devitrification resistance declines, or melt temperature rises, and transmittance easily reduces.Therefore, ZrO
2content be 0 ~ 2%, be preferably 0 ~ 1.5%, be more preferably 0.1 ~ 1%, be more preferably 0.2 ~ 0.5%.
La
2o
3, Gd
2o
3, Ta
2o
5, WO
3, Nb
2o
5, TiO
2, Y
2o
3, Yb
2o
3and GeO
2for reaching high refractive index and the composition of the optical characteristics of high dispersive.In addition, also there is the effect that weathering resistance is improved.La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2content be 0.1 ~ 20%, be preferably 0.3 ~ 15%, be more preferably 0.5 ~ 10%, be more preferably 1 ~ 7.5%.When the content of these compositions is very few, be difficult to reach above-mentioned effect, on the other hand, time too much, easily produce the unfavorable conditions such as devitrification resistance decline, melt temperature rising or transmittance reduction.
In addition, the effect of above-mentioned each composition and preferred content as follows.
La
2o
3and Gd
2o
3it is the composition making transmittance decline, specific refractory power is improved hardly.But, when its content is too much, while devitrification resistance declines, be difficult to the glass obtaining high dispersive.Therefore, the content of these compositions is preferably 0 ~ 20% respectively, is more preferably 0.1 ~ 15%, is more preferably 1 ~ 10%.
Ta
2o
5, WO
3and Nb
2o
5it is the composition making transmittance decline hardly, improve specific refractory power and dispersion.But when its content is too much, devitrification resistance easily declines.Therefore, the content of these compositions is preferably 0 ~ 15% respectively, is more preferably 0.1 ~ 10%, is more preferably 1 ~ 5%.
TiO
2it is the composition with the effect improving specific refractory power and dispersion.In addition, there is the effect that devitrification resistance is improved.But, when its content is too much, have the tendency that transmittance declines.Particularly as impurity, Fe composition in a large number containing sometimes (such as more than 20ppm), has the significantly reduced tendency of transmittance in glass.In addition, devitrification resistance easily declines.Therefore, TiO
2content be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%, be more preferably 1 ~ 10%.
Y
2o
3, Yb
2o
3and GeO
2there is the effect making transmittance decline hardly, improve specific refractory power and dispersion.But when its content is too much, devitrification resistance easily declines.Therefore, the content of these compositions is preferably 0 ~ 20% respectively, is more preferably 0.1 ~ 20%, is more preferably 1 ~ 10%.
MgO, CaO, SrO and BaO (alkaline earth metal oxide) are the compositions played a role as melting agent.In addition, have and weathering resistance is improved, suppress glass ingredient to the stripping in the various clean solution such as grinding washing water or the rotten effect suppressing the glass surface under high temperature and humidity state.But, when the content of these compositions is too much, there is liquidus temperature to rise (liquid phase viscosity decline), in melting or molding procedure, the tendency that devitrification thing is easily separated out.Its result, batch production becomes difficulty.In addition, these compositions have and do not make specific refractory power and the very large feature of Abbe number variation.In view of more than, the content of MgO+CaO+SrO+BaO is 0 ~ 1%, is preferably 0 ~ 0.9%, is more preferably 0.1 ~ 0.7%, is more preferably 0.2 ~ 0.5%.
In in the of the present invention 2nd, in order to obtain devitrification resistance excellence, glass that physical strength is high, preferably adjust SnO+P
2o
5content.Specifically, SnO+P
2o
5content be preferably more than 30%, be more preferably more than 40%, be more preferably more than 50%.In addition, the upper limit is not particularly limited, and considers the content of other compositions, is preferably less than 99.9%, is more preferably less than 99.5%, is more preferably less than 99%.
In in the of the present invention 2nd, in order to obtain high refractive index, have excellent weather resistance, glass that physical strength is high, preferably adjustment (SnO+La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2)/P
2o
5ratio.Specifically, aforementioned proportion is preferably more than 1.2, is more preferably more than 1.5, is more preferably more than 1.75.The upper limit is not particularly limited, but time excessive, is difficult to vitrifying, is therefore preferably less than 300, is more preferably less than 100, is more preferably less than 10, is particularly preferably less than 5.
In in the of the present invention 2nd, in order to obtain high refractive index, have excellent weather resistance, glass that physical strength is high, preferably adjustment (SnO+La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2+ MgO+CaO+SrO+BaO)/P
2o
5ratio.Specifically, aforementioned proportion is preferably more than 1.2, is more preferably more than 1.5, is more preferably more than 1.75.For less than 1.2 time, be difficult to obtain the high glass of high refractive index, the glass had excellent weather resistance and mechanical characteristics.The upper limit is not particularly limited, but time excessive, is difficult to vitrifying, is therefore preferably less than 300, is more preferably less than 100, is more preferably less than 10, is particularly preferably less than 5.
The opticglass of the 2nd aspect of the present invention, except mentioned component, can also containing following composition.
ZnO is also the composition that as melting agent plays a role same with alkaline-earth oxide.In addition, have and weathering resistance is improved, suppress glass ingredient to the stripping in the various clean solution such as grinding washing water or the rotten effect suppressing the glass surface under high temperature and humidity state.In addition, ZnO also has the effect making vitrifying stable.In view of more than, the content of ZnO is preferably 0 ~ 10%, is more preferably 0.1 ~ 5%, is more preferably 0.2 ~ 1%.When the content of ZnO is too much, the transmissivity of visibility region or near ultraviolet region easily declines, or easy devitrification.In addition, there is partial dispersion than the tendency risen.
Li
2the O composition that to be that the effect making softening temperature decline in alkalimetal oxide is maximum, liquidus temperature rises few.In addition, there is the effect making partial dispersion than decline.But, because Li
2o improves point phasic property of glass, so when its content is too much, has the worry that liquidus temperature rises, devitrification thing is easily separated out, workability is reduced.In addition, Li
2o easily makes chemical durability decline, also easily make transmittance decline.Therefore, Li
2the content of O is preferably 0 ~ 10%, is more preferably 0 ~ 8%, is more preferably 0.1 ~ 5%.
Na
2o and Li
2o has the effect that softening temperature is declined equally.In addition, there is the effect making partial dispersion than decline.But, when its content is too much, have specific refractory power significantly to decline or encourage striped generate tendency.In addition, have liquidus temperature to rise, devitrification thing is easily separated out, the worry that workability reduces.Therefore, Na
2the content of O is preferably 0 ~ 10%, is more preferably 0 ~ 8%, is more preferably 0.1 ~ 5%.
K
2o also with Li
2o has the effect that softening temperature is declined equally.In addition, also there is the effect making partial dispersion than decline.But, when its content is too much, have specific refractory power significantly to decline or weathering resistance decline tendency.In addition, liquidus temperature rises, and devitrification thing is easily separated out.Therefore, K
2the content of O is preferably 0 ~ 10%, is more preferably 0 ~ 8%, is more preferably 0.1 ~ 5%.
In addition, Li
2o+Na
2o+K
2the content of O is preferably 0 ~ 10%, is more preferably 0 ~ 8%.Li
2o+Na
2o+K
2when the content of O is too much, have easy devitrification, tendency that chemical durability also reduces.In addition, be difficult to obtain desired optical characteristics.Also has the tendency that transmittance reduces.
B
2o
3and SiO
2it is the constituent of glass skeleton.In addition, these compositions have the effect improving transmittance, and the effect particularly suppressing the transmittance near ultraviolet region to decline is high.Special in the glass of high refractive index, the effect that the transmittance easily obtaining being produced by these compositions improves.In addition, also there is the effect that devitrification resistance and chemical durability are improved.
B
2o
3content be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%.B
2o
3content too much time, specific refractory power easily reduces.In addition, weathering resistance and chemical durability easily decline.
SiO
2content be preferably 0 ~ 20%, be more preferably 0.1 ~ 15%.SiO
2content too much time, specific refractory power easily reduces.In addition, remained in glass by the striped and bubble not dissolving generation, have the possibility that can not meet as the required grade such as optical lens glass.
In in the of the present invention 2nd, in order to obtain the glass with high refractive index characteristic, preferably by B
2o
3+ ZnO is set to less than 20%, is more preferably set to less than 10%.In addition, in order to obtain devitrification resistance, weathering resistance and chemical durability excellence and the glass of the transmittance excellence of visibility region and near ultraviolet region, preferably by B
2o
3+ ZnO is set to more than 0.1%, is more preferably set to more than 1%.
Al
2o
3be can and SiO
2or B
2o
3form the composition of glass skeleton together.In addition, there is the effect that weathering resistance is improved, particularly suppress the P in glass
2o
5large to the effect of selectivity stripping in water with compositions such as alkalimetal oxides.Al
2o
3content be preferably 0 ~ 10%, be more preferably 0.1 ~ 5%.Al
2o
3content excessive time, easy devitrification.In addition, melt temperature uprises, easily residual by the striped and the bubble that do not dissolve generation in glass.Its result, has the possibility that can not meet as the required grade such as optical lens glass.In addition, the tendency having transmittance to decline.
TeO
2there is the effect making transmittance decline hardly, improve specific refractory power and dispersion.In addition, there is the effect making partial dispersion than decline.But when its content is too much, devitrification resistance easily declines.Therefore, TeO
2content be preferably 0 ~ 15%, be more preferably 0.1 ~ 10%, be more preferably 1 ~ 5%.
As limpid dose, Cl, S or Br can be contained.The content of Cl+S+Br is preferably 0.01 ~ 1%, is more preferably 0.05 ~ 0.5%.When the content of Cl+S+Br is very few, have as the insufficient tendency of the effect of limpid dose.On the other hand, when the content of Cl+S+Br is too much, volatilize when melting, easily corrode melt container etc.
Fe
2o
3, NiO and CoO be the composition that transmittance is declined.Thus, the content of these compositions is preferably less than 0.1% respectively.
In addition, because the rare earth composition of Ce, Pr, Nd, Eu, Tb and Er etc. also has the danger making transmittance decline, so the content of these compositions is to be scaled oxide basis, preferably 0.1% is less than respectively.
In addition, In and Ga has the danger that transmittance is declined, in addition, because be high price, so to be scaled oxide basis, be preferably less than 0.1% respectively.
In addition, from reason environmentally, the opticglass of the 2nd aspect of the present invention, in fact not containing (being specifically less than 0.1% respectively) lead composition (such as PbO) and arsenic composition (such as As
2o
3).
The specific refractory power (nd) of the opticglass of the 2nd aspect of the present invention is preferably more than 1.6, is more preferably more than 1.65, is more preferably more than 1.7, is particularly preferably more than 1.72.In addition, about the upper limit, be not particularly limited, but, when specific refractory power is too high, because there is the tendency that glass becomes unstable, so be preferably less than 1.95, be more preferably less than 1.9.
The Abbe number (ν d) of the opticglass of the 2nd aspect of the present invention is preferably less than 40, is more preferably less than 35, is more preferably less than 30, is particularly preferably less than 28, most preferably is less than 25.In addition, about lower limit, be not particularly limited, but, when Abbe number is too low, because there is the tendency that glass becomes unstable, so be preferably more than 15, be more preferably more than 16.
In addition, the opticglass of the 2nd aspect of the present invention, Abbe number (ν d) and partial dispersion ratio (θ g, F) preferably meet the relation of (θ g, F)≤-0.0047 × (ν d)+0.76.Meet this relation by Abbe number and partial dispersion ratio, easily reach high dispersive and the optical characteristics of lower part dispersion ratio.
The opticglass of the 2nd aspect of the present invention, preferred degree of staining λ
70be less than 500nm, be more preferably below 470nm, be more preferably below 460nm.Degree of staining λ
70time excessive, there is the printing opacity rate variance of visibility region or near ultraviolet region, be difficult in middle tendencies used such as various optical lenses.
The opticglass of the 2nd aspect of the present invention, yield-point is preferably less than 500 DEG C, is more preferably less than 450 DEG C, is more preferably less than 425 DEG C, is particularly preferably less than 420 DEG C.When yield-point is too high, the compression molding under low temperature becomes difficulty, the problem be oxidized, glass ingredient volatilizees the mold fouling produced easily occurs, the problem of the fusion of glass and mould etc. also easily occurs by mould.
The opticglass of the 2nd aspect of the present invention, the water tolerance based on JOGIS is preferably more than 3 grades, acid resistance is preferably more than 2 grades.Water tolerance and acid resistance if this scope, with regard to be difficult to after by attrition process clean and hot and humid under use and produce surface degradation.
Then, the method that the opticglass manufacturing the 2nd aspect of the present invention is described and the opticglass using the 2nd aspect of the present invention manufacture the method for the optical element such as light pick up tube lens and photography lens.
First, after coordinating raw material in the mode becoming desired composition, in melting furnace, melting is carried out.Particularly, as raw material, use stannous pyrophosphate (Sn
2p
2o
7), the glass obtained thus easily becomes homogeneous.In addition, after melting making glass cullet, use these glass cullet to carry out second melting, the adjustment of specific refractory power and homogenizing of composition can be realized thus.Homogenized by composition, the glass that transmittance is high can be obtained.In addition, during second melting, use the high glass cullet of specific refractory power and the low glass cullet of specific refractory power, the precise hard_drawn tuhes of specific refractory power can be carried out.
In addition, metal Sn and the metal A l of reductive agent is become, with WO
3, Nb
2o
5, TiO
2deng high refractive index composition and the used time, have the tendency that the transmissivity of visibility region or near ultraviolet region declines.Thus, preferred not containing metal Sn and metal A l in the feed.
The preferred torpescence atmosphere of melting atmosphere or reducing atmosphere.Such as, by melting in the torpescence such as nitrogen and argon gas atmosphere, the glass of homogeneous easily can be obtained.As glass melting container, the metal, refractory body, silica glass, vitreous carbon etc. of platinum and gold etc. can be used.In metal container, particularly gold plate, because be difficult to cause and the alloy reaction of SnO and preferably.In addition, as metal container, preferably make ZrO
2deng oxide compound dispersion strengthening material.
Then, to drip melten glass from spray nozzle front end, edge forming cooling (drop is shaping), obtains the modular glass be made up of the opticglass of the 2nd aspect of the present invention thus.Or melten glass quenching is cast, glass block of producing once, carry out grinding, grinding, clean, obtain modular glass.Nozzle material time shaping as drop, preferably uses gold.Use the metal nozzle glass to a large amount of the 2nd aspect of the present invention containing SnO carry out drop shaping time, glass is easily attached to the exit perimeter of nozzle, results from the glass of attachment, easily shaping striped occurs.Because gold is low with the wettability of the glass of the 2nd aspect of the present invention, so be difficult to unfavorable condition as described above occurs.
Then, drop into modular glass being applied with in precision machined mould, be heated to soft state extrusion forming, make the transferring surface shape of mould (compression molding) on modular glass.In order to suppress the oxidation of mould, the torpescence atmosphere such as atmosphere preferred nitrogen atmosphere during extrusion forming.Operate in this wise, the optical element of light pick up tube lens and photography lens etc. can be obtained.
Embodiment
Below, explain the present invention based on embodiment, but the present invention is not limited by these embodiments.
Table 1 ~ 3 represent embodiment (No.1 ~ 17,21 ~ 23) and the comparative example (No.18 ~ 20) of the 1st aspect of the present invention.
[table 1]
[table 2]
[table 3]
Each sample is prepared according to following operation.
First, coordinate raw material in the mode becoming each composition shown in table, in nitrogen atmosphere, use gold plate with 700 ~ 1000 DEG C of meltings 1 hour.The metal sheet of preheating flows out melten glass, after annealing, makes the sample being suitable for each mensuration.
About the sample obtained, measure specific refractory power (nd), Abbe number (ν d), partial dispersion ratio (θ g, F), thermal expansivity, yield-point (Tf), Young's modulus, degree of staining λ
70.In addition, vitrifying, water tolerance, acid resistance and weathering resistance is evaluated.Result is represented in table 1 ~ 3.
Specific refractory power represents with the measured value of the d line (587.6nm) of relative helium lamp.
Abbe number uses the value of the specific refractory power of the specific refractory power of above-mentioned d line, the F line (486.1nm) of hydrogen lamp and C line (656.3nm), is calculated by the formula of Abbe number (ν d)=[(nd-1)/(nF-nC)].
With regard to partial dispersion ratio, measure the refractive index n F of refractive index n C, F line and the refractive index n g of g line (wavelength 435.835nm) of the C line of hydrogen lamp, calculated by the formula of partial dispersion ratio (θ g, F)=(ng-nF)/(nF-nC).
Yield-point and thermal expansivity use thermal expansion measurement device (dilato meter) to measure.In addition, thermal expansivity adopts the value in 30 ~ 200 DEG C of temperature ranges.
Young's modulus is measured by flexural resonance method in room temperature.
With regard to degree of staining λ
70, about thickness 10mm ± 0.1mm by the sample of optical grinding, use spectrophotometer, with the transmissivity of the measuring space of 0.5nm in 200 ~ 800nm wavelength region may, by the minimal wave length evaluation of expression 70% transmissivity.
With regard to vitrifying, by each sample of observation by light microscope, being "○" by the average evaluation not confirming devitrification on surface or inside, is "×" by the average evaluation confirming devitrification.
Water tolerance and acid resistance measure based on the powder method of JOGIS defined.
With regard to weathering resistance, use high temperature and humidity test machine, after making each sample expose 500 hours under the condition of temperature 85 DEG C with humidity 85%, vicissitudinous average evaluation outward appearance is not had to be "○", the average evaluation changed a little as seen by gloss is " △ ", and the average evaluation significantly losing gloss or generate crack is "×".
Embodiment No.1 ~ 17,21 ~ 23 sample, there is desired optical characteristics, yield-point, degree of staining λ
70, and water tolerance, acid resistance and weathering resistance are also excellent.On the other hand, the sample of comparative example No.18, non-vitrifying, the sample of No.19, specific refractory power is low is 1.5640, and in addition, weathering resistance is poor.The sample of No.20, specific refractory power is low is 1.5826, and in addition, each characteristic of water tolerance, acid resistance and weathering resistance is poor.
Table 4 ~ 6 represent embodiment (No.31 ~ 54) and the comparative example (No.55,56) of the 2nd aspect of the present invention.
[table 4]
[table 5]
[table 6]
Each sample is prepared according to following operation.
First, coordinate raw material in the mode becoming each composition shown in table, in nitrogen atmosphere, use gold plate with 700 ~ 1000 DEG C of meltings 1 hour.The metal sheet of preheating flows out the melten glass obtained, after annealing, makes the sample being suitable for each mensuration.
About the sample obtained, measure specific refractory power (nd), Abbe number (ν d), partial dispersion ratio (θ g, F), yield-point (Tf), degree of staining λ
70.In addition, vitrifying, water tolerance, acid resistance, weathering resistance is evaluated.Result is represented in table 1 ~ 3.
Specific refractory power represents with the measured value of the d line (587.6nm) of relative helium lamp.
Abbe number uses the value of the specific refractory power of the specific refractory power of above-mentioned d line, the F line (486.1nm) of hydrogen lamp and C line (656.3nm), is calculated by the formula of Abbe number (ν d)=(nd-1)/(nF-nC).
With regard to partial dispersion ratio, measure the refractive index n F of refractive index n C, F line and the refractive index n g of g line (wavelength 435.835nm) of the C line of hydrogen lamp, calculated by the formula of partial dispersion ratio (θ g, F)=(ng-nF)/(nF-nC).
Yield-point uses thermal expansion measurement device (dilato meter) to measure.
With regard to degree of staining λ
70, about thickness 10mm ± 0.1mm by the sample of optical grinding, use spectrophotometer, with the transmittance of the measuring space of 0.5nm in 200 ~ 800nm wavelength region may, by the minimal wave length evaluation of expression 70% transmittance.
With regard to vitrifying, observing each sample by opticmicroscope (× 10), will be "○" on surface and the inner average evaluation not confirming devitrification, will be "×" in surface or inside confirmation to the average evaluation of devitrification.
Water tolerance and acid resistance measure based on the powder method of JOGIS defined.
With regard to weathering resistance, use high temperature and humidity test machine, after making each sample expose 500 hours under the condition of temperature 85 DEG C with humidity 85%, vicissitudinous average evaluation outward appearance is not had to be "○", the average evaluation changed a little as seen by gloss is " △ ", and the average evaluation significantly losing gloss or generate crack is "×".
The sample of embodiment No.31 ~ 54, has desired optical characteristics, yield-point, degree of staining λ
70, and water tolerance, acid resistance and weathering resistance are also excellent.On the other hand, the sample of comparative example No.55, specific refractory power is low is 1.5640, and Abbe number is high is 52.5, in addition, water tolerance and weathering resistance poor.The sample of No.56, water tolerance and weathering resistance poor.
Utilizability in generation
Opticglass of the present invention, the compression molding glass material as light pick up tube lens, pick up camera, general camera shooting lens etc. for CD, MD, DVD, other various optical disk systems is good.In addition, also may be used for the glass material of the optical communication use of the forming method manufacture beyond with compression molding etc.In addition, by by opticglass of the present invention and fluorophor powder Composite, also can use as the Wavelength conversion member for making UV-light and visible wavelength change.
Claims (25)
1. an opticglass, is characterized in that:
In mol%, containing the SnO of 43.5 ~ the 80% and P of 0.1 ~ 29.9%
2o
5+ B
2o
3+ SiO
2, and in fact not containing lead composition and arsenic composition.
2. opticglass as claimed in claim 1, is characterized in that:
P
2o
5content be 0.1 ~ 29.5%.
3. opticglass as claimed in claim 1 or 2, is characterized in that:
In mol%, SnO/ (P
2o
5+ B
2o
3+ SiO
2) be more than 1.5.
4. the opticglass according to any one of claims 1 to 3, is characterized in that:
In mol%, the CaO+SrO+BaO+MgO+ZnO of 0 ~ 25% is also contained.
5. the opticglass according to any one of Claims 1 to 4, is characterized in that:
In mol%, the Al of 0 ~ 10% is also contained
2o
3+ ZrO
2.
6. the opticglass according to any one of Claims 1 to 5, is characterized in that:
Yield-point is less than 500 DEG C.
7. the opticglass according to any one of claim 1 ~ 6, is characterized in that:
Water tolerance based on JOGIS is more than 2 grades.
8. the opticglass according to any one of claim 1 ~ 7, is characterized in that:
Specific refractory power is more than 1.6, and Abbe number is less than 40.
9. the opticglass according to any one of claim 1 ~ 8, is characterized in that:
Abbe number (ν d) and partial dispersion ratio (θ g, F) meet the relation of (θ g, F)≤-0.0047 × (ν d)+0.76.
10. the opticglass according to any one of claim 1 ~ 9, is characterized in that:
Degree of staining λ
70be less than 500nm.
11. opticglass according to any one of claim 1 ~ 10, is characterized in that:
It is for optical lens.
12. opticglass according to any one of claim 1 ~ 11, is characterized in that:
It is for compression molding.
13. 1 kinds of optical elements, is characterized in that:
Employ the opticglass according to any one of claim 1 ~ 12.
14. 1 kinds of opticglass, is characterized in that:
In mol%, containing the SnO of 23.5 ~ 85%, the P of 0.1 ~ 49.9%
2o
5, 0 ~ 2% ZrO
2, 0.1 ~ 20% La
2o
3+ Gd
2o
3+ Ta
2o
5+ WO
3+ Nb
2o
5+ TiO
2+ Y
2o
3+ Yb
2o
3+ GeO
2with 0 ~ 1% MgO+CaO+SrO+BaO, and in fact not containing lead composition and arsenic composition.
15. opticglass as claimed in claim 14, is characterized in that:
In mol%, containing 0 ~ 10% Li
2o+Na
2o+K
2o.
16. opticglass as described in claims 14 or 15, is characterized in that:
In mol%, containing 0 ~ 10% B
2o
3+ ZnO.
17. opticglass according to any one of claim 14 ~ 16, is characterized in that:
In mol%, containing 0.01 ~ 1% Cl+S+Br.
18. opticglass according to any one of claim 14 ~ 17, is characterized in that:
Yield-point is less than 500 DEG C.
19. opticglass according to any one of claim 14 ~ 18, is characterized in that:
Water tolerance based on JOGIS is more than 3 grades.
20. opticglass according to any one of claim 14 ~ 19, is characterized in that:
Specific refractory power is more than 1.6, and Abbe number is less than 40.
21. opticglass according to any one of claim 14 ~ 20, is characterized in that:
Abbe number (ν d) and partial dispersion ratio (θ g, F) meet the relation of (θ g, F)≤-0.0047 × (ν d)+0.76.
22. opticglass according to any one of claim 14 ~ 21, is characterized in that:
Degree of staining λ
70be less than 500nm.
23. opticglass according to any one of claim 14 ~ 22, is characterized in that:
It is for optical lens.
24. opticglass according to any one of claim 14 ~ 23, is characterized in that:
It is for compression molding.
25. 1 kinds of optical elements, is characterized in that:
Employ the opticglass according to any one of claim 14 ~ 24.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013078169 | 2013-04-04 | ||
| JP2013-078169 | 2013-04-04 | ||
| JP2014-024239 | 2014-02-12 | ||
| JP2014024239A JP2015151280A (en) | 2014-02-12 | 2014-02-12 | optical glass |
| JP2014042310A JP6347319B2 (en) | 2013-04-04 | 2014-03-05 | Optical glass |
| JP2014-042310 | 2014-03-05 | ||
| PCT/JP2014/057313 WO2014162869A1 (en) | 2013-04-04 | 2014-03-18 | Optical glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104936916A true CN104936916A (en) | 2015-09-23 |
Family
ID=54123303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480005367.0A Pending CN104936916A (en) | 2013-04-04 | 2014-03-18 | Optical glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104936916A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114728837A (en) * | 2019-11-14 | 2022-07-08 | 日本电气硝子株式会社 | Glass article |
| CN115210191A (en) * | 2020-04-06 | 2022-10-18 | 日本电气硝子株式会社 | Optical glass |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495142A (en) * | 2002-08-23 | 2004-05-12 | Ф�ز������쳧 | Leadless and specially arseniumless optical double-crown glass |
| CN101360688A (en) * | 2006-03-13 | 2009-02-04 | 日本电气硝子株式会社 | Process for melting glass and glass |
| CN101553440A (en) * | 2006-07-26 | 2009-10-07 | 达尔豪西大学 | Glasses having a reduced stress-optic coefficient |
| JP2012193065A (en) * | 2011-03-16 | 2012-10-11 | Nippon Electric Glass Co Ltd | Optical glass |
-
2014
- 2014-03-18 CN CN201480005367.0A patent/CN104936916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495142A (en) * | 2002-08-23 | 2004-05-12 | Ф�ز������쳧 | Leadless and specially arseniumless optical double-crown glass |
| CN101360688A (en) * | 2006-03-13 | 2009-02-04 | 日本电气硝子株式会社 | Process for melting glass and glass |
| CN101553440A (en) * | 2006-07-26 | 2009-10-07 | 达尔豪西大学 | Glasses having a reduced stress-optic coefficient |
| JP2012193065A (en) * | 2011-03-16 | 2012-10-11 | Nippon Electric Glass Co Ltd | Optical glass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114728837A (en) * | 2019-11-14 | 2022-07-08 | 日本电气硝子株式会社 | Glass article |
| CN115210191A (en) * | 2020-04-06 | 2022-10-18 | 日本电气硝子株式会社 | Optical glass |
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| WD01 | Invention patent application deemed withdrawn after publication |
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