CN102992615A - Optical glass for mold press forming - Google Patents

Optical glass for mold press forming Download PDF

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Publication number
CN102992615A
CN102992615A CN2012104495146A CN201210449514A CN102992615A CN 102992615 A CN102992615 A CN 102992615A CN 2012104495146 A CN2012104495146 A CN 2012104495146A CN 201210449514 A CN201210449514 A CN 201210449514A CN 102992615 A CN102992615 A CN 102992615A
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glass
composition
mold press
zno
optical glass
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俣野高宏
佐藤史雄
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Abstract

To provide optical glass for mold press forming which satisfies all of requirements that the glass (1) does not contain a lead components, an arsenic component or an F component which are environmentally undesirable, (2) has a glass transition temperature of not higher than 650[deg.]C, (3) has a high refractive index and low dispersion, and (4) is excellent in resistance against devitrification during molding a preform. The optical glass has a composition containing, in mass%, 3 to 21% of SiO2, 8 to 23% of B2O3, 6 to 40% of ZnO, 2 to 10% of ZrO2, 20 to 46% of La2O3, 0 to 16% of Gd2O3, 7 to 25% of Ta2O5, and 1 to 10% of Nb2O5, and substantially no lead component, arsenic component and F component.

Description

Optical glass for mold press molding
The application is that the application number that proposed on October 30th, 2008 is dividing an application of 200810168378.7 patent application of the same name.
Technical field
The present invention relates to optical glass for mold press molding.High in particular to specific refractory power and Abbe number, the laser disc that is fit to various laser disc system reads the optical glass for mold press molding of the imaging lens of lens (optical pick-up lens), pick up camera, ordinary camera etc.
Background technology
General as follows making of imaging lens that the laser disc of CD, MD, DVD, other various laser disc system reads lens, pick up camera, ordinary camera.
At first, melten glass is dripped from the tip of nozzle, make droplet-like glass (drop moulding), grind and cut, grind, clean, make premolding glass.Perhaps, with the casting of melten glass chilling, temporarily make the glass ingot bar, grind and cut, grind, clean, make premolding glass.Then, the premolding glass heats is softening, adopt through precision machined mould pressurizing moulding, with the die surface shape transferred thereon at making lens on glass.Such forming method is commonly referred to as compression molding method.
When adopting compression molding method, for suppress mould deteriorated in the lens precise compression molding, need to have alap glass transition temperature Tg (below at least 650 ℃), the scheme (for example, with reference to TOHKEMY 2003-267748 communique, TOHKEMY 2003-248897 communique, TOHKEMY 2006-16295 communique) of various glass has been proposed for this reason.
And, if devitrification occurs when making premolding glass, then do not reach the fundamental property as moulded lens, so the glass of making the devitrification resistance excellence is very important.And, along with the consciousness of environmental problem is improved, wish that glass ingredient does not use the opticglass of the objectionable impurities such as plumbous.In addition, in recent years, take Cost reduction as purpose, read aspect the optical lenses such as lens, imaging lens at the laser disc of various laser disc system, research attenuate lens or minimizing lens number for realizing this purpose, need high refractive index and the low glass material that disperses (Abbe number is large).
Summary of the invention
Generally speaking, in order to make the opticglass of high refractive index, the Abbe number of reducing is arranged, namely be tending towards the trend of high dispersive, and high refractive index and the low glass that disperses are difficult to make.For example, specific refractory power more than 1.86 and the opticglass of Abbe number more than 35 be what be difficult to make.And, if known making high refractive index and the low glass that disperses, the trend that then has devitrification resistance to worsen.
For this reason, the object of the present invention is to provide a kind of optical glass for mold press molding that can satisfy following each requirement fully: (1) is not contained in lead composition bad on the environment, arsenic composition and F composition, (2) second-order transition temperature is below 650 ℃, (3) high refractive index and low the dispersion, the devitrification resistance during (4) premolding is good.
The present inventor etc. have carried out various experiments, found that, by containing the SiO of suitable proportion 2, B 2O 3, ZnO, ZrO 2, La 2O 3, Gd 2O 3, Ta 2O 5, Nb 2O 5Each composition can be reached above-mentioned purpose, thereby has proposed the present invention.
That is, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 320～46%, Gd 2O 30～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition.In addition, in the present invention, " not containing in fact lead composition, arsenic composition and F composition " refers to not contain these compositions in the original idea upper glass, do not mean and gets rid of inevitable impurity fully.Objective, mean the content of these compositions that contain as impurity in quality %, respectively below 0.1%.In addition, in the present invention, for the composition that is defined as " 0～", " 0% " namely also can mean situation about not containing fully.
The second, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition.
The 3rd, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 57～18%, Nb 2O 5Below 1～10%(, be called glass and form A).
The 4th, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 10～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 518～25%, Nb 2O 5Below 1～10%(, be called glass and form B).
The 5th, optical glass for mold press molding of the present invention is characterised in that, in quality %, also contains Li 2O 0～5%.
The 6th, optical glass for mold press molding of the present invention is characterised in that, in quality %, Li 2O+ZnO is more than 8%.At this, " Li 2O+ZnO " mean Li 2The total amount of O and ZnO.
The 7th, optical glass for mold press molding of the present invention is characterised in that, in quality %, also contains WO 30～10% and TiO 20～20%.
The 8th, optical glass for mold press molding of the present invention is characterised in that, in quality %, Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5Be below 34%.At this, " Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5" mean Gd 2O 3, Ta 2O 5, WO 3, TiO 2And Nb 2O 5Total amount.
The 9th, optical glass for mold press molding of the present invention is characterised in that, in quality %, SiO 2+ B 2O 3+ ZnO+La 2O 3Be more than 60%.At this, " SiO 2+ B 2O 3+ ZnO+La 2O 3" mean SiO 2, B 2O 3, ZnO and La 2O 3Total amount.
The tenth, optical glass for mold press molding of the present invention is characterised in that, according to quality criteria, and (SiO 2+ B 2O 3+ ZnO+La 2O 3)/(Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5) be more than 2.0.
The 11, optical glass for mold press molding of the present invention is characterised in that, in quality %, ZnO+ZrO 2+ La 2O 3+ Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5Be more than 55%." ZnO+ZrO 2+ La 2O 3+ Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5" mean ZnO, ZrO 2, La 2O 3, Gd 2O 3, Ta 2O 5, WO 3, TiO 2And Nb 2O 5Total amount.
The 12, optical glass for mold press molding of the present invention is characterised in that, in quality %, ZnO+Ta 2O 5+ Nb 2O 5Be more than 30%.At this, " ZnO+Ta 2O 5+ Nb 2O 5" mean ZnO, Ta 2O 5And Nb 2O 5Total amount.
The 13, optical glass for mold press molding of the present invention is characterised in that, according to quality criteria, and (SiO 2+ B 2O 3)/Ta 2O 5Be below 1.0.At this, " SiO 2+ B 2O 3" mean SiO 2And B 2O 3Total amount.
The 14, optical glass for mold press molding of the present invention is characterised in that, according to quality criteria, and (La 2O 3+ Gd 2O 3)/Ta 2O 5Be below 2.5.At this, " La 2O 3+ Gd 2O 3" mean La 2O 3And Gd 2O 3Total amount.
The 15, optical glass for mold press molding of the present invention is characterised in that, according to quality criteria, and Li 2O/Ta 2O 5Be below 0.05.
The 16, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 24～10%, La 2O 320～30%, Gd 2O 34～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition (forming C hereinafter referred to as glass).
The 17, optical glass for mold press molding of the present invention is characterised in that, in quality %, contains WO 30～3%, TiO 20～20%.
The 18, optical glass for mold press molding of the present invention is characterised in that, in quality %, La 2O 3+ Gd 2O 3Be below 45%.
The 19, optical glass for mold press molding of the present invention is characterised in that, according to quality criteria, and (SiO 2+ La 2O 3+ Gd 2O 3)/(ZnO+Li 2O) be below 2.9.
Optical glass for mold press molding of the present invention is because second-order transition temperature is low, and at low temperatures compression molding is so it is deteriorated to suppress mould.And because of the lead composition, arsenic composition and the F composition that do not contain as objectionable constituent, so be preferred glass on the environment.And, can make high refractive index and the low glass that disperses.Can also in the equal situation of specific refractory power and existing glass, make the glass of lower dispersion, perhaps in the equal situation of Abbe number and existing glass, make the more glass of high refractive index.Therefore, can make the lens thin-walled property and/or cut down the lens number, reduce the component cost of optical device.In addition, owing to when premolding, do not produce the devitrification thing that hinders the transparency, so when using as moulded lens, do not have problems.
Embodiment
Optical glass for mold press molding of the present invention is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 320～46%, Gd 2O 30～16%, Ta 2O 57～25%, Nb 2O 51～10%, do not contain in fact lead composition, arsenic composition, F composition.
In mentioned component, ZnO, ZrO 2, La 2O 3, Gd 2O 3, Ta 2O 5, Nb 2O 5Has the effect that improves glass refraction.It is characterized in that, in these compositions, ZnO, ZrO 2, La 2O 3, Gd 2O 3Basically can significantly not reduce Abbe number, especially ZnO, ZrO 2, La 2O 3, reduce hardly Abbe number.
SiO 2And B 2O 3Have the effect, the especially B that improve Abbe number 2O 3The effect that improves Abbe number is large.
In addition, ZnO, Ta 2O 5, Nb 2O 3Reduce with respect to Abbe number, the rate of rise of specific refractory power is large, is be used to reaching high refractive index of the present invention, the most effective composition of low dispersion.
Below, specify the reason of stipulating as mentioned above each component content.Need to prove do not having in the situation of special declaration, following " % " means " quality % ".
SiO 2Be the composition that consists of the glass skeleton, have the effect that suppresses devitrification and improve weathering resistance.Also has the effect that improves Abbe number.SiO 2Content be 3～21%, be preferably 3～20%, more preferably 3.5～16%, more preferably 3.5～10%.In addition, work as SiO 2When increasing, the trend that specific refractory power reduces, softening temperature increases is arranged.On the other hand, work as SiO 2During minimizing, there is become unstable, devitrification resistance of glass to worsen, produce the trend that the weathering resistancies such as phase-splitting and acid resistance and water tolerance worsen.In addition, particularly at La 2O 3In few situation (for example glass forms C), in order to improve devitrification resistance, SiO 2Be preferably more than 5%, more preferably more than 6%.
B 2O 3Being the composition that consists of the glass skeleton, also is the composition that improves Abbe number most.Its content is 8～23%, is preferably 8.5～20%, more preferably 9～15%.In addition, work as B 2O 3When increasing, when glass ware forming, generate by B easily 2O 3And La 2O 3The devitrification thing that forms, and when specific refractory power reduced, weathering resistance worsened.On the other hand, work as B 2O 3When few, has the trend that is difficult to obtain high Abbe number.And, by with the composition displacement that improves specific refractory power, can be when reaching high refractive index, when being suppressed at glass ware forming by B 2O 3And La 2O 3The devitrification thing that forms.
ZnO is the composition that improves specific refractory power, still reduces the composition of glass viscosity, therefore can reduce second-order transition temperature, and then can access the glass that is difficult to the mould welding.And, be to reach high refractive index and the low composition that disperses by a large amount of interpolations.And, also have the effect that improves weathering resistance.In addition, owing to compare with alkaline-earth metal composition (MgO, CaO, SrO, BaO), tendency toward devitrification is not strong, so even contain in a large number, can access homogeneous glass yet.Its content is 6～40%, is preferably 6.5～40%, more preferably 8.5～30%, more preferably 10～25%, most preferably be 15～21%.When ZnO content is too much, weathering resistance is worsened.On the other hand, when very few, be difficult to obtain the low glass of second-order transition temperature, and easy and mould welding.
ZrO 2It is the composition that in the composition that improves specific refractory power, Abbe number is reduced.And form the glass skeleton as intermidate oxide, therefore also have the devitrification resistance of improvement (to by B 2O 3And La 2O 3The inhibition of the devitrification thing that forms), perhaps improve the effect of chemical durability.But, work as ZrO 2When content increased, second-order transition temperature improved, and the compression molding deterioration simultaneously, is separated out with ZrO 2Devitrification thing for principal constituent.ZrO 2Content be 2～10%, be preferably 3～8%, more preferably 4～8%.In addition, work as La 2O 3When few (for example glass forms C), in order to improve specific refractory power, preferred ZrO 2Be more than 4%.
La 2O 3Has the effect that Abbe number is reduced and improve specific refractory power.Its content is 20～46%.When being less than 20%, the trend that is difficult to fully obtain high refractive index being arranged, and more than 46% the time, when glass ware forming, generate by B easily 2O 3And La 2O 3The devitrification thing that forms has the trend that devitrification resistance worsens.La 2O 3Content be preferably 25～45%, more preferably 30～45%, more preferably 31～42%, be particularly preferably 32～40%, most preferably be 32～37%.
In addition, in the characteristic than high refractive index and low dispersion, when more preferably wishing to obtain devitrification resistance, La 2O 3Scope be preferably below 30%, more preferably below 28%.
Gd 2O 3It is the composition that improves specific refractory power.Also has the raising devitrification resistance (to by B 2O 3And La 2O 3The inhibition of the devitrification thing that forms) effect is the composition that can enlarge range of working temperature.On the other hand, when content was many, the phase-splitting trend of glass strengthened, and is difficult to obtain homogeneous glass.In addition, containing B 2O 3And La 2O 3Compositional system in, by La 2O 3, Ta 2O 5And B 2O 3The devitrification thing that forms is separated out (surperficial devitrification) easily on the surface, liquidus temperature raises, and Abbe number reduces.But, Gd 2O 3Reduce composition (for example, the Ta of Abbe number with other 2O 5, WO 3, TiO 2Deng) compare, can say that the reduction ratio of Abbe number is low.Gd 2O 3Content be 0～16%, be preferably 4～16%, more preferably 5～12%.In addition, work as La 2O 3When few (for example glass forms C), improve in order to make specific refractory power, preferably make Gd 2O 3Be more than 4%.
Ta 2O 5Have and improve specific refractory power, chemical durability and devitrification resistance (to by B 2O 3And La 2O 3The inhibition of the devitrification thing that forms) effect.Or with respect to the reduction of Abbe number, specific refractory power improves large composition, is be used to obtaining high refraction, low effective constituent of disperseing.Its content is 7～25%, is preferably 7～22.5%, more preferably 7～18%, more preferably 10～18%.Ta 2O 5In the time of too much, Abbe number reduces, and is difficult to obtain desirable optical characteristics.And, by La 2O 3, Gd 2O 3, Ta 2O 5And B 2O 3The devitrification thing that forms is separated out easily, and liquidus temperature improves easily.And, owing to also improved cost, thus consider from economic point of view, not preferred yet.On the other hand, when containing 7% when above, can easily obtain the specific refractory power (nd) more than 1.85.In addition, when more preferably wishing to obtain high refractive index than low dispersion, preferably contain 18～25% Ta 2O 5(for example glass forms B).At this moment, the content of preferably regulating other composition in order to do one's utmost to reduce Abbe number.For example, when adding the ZnO more than 10%, the effect that weakens the Abbe number reduction is large.
Nb 2O 5It is the large composition of effect that improves glass refraction.And, containing a large amount of Ta 2O 5Glass in, have the devitrification resistance of improvement (to by La 2O 3, Ta 2O 5And B 2O 3The inhibition of the devitrification thing that forms) effect.Or with respect to the reduction of Abbe number, the composition that the raising of specific refractory power is large is be used to obtaining high refractive index and low effective constituent of disperseing.Nb 2O 5Content be 1～10%, be preferably 2～5%.Work as Nb 2O 5In the time of too much, with Nb 2O 5For the devitrification thing of principal constituent is separated out (surperficial devitrification) easily from the teeth outwards.On the other hand, contain 1% when above, obtain easily the specific refractory power (nd) more than 1.85.
Reason from environment is considered lead composition (PbO), arsenic composition (As 2O 3) and F composition (F 2) should avoid in fact the importing to glass.Therefore, in the present invention, do not contain in fact these compositions.
In addition, optical glass for mold press molding of the present invention can also contain WO except mentioned component 3And TiO 2These compositions have the effect of the specific refractory power that improves glass, with ZnO, Ta 2O 5, Nb 2O 5Compare, little with respect to the specific refractory power raising that Abbe number reduces, when a large amount of the interpolation, be difficult to keep high refractive index, the low dispersion, need to take into full account with the balance of other composition and use.In addition, can contain Li 2O.Li 2Alkalimetal oxide (the R' that O is such 2O) be composition for reducing softening temperature.
WO 3Has the effect that improves specific refractory power.In addition, owing to form the skeleton of glass as intermidate oxide, therefore also be improved devitrification resistance (to by B 2O 3And La 2The inhibition of the devitrification thing that O forms) effect.WO 3Content be preferably below 10%, more preferably below 5%, more preferably below 3%, be particularly preferably below 2.5%, most preferably be below 1.5%.WO 3In the time of too much, cause Abbe number to reduce, be difficult to obtain desired optical characteristics.And, might make absorption limit in the transmitance to the long wavelength side displacement, the transmitance in short wavelength zone is reduced.In addition, in order fully to obtain above-mentioned effect, preferably contain more than 0.1%.In addition, especially at La 2O 3When few (for example glass forms C), reduce in order to suppress Abbe number, improve simultaneously specific refractory power, WO 3Be preferably 0～3%.
TiO 2It is the composition that improves glass refraction.In addition, also has the raising devitrification resistance (to by B 2O 3And La 2O 3The inhibition of the devitrification thing that forms) effect.TiO 2Can be added into 20%, but when too much, Abbe number be reduced.And because the absorption of ultraviolet region is large, and absorption limit reduces the transmitance in short wavelength zone to the long wavelength side displacement, and therefore, the transmitance of 390～440nm reduces, and might give as the short wavelength and bring obstacle with the use of lens.Therefore, TiO 2Content be preferably below 5%, more preferably below 2.5%.In addition, in order fully to obtain above-mentioned effect, preferably contain more than 0.1%.
The viewpoint that particularly reduces from the transmitance that suppresses the short wavelength zone is considered, preferably makes their total amount WO 3+ TiO 2Be below 10%, more preferably below 5%.
Li 2O is at R ' 2Among the O, it is maximum to reduce the softening temperature effect.But, because Li 2Minute phasic property of O is strong, therefore, when addition is too much, might separate out with B 2O 3And La 2O 3Be the devitrification thing of principal constituent, liquidus temperature increases, and workability worsens.And, at Li 2When O was many, the volatile matter that produces during compression molding increased, and easy and mould welding makes the compression molding difficult.Therefore, its content is preferably below 5%, more preferably below 3%, more preferably below 1.5%.In addition, in order fully to obtain above-mentioned effect, preferably contain more than 0.1%.
In having the optical glass for mold press molding of the present invention of above-mentioned composition, in order to obtain high refractive index and the low glass that disperses, preferred appropriate regulation SiO 2And B 2O 3The total amount of content.Particularly, its total amount SiO 2+ B 2O 3Be preferably 12～33%, more preferably 12～25%, more preferably 14～22%.When the total amount of these compositions is very few, be difficult to keep low the dispersion, on the other hand, in the time of too much, be difficult to form the glass of high refractive index.
In having the optical glass for mold press molding of the present invention of above-mentioned composition, in order to obtain the glass of low dispersion the (Abbe number is high), can limit the Gd as the composition that reduces Abbe number 2O 3, Ta 2O 5, WO 3, TiO 2And Nb 2O 5Total amount.Particularly, preferably with Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5Be adjusted to below 34%, more preferably be adjusted to 10～30%.When the total amount of these compositions is too much, be difficult to obtain the low glass that disperses.On the other hand, when the total amount of these compositions is very few, the trend that is difficult to obtain glass of high refractive index is arranged.
Equally, be the glass 41 or more in order to obtain low glass, the especially Abbe number (ν d) that disperses, can make as the raising Abbe number or can significantly not reduce the SiO of the composition of Abbe number 2, B 2O 3, ZnO, La 2O 3The total amount of content more than prescribed value.Particularly, SiO 2+ B 2O 3+ ZnO+La 2O 3Be preferably more than 60% more preferably 60～90%, more preferably 70～90%.When the total amount of these compositions was very few, it was large to be difficult to obtain the low possibility of glass of disperseing.In addition, when the total amount of these compositions is too much, might be difficult to obtain the glass of high refractive index.
Equally, in order to obtain the low glass that disperses, improve Abbe number or can significantly not reduce the composition (La of Abbe number 2O 3, SiO 2, B 2O 3, ZnO) with the composition (Gd that reduces Abbe number 2O 3, Ta 2O 5, WO 3, TiO 2, Nb 2O 5) to average out be very important.Particularly, preferably with (SiO 2+ B 2O 3+ ZnO+La 2O 3)/(Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5) ratio be adjusted to the scope of regulation, particularly, according to quality criteria, be adjusted to more than 2.0, more preferably be adjusted to 2.3～4.0, further preferably be adjusted to 2.4～3.5.This is worth when too small, and Abbe number reduces easily.The trend that the glass that is difficult to obtain high refractive index is then arranged when on the other hand, excessive.
In having the optical glass for mold press molding of the present invention of above-mentioned composition, in order to obtain the glass of high refractive index, especially specific refractory power (nd) is the glass more than 1.86, and in order to obtain the low glass that disperses, especially Abbe number is the glass more than 37, preferably makes as the ZnO+Ta that improves the few composition of specific refractory power and Abbe number reduction 2O 5+ Nb 2O 5The total amount of content is more than prescribed value.Particularly, the total amount that preferably makes them is more than 30%, more preferably 30～40%, more preferably 31～35%.When the total amount of these compositions is very few, the trend that is difficult to obtain glass of high refractive index is arranged.On the other hand, when the total amount of these compositions is too much, have to be difficult to obtain low trend of disperseing glass.
In addition, same, in order to obtain the glass of high refractive index, preferably make (SiO 2+ B 2O 3)/Ta 2O 5More than prescribed value.Particularly, preferably making the ratio of these compositions is below 1.0.When the ratio of these compositions is excessive, the trend that is difficult to obtain glass of high refractive index is arranged.On the other hand, when the ratio of these compositions is too small, have to be difficult to obtain low trend of disperseing glass.
And, same, in order to obtain the glass of high refractive index, preferably make (La 2O 3+ Gd 2O 3)/Ta 2O 5More than prescribed value.Particularly, preferably making the ratio of these compositions is below 2.5.When the ratio of these compositions is too much, make by La easily 2O 3, Gd 2O 3, Ta 2O 5And B 2O 3The devitrification thing that forms is separated out, and liquidus temperature improves easily.On the other hand, when the ratio of these compositions is very few, the trend that is difficult to obtain glass of high refractive index is arranged.
In addition, same, in order to obtain glass of high refractive index, preferably make Li 2O/Ta 2O 5More than prescribed value.Particularly, preferably making the ratio of these compositions is below 0.05.When the ratio of these compositions is too much, make by La easily 2O 3, Gd 2O 3, Ta 2O 5And B 2O 3The devitrification thing that forms is separated out, and liquidus temperature improves easily.On the other hand, when the ratio of these compositions is very few, the trend that is difficult to obtain the low glass of softening temperature is arranged.
In addition, in having the optical glass for mold press molding of the present invention of above-mentioned composition, be glass more than 1.85 in order to obtain the glass of high refractive index, especially specific refractory power (nd), preferably make ZnO, ZrO as the composition that improves specific refractory power 2, La 2O 3, Gd 2O 3, Ta 2O 5, WO 3, TiO 2, Nb 2O 5The total amount of content is more than prescribed value.Particularly, the total amount that preferably makes them is more than 55%, more preferably 55～89%, more preferably 60～87%.When the total amount of these compositions is very few, the trend that is difficult to obtain glass of high refractive index is arranged.In addition, when the total amount of these compositions is too much, by being difficult to obtain low trend of disperseing glass.Be particularly preferably, as ZnO, the Ta of the large composition of the specific refractory power rate of rise that reduces with respect to Abbe number 2O 5And Nb 2O 5Total amount be more than 30%.
In addition, in having the optical glass for mold press molding of the present invention of above-mentioned composition, in order to reach lower glass transition temperatures, particularly, have ZnO and the Li that reduces the softening temperature effect in order to reach the second-order transition temperature below 650 ℃, preferably to make 2The total amount of the content of O is more than prescribed value.Particularly, ZnO+Li 2O is preferably more than 8%, and more preferably 8～40%, more preferably 10～30%.When their total amount is very few, the trend that has second-order transition temperature (Tg) to improve, be difficult at low temperatures compression molding.On the other hand, when their total amount is too much, in the melting of premolding glass, molding procedure, exist with B 2O 3, La 2O 3For the devitrification thing of principal constituent is separated out easily, liquidus temperature improves, thus the trend that makes scope of work narrow down, be difficult to produce in batches.
In addition, except mentioned component, optical glass for mold press molding of the present invention can also add various compositions in the scope of glass performance of the present invention.As such composition, for example, can enumerate Al 2O 3, CaO, BaO, SrO, Na 2O, K 2O, Y 2O 3, Yb 2O 3, finings etc.
Al 2O 3Be can with SiO 2, B 2O 3Consist of together the composition of glass skeleton.And have the effect that improves weathering resistance, the composition effect of selectivity stripping in the water that especially suppresses in the glass is remarkable.Its content is preferably below 10%, is particularly preferably below 5%.And Al 2O 3When many, the easy devitrification of glass.And exist meltbility deterioration, texture or bubble to remain in the glass, can not satisfy as the possibility of lens with quality that glass requires.
The alkaline earth metal oxide of CaO, BaO, SrO and so on (RO) plays a role as fusing assistant, and has the effect that improves specific refractory power when not reducing Abbe number.When RO is too much, in premolding glass melting, molding procedure, separate out with B easily 2O 3And La 2O 3Be the devitrification thing of principal constituent, and liquidus temperature raises easily, scope of work narrows down easily.The result has the trend that is difficult to produce in batches.And the RO composition makes weathering resistance worsen easily when too much on the contrary, and glass ingredient increases to the stripping in ground and cleaned water or the various cleaning solution, and how under the wet states, the rotten of glass surface is tending towards remarkable at high temperature.Therefore, in total amount, CaO, BaO and SrO are preferably below 20%.
CaO does not reduce the Abbe number of glass and the composition that improves specific refractory power.In addition, owing to prevent that the effect that alkali metal component and alkaline-earth metal composition are separated out at glass surface under the many wet conditions of high temperature is high, therefore be for the effective constituent that improves weathering resistance.CaO content is preferably 0～10%, and more preferably 0～5%.
BaO is the composition that improves glass refraction.And, to compare with CaO, the amount of separating out from glass surface under the state that high temperature wets more is few.The content of BaO is preferably below 20%, more preferably below 5%.
SrO is the composition that improves glass refraction.And, to compare with CaO, the amount of separating out from glass surface under the state that high temperature wets more is few.Therefore, by using energetically SrO, can access the goods that have excellent weather resistance.Its content is preferably below 20%, more preferably below 10%, more preferably below 5%.
In addition, except CaO, BaO and SrO, in order to improve specific refractory power, can also add the MgO as the RO composition.When adding MgO, its content is preferably below 10%, more preferably below 5%.When MgO is too much, there is the trend of easy devitrification.
Na 2O and Li 2O is same, has the effect that reduces softening temperature.But, when its content is many, when melting by B 2O 3And Na 2The volatile matter that O forms increases, thereby has encouraged the generation of texture.In addition, separate out with B easily 2O 3And La 2O 3Be the devitrification thing of principal constituent, and liquidus temperature raises easily.The volatile matter that produces when in addition, also having compression molding increases, easily and mould welding and make the trend of compression molding difficulty.Na 2O content is preferably below 10%, more preferably below 5%.
K 2O and Li 2O is same, also has the effect that reduces softening temperature.Add K 2During O, its content is preferably 0～10%, and more preferably 0～5%.Work as K 2When O is too much, the trend that has weathering resistance to worsen.And, separate out with B easily 2O 3And La 2O 3Be the devitrification thing of principal constituent, and liquidus temperature raises easily.The volatile matter that produces when in addition, also having compression molding increases, easily and mould welding and make the trend of compression molding difficulty.
Y 2O 3And Yb 2O 3Not reduce Abbe number and the composition that improves specific refractory power.Therefore, by with La 2O 3Replace, can improve devitrification resistance.In addition, by an amount of interpolation, has inhibition B 2O 3-ZnO-La 2O 3It is the effect of the incidental phase-splitting of glass.Y 2O 3And Yb 2O 3Content preferably respectively be below 15%, more preferably respectively be below 8%.Y 2O 3Or Yb 2O 3Content when too much, the trend that has easy devitrification, range of working temperature to narrow down.And in glass, produce easily texture.
As finings, for example, can add Sb 2O 3But, excessively painted for fear of to glass, finings content is preferably below 1%.
In above-mentioned compositing range, as the object lesson of preferred compositing range, can enumerate described glass and form A～C.
Glass forms A and is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 57～18%, Nb 2O 51～10% as composition, and does not contain in fact lead composition, arsenic composition and F composition.Form according to this, obtain easily having high refractive index and the low optical glass for mold press molding that disperses.
And, as the preferred compositing range of glass composition A, can enumerate, in quality %, contain SiO 23.5～21.0%, B 2O 39～15%, ZnO 15～21%, Li 2O 0.1～2.0%, TiO 20～2.5%, ZrO 23～8%, La 2O 332～40%, Gd 2O 35～12%, Ta 2O 510～15%, Nb 2O 51～5%, WO 30～3%, and do not contain in fact lead composition, arsenic composition and F composition.
Glass forms B and is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 10～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 518～25%, Nb 2O 51～10%, and do not contain in fact lead composition, arsenic composition and F composition.Form according to this, can access the especially optical glass for mold press molding of high refractive index.
Glass forms C and is characterised in that, in quality %, contains SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 24～10%, La 2O 320～30%, Gd 2O 34～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition.According to this composition, although can access specific refractory power and the Abbe number average is slightly low, the optical glass for mold press molding of devitrification resistance excellence.
As the more preferably scope of glass composition C, can enumerate, in quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 24～10%, La 2O 320～30%, Gd 2O 34～16%, Ta 2O 57～25%, Nb 2O 51～10%, WO 30～3%, TiO 20～20%, and do not contain lead composition, arsenic composition and F composition.
In addition, form among the C, in quality %, if with La at glass 2O 3+ Gd 2O 3Be defined as below 45%, be preferably below 42%, then can access the more excellent glass of devitrification resistance.
And, form among the C, according to quality criteria, by making (SiO at glass 2+ La 2O 3+ Gd 2O 3)/(ZnO+Li 2O) ratio is below 2.9, be preferably below 2.6, more preferably below 2.5, obtain easily the low glass of second-order transition temperature.
Optical glass for mold press molding of the present invention can access the specific refractory power (nd) that has more than 1.82, the glass of the Abbe number more than 35 (ν d).Especially can access the specific refractory power (nd) that has more than 1.86, the glass of the Abbe number more than 38 (ν d), can access especially have 1.87～1.95 specific refractory power (nd), the glass of 38～42 Abbe number (ν d), can use with optical lens by few as dispersion, high performance compact optical element.And it is below 650 ℃ that optical glass for mold press molding of the present invention can make second-order transition temperature, especially below 640 ℃, particularly below 630 ℃.When the softening temperature of glass is low, then at low temperatures compression molding, thus can suppress the mold fouling that causes because of mould oxidation, glass ingredient volatilization and the welding of glass and mould.
Then, the method for using glass manufacture laser disc of the present invention to read lens and imaging lens etc. is described.
At first, frit reconciled into desired composition after, melting in glass melting furnace.Then, melten glass is dripped by the tip of nozzle, make droplet-like glass, obtain premolding glass.Perhaps with the casting of melten glass chilling, make temporarily glass block, cut, grind, clean by grinding, obtain premolding glass.Then, through adding premolding glass in the precision machined mould, be heated to soft state and carry out extrusion forming, with the die surface shape transferred thereon on glass.This forming method is called as compression molding method, is widely adopted.Like this, just can access laser disc and read lens and imaging lens.
［ embodiment ］
Below, specify the present invention according to embodiment, but the present invention is not limited to these embodiment.
Table 1
Table 2
Figure BDA00002386968100151
Table 3
Figure BDA00002386968100161
Table 4
Figure BDA00002386968100171
Table 5
Figure BDA00002386968100181
Table 6
Figure BDA00002386968100191
Table 7
Figure BDA00002386968100201
Table 8
Figure BDA00002386968100211
Table 9
Figure BDA00002386968100221
Table 10
Figure BDA00002386968100231
Table 1～9 expression embodiments of the invention 1～59, table 10 expression comparative example 1～6.In addition, embodiment 1～5,7～9,11,12,42～47,50,52,55～57,59 expression glass form A, and embodiment 6,10,13,14,48,49,53,54,58 expression glass form B, and embodiment 15～41,51 expression glass form C.
Each sample such as modulated.
At first, the mediation frit is each shown in the table and forms, and uses platinum crucible, 1300～1450 ℃ of lower meltings 3 hours.After the melting, liquation is placed curtain coating on the carbon plate, after annealing again, make the sample that is suitable for each mensuration.
Measure specific refractory power (nd), Abbe number (ν d), second-order transition temperature (Tg), liquidus temperature and the surperficial devitrification temperature of gained sample.And evaluation mould weldability.Its result is illustrated in table 1～10.
As seen from table, the specific refractory power of each sample of the embodiment of the invention 1～59 (nd) is more than 1.8178, and Abbe number (ν d) is more than 37.0, and second-order transition temperature is below 633 ℃.And devitrification resistance is good, it is believed that, does not have devitrification when premolding.And confirm embodiment 1～6,15,16, each sample of 50 not with the mould welding.
In addition, specific refractory power (nd) represents with the measured value with respect to the d line (587.6nm) of helium lamp.
The refractive index value of the C line (656.3nm) of the specific refractory power of the above-mentioned d line of Abbe number (ν d) use and the F line (486.1nm) of hydrogen lamp and hydrogen lamp is calculated by the formula of Abbe number (ν d)=[(nd-1)/(nF-nC)].
Second-order transition temperature (Tg) is estimated according to the value that adopts thermal expansion measurement device (dilato meter) to measure.
Devitrification resistance is judged according to liquidus temperature and surperficial devitrification temperature.Liquidus temperature is measured by following method: under 1350 ℃ of conditions of-18 hours, with electric furnace glass again after the melting, is kept taking out from electric furnace after 5 minutes in having the electric furnace of thermograde, naturally cooling in air is with the position of separating out of opticmicroscope searching devitrification thing.The surface devitrification temperature is measured by following method: under 1350 ℃ of conditions of-30 minutes, with electric furnace with glass again after the melting, in having the electric furnace of thermograde, keep after 5 minutes, from electric furnace, take out, naturally cooling in air is sought the position of separating out of devitrification thing and is measured with opticmicroscope.In the evaluation of above-mentioned liquidus temperature and surperficial devitrification temperature, the glass that liquidus temperature is estimated melting before moulding during, because being trapped in for a long time the devitrification degree that shows in the stove, surperficial devitrification temperature is then estimated the surperficial devitrification degree that the glass surface after moulding shows.In addition, as long as liquidus temperature below 1200 ℃, then reaches 10 easily 0.5The liquid phase viscosity that dPas is above even carry out the drop moulding, also needn't worry to occur devitrification.In addition, if surperficial devitrification temperature, can judge then that devitrification resistance is good below 1270 ℃.
Estimate with the weldability of mould is following.At first, the mediation frit uses platinum crucible after 3～5 hours, glass melt to be placed curtain coating and annealing on the carbon platform 1300～1500 ℃ of lower meltings, is processed into the cylindric sample of diameter 5mm, high 5mm.Then, sample is rested on the WC mould, at N 2Be heated to 800 ℃ in the atmosphere, kept 15 minutes.After the heating, remove sample, observe in the circle of the die surface diameter 5mm that contacts with sample, estimating has weldless.
The second-order transition temperature of die pressing optical glass of the present invention is low, and the devitrification resistance during premolding is good.And, because specific refractory power and Abbe number are high, therefore can make CD, MD, DVD, and the laser disc of other various optical disk systems read lens, the contour performance-based of the imaging lens of pick up camera, ordinary camera.And, also can use as the glass material by the forming method moulding beyond the mold pressing.

Claims (19)

1. optical glass for mold press molding is characterized in that:
In quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 320～46%, Gd 2O 30～16%, Ta 2O 57～25%, Nb 2O 51～10%, Li 2The composition of O more than 0.1%, and do not contain in fact lead composition, arsenic composition and F composition.
2. optical glass for mold press molding as claimed in claim 1 is characterized in that:
In quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition.
3. optical glass for mold press molding as claimed in claim 2 is characterized in that:
In quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 57～18%, Nb 2O 51～10% composition.
4. optical glass for mold press molding as claimed in claim 2 is characterized in that:
In quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 10～40%, ZrO 22～10%, La 2O 330～46%, Gd 2O 30～16%, Ta 2O 518～25%, Nb 2O 51～10% composition.
5. such as each described optical glass for mold press molding in the claim 1～4, it is characterized in that: in quality %, also contain Li 2O 0.1～5%.
6. such as each described optical glass for mold press molding in the claim 1～5, it is characterized in that: in quality %, Li 2O+ZnO is more than 8%.
7. such as each described optical glass for mold press molding in the claim 1～6, it is characterized in that: in quality %, also contain WO 30～10% and TiO 20～20%.
8. such as each described optical glass for mold press molding in the claim 1～7, it is characterized in that: in quality %, Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5Be below 34%.
9. such as each described optical glass for mold press molding in the claim 1～8, it is characterized in that: in quality %, SiO 2+ B 2O 3+ ZnO+La 2O 3Total content be more than 60%.
10. such as each described optical glass for mold press molding in the claim 1～9, it is characterized in that: according to quality criteria, (SiO 2+ B 2O 3+ ZnO+La 2O 3)/(Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5) be more than 2.0.
11. such as each described optical glass for mold press molding in the claim 1～10, it is characterized in that: in quality %, ZnO+ZrO 2+ La 2O 3+ Gd 2O 3+ Ta 2O 5+ WO 3+ TiO 2+ Nb 2O 5Be more than 55%.
12. such as each described optical glass for mold press molding in the claim 1～11, it is characterized in that: in quality %, ZnO+Ta 2O 5+ Nb 2O 5Be more than 30%.
13. such as each described optical glass for mold press molding in the claim 1～12, it is characterized in that: according to quality criteria, (SiO 2+ B 2O 3)/Ta 2O 5Be below 1.0.
14. such as each described optical glass for mold press molding in the claim 1～13, it is characterized in that: according to quality criteria, (La 2O 3+ Gd 2O 3)/Ta 2O 5Be below 2.5.
15. such as each described optical glass for mold press molding in the claim 1～14, it is characterized in that: according to quality criteria, Li 2O/Ta 2O 5Be below 0.05.
16. optical glass for mold press molding as claimed in claim 1 is characterized in that:
In quality %, contain SiO 23～21%, B 2O 38～23%, ZnO 6～40%, ZrO 24～10%, La 2O 320～30%, Gd 2O 34～16%, Ta 2O 57～25%, Nb 2O 51～10% composition, and do not contain in fact lead composition, arsenic composition and F composition.
17. optical glass for mold press molding as claimed in claim 16 is characterized in that:
In quality %, contain WO 30～3%, TiO 20～20%.
18. such as claim 16 or 17 described optical glass for mold press molding, it is characterized in that:
In quality %, La 2O 3+ Gd 2O 3Be below 45%.
19. such as each described optical glass for mold press molding in the claim 16～18, it is characterized in that: according to quality criteria, (SiO 2+ La 2O 3+ Gd 2O 3)/(ZnO+Li 2O) be below 2.9.
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