CN104341102B

CN104341102B - Optical glass and optical element

Info

Publication number: CN104341102B
Application number: CN201410366725.2A
Authority: CN
Inventors: 桃野净行
Original assignee: Ohara Inc
Current assignee: Ohara Inc
Priority date: 2013-07-31
Filing date: 2014-07-29
Publication date: 2018-08-07
Anticipated expiration: 2034-07-29
Also published as: JP2015030631A; CN104341102A; JP5979723B2; CN108455840A

Abstract

The present invention relates to optical glass and optical elements.Problem of the present invention is that more inexpensively obtaining refractive index (nd) and Abbe number (ν d) is in desired range and devitrification resistance is high optical glass and optical element.The optical glass of the present invention contains 10.0~40.0% B in terms of quality %₂O₃Ingredient, 25.0~55.0% La₂O₃Ingredient and Y more than 0%₂O₃Ingredient, mass ratio Y₂O₃/(Y₂O₃+Gd₂O₃) it is 0.500 or more, the optical glass has 39 or more Abbe number (ν d).The optical element of the present invention is using the optical glass as base material.

Description

Optical glass and optical element

Technical field

The present invention relates to optical glass and optical elements.

Background technology

In recent years, it is rapidly developed using the digitlization of the equipment of optical system and high-precision densification, in digital camera, video camera The images such as equal photographic equipments, projector, projection TV play in the various field of optical equipment such as (projection) equipment, to reducing optics The number of the optical elements such as the lens, the prism that are used in system makes the requirement of optical system overall lighting and miniaturization increasingly Strongly.

In the optical glass for making optical element, the lighting and miniaturization of optical system overall especially can be achieved The low dispersing glass of high refractive index with 1.70 or more refractive index (nd) and with 39 or more 60 Abbe numbers (ν d) below Demand is very high.As the low dispersing glass of above-mentioned high refractive index, it is known that using Patent Documents 1 to 4 as glass combination as representative Object.

[patent document 1] Japanese Unexamined Patent Application 58-058669 bulletins

[patent document 2] Japanese Unexamined Patent Publication 11-071129 bulletins

[patent document 3] Japanese Unexamined Patent Publication 2008-001551 bulletins

[patent document 4] Japanese Unexamined Patent Publication 2011-093780 bulletins

Invention content

As the method for making optical element by optical glass, it is known that following methods：For example, to being formed by optical glass Material block (gob) or glass blocks (glass block) method that is ground and is ground the shape for obtaining optical element, will to by The material block or glass blocks that optical glass is formed are reheated and are molded glass forming body obtained from (reheating is molded) and carried out The method of grinding and grinding, and the preform material that will be obtained by material block or glass blocks using the mold crossed through Ultra-precision Turning The method for being molded (precise compression molding) and obtaining the shape of optical element.All methods are required to the glass by having melted Raw material can obtain stable glass when forming material block or glass blocks.Herein, the glass of the material block or glass blocks that constitute is opposite It is reduced in the stability (devitrification resistance) of devitrification when the inside of glass crystallizes, has been unable to get and has been suitable as optics The glass of element.

In addition, in order to reduce the material cost of optical glass, it is expected that constituting the raw material cost of each ingredient of optical glass as possible Inexpensively.In addition, in order to reduce the manufacturing cost of optical glass, it is expected that the meltbility of raw material is high, melt at lower temperatures.It can It is that the glass described in Patent Documents 1 to 4 is it's hard to say fully meet above-mentioned each requirement.

The present invention is to complete in view of the above problems, and its object is to more inexpensively obtain refractive index (nd) and Abbe number The glass that (ν d) is in desired range and devitrification resistance is high.

Experimental study with great concentration has been repeated in the inventors of the present invention in order to solve the above problems, as a result, it has been found that, by B₂O₃ Ingredient and La₂O₃In ingredient and use Y₂O₃Ingredient, also, by mass ratio Y₂O₃/(Y₂O₃+Gd₂O₃) set within the limits prescribed, Thus the material cost of glass reduces, and the liquidus temperature of glass is lower, so as to complete the present invention.Specifically, this hair It is bright that scheme as described below is provided.

(1) a kind of optical glass, wherein in terms of quality %, contain 10.0~40.0% B₂O₃Ingredient, 25.0~ 55.0% La₂O₃Ingredient and Y more than 0%₂O₃Ingredient, mass ratio Y₂O₃/(Y₂O₃+Gd₂O₃) it is 0.500 or more, the light Learning glass has 39 or more Abbe number (ν d).

(2) optical glass as described in (1), wherein in terms of quality %, Gd₂O₃The content of ingredient is less than 10.0%.

(3) optical glass as described in (1) or (2), wherein in terms of quality %,

Li₂O ingredients are 0~10.0%,

ZnO component is 0~25.0%.

(4) optical glass as described in any one of (1) to (3), wherein SiO₂The content of ingredient is 30.0% or less.

(5) optical glass as described in any one of (1) to (4), wherein in terms of quality %,

Ta₂O₅Ingredient is 0~18.0%,

Yb₂O₃Ingredient is 0~20.0%.

(6) optical glass as described in any one of (1) to (5), wherein Ln₂O₃Ingredient (in formula, Ln be selected from La, Gd, Y, one or more of Yb) quality and be 25.0% or more 75.0% or less.

(7) optical glass as described in any one of (1) to (6), wherein in terms of quality %,

MgO ingredients are 0~20.0%,

CaO ingredients are 0~20.0%,

SrO ingredients are 0~20.0%,

BaO ingredients are 0~25.0%.

(8) optical glass as described in any one of (1) to (7), wherein RO ingredients (in formula, R be selected from Mg, Ca, Sr, One or more of Ba) quality and be 25.0% or less.

(9) optical glass as described in any one of (1) to (8), wherein in terms of quality %,

TiO₂Ingredient is 0~15.0%,

Nb₂O₅Ingredient is 0~20.0%,

WO₃Ingredient is 0~20.0%.

(10) optical glass as described in any one of (1) to (9), wherein TiO₂Ingredient, Nb₂O₅Ingredient and WO₃Ingredient Content and be 30.0% or less.

(11) optical glass as described in any one of (1) to (10), wherein in terms of quality %,

Na₂O ingredients are 0~10.0%,

K₂O ingredients are 0~10.0%,

Cs₂O ingredients are 0~10.0%.

(12) optical glass as described in any one of (1) to (11), wherein Rn₂O ingredients (in formula, Rn be selected from Li, One or more of Na, K, Cs) quality and be 15.0% or less.

(13) optical glass as described in any one of (1) to (12), wherein in terms of quality %,

P₂O₅Ingredient is 0~10.0%,

GeO₂Ingredient is 0~10.0%,

ZrO₂Ingredient is 0~15.0%,

Al₂O₃Ingredient is 0~10.0%,

Ga₂O₃Ingredient is 0~10.0%,

Bi₂O₃Ingredient is 0~10.0%,

TeO₂Ingredient is 0~20.0%,

SnO₂Ingredient is 0~1.0%,

Sb₂O₃Ingredient is 0~1.0%.

(14) optical glass as described in any one of (1) to (13) has 39 with 1.70 or more refractive index (nd) Above 60 Abbe number (ν d) below.

(15) optical glass as described in any one of (1) to (14) has 1300 DEG C of liquidus temperatures below.

(16) optical glass as described in any one of (1) to (15) has 5.50 proportions below.

(17) a kind of optical element, using the optical glass described in any one of (1) to (16) as base material.

(18) a kind of optical instrument, with the optical element described in (17).

According to the present invention it is possible to more inexpensively obtain refractive index (nd) and Abbe number (ν d) in desired range, simultaneously And the glass that devitrification resistance is high.

Specific implementation mode

The optical glass of the present invention contains 10.0~40.0% B in terms of quality %₂O₃Ingredient, 25.0~55.0% La₂O₃Ingredient and Y more than 0%₂O₃Ingredient, mass ratio Y₂O₃/(Y₂O₃+Gd₂O₃) it is 0.500 or more, the optical glass tool There is 39 or more Abbe number (ν d).By in B₂O₃Ingredient and La₂O₃In ingredient and use Y₂O₃Ingredient, also, by mass ratio Y₂O₃/ (Y₂O₃+Gd₂O₃) set within the limits prescribed, even if the thus Gd as expensive ingredient₂O₃Ingredient, Ta₂O₅The usage amount of ingredient It is few, it can also be readily derived stable glass.Also, by with B₂O₃Ingredient and La₂O₃Based on ingredient, to 39 with On Abbe number (ν_d), and liquidus temperature is also easily reduced.Therefore, refractive index (nd) and Abbe number can more inexpensively be obtained The optical glass and use its optical element that (ν d) is in desired range and devitrification resistance is high.

Hereinafter, explain the embodiment of the optical glass of the present invention in detail, but the present invention is not by following implementation Any restriction can carry out suitably changing to implement in the range of the purpose of the present invention.It should be noted that for repeating Illustrate place, suitably omits the description sometimes, but do not limit the purport of invention.

[glass ingredient]

The compositing range for constituting each ingredient of the optical glass of the present invention is as described below.In this specification, about each ingredient Content be unless otherwise specified with the quality % tables relative to the glass gross mass formed for being scaled oxide The content shown.Herein, so-called " composition for being scaled oxide " refers to, it is assumed that the raw material of the glass constituent as the present invention And oxide, double salt, metal fluoride used etc. is all decomposed in melting and is converted into oxide, at this point, with the life It is 100 mass % at the gross mass of oxide, to indicate the composition of each ingredient contained in glass.

＜ is about required ingredient, optional member ＞

B₂O₃Ingredient is indispensable required ingredient as network former.

In particular, by containing 10.0% or more B₂O₃Ingredient can be improved the devitrification resistance of glass, also, can reduce glass The dispersion of glass.Therefore, B₂O₃The lower limit of the content of ingredient is preferably 10.0%, is more preferably 11.0%, more preferably 15.0%.

On the other hand, by making B₂O₃The content of ingredient is 40.0% hereinafter, the refractive index of bigger can be easy to get, and can be pressed down The deterioration of chemical durability processed.Therefore, B₂O₃The upper limit of the content of ingredient is preferably 40.0%, is more preferably 38.0%, more preferably It is 36.0%.

For B₂O₃H can be used as raw material in ingredient₃BO₃、Na₂B₄O₇、Na₂B₄O₇·10H₂O、BPO₄Deng.

La₂O₃Ingredient is the ingredient for improving the refractive index of glass and reducing dispersion (increasing Abbe number).In particular, passing through Contain 25.0% or more La₂O₃Ingredient can obtain desired high refractive index.Therefore, La₂O₃The lower limit of the content of ingredient is excellent Be selected as 25.0%, be more preferably 28.0%, more preferably 31.0%, more preferably 34.0%, more preferably 36.0%, more preferably It is 39.0%, more preferably 42.0%, more preferably 45.0%.

On the other hand, by making La₂O₃The content of ingredient is 55.0% hereinafter, the devitrification resistance of glass can be improved.Therefore, La₂O₃The upper limit of the content of ingredient is preferably 55.0%, is more preferably 52.0%, more preferably 50.0%.

For La₂O₃La can be used as raw material in ingredient₂O₃、La(NO₃)₃·XH₂O (X is arbitrary integer) etc..

Y₂O₃When ingredient is that content is more than 0%, the material of glass can be inhibited while maintaining high refractive index and high Abbe number Expect cost, and low-gravity ingredient can be dropped.Therefore, Y₂O₃The content of ingredient is preferably greater than that 0%, lower limit is more preferably 2.0%, it is more preferably 4.0%, more preferably 4.5%, more preferably 6.5%, more preferably 8.0%.

On the other hand, by making Y₂O₃The content of ingredient is 30.0% hereinafter, can inhibit the reduction of the refractive index of glass, and And improve the devitrification resistance of glass.Therefore, Y₂O₃The upper limit of the content of ingredient is preferably 30.0%, is more preferably 25.0%, more Preferably 20.0%, it is more preferably 15.0%.

For Y₂O₃Y can be used as raw material in ingredient₂O₃、YF₃Deng.

Gd₂O₃Ingredient be content be more than 0% when, can be improved the refractive index of glass and can be improved Abbe number it is optional at Point.

On the other hand, by making Gd particularly expensive in rare earth element₂O₃Constituent reduction to less than 10.0% can incite somebody to action The proportion of glass is suppressed to low-level, and it is possible to inhibit the material cost of glass.In addition, it is possible thereby to inhibit glass Ah Shellfish number exceeds necessary rising.Therefore, Gd₂O₃The content of ingredient is respectively preferably less than 10.0%, be more preferably less than 8.0%, it is more preferably less than 5.0%.

For Gd₂O₃Gd can be used as raw material in ingredient₂O₃、GdF₃Deng.

Y₂O₃The content of ingredient is relative to Y₂O₃Ingredient and Gd₂O₃The ratio of the total amount of ingredient is preferably 0.500 or more.By This, by with La₂O₃Terres rares ingredient there are many containing at subassembly cooperation, thus while being easy to get stable glass, The proportion of glass can be inhibited in low-level, also, can inhibit the material cost of glass.Therefore, mass ratio Y₂O₃/(Y₂O₃+ Gd₂O₃) lower limit be preferably 0.500, be more preferably 0.600, more preferably 0.700.

It should be noted that the upper limit of the mass ratio can be 1.000.

For Li₂O ingredients are can to improve the meltbility of glass, and can reduce containing sometimes with the amount more than 0% The optional member of glass transition temperature.

On the other hand, by making Li₂The content of O ingredients is 10.0% hereinafter, the viscosity of glass can be improved, therefore can subtract The brush line of few glass.In addition, thus, it is possible to be not easy to reduce the refractive index of glass, the chemical durability of glass can be improved, also, Devitrification resistance can be improved.Therefore, Li₂The upper limit of the content of O ingredients is preferably 10.0%, is more preferably 5.0%, more preferably small In 3.0%, more preferably less than 2.0%, more preferably less than 1.0%.

For Li₂Li can be used as raw material in O ingredients₂CO₃、LiNO₃、Li₂CO₃Deng.

ZnO component is contained sometimes with the amount more than 0%, can be reduced glass transition temperature and can be improved chemical durable The optional member of property.Therefore, the content of ZnO component is preferably greater than 0%, and lower limit can more preferably be 1.0%, be more preferably 1.5%.

On the other hand, by making the content of ZnO component be 25.0% hereinafter, can inhibit the reduction of the refractive index of glass, resistance to The reduction of increased devitrification resistance.In addition, the viscosity of melten glass thus can be improved, therefore the generation of the brush line of glass can be reduced.Therefore, The upper limit of the content of ZnO component is preferably 25.0%, is more preferably 20.0%, more preferably 15.0%, more preferably 10.0%, More preferably less than 5.0%.

For ZnO component, ZnO, ZnF can be used as raw material₂Deng.

SiO₂Ingredient is that the viscosity of melten glass can be improved, can reduce the coloring of glass containing sometimes with the amount more than 0%, Also, the optional member of devitrification resistance can be improved.Therefore, SiO₂The content of ingredient is preferably greater than 0%, and lower limit is more preferably 1.0%, it is more preferably 1.3%, more preferably 2.0%.

On the other hand, by making SiO₂The content of ingredient is 30.0% hereinafter, can inhibit the raising of glass transition temperature, and And it can inhibit the reduction of refractive index.Therefore, SiO₂The upper limit of the content of ingredient is preferably 30.0%, is more preferably 20.0%, more Preferably 15.0%, more preferably less than 10.0%, more preferably less than 8.0%.

For SiO₂SiO can be used as raw material in ingredient₂、K₂SiF₆、Na₂SiF₆Deng.

Ta₂O₅Ingredient is contained sometimes with the amount more than 0%, and the refractive index of glass can be improved, devitrification resistance can be improved, also, The optional member of the viscosity of melten glass can be improved.

On the other hand, by making expensive Ta₂O₅The content of ingredient is 18.0% hereinafter, the material cost of glass can be reduced, Therefore more cheap optical glass can be made.In addition, the melting temperature of raw material reduces as a result, the energy quilt needed for raw material melting It reduces, therefore can also reduce the manufacturing cost of optical glass.Therefore, Ta₂O₅The upper limit of the content of ingredient is preferably 18.0%, compared with Preferably 16.0%, it is more preferably 13.0%, more preferably 9.0%.

For Ta₂O₅Ta can be used as raw material in ingredient₂O₅Deng.

Yb₂O₃Ingredient is the refractive index of glass to can be improved containing sometimes with the amount more than 0%, also, can reduce appointing for dispersion It hanks point.

On the other hand, by making Yb₂O₃The content of ingredient is 20.0% hereinafter, the material cost of glass can be reduced, therefore can Make more cheap optical glass.In addition, the devitrification resistance of glass thus can be improved.Therefore, Yb₂O₃The content of ingredient is preferably 20.0% hereinafter, be more preferably less than 10.0%, more preferably less than 5.0%, more preferably less than 3.0%, it is more preferably small In 1.0%, be most preferably not contain.

For Yb₂O₃Yb can be used as raw material in ingredient₂O₃Deng.

Ln₂O₃The content of ingredient (in formula, Ln be selected from one or more of La, Gd, Y, Yb) and (quality and) preferably 25.0% or more 75.0% or less.

Especially by make this and be 25.0% or more, the dispersion of glass can be reduced.Therefore, Ln₂O₃The quality sum of ingredient Lower limit is preferably 25.0%, be more preferably 30.0%, more preferably 36.0%, more preferably 41.0%, more preferably 44.0%, More preferably 47.0%, it is more preferably 50.0%, more preferably 53.0%.

On the other hand, by making this and for 75.0% hereinafter, the liquidus temperature of glass is lower, therefore devitrification can be improved Property.Therefore, Ln₂O₃The upper limit of the quality sum of ingredient is preferably 75.0%, is more preferably 70.0%, is more preferably 65.0%, is more excellent It is selected as 61.0%.

La₂O₃The content of ingredient is relative to La₂O₃Ingredient, Y₂O₃Ingredient, Gd₂O₃Ingredient and Yb₂O₃The ratio of the total amount of ingredient Preferably 0.600 or more 0.900 or less.By making the ratio in the range below 0.600 or more 0.900, even if in Ln₂O₃ In the case that the total amount of ingredient is more, devitrification resistance can also be improved.Therefore, mass ratio La₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+ Yb₂O₃) lower limit be preferably 0.600, be more preferably 0.650, more preferably 0.700, more preferably 0.750.On the other hand, should The upper limit of mass ratio is preferably 0.900, is more preferably 0.880, more preferably 0.850.

MgO ingredients, CaO ingredients, SrO ingredients and BaO ingredients are that glass raw material can be improved containing sometimes with the amount more than 0% Meltbility, the devitrification resistance of glass optional member.

On the other hand, by making MgO ingredients, CaO ingredients and the respective content of SrO ingredients be 20.0% or less and/or make The content of BaO ingredients is 25.0% contains the reduction of refractive index caused by mentioned component, resistance to hereinafter, thus can inhibit by excess The reduction of increased devitrification resistance.Therefore, the upper limit of MgO ingredients, CaO ingredients and the respective content of SrO ingredients is preferably 20.0%, more preferably It is 15.0%, more preferably 10.0%, more preferably 7.0%, more preferably 4.5%, more preferably 3.0%.In addition, BaO at The upper limit for the content divided is preferably 25.0%, is more preferably 15.0%, is more preferably 10.0%, is more preferably 5.0%, more preferably It is 3.0%.

For MgO ingredients, CaO ingredients, SrO ingredients and BaO ingredients, MgCO can be used as raw material₃、MgF₂、CaCO₃、 CaF₂、Sr(NO₃)₂、SrF₂、BaCO₃、Ba(NO₃)₂、BaF₂Deng.

The total (quality and) of the content of RO ingredients (in formula, R be selected from one or more of Mg, Ca, Sr, Ba) is preferably 25.0% or less.It can inhibit the drop containing the reduction of glass refraction caused by RO ingredients, devitrification resistance by excess as a result, It is low.Therefore, the upper limit of the quality sum of RO ingredients is preferably 25.0%, is more preferably 15.0%, more preferably less than 10.0%, more Preferably 8.5% hereinafter, more preferably 5.0% or less.

TiO₂Ingredient is that the refractive index of glass can be improved containing sometimes with the amount more than 0%, Abbe number is adjusted so as to it is relatively low, Also, the optional member of devitrification resistance can be improved.

On the other hand, by making TiO₂Content be 15.0% hereinafter, the coloring of glass can be reduced, improve visible transmission Rate, also, can inhibit Abbe number exceed necessary reduction.In addition, can inhibit by excessively containing TiO₂It is lost caused by ingredient Thoroughly.Therefore, TiO₂The upper limit of the content of ingredient is preferably 15.0%, is more preferably 10.0%, is more preferably 5.0%, more preferably It is 3.0%.

For TiO₂TiO can be used as raw material in ingredient₂Deng.

Nb₂O₅Ingredient is the refractive index of glass to can be improved, also, devitrification resistance can be improved containing sometimes with the amount more than 0% Optional member.

On the other hand, by making Nb₂O₅The content of ingredient is 20.0% hereinafter, can inhibit by excessively containing Nb₂O₅Ingredient and The reduction of the devitrification resistance of caused glass, the reduction of the transmissivity of visible light.Therefore, Nb₂O₅The upper limit of the content of ingredient is preferred For 20.0%, be more preferably 15.0%, more preferably 10.0%, more preferably 8.0%.

For Nb₂O₅Nb can be used as raw material in ingredient₂O₅Deng.

WO₃Ingredient be can be reduced containing sometimes with the amount more than 0% glass caused by other high refractive index ingredients Color, while refractive index can be improved, also, the optional member of the devitrification resistance of glass can be improved.In addition, WO₃Ingredient is also can Reduce the ingredient of glass transition temperature.

On the other hand, by making WO₃The content of ingredient is 20.0% hereinafter, can reduce by WO₃Glass caused by ingredient Coloring improves transmission of visible light.Therefore, WO₃The upper limit of the content of ingredient is preferably 20.0%, is more preferably 10.0%, more Preferably 5.0%, it is more preferably 3.0%.

For WO₃WO can be used as raw material in ingredient₃Deng.

Herein, TiO₂Ingredient, Nb₂O₅Ingredient and WO₃The content of ingredient and (quality and) be preferably 30.0% or less.By This, can inhibit the reduction of Abbe number, therefore readily available desired Abbe number.In addition, can reduce by excessive containing described It is coloured caused by ingredient, devitrification resistance can be improved.Therefore, quality and (TiO₂+Nb₂O₅+WO₃) the upper limit be preferably 30.0%, More preferably it is 20.0%, more preferably 15.0%, more preferably 11.0%, more preferably 8.0%.

Na₂O ingredients, K₂O ingredients and Cs₂O ingredients are can be improved the meltbility of glass containing sometimes with the amount more than 0%, carried The devitrification resistance of high glass, also, reduce the optional member of glass transition temperature.

On the other hand, by making Na₂O ingredients, K₂O ingredients and Cs₂The respective content of O ingredients is 10.0% or less, it is difficult to be dropped The refractive index of low glass, also, devitrification resistance can be improved.Therefore, Na₂O ingredients, K₂O ingredients and Cs₂The respective content of O ingredients The upper limit is preferably 10.0%, is more preferably 5.0%, more preferably 3.0%.

For Na₂O ingredients, K₂O ingredients and Cs₂NaNO can be used as raw material in O ingredients₃、NaF、Na₂SiF₆、K₂CO₃、 KNO₃、KF、KHF₂、K₂SiF₆、Cs₂CO₃、CsNO₃Deng.

Rn₂The total amount of O ingredients (in formula, Rn is selected from one or more of Li, Na, K, Cs) is preferably 15.0% or less. It can inhibit the reduction of the refractive index of glass as a result, also, devitrification resistance can be improved.Therefore, Rn₂The upper limit of the quality sum of O ingredients Preferably 15.0%, more preferably it is 10.0%, more preferably 5.0%, more preferably 3.0%.

P₂O₅Ingredient is that the optional member of the devitrification resistance of glass can be improved containing sometimes with the amount more than 0%.It is especially logical Crossing makes P₂O₅The content of ingredient is 10.0% hereinafter, can inhibit the chemical durability of glass, particularly the reduction of water resistance.Therefore, P₂O₅The upper limit of the content of ingredient is preferably 10.0%, is more preferably 5.0%, more preferably 3.0%.

For P₂O₅Al (PO can be used as raw material in ingredient₃)₃、Ca(PO₃)₂、Ba(PO₃)₂、BPO₄、H₃PO₄Deng.

GeO₂Ingredient is the refractive index of glass to can be improved, also, devitrification resistance can be improved containing sometimes with the amount more than 0% Optional member.But due to GeO₂Cost of material is high, if therefore its amount at most material cost increase, thus can cut down by subtracting Few Ta₂O₅Ingredient etc. and the effect of cost reduction brought.Therefore, GeO₂The upper limit of the content of ingredient is preferably 10.0%, more excellent It is selected as 5.0%, more preferably 1.0%, is not contained most preferably.

For GeO₂GeO can be used as raw material in ingredient₂Deng.

For ZrO₂Ingredient can help to the high index of refraction of glass and low decentralized with the amount more than 0% containing sometimes, Also, the devitrification resistance of glass can be improved.Therefore, ZrO₂The content of ingredient is preferably greater than 0%, and lower limit can more preferably be 1.0%, it is more preferably 3.0%, more preferably 5.0%.

On the other hand, by making ZrO₂Ingredient is 15.0% hereinafter, can inhibit by excessively containing ZrO₂Glass caused by ingredient The reduction of the devitrification resistance of glass.Therefore, ZrO₂The upper limit of the content of ingredient is preferably 15.0%, is more preferably 10.0%, is more excellent It is selected as 7.0%.

For ZrO₂ZrO can be used as raw material in ingredient₂、ZrF₄Deng.

Al₂O₃Ingredient and Ga₂O₃Ingredient is contained sometimes with the amount more than 0%, and the chemical durability of glass can be improved, also, The optional member of the devitrification resistance of glass can be improved.

On the other hand, by making Al₂O₃Ingredient and Ga₂O₃The respective content of ingredient is 10.0% hereinafter, can inhibit by excess Reduction containing the devitrification resistance of glass caused by these ingredients.Therefore, Al₂O₃Ingredient and Ga₂O₃The respective content of ingredient The upper limit is preferably 10.0%, is more preferably 5.0%, more preferably 3.0%.

For Al₂O₃Ingredient and Ga₂O₃Al can be used as raw material in ingredient₂O₃、Al(OH)₃、AlF₃、Ga₂O₃、Ga(OH)₃ Deng.

Bi₂O₃Ingredient is refractive index to can be improved containing sometimes with the amount more than 0%, also, can reduce appointing for glass transition temperature It hanks point.

On the other hand, by making Bi₂O₃The content of ingredient is 10.0% hereinafter, the devitrification resistance of glass can be improved, also, The coloring of glass can be reduced and improve transmission of visible light.Therefore, Bi₂O₃The upper limit of the content of ingredient is preferably 10.0%, more excellent It is selected as 5.0%, more preferably 3.0%.

For Bi₂O₃Bi can be used as raw material in ingredient₂O₃Deng.

TeO₂Ingredient is refractive index to can be improved containing sometimes with the amount more than 0%, also, can reduce appointing for glass transition temperature It hanks point.

But for TeO₂For, in the fusion tank that the crucible of platinum or the part that is contacted with melten glass are formed by platinum In when carrying out molten raw, there are problems that can be with platinum alloy.Therefore, TeO₂The upper limit of the content of ingredient is preferably 20.0%, more preferably it is 10.0%, more preferably 5.0%, does not contain more preferably.

For TeO₂TeO can be used as raw material in ingredient₂Deng.

SnO₂Ingredient is can be reduced the oxidation of melten glass containing sometimes with the amount more than 0%, make its clarification, also, can carry The optional member of the transmission of visible light of high glass.

On the other hand, by making SnO₂The content of ingredient is 1.0% hereinafter, can reduce caused by the reduction by melten glass The coloring of glass, the devitrification of glass.In addition, due to SnO₂The alloying quilt of ingredient and fusion apparatus (the especially noble metals such as Pt) It reduces, therefore the long lifetime of fusion apparatus can be sought.Therefore, SnO₂The upper limit of the content of ingredient is preferably 1.0%, more preferably It is 0.7%, more preferably 0.5%.

For SnO₂SnO, SnO can be used as raw material in ingredient₂、SnF₂、SnF₄Deng.

Sb₂O₃Ingredient is contained sometimes with the amount more than 0%, can be by the optional member of melten glass deaeration.

On the other hand, if Sb₂O₃Amount is excessive, then, it is seen that the transmissivity in the short wavelength region in light region is deteriorated.Therefore, Sb₂O₃The upper limit of the content of ingredient is preferably 1.0%, is more preferably 0.7%, more preferably 0.5%.

For Sb₂O₃Sb can be used as raw material in ingredient₂O₃、Sb₂O₅、Na₂H₂Sb₂O₇·5H₂O etc..

It should be noted that making glass clarifying and carrying out the ingredient of deaeration to be not limited to above-mentioned Sb₂O₃Glass can be used in ingredient Well known fining agent, deaeration agent in manufacturing field or combination thereof.

＜ is about the ingredient ＞ that should not contain

Then, illustrate the ingredient that should not contain in the optical glass of the present invention and if undesirable ingredient containing if.

It can be added as needed on other compositions in the range of not damaging the characteristic of glass of the present application.Wherein, Each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo other than Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu With property as follows, therefore, especially in the optical glass using the wavelength of visibility region, preferably it is substantially free of Have, the property is, even if individually contain it is a small amount of or it is compound containing it is a small amount of when glass if can colour, visible Absorption is generated at the specific wavelength in light region.

In addition, the lead compounds such as PbO and As₂O₃Equal arsenic compounds are the big ingredients of environmental pressure, therefore, it is desirable to substantially It does not contain, that is, other than being inevitably mixed into, be entirely free of.

In turn, each ingredient of Th, Cd, Tl, Os, Be and Se has control what it was used in recent years as harmful chemical substance Tendency.Not only in the manufacturing process of glass, but also in manufacturing procedure and the punishment after commercialization, need in environmental cure Measure.Therefore, when paying attention to influence environmentally, these are preferably contained substantially no.

For the glass composition of the present invention, composition is with relative to being scaled glass gross mass that oxide forms Quality % is indicated, therefore, is not indicated with the record of mole % directly, but the glass group of each characteristic required in meeting the present invention The composition indicated based on mole % for closing each ingredient present in object is formed with to be scaled oxide and is counted, substantially takes the following value.

B₂O₃Ingredient is 25.0~60.0 moles of %,

La₂O₃Ingredient is 10.0~30.0 moles of %, and

Y₂O₃Ingredient is more than 0%~15.0 mole %,

And

Gd₂O₃Ingredient is 0~5.0 mole of %,

Li₂O ingredients are 0~30.0 mole of %,

ZnO component is 0~30.0 mole of %,

SiO₂Ingredient is 0~45.0 mole of %,

Ta₂O₅Ingredient is 0~5.0 mole of %,

Yb₂O₃Ingredient is 0~5.0 mole of %,

MgO ingredients are 0~25.0 mole of %,

CaO ingredients are 0~25.0 mole of %,

SrO ingredients are 0~15.0 mole of %,

BaO ingredients are 0~20.0 mole of %,

TiO₂Ingredient is 0~20.0 mole of %,

Nb₂O₅Ingredient is 0~10.0 mole of %,

WO₃Ingredient is 0~10.0 mole of %,

Na₂O ingredients are 0~20.0 mole of %,

K₂O ingredients are 0~10.0 mole of %,

Cs₂O ingredients are 0~5.0 mole of %,

P₂O₅Ingredient is 0~10.0 mole of %,

GeO₂Ingredient is 0~10.0 mole of %,

ZrO₂Ingredient is 0~15.0 mole of %,

Al₂O₃Ingredient is 0~10.0 mole of %,

Ga₂O₃Ingredient is 0~5.0 mole of %,

Bi₂O₃Ingredient is 0~5.0 mole of %,

TeO₂Ingredient is 0~15.0 mole of %,

SnO₂Ingredient is 0~1.0 mole of %, or

Sb₂O₃Ingredient is 0~0.5 mole of %.

[manufacturing method]

The optical glass of the present invention for example makes in the following way.That is, uniformly mixing above-mentioned raw materials, each ingredient is made to exist In the range of defined content, the mixture of making is put into platinum crucible, according to the melting difficulty that glass forms, in electricity Within the temperature range of 1100~1500 DEG C melt within 2~5 hours in stove, and stir and homogenize, is then reduced to appropriate Then temperature is cast into mold, Slow cooling.Thus it makes.

[physical property]

The optical glass of the present invention preferably has high refractive index and high Abbe number (low dispersion).Especially optics of the invention Refractive index (the n of glass_d) lower limit be preferably 1.70, be more preferably 1.73, more preferably 1.75.The upper limit of the refractive index can be with Preferably 2.20, more preferably it is 2.10, more preferably 2.00.In addition, Abbe number (the ν of the optical glass of the present invention_d) lower limit Preferably 39, more preferably it is 40, more preferably 42, the upper limit is preferably 60, is more preferably 58, more preferably 55.

In addition, Abbe number (the ν of the optical glass of the present invention_d) and refractive index (n_d) between, preferably satisfy (ν_d) >=(- 125 ×n_d+ 260) relationship more preferably meets (ν_d) >=(- 125 × n_d+ 265) relationship more preferably meets (ν_d) >=(- 125 × n_d+ 267) relationship further preferably meets (ν_d) >=(- 125 × n_d+ 270) relationship.

By having such high refractive index, even if to which larger light can be obtained if seeking the slimming of optical element Amount of refraction.In addition, by having such low dispersion, even to simple lens, it is burnt caused by the wavelength difference of light Point deviation (aberration) also becomes smaller.Moreover, by having such low dispersion, for example, with the light with high dispersive (low Abbe number) When learning element combination, high imaging characteristic etc. can be sought.

Therefore, optical glass of the invention is useful in optical design, especially, can not only realize high imaging characteristic Deng, and the miniaturization of optical system is can also be achieved, the degree of freedom of expansible optical design.

The preferred devitrification resistance of optical glass of the present invention is high, more specifically, preferably has low liquidus temperature.That is, this hair The upper limit of the liquidus temperature of bright optical glass is preferably 1300 DEG C, is more preferably 1280 DEG C, more preferably 1250 DEG C.As a result, Even if flowing out melten glass at a lower temperature, the crystallization of manufactured glass is also reduced by, and therefore, can especially be reduced by melting Melt devitrification when state forms glass, the influence of the optical characteristics of the optical element to having used glass can be reduced.In addition, due to Reducing the melting temperature of glass can formed glass, therefore the energy that consumes when molding by inhibiting glass can drop The manufacturing cost of low glass.On the other hand, the lower limit of the liquidus temperature of optical glass of the invention is not particularly limited, and passes through this The lower limit for inventing the liquidus temperature of obtained glass can be preferably 500 DEG C, more preferably be 600 DEG C, more preferably 700 DEG C.It needs It is noted that " liquidus temperature " in this specification indicates following temperature：It is packed into the platinum crucible of the capacity of 50ml The glass specimen of the cullet shape of 30cc is put into platinum crucible and complete molten condition is made at 1350 DEG C, is cooled to regulation Temperature, kept for 12 hours, take out to outside stove, be cooled to, observe in glass surface and glass has nodeless mesh immediately after, will The minimum temperature for not confirming crystallization is used as " liquidus temperature ".Herein, defined temperature when cooling is until 1300 DEG C Every 10 DEG C of temperature.

For the optical glass of the present invention, the preferably transmission of the transmission of visible light especially light of the long side of visible light intermediate waves Rate is high, and the coloring being generated by it is few.

In particular, for the optical glass of the present invention, if the transmissivity with glass indicates, with the sample of thickness 10mm Meter shows the wavelength (λ of spectral-transmission favtor 80%₈₀) the upper limit be preferably 500nm, more preferably be 450nm, more preferably 420nm.

In addition, the present invention optical glass in, in terms of the sample of thickness 10mm, display spectral-transmission favtor 5% it is most short Wavelength (λ₅) the upper limit be preferably 400nm, more preferably be 380nm, more preferably 360nm.

Near ultraviolet region, glass improves the absorption edge of glass relative to the transparency of visible light, therefore, can as a result, It is preferred that the optical glass is made the optical element that light penetrates for lens etc..

The optical glass preferred specific gravity of the present invention is small.More specifically, the proportion of optical glass of the invention is preferably 5.50[g/cm³] below.As a result, optical element, be lowered using the quality of its optical instrument, therefore can contribute to optics The lighting of instrument.Therefore, the upper limit of the proportion of optical glass of the invention is preferably 5.50, is more preferably 5.30, more preferably It is 5.20, more preferably 4.90.It should be noted that the present invention optical glass proportion usually approximately in 3.00 or more, more Specifically 3.50 or more, more specifically 4.00 or more.

The proportion of the optical glass of the present invention is based on Japanese Optical nitre industry can standard JOGIS05-1975 " optics glass The assay method of the proportion of glass " is measured.

[glass forming body and optical element]

By the optical glass made, the moulds such as the molded, precision press formation of method or reheating of such as attrition process are used Molded method can make glass forming body.That is, optical glass is ground and is ground etc. mechanical processings make glass at Type body, or the preform made of optical glass is carried out carrying out attrition process after reheating is molded to make glass molding Body, or to being ground the preform being processed into, using well known float glass process molding etc. and the preform that is formed into Row precision press formation can make glass forming body.It should be noted that the method for making glass forming body is not limited to these sides Method.

The glass forming body formed as a result, by the optical glass of the present invention has a variety of optical elements and optical design With wherein particularly preferred for optical elements such as lens, prisms.The big glass forming body of diameter can be formed as a result, therefore can The enlargement for realizing optical element, moreover, can realize fine and high-precision when for optical instruments such as camera, projectors Imaging characteristic and projection property.

[embodiment]

By the refractive index of the composition and these glass of the embodiment of the present invention (No.1~No.9) and comparative example (No.A) (n_d), Abbe number (ν_d), liquidus temperature, spectral-transmission favtor show 5% and 80% wavelength (λ₅And λ₈₀) and the result of proportion show In 1~table of table 2.It should be noted that embodiment below is only to illustrate purpose, it is not limited in the embodiment.

The glass of the embodiment of the present invention and comparative example makes as follows：It is selected as the raw material point of each ingredient The common light such as not comparable oxide, hydroxide, carbonate, nitrate, fluoride, hydroxide, metaphosphoric acid compound The high-purity raw used in glass is learned, is weighed simultaneously in the way of as the ratio of each embodiment shown in table formed After evenly mixing, it puts into platinum crucible, according to the melting difficulty that glass forms, the temperature using electric furnace at 1100~1500 DEG C It spends in range and melt within 2~5 hours, then stirring homogenizes, and then casts into mold etc., and Slow cooling makes glass.

Herein, the refractive index of the glass of Examples and Comparative Examples and Abbe number are based on Japanese Optical nitre industry meeting standard JOGIS01-2003 is measured.Herein, refractive index and Abbe number pass through to by making Slow cooling cooling rate be -25 DEG C/hr Obtained glass is measured and finds out.

It is surveyed in addition, the transmissivity of the glass of Examples and Comparative Examples is based on Japanese Optical nitre industry meeting standard JOGIS02 It is fixed.It should be noted that in the present invention, by measuring the transmissivity of glass, the presence or absence of coloring of glass and degree are found out.Specifically For, grinding object parallel for the opposite of 10 ± 0.1mm of thickness measures the spectral transmission of 200~800nm according to JISZ8722 Rate finds out λ₅(wavelength when transmissivity 5%) and λ₈₀(wavelength when transmissivity 80%).

In addition, the liquidus temperature of the glass of Examples and Comparative Examples is found out as follows：Into the platinum crucible of the capacity of 50ml It is packed into the glass specimen of the cullet shape of 30cc, it is complete molten condition that it is made in platinum crucible and at 1350 DEG C, is cooled to 1300 DEG C~1160 DEG C of any temperature every 10 DEG C of settings, is kept for 12 hours, is taken out to outside stove, is cooled to, then stands Observing in glass surface and glass has nodeless mesh, finds out the minimum temperature for not confirming crystallization.

In addition, the proportion of the glass of Examples and Comparative Examples is based on Japanese Optical nitre industry meeting standard JOGIS05- 1975 " assay methods of the proportion of optical glass " measure.

[table 1]

[table 2]

As shown in Table, for the optical glass of the embodiment of the present invention, by making mass ratio Y₂O₃/(Y₂O₃+ Gd₂O₃) it is 0.500 or more, Gd can be reduced₂O₃、Ta₂O₅Deng usage amount, therefore can more inexpensively obtain.On the other hand, for For the glass of comparative example (No.A), contain more mole and Gd₂O₃、Ta₂O₅, thus will also realize that material cost height.

The liquidus temperature of the optical glass of the embodiment of the present invention be 1300 DEG C hereinafter, more specifically be 1230 DEG C with Under, in desired range.Therefore, it is seen that the liquidus temperature of the optical glass of the embodiment of the present invention is low, and devitrification resistance is high.

In addition, the λ of the optical glass of the embodiment of the present invention₈₀(wavelength when transmissivity 80%) is 500nm hereinafter, more Specifically it is 440nm or less.In addition, the λ of the optical glass of the embodiment of the present invention₅(wavelength when transmissivity 5%) is 400nm is hereinafter, be more specifically 328nm or less.

In addition, refractive index (the n of the optical glass of the embodiment of the present invention_d) be 1.70 or more, more specifically for 1.73 or more, and the refractive index is 2.20 hereinafter, being more specifically 1.90 hereinafter, in desired range.

In addition, Abbe number (the ν of the optical glass of the embodiment of the present invention_d) be 35 or more, more specifically for 40 with On, and the Abbe number is 60 hereinafter, being more specifically 55 hereinafter, in desired range.

In addition, the proportion of the optical glass of the embodiment of the present invention be 5.50 hereinafter, more specifically be 5.30 hereinafter, In desired range.

Therefore, for the optical glass of the embodiment of the present invention, it is seen that the Gd as expensive ingredient₂O₃、Ta₂O₅ Deng usage amount be reduced compared with the glass of comparative example, and refractive index and Abbe number be in desired range, devitrification Property it is high, coloring is few, and proportion is small.

In turn, using the optical glass of the embodiment of the present invention, glass blocks is formed, which is ground and is ground Mill, is processed into the shape of lens and prism.As a result, the shape of various lens and prism can be steadily processed into.

More than, it is described in detail by the present invention, but the purpose that the present embodiment only illustrates eventually for illustrative purposes, answers Work as understanding, without departing from the purport and range of the present invention, those skilled in the art can be variously changed.

Claims

1. a kind of optical glass, wherein in terms of quality %, contain 16.480~26.710% B₂O₃Ingredient, 45.130~ 55.0% La₂O₃Ingredient and 10.230~15.0% Y₂O₃The ZrO below of ingredient, 3.0% or more and 10.0%₂Ingredient and 1.0% less than 10.0% SiO₂Ingredient,

The content of ZnO component is less than 5.0%,

Yb₂O₃The content of ingredient is less than 1.0%,

Nb₂O₅The content of ingredient is 3.880% or less,

Ln₂O₃The quality of ingredient and for 58.400% or more and 70.0% hereinafter, in formula, Ln is a kind in La, Gd, Y, Yb More than,

Mass ratio Y₂O₃/(Y₂O₃+Gd₂O₃) it is 0.500 or more and 1.000 or less,

Mass ratio La₂O₃/(La₂O₃+Y₂O₃+Gd₂O₃+Yb₂O₃) be 0.772 or more and 0.850 hereinafter,

The optical glass has 1.78800 or more and 1.82370 refractive index n below_d, have 43.06 or more and 47.40 with Under Abbe number ν_d,

The optical glass has 1150 DEG C of liquidus temperatures below,

The liquidus temperature is following temperature：Complete molten condition is made in glass specimen, cooling is until 1300 DEG C below every 10 DEG C of temperature does not observe the minimum of crystallization after being kept for 12 hours and carrying out cooling in obtained glass surface and glass Temperature,

In terms of the sample of thickness 10mm, the wavelength X of spectral-transmission favtor 5% is shown₅For 328nm hereinafter, showing spectral-transmission favtor 80% wavelength X₈₀For 440nm or less.

2. optical glass as described in claim 1, wherein in terms of quality %, Gd₂O₃The content of ingredient is less than 10.0%.

3. optical glass as described in claim 1, wherein in terms of quality %,

Li₂O ingredients are 0~10.0%.

4. optical glass as described in claim 1, wherein in terms of quality %,

Ta₂O₅Ingredient is 0~18.0%.

5. optical glass as described in claim 1, wherein in terms of quality %,

MgO ingredients are 0~20.0%,

CaO ingredients are 0~20.0%,

SrO ingredients are 0~20.0%,

BaO ingredients are 0~25.0%.

6. optical glass as described in claim 1, wherein the quality of RO ingredients and for 25.0% hereinafter, in RO formulas, R is choosing From one or more of Mg, Ca, Sr, Ba.

7. optical glass as described in claim 1, wherein in terms of quality %,

TiO₂Ingredient is 0~15.0%,

WO₃Ingredient is 0~20.0%.

8. optical glass as described in claim 1, wherein TiO₂Ingredient, Nb₂O₅Ingredient and WO₃The content of ingredient and be 30.0% or less.

9. optical glass as described in claim 1, wherein in terms of quality %,

Na₂O ingredients are 0~10.0%,

K₂O ingredients are 0~10.0%,

Cs₂O ingredients are 0~10.0%.

10. optical glass as described in claim 1, wherein Rn₂The quality of O ingredients and for 15.0% hereinafter, Rn₂In O formulas, Rn To be selected from one or more of Li, Na, K, Cs.

11. optical glass as described in claim 1, wherein in terms of quality %,