CN107721160A - Optical glass, preforming material and optical element - Google Patents

Optical glass, preforming material and optical element Download PDF

Info

Publication number
CN107721160A
CN107721160A CN201711008789.5A CN201711008789A CN107721160A CN 107721160 A CN107721160 A CN 107721160A CN 201711008789 A CN201711008789 A CN 201711008789A CN 107721160 A CN107721160 A CN 107721160A
Authority
CN
China
Prior art keywords
composition
glass
optical glass
less
mole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711008789.5A
Other languages
Chinese (zh)
Inventor
桃野净行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ohara Inc
Original Assignee
Ohara Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2013239213A external-priority patent/JP5875572B2/en
Priority claimed from JP2013241228A external-priority patent/JP6014573B2/en
Application filed by Ohara Inc filed Critical Ohara Inc
Publication of CN107721160A publication Critical patent/CN107721160A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The problem of the present invention, which is to provide, can more inexpensively obtain refractive index (nd) and Abbe number (νd) in desired scope and easily carry out the optical glass and preforming material and optical element of precise compression molding and the high preforming material of devitrification resistance.The optical glass of the present invention, in terms of mole %, contains the B below more than 10.0% 50.0%2O3Composition, less than more than 5.0% 30.0% La2O3Composition, there is more than 1.80 refractive index (nd), with less than more than 30 45 Abbe number (νd)。

Description

Optical glass, preforming material and optical element
The application be the applying date on April 3rd, 2014, Application No. 201410133778.X, it is entitled " optical glass, The divisional application of the application of preforming material and optical element ".
Technical field
The present invention relates to optical glass, preforming material and optical element.
Background technology
In recent years, using optical system equipment digitlization and high-precision densification develop rapidly, taken the photograph in digital camera, video camera etc. In the various field of optical equipment such as the image players such as shadow equipment, projector, projection TV (projection) equipment, to reducing optical system The number of the optical elements such as the middle lens used, prism, make the requirement of optical system integral light and miniaturization increasingly strong.
In the optical glass for making optical element, particularly, the tool of the overall lighting of optical system and miniaturization can be achieved There is more than 1.80 refractive index (nd) and with less than more than 30 45 Abbe number (νd) can precise compression molding high index of refraction The demand of low dispersing glass is very high.As the low dispersing glass of such high index of refraction, it is known to patent document 1~4 be generation Glass composition as table.
[patent document 1] Japanese Unexamined Patent Publication 06-305769 publications
[patent document 2] Japanese Unexamined Patent Publication 2006-137662 publications
[patent document 3] Japanese Unexamined Patent Publication 2006-240889 publications
[patent document 4] Japanese Unexamined Patent Publication 2008-201661 publications.
The content of the invention
The lens used in optical system have spherical lens and non-spherical lens, if using non-spherical lens, can reduce optics The number of element.In addition, for the various optical elements beyond lens, it is also known that have the member in the face for foring complicated shape Part.However, using conventional grinding, grinding step, it is desirable to obtain it is aspherical or form complexity shape face when, it is necessary to Costly and complicated flow chart.Therefore, will be by material block (gob) or glass blocks using the mould crossed by Ultra-precision Turning The preforming material direct weighting that (glass block) is obtained is molded and obtains the method for the shape of optical element, i.e., accurate mould Molded method is currently main flow.
In addition, in addition to by the method for preforming material precise compression molding, it is also known that following method：Will be by glass material shape Into material block or glass blocks reheat and be molded (reheating is molded), so as to obtain glass forming body, to the glass shaping Body is ground and ground.
As the manufacture method of such precise compression molding, the molded middle preforming material used of reheating, have to utilize and drip Method is entered as method that melten glass directly manufactures, to processed goods obtained from by glass blocks hot repressing or grinding balling-up shape The method of row grinding grinding.For either method, optical element is obtained in order to which melten glass is molded into desired shape, It is required to easily carry out precise compression molding, and the glass formed is not susceptible to devitrification.
In addition, in order to reduce the material cost of optical glass, the expense of raw materials of each composition of composition optical glass it is expected as far as possible It is cheap.In addition, in order to reduce the manufacturing cost of optical glass, it is expected that the meltbility of raw material is high, i.e., melt at a lower temperature.But It is that the glass composition described in patent document 1~4 hardly fully meets above-mentioned each requirement.
The present invention is to complete in view of the above problems, it is therefore intended that more inexpensively obtains refractive index (nd) and Abbe number (νd) In desired scope, and precise compression molding is easily carried out, and the preforming material that devitrification resistance is high.
Experimental study has been repeated in order to solve above-mentioned problem in the present inventor etc., as a result finds, for containing B2O3Composition And La2O3The glass of composition, it can obtain refractive index (nd) and Abbe number (νd) in desired scope, and easily carry out essence The optical glass of close compression molding, so as to complete the present invention.
Especially, the present inventor etc. has found, can obtain refractive index (nd) and Abbe number (νd) in desired scope, and drop The high Gd of low material cost2O3Composition and Ta2O5The content of composition, and easily carry out the optical glass of precise compression molding.
In addition, the present inventor etc. has found, refractive index (n can obtaind) and Abbe number (νd) in desired scope, and contain The Y of lower cost for material in the composition for contributing to high index of refraction high dispersive2O3Composition, and easily carry out precise compression molding Optical glass.
Specifically, the scheme as present invention offer is following.
(1) a kind of optical glass, in terms of mole %, the B below more than 10.0% 50.0% is contained2O3Composition, more than 5.0% Less than 30.0% La2O3Composition, there is more than 1.80 refractive index (nd), with less than more than 30 45 Abbe number (νd)。
(2) optical glass described in (1), in terms of mole %, Y2O3The content of composition is less than 20.0%.
(3) optical glass described in (1) or (2), in terms of mole %, the Y more than 0% and for less than 20.0% is contained2O3Composition.
(4) optical glass any one of (1)~(3), in terms of mole %, Y2O3The content of composition is less than 10.0%.
(5) optical glass any one of (1)~(4), in terms of mole %,
Gd2O3Composition is 0~10.0%,
Yb2O3Composition is 0~10.0%,
Lu2O3Composition is 0~10.0%.
(6) optical glass any one of (1)~(5), in terms of mole %, Ta2O5The content of composition is less than 10.0%.
(7) optical glass any one of (1)~(6), mole and (Gd2O3+Yb2O3+Ta2O5) it is less than 10.0%.
(8) optical glass any one of (1)~(7), mole and (Gd2O3+Ta2O5) it is less than 5.0%.
(9) optical glass any one of (1)~(8), in terms of mole %, Ta2O5The content of composition is less than 1.0%.
(10) optical glass any one of (1)~(9), in terms of mole %, Gd2O3The content of composition is less than 1.0%.
(11) optical glass any one of (1)~(10), Ln2O3(in formula, Ln is selected from La, Gd, Y, Yb, Lu to composition One or more of) mole and for less than more than 10.0% 40.0%.
(12) optical glass any one of (1)~(11), contains above-mentioned Ln2O3Two or more composition in composition.
(13) optical glass any one of (1)~(12), in terms of mole %,
TiO2Composition is 0~20.0%,
Nb2O5Composition is 0~10.0%.
(14) optical glass any one of (1)~(13), in terms of mole %, WO3The content of composition is less than 20.0%.
(15) optical glass any one of (1)~(14), in terms of mole %, less than more than 1.0% 20.0% is contained WO3Composition.
(16) optical glass any one of (1)~(15), mole and (TiO2+WO3+Nb2O5) it is 1.0~30.0%.
(17) optical glass any one of (1)~(16), in terms of mole %, less than more than 10.0% 38.0% is contained ZnO component.
(18) optical glass any one of (1)~(17), in terms of mole %, ZrO2The content of composition be 10.0% with Under.
(19) optical glass any one of (1)~(18), in terms of mole %, SiO2The content of composition be 15.0% with Under.
(20) optical glass any one of (1)~(19), in terms of mole %, Li2The content of O compositions is less than 8.0%.
(21) optical glass any one of (1)~(20), in terms of mole %,
Na2O compositions are 0~15.0%,
K2O compositions are 0~10.0%,
Cs2O compositions are 0~10.0%.
(22) optical glass any one of (1)~(21), Rn2(in formula, Rn is in Li, Na, K, Cs to O compositions More than one) mole and for less than 20.0%.
(23) optical glass any one of (1)~(22), in terms of mole %,
MgO compositions are 0~10.0%,
CaO compositions are 0~10.0%,
SrO compositions are 0~10.0%,
BaO compositions are 0~10.0%.
(24) optical glass any one of (1)~(23), (in formula, R is one in Mg, Ca, Sr, Ba to RO compositions More than kind) mole and for less than 11.0%.
(25) optical glass any one of (1)~(24), in terms of mole %,
GeO2Composition is 0~10.0%,
P2O5Composition is 0~10.0%,
Bi2O3Composition is 0~15.0%,
TeO2Composition is 0~15.0%,
Al2O3Composition is 0~15.0%,
Ga2O3Composition is 0~15.0%,
Sb2O3Composition is 0~1.0%,
Had instead of part or all and the fluoride that contains of one or more kinds of oxides of above-mentioned each element The content of fluorine atom be 0~15.0 mole of %.
(26) optical glass any one of (1)~(25), there is less than more than 1.80 1.95 refractive index (nd), have Less than more than 30 45 Abbe number (νd)。
(27) optical glass any one of (1)~(26), glass transition temperature (Tg) are more than 580 DEG C and for 630 DEG C Below.
(28) optical glass any one of (1)~(27), there is less than 1100 DEG C of liquidus temperature.
(29) a kind of preforming material, formed as the optical glass any one of (1)~(28).
(30) a kind of optical element, it is to make the preforming material extrusion forming described in (29).
(31) a kind of optical element, using the optical glass any one of (1)~(28) as main material.
(32) a kind of optical device, possesses the optical element described in (30).
(33) a kind of optical device, possesses the optical element described in (31).
By the present invention, refractive index (n can be more inexpensively obtainedd) and Abbe number (νd) in desired scope, and easily Carry out precise compression molding, and the preforming material that devitrification resistance is high.
Embodiment
The optical glass of the present invention, in terms of mole %, contains the B below more than 10.0% 50.0%2O3Composition, more than 5.0% Less than 30.0% La2O3Composition, there is more than 1.80 refractive index (nd) and with less than more than 30 45 Abbe number (νd)。
Especially, the 1st optical glass, in terms of mole %, the B below more than 10.0% 50.0% is contained2O3Composition, 5.0% with Upper less than 30.0% La2O3Composition, mole and (Gd2O3+Ta2O5) it is less than 5.0%, the refractive index (n with more than 1.80d) and With less than more than 30 45 Abbe number (νd)。
In addition, the 2nd optical glass, in terms of mole %, contains the B below more than 10.0% 50.0%2O3Composition, more than 5.0% Less than 30.0% La2O3Composition, the Y more than 0% and for less than 20.0%2O3Composition, there is more than 1.80 refractive index (nd) And with less than more than 30 45 Abbe number (νd)。
Especially, in the 1st optical glass, by reducing Gd2O3Composition and Ta2O5The content of composition, can reduce the material of glass into This.On the other hand, especially, in the 2nd optical glass, by containing Y2O3Composition, the material cost of glass can be reduced.It is also, logical Cross with B2O3Composition and La2O3Based on composition, so as to less than more than 1.80 1.95 refractive index (nd) and more than 30 45 Following Abbe number (νd) while, liquidus temperature also easy step-down.
Present inventor has found, by with less than more than 1.80 1.95 refractive index (nd) and less than more than 30 45 Ah Shellfish number (νd) glass in, reduce the high Gd of material cost2O3Composition and Ta2O5The content of composition, while also contribute to height The Y of lower cost for material in the composition of refractive index high dispersive2O3Composition, and the content of each composition is adjusted, thus, with vitrifying The low optical glass of transition temperature is compared, and can be reduced devitrification when glass makes, thus, can be obtained being easier to make for being press-formed Glass.
By the above, following optical glass can be inexpensively obtained, the optical glass can obtain refractive index (nd) and Abbe Number (νd) in desired scope, and precise compression molding is easily carried out, and the preforming material that devitrification resistance is high.
The embodiment of optical glass of the invention described further below.The present invention is not by any limit of following embodiment System, in the range of the purpose of the present invention, appropriate change can be carried out and implemented.It should be noted that for repeat specification it Place, is suitably omitted the description, but do not limit the purport of invention sometimes.
[glass ingredient]
The compositing range for forming each composition of the optical glass of the present invention is as described below.In this specification, on containing for each composition Amount, it is to be contained with what mole % of the glass total material amount formed relative to oxide conversion was represented unless otherwise specified Amount.Herein, " oxide conversion composition " refers to, it is assumed that the oxidation used as the raw material of the glass constituent of the present invention Thing, double salt, metal fluoride etc. are all decomposed in melting and are converted into oxide, now, with the total of the generation oxide Amount of substance is 100 moles of %, to represent the composition of each composition contained in glass.
＜ is on required composition, optional member ＞
B2O3Composition, it is as network former in the largely optical glass of the invention containing rare-earth oxide Required composition.Especially, by making B2O3The content of composition is more than 10.0%, can improve the devitrification resistance of glass, and The Abbe number of glass can be improved.Therefore, B2O3The lower limit of the content of composition is preferably 10.0%, and more preferably 15.0%, further Preferably 20.0%, more preferably 25.0%.
On the other hand, by making B2O3The content of composition is less than 50.0%, readily available larger refractive index, and can be pressed down The deterioration of chemical durability processed.Therefore, B2O3The upper limit of the content of composition is preferably 50.0%, and more preferably 45.0%, further Preferably 40.0%.
For B2O3Composition, H can be used as raw material3BO3、Na2B4O7、Na2B4O7·10H2O、BPO4Deng.
La2O3Composition is to improve the refractive index of glass and improve the required composition of the Abbe number of glass.Therefore, La2O3Composition The lower limit of content be preferably 5.0%, more preferably 10.0%, more preferably 13.0%.
On the other hand, by making La2O3The content of composition is less than 30.0%, can be lost by improving the stability of glass to reduce Thoroughly.Accordingly, with respect to the La of the glass total material amount of oxide conversion composition2O3The upper limit of the content of composition is preferably 30.0%, More preferably 25.0%, more preferably 20.0%, more preferably 17.0%.
For La2O3Composition, La can be used as raw material2O3、La(NO3)3·XH2O (X is arbitrary integer) etc..
Y2O3When composition is containing more than 0%, high index of refraction can maintained and while high Abbe number, suppress the material of glass into Originally, the optional member of specific gravity of glass and compared with other rare earth constituents can be reduced.Especially, in the 2nd optical glass, Y2O3Composition is required composition.Therefore, Y2O3The content of composition is preferably greater than 0%, and lower limit is more preferably 0.5%, further preferably For 1.0%, more preferably 2.0%, more preferably 3.0%.
On the other hand, by making Y2O3The content of composition is less than 20.0%, can suppress the reduction of the refractive index of glass, and can Improve the devitrification resistance of glass.Therefore, Y2O3The upper content limit of composition is preferably 20.0%, and more preferably 10.0%, it is further excellent Elect 8.0%, more preferably 6.0% as.
For Y2O3Composition, Y can be used as raw material2O3、YF3Deng.
Gd2O3Composition can improve the refractive index of glass when being containing more than 0%, and can improve the optional member of Abbe number.
On the other hand, in rare earth element, especially by the Gd for making costliness2O3Composition is less than 10.0%, can reduce glass Material cost, therefore, can more inexpensively make optical glass.Must in addition, can thus suppress exceeding for the Abbe number of glass The rising wanted.Therefore, Gd2O3The content of composition is preferably smaller than 10.0%, more preferably less than 5.0% respectively, is further preferably no larger than 1.0%, 0.5% is further preferably no larger than, is further preferably no larger than 0.3%, is further preferably no larger than 0.1%.
For Gd2O3Composition, Gd can be used as raw material2O3、GdF3Deng.
Yb2O3Composition and Lu2O3When composition is containing more than 0%, the refractive index of glass can be improved, and Abbe number can be improved Optional member.
On the other hand, by making Yb2O3Composition and Lu2O3The content of composition is respectively less than 10.0%, can reduce the material of glass Cost, therefore can more inexpensively make optical glass.In addition, it can thus improve the devitrification resistance of glass.Therefore, Yb2O3Composition and Lu2O3The upper limit of the content of composition is respectively preferably 10.0%, more preferably 5.0%, more preferably 3.0%, further excellent Elect 1.0%, more preferably 0.1% as.From the viewpoint of material cost is reduced, Yb can also not contained2O3Composition and Lu2O3Composition.
For Yb2O3Composition and Lu2O3Composition, Yb can be used as raw material2O3、Lu2O3Deng.
Ta2O5When composition is containing more than 0%, the refractive index of glass can be improved, and the optional member of devitrification resistance can be improved.
On the other hand, by making expensive Ta2O5Composition is less than 10.0%, can reduce the material cost of glass, therefore can be more honest and cleaner Make optical glass valency.In addition, thus the melting temperature step-down of raw material, the energy required for the melting of raw material reduce, therefore Also the manufacturing cost of optical glass can be reduced.Therefore, Ta2O5The content of composition is preferably smaller than 10.0%, more preferably less than 5.0%, 1.0%, more preferably less than 0.7%, more preferably less than 0.4% are further preferably no larger than, it is further preferably small In 0.3%, more preferably less than 0.2%, more preferably less than 0.1%.
For Ta2O5Composition, Ta can be used as raw material2O5Deng.
Gd2O3Composition, Yb2O3Composition and Ta2O5The content of composition and preferably less than 10.0%.Thus it is expensive that these can be reduced Composition content, therefore the material cost of glass can be suppressed.Mole and (Gd therefore,2O3+Yb2O3+Ta2O5) the upper limit it is preferred For 10.0%, more preferably 7.0%, more preferably 5.0%, more preferably 3.5%, more preferably 2.0%, More preferably 1.0%, it is further preferably no larger than 0.5%.
Gd2O3Composition and Ta2O5The total amount of composition is preferably smaller than 5.0%.Thus the content of these expensive compositions can be reduced, Therefore the material cost of glass can be suppressed.Mole and (Gd therefore,2O3+Ta2O5) be preferably smaller than 5.0%, more preferably 3.5% with Under, 1.0% is further preferably no larger than, is further preferably no larger than 0.5%.
Ln2O3The content of composition (in formula, Ln be selected from one or more of La, Gd, Y, Yb, Lu) and (mole and) be preferably Less than more than 10.0% 40.0%.
Especially, by making this and being more than 10.0%, both refractive index and Abbe number of glass can be improved, therefore easy can obtain To the glass with desired refractive index and Abbe number.Therefore, Ln2O3The lower limit of mole sum of composition is preferably 10.0%, more Preferably 15.0%, more preferably 16.0%, more preferably 17.0%, more preferably 18.0%.
On the other hand, by making this and being less than 40.0%, the liquidus temperature step-down of glass, therefore the devitrification of glass can be reduced. Therefore, Ln2O3The upper limit of mole sum of composition is preferably 40.0%, more preferably 30.0%, more preferably 25.0%, is entered One step is preferably 22.0%.
The optical glass of the present invention preferably comprises above-mentioned Ln2O3Two or more composition in composition.Thus, the liquid phase temperature of glass Further step-down is spent, therefore can obtain the higher glass of devitrification resistance.Especially, as Ln2O3Composition, from glass can be easily reduced The aspect of the liquidus temperature of glass and from the aspect of can making cheap optical glass, is preferably comprised comprising La2O3Composition and Y2O3The two or more compositions of composition.
TiO2When composition is containing more than 0%, the refractive index and Abbe number of glass can be improved, and by reducing the liquid phase of glass Temperature and the optional member that devitrification resistance can be improved.
On the other hand, by making TiO2The content of composition is less than 20.0%, can be reduced by TiO2The excess of composition contains and led The devitrification of cause, reduction of the glass relative to the transmissivity of visible ray (especially below wavelength 500nm) can be suppressed.Therefore, TiO2 The upper limit of the content of composition is preferably 20.0%, more preferably 15.0%, more preferably 12.0%, more preferably 10.0%.
For TiO2Composition, TiO can be used as raw material2Deng.
Nb2O5When composition is containing more than 0%, the refractive index that can improve glass reduces Abbe number, and by reducing glass Liquidus temperature and the optional member that devitrification resistance can be improved.
On the other hand, by making Nb2O5The content of composition is less than 10.0%, can reduce Nb2O5The excess of composition contains and caused Devitrification, also, reduction of the glass relative to the transmissivity of visible ray (especially below wavelength 500nm) can be suppressed.Therefore, Nb2O5The upper limit of the content of composition is preferably 10.0%, more preferably 8.0%, more preferably 6.0%, more preferably 5.0%.
For Nb2O5Composition, Nb can be used as raw material2O5Deng.
WO3When composition is containing more than 0%, the coloring of glass caused by other high index of refraction compositions can be reduced, and can carry High index of refraction, glass transition temperature can be reduced, and the optional member of the devitrification resistance of glass can be improved.Therefore, WO3Composition Content be preferably greater than 0%, more preferably greater than 0.3%, further preferably greater than 0.5%, further preferably greater than 1.0%.
On the other hand, by making WO3The content of composition is less than 20.0%, can reduce WO3The coloring of glass caused by composition, is carried High visible light transmissivity.Therefore, WO3The upper limit of the content of composition is preferably less than 20.0%, and more preferably less than 17.0%, enter One step is preferably less than 15.0%, more preferably less than 13.0%.
For WO3Composition, WO can be used as raw material3Deng.
TiO2Composition, WO3Composition and Nb2O5Composition mole and preferably less than more than 1.0% 30.0%.
Especially, by making this mole and being more than 1.0%, even if reducing Ta2O5Composition etc., it also can obtain desired optics Constant, therefore can more inexpensively make the optical glass with desired optical characteristics.Mole and (TiO therefore,2+WO3+ Nb2O5) lower limit be preferably 1.0%, more preferably 2.5%, more preferably 5.0%.
On the other hand, by making this mole and being less than 30.0%, can suppress caused by the excess of these compositions contains The rising of liquidus temperature, therefore, the devitrification of optical glass can be reduced.Mole and (TiO therefore,2+WO3+Nb2O5) the upper limit it is preferred For 30.0%, more preferably 25.0%, more preferably 20.0%.
ZnO component be containing more than 0% when, glass transition temperature can be reduced, and can improve chemical durability it is optional into Point.Therefore, the content of ZnO component can be preferably greater than 0%, and lower limit can be more preferably 10.0%, more preferably 12.0%, more preferably 15.0%, more preferably 20.0%, more preferably 24.0%.
On the other hand, it is less than 38.0% by the content for making ZnO component, liquidus temperature can be reduced, also, vitrifying can be reduced The devitrification caused by exceeding necessary reduction of transition temperature.Therefore, the upper limit of the content of ZnO component is preferably 38.0%, more Preferably 36.0%, more preferably 35.0%.
For ZnO component, ZnO, ZnF can be used as raw material2Deng.
ZrO2When composition is containing more than 0%, the refractive index and Abbe number of glass can be improved, and appointing for devitrification resistance can be improved Hank point.Therefore, ZrO2The content of composition can be preferably greater than 0%, more preferably greater than 0.5%, further preferably greater than 0.8%.
On the other hand, by making ZrO2The content of composition is less than 10.0%, can reduce ZrO2The excess of composition contains and caused Devitrification.Therefore, ZrO2The upper limit of the content of composition is preferably 10.0%, more preferably 8.0%, more preferably 5.0%.
For ZrO2Composition, ZrO can be used as raw material2、ZrF4Deng.
SiO2When composition is containing more than 0%, the viscosity of melten glass can be improved, the coloring of glass can be reduced, and can improve The optional member of devitrification resistance.Therefore, SiO2The content of composition is preferably greater than 0%, and lower limit can be more preferably 1.0%, enter one Step is preferably 3.0%, more preferably 4.0%.
On the other hand, by making SiO2The content of composition is less than 15.0%, can suppress the rising of glass transition temperature, and The reduction of refractive index can be suppressed.Therefore, SiO2The upper limit of the content of composition is preferably 15.0%, and more preferably 12.0%, enter one Step is preferably 10.0%, more preferably 9.0%.
For SiO2Composition, SiO can be used as raw material2、K2SiF6、Na2SiF6Deng.
Li2When O compositions are containing more than 0%, the optional member of glass transition temperature can be reduced.
On the other hand, by making Li2The content of O compositions is less than 8.0%, can reduce the liquidus temperature of glass, reduces devitrification, can Improve chemical durability.Therefore, Li2The content of O compositions is preferably less than 8.0%, and more preferably less than 4.0%, further preferably Less than 2.0%, 1.0% is further preferably no larger than.
For Li2O compositions, Li can be used as raw material2CO3、LiNO3、Li2CO3Deng.
Na2O compositions, K2O compositions and Cs2When O compositions are containing more than 0%, the meltbility of glass can be improved, vitrifying can be reduced Transition temperature, and the optional member of devitrification resistance can be improved.
On the other hand, by making Na2The content of O compositions is less than 15.0%, and/or makes K2O compositions and Cs2O compositions are respective to be contained Measure as less than 10.0%, may be such that the refractive index for being difficult to reduce glass, and the devitrification of glass can be reduced.Therefore, Na2O compositions The upper limit of content be preferably 15.0%, more preferably 10.0%, more preferably 5.0%, more preferably 3.0%. In addition, K2O compositions and Cs2The upper limit of the content of O compositions is respectively preferably 10.0%, more preferably 5.0%, more preferably 3.0%.
For Na2O compositions, K2O compositions and Cs2O compositions, Na can be used as raw material2CO3、NaNO3、NaF、Na2SiF6、 K2CO3、KNO3、KF、KHF2、K2SiF6、Cs2CO3、CsNO3Deng.
Rn2The content of O compositions (in formula, Rn be selected from one or more of Li, Na, K) and (mole and) be preferably 20.0% Below.Thus, the refractive index for being difficult to reduce glass is may be such that, and the devitrification of glass can be reduced.Therefore, Rn2Mole of O compositions The upper limit of sum is preferably 20.0%, more preferably 10.0%, more preferably 5.0%, more preferably 3.5%, enters one Step is preferably 1.7%.
When MgO compositions, CaO compositions, SrO compositions and BaO compositions are containing more than 0%, refractive index, the melting of glass can adjust Property, the optional member of devitrification resistance.
On the other hand, can by making MgO compositions, CaO compositions, SrO compositions and the respective content of BaO compositions be less than 10.0% Make it easy to obtain desired refractive index, and the excess that can suppress these compositions contains the devitrification of caused glass.Therefore, MgO compositions, CaO compositions, the upper limit of SrO compositions and the respective content of BaO compositions are preferably 10.0%, and more preferably 5.0%, enter One step is preferably 3.0%.
For MgO compositions, CaO compositions, SrO compositions and BaO compositions, MgCO can be used as raw material3、MgF2、CaCO3、 CaF2、Sr(NO3)2、SrF2、BaCO3、Ba(NO3)2、BaF2Deng.
The content of RO compositions (in formula, R be selected from one or more of Mg, Ca, Sr, Ba) and (mole and) be preferably 11.0% Below.Thus, readily available desired high index of refraction.Therefore, the upper limit of mole sum of RO compositions is preferably 11.0%, more Preferably 5.0%, more preferably 3.0%.
GeO2When composition is containing more than 0%, the refractive index of glass can be improved, and the optional member of devitrification resistance can be improved.
However, GeO2Because cost of material is high, if therefore its content at most production cost uprise, therefore, by reducing Gd2O3Into Divide, Ta2O5Composition etc. and obtain effect reduce.Therefore, GeO2The upper limit of the content of composition is preferably 10.0%, more preferably 5.0%, more preferably 3.0%, more preferably 1.0%, more preferably 0.1%.From reduction material cost Viewpoint considers that can be free of has GeO2Composition.
For GeO2Composition, GeO can be used as raw material2Deng.
P2O5When composition is containing more than 0%, the liquidus temperature of glass can be reduced, improves the optional member of devitrification resistance.
On the other hand, by making P2O5The content of composition is less than 10.0%, and the chemical durability that can suppress glass is especially resistance to Water-based reduction.Therefore, P2O5The upper limit of the content of composition is preferably 10.0%, and more preferably 5.0%, more preferably 3.0%.
For P2O5Composition, Al (PO can be used as raw material3)3、Ca(PO3)2、Ba(PO3)2、BPO4、H3PO4Deng.
Bi2O3When composition is containing more than 0%, refractive index can be improved, and the optional member of glass transition temperature can be reduced.
On the other hand, by making Bi2O3The content of composition is less than 15.0%, can reduce the liquidus temperature of glass, improve resistance to mistake Permeability.Therefore, Bi2O3The content of composition is preferably less than 15.0%, and more preferably less than 10.0%, it is further preferably no larger than 5.0%, it is further preferably no larger than 3.0%.
For Bi2O3Composition, Bi can be used as raw material2O3Deng.
TeO2When composition is containing more than 0%, refractive index can be improved, and the optional member of glass transition temperature can be reduced.
On the other hand, with regard to TeO2For, it is being the melting that is formed by platinum with the crucible of platinum or the part contacted with melten glass When groove carrys out molten raw, can be with platinum alloy the problem of be present.Therefore, TeO2The content of composition be preferably 15.0% with Under, more preferably less than 10.0%, 5.0% is further preferably no larger than, is further preferably no larger than 3.0%.
For TeO2Composition, TeO can be used as raw material2Deng.
Al2O3Composition and Ga2O3When composition is containing more than 0%, the chemical durability of glass can be improved, and melting can be improved The optional member of the devitrification resistance of glass.
On the other hand, by making Al2O3Composition and Ga2O3The respective content of composition is less than 15.0%, can reduce the liquid phase of glass Temperature, improve devitrification resistance.Therefore, Al2O3Composition and Ga2O3The upper limit of the respective content of composition is preferably 15.0%, more preferably For 10.0%, more preferably 5.0%, more preferably 3.0%.
For Al2O3Composition and Ga2O3Composition, Al can be used as raw material2O3、Al(OH)3、AlF3、Ga2O3、Ga(OH)3Deng.
SnO2When composition is containing more than 0%, the oxidation of melten glass is reduced, makes its clarification, and the visible of glass can be improved The optional member of light transmission.
On the other hand, by making SnO2The content of composition is less than 1.0%, glass caused by can reducing the reduction of melten glass Coloring and the devitrification of glass.Further, since SnO2The alloying of composition and fusion apparatus (noble metal such as especially Pt) is reduced, Therefore the long lifetime of fusion apparatus can be sought.Therefore, SnO2The content of composition is preferably less than 1.0%, and more preferably 0.5% Hereinafter, it is further preferably no larger than 0.1%.
For SnO2Composition, SnO, SnO can be used as raw material2、SnF2、SnF4Deng.
Sb2O3, can be by the optional member of melten glass deaeration when composition is containing more than 0%.
On the other hand, Sb2O3When measuring excessive, it is seen that the transmissivity in the short wavelength region in light region is deteriorated.Therefore, Sb2O3Composition The upper limit of content be preferably 1.0%, more preferably 0.7%, more preferably 0.5%.
For Sb2O3Composition, Sb can be used as raw material2O3、Sb2O5、Na2H2Sb2O7·5H2O etc..
It should be noted that making glass clarifying and carrying out the composition of deaeration to be not limited to above-mentioned Sb2O3Composition, glass system can be used Make known fining agent, deaeration agent or the combinations thereof in field.
When F compositions are containing more than 0%, the Abbe number of glass can be improved, and glass transition temperature can be reduced, and can be carried The optional member of high devitrification resistance.
However, the content of F compositions be replace above-mentioned each element one or more kinds of oxides part or all and It is steady therefore, it is difficult to obtain because the volatilization quantitative change of F compositions is more when the total amount in terms of F of the fluoride contained is more than 15.0% Fixed optical constant, it is difficult to obtain the glass of homogeneous.
Therefore, the upper limit of the content of F compositions is preferably 15.0%, more preferably 10.0%, most preferably 5.0%.
By using such as ZrF4、AlF3、NaF、CaF2Deng raw material is used as, F compositions can be contained in glass.
＜ is on the composition ＞ that should not contain
Next, explanation should not in the optical glass of the present invention composition that contain and if undesirable composition containing if.
As needed, in the range of the characteristic of glass of the present application is not damaged, other compositions can be added.Wherein, except Beyond Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo has such as Lower such property, therefore, especially in the optical glass using the wavelength of visibility region, preferably contain substantially no, institute Stating property is, even in individually containing it is a small amount of or it is compound containing it is a small amount of when, glass can also colour, in visible region Specific wavelength at produce absorption.
In addition, the lead compound such as PbO and As2O3It is the big composition of carrying capacity of environment Deng arsenic compound, therefore, it is desirable to be substantially free of Have, i.e. in addition to being inevitably mixed into, be entirely free of.
And then each composition of Th, Cd, Tl, Os, Be and Se has the tendency of to control it to use in recent years as harmful chemical substance. Not only in the manufacturing process of glass, and manufacturing procedure and until commercialization after punishment, it is necessary to arranging in environmental cure Apply.Therefore, when paying attention to influence environmentally, these are preferably contained substantially no.
For the glass composition of the present invention, its glass total material amount for forming to form relative to oxide conversion is rubbed Your % is represented, therefore, is not represented with quality % record directly, but the glass combination of each characteristic required in the present invention is met The composition represented based on quality % of each composition present in thing, formed and counted with oxide conversion, generally take following value.
B2O3Composition is 5.0~30.0 mass %,
La2O3Composition is 10.0~60.0 mass %, and
And
Y2O3Composition is 0~40.0 mass %,
Gd2O3Composition is 0~30.0 mass %,
Yb2O3Composition is 0~20.0 mass %,
Lu2O3Composition is 0~20.0 mass %,
Ta2O5Composition is 0~30.0 mass %,
TiO2Composition is 0~15.0 mass %,
Nb2O5Composition is 0~20.0 mass %,
WO3Composition is 0~40.0 mass %,
ZnO component is 0~25.0 mass %,
ZrO2Composition is 0~10.0 mass %,
SiO2Composition is 0~8.0 mass %,
Li2O compositions are 0~2.0 mass %,
Na2O compositions are 0~10.0 mass %,
K2O compositions are 0~8.0 mass %,
Cs2O compositions are 0~15.0 mass %,
MgO compositions are 0~3.0 mass %,
CaO compositions are 0~5.0 mass %,
SrO compositions are 0~8.0 mass %,
BaO compositions are 0~10.0 mass %,
GeO2Composition is 0~12.0 mass %,
P2O5Composition is 0~10.0 mass %,
Bi2O3Composition is 0~40.0 mass %,
TeO2Composition is 0~15.0 mass %,
Al2O3Composition is 0~12.0 mass %,
Ga2O3Composition is 0~20.0 mass %,
Sb2O3Composition is 0~3.0 mass %,
And instead of above-mentioned each element one or more kinds of oxides part or all and in the fluoride that contains Using the total amount that F is counted as 0~3.0 mass %.
Especially, the composition represented based on quality % of each composition present in the 1st optical glass, formed with oxide conversion Meter, generally takes following value.
B2O3Composition is 5.0~30.0 mass %, and
La2O3Composition is 10.0~60.0 mass %,
And
Y2O3Composition is 0~20.0 mass %,
Gd2O3Composition is 0~3.0 mass %,
Yb2O3Composition is 0~20.0 mass %,
Lu2O3Composition is 0~20.0 mass %,
Ta2O5Composition is 0~4.0 mass %,
TiO2Composition is 0~15.0 mass %,
Nb2O5Composition is 0~20.0 mass %,
WO3Composition is 0~40.0 mass %,
ZnO component is 0~25.0 mass %,
ZrO2Composition is 0~10.0 mass %,
SiO2Composition is 0~8.0 mass %,
Li2O compositions are 0~2.0 mass %,
Na2O compositions are 0~10.0 mass %,
K2O compositions are 0~8.0 mass %,
Cs2O compositions are 0~15.0 mass %,
MgO compositions are 0~3.0 mass %,
CaO compositions are 0~5.0 mass %,
SrO compositions are 0~8.0 mass %,
BaO compositions are 0~10.0 mass %,
GeO2Composition is 0~12.0 mass %,
P2O5Composition is 0~10.0 mass %,
Bi2O3Composition is 0~40.0 mass %,
TeO2Composition is 0~15.0 mass %,
Al2O3Composition is 0~12.0 mass %,
Ga2O3Composition is 0~20.0 mass %,
Sb2O3Composition is 0~3.0 mass %,
And instead of above-mentioned each element one or more kinds of oxides part or all and in the fluoride that contains Using the total amount that F is counted as 0~3.0 mass %.
On the other hand, the composition represented based on quality % of each composition present in the 2nd optical glass, formed with oxide conversion Meter, generally takes following value.
B2O3Composition is 5.0~30.0 mass %,
La2O3Composition is 10.0~60.0 mass %, and
Y2O3Composition be more than the mass % of 0 mass %~40.0,
And
Gd2O3Composition is 0~30.0 mass %,
Yb2O3Composition is 0~20.0 mass %,
Lu2O3Composition is 0~20.0 mass %,
Ta2O5Composition is 0~30.0 mass %,
TiO2Composition is 0~15.0 mass %,
Nb2O5Composition is 0~20.0 mass %,
WO3Composition is 0~40.0 mass %,
ZnO component is 0~25.0 mass %,
ZrO2Composition is 0~10.0 mass %,
SiO2Composition is 0~8.0 mass %,
Li2O compositions are 0~2.0 mass %,
Na2O compositions are 0~10.0 mass %,
K2O compositions are 0~8.0 mass %,
Cs2O compositions are 0~15.0 mass %,
MgO compositions are 0~3.0 mass %,
CaO compositions are 0~5.0 mass %,
SrO compositions are 0~8.0 mass %,
BaO compositions are 0~10.0 mass %,
GeO2Composition is 0~12.0 mass %,
P2O5Composition is 0~10.0 mass %,
Bi2O3Composition is 0~40.0 mass %,
TeO2Composition is 0~15.0 mass %,
Al2O3Composition is 0~12.0 mass %,
Ga2O3Composition is 0~20.0 mass %,
Sb2O3Composition is 0~3.0 mass %,
And instead of above-mentioned each element one or more kinds of oxides part or all and in the fluoride that contains Using the total amount that F is counted as 0~3.0 mass %.
[manufacture method]
The optical glass of the present invention for example makes in the following way.That is, according to making scope of each composition in defined content Interior mode uniformly mixes above-mentioned raw materials, and manufactured mixture is put into platinum crucible, the melting difficulty or ease formed according to glass Degree, within the temperature range of 1100~1500 DEG C melt within 2~5 hours in electric furnace, and stir and homogenize, be then reduced to Appropriate temperature, then casts into mould, Slow cooling.Thus make.
[physical property]
The optical glass of the present invention preferably has high index of refraction and high Abbe number (low scattered).Especially, optics glass of the invention Refractive index (the n of glassd) lower limit be preferably 1.80, more preferably 1.81, more preferably 1.82.The refractive index (nd) it is upper Limit is preferably 1.95, more preferably 1.93, more preferably 1.92.In addition, Abbe number (the ν of the optical glass of the present inventiond) Lower limit be preferably 30, more preferably 32, more preferably 33.The Abbe number (νd) the upper limit be preferably 45, more preferably 43, more preferably 41.
By with such high index of refraction, even if so as to seek the slimming of optical element, also can obtain the refraction of big light Amount.In addition, by the way that with such low scattered, even so as to simple lens, focus is inclined caused by the wavelength difference of light Poor (aberration) also diminishes.Moreover, by with such low scattered, for example, with the optics member with high dispersive (low Abbe number) When part combines, 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 etc., and And it can also realize the miniaturization of optical system, the free degree of expansible optical design.
For the transmissivity of the optical glass, preferably the transmission of visible light especially light of the long side of visible ray intermediate waves of the present invention Height, the coloring being generated by it are lacked.
Especially, using the sample of the thick 10mm in the optical glass of the present invention, the most shortwave of 70% spectral-transmission favtor is shown Long (λ70) the upper limit be preferably 450nm, more preferably 420nm, more preferably 400nm.
In addition, using the sample of the thick 10mm in optical glass of the invention, the minimal wave length of 5% spectral-transmission favtor is shown (λ5) the upper limit be preferably 400nm, more preferably 380nm, more preferably 360nm.
Thus, near ultraviolet region, glass improves the absorption edge of glass relative to the transparency of visible ray, thus, it may be preferable to The optical glass is made to the optical element of light transmission for lens etc..
The devitrification resistance of the optical glass of the present invention is high, more specifically, preferably with low liquidus temperature.That is, it is of the invention The upper limit of the liquidus temperature of optical glass is preferably 1100 DEG C, more preferably 1080 DEG C, more preferably 1060 DEG C.Thus, Melten glass is flowed out under lower temperature, the crystallization of manufactured glass is also reduced by, and therefore, can be reduced from molten condition Devitrification during glass is formed, the influence of the optical characteristics of optical element to having used glass can be reduced.In addition, can steady production The scope of the temperature of preforming material broadens, and therefore, even if reducing the melting temperature of glass, can also form preforming material, can Suppress to form the energy consumed during preforming material.On the other hand, to the present invention optical glass liquidus temperature lower limit It is not particularly limited, the liquidus temperature of glass is generally more than 800 DEG C as obtained from the present invention, specially more than 850 DEG C, More specifically more than 900 DEG C, such situation is more.It should be noted that " liquidus temperature " in this specification refer to it is as follows Temperature：Into the platinum crucible of 50ml capacity load 30cc cullet shape glass specimen, be put into platinum crucible and Complete molten condition is made at 1250 DEG C, is cooled to defined temperature, is kept for 12 hours, takes out to outside stove, be cooled to, then There is nodeless mesh in sight glass surface and glass immediately, using the minimum temperature for not finding crystallization now as " liquidus temperature ". Herein, defined temperature during cooling is every 10 DEG C of temperature between 1180 DEG C~800 DEG C.
The optical glass of the present invention preferably has greater than 580 DEG C and the glass transition temperature (Tg) for less than 630 DEG C.
Especially, by making optical glass that there is the glass transition temperature more than 580 DEG C, even so as to more than 1.80 Less than 1.95 refractive index (nd) and less than more than 30 45 Abbe number (νd) the low scattered optical glass of high index of refraction, also not The crystallization of glass easily occurs, therefore, devitrification when glass makes can be reduced, thus, can obtain what is be easily press-formed Glass.Especially, the big glass of refractive index high Abbe number, more there is the crystallization that glass easily occurs, therefore, Pass through the obvious technical effects for making glass transition temperature within the temperature range of more than 580 DEG C to obtain.Therefore, it is of the invention The glass transition temperature of optical glass is preferably greater than 580 DEG C, more preferably greater than 590 DEG C, further preferably greater than 600 DEG C.
On the other hand, by making optical glass that there is less than 630 DEG C of glass transition temperature, glass can be made in relatively low temperature Lower softening, therefore, easily glass can be press-formed at a lower temperature.Furthermore it is also possible to reduce for being press-formed Mould oxidation, can be achieved mould long lifetime.Therefore, the upper limit of the glass transition temperature of optical glass of the invention Preferably 630 DEG C, more preferably 625 DEG C, more preferably 620 DEG C.
It should be noted that even if glass transition temperature is more than 580 DEG C, by using such as Japanese Unexamined Patent Publication 2007-186384 Number such forming machine and mould etc. shown in publication, can also reduce the damage on the surface to pressurization mould, can improve mould material The durability of material, therefore, what is generally carried out is the accurate pressurization of the optical glass with the glass transition temperature more than 580 DEG C Shaping.
The optical glass preferred specific gravity of the present invention is small.More specifically, the proportion of optical glass of the invention is 5.50 [g/cm3] Below.Thus, optical element and the quality using its optical device can be reduced, therefore, can aid in the light of optical device Matter.Therefore, the upper limit of the proportion of optical glass of the invention is preferably 5.50, more preferably 5.40, preferably 5.30.Need Illustrate, the proportion of optical glass of the invention is generally more than 3.00, in more detail, more more than 3.50, further In detail, more than 4.00.
The proportion of the optical glass of the present invention be based on the industry of Japanese Optical nitre understand standard JOGIS05-1975 " optical glass The assay method of proportion " is measured.
[preforming material and optical element]
The optical glass made of, using the compression-moulding methods such as hot repressing shaping, precision press formation, glass can be made Formed body.That is, the preform of compression molding is made by optical glass, it is molded to preform progress reheating, then Be ground processing, can make glass forming body, or to be ground processing and manufactured preform, using on known The preform of the shapings such as floating shaping carries out precision press formation, can make glass forming body.It should be noted that make glass The means of formed body are not limited to these means.
Like this, optical glass of the invention is useful for a variety of optical elements and optical design.Wherein, it is therefore particularly preferred that Preform is formed by the optical glass of the present invention, molded, precision press formation of reheating etc. is carried out using the preform, comes Make the optical elements such as lens, prism.Thus, the big preform of diameter can be formed, therefore, the large-scale of optical element can be achieved Change, moreover, when for optical devices such as camera, projectors, fine and high-precision imaging characteristic and projection can be achieved Characteristic.
[embodiment]
The composition of embodiments of the invention (No.A1~No.A75, No.B1~No.B71) and comparative example (No.a) and Refractive index (the n of these glassd), Abbe number (νd), glass transition temperature (Tg), liquidus temperature, spectral-transmission favtor be shown as 5%th, 70% wavelength (λ5、λ70) and the result of proportion be shown in 1~table of table 20.Herein, embodiment (No.A1~No.A75) is The example of 1st optical glass, embodiment (No.B1~No.B71) are the examples of the 2nd optical glass.It is it should be noted that following Embodiment be only illustrate purpose, be not limited in these embodiments.
The glass of embodiments of the invention and comparative example makes as follows：It is selected as the raw material difference phase of each composition When oxide, hydroxide, carbonate, nitrate, fluoride, hydroxide, the common optics glass such as metaphosphoric acid compound The high-purity raw used in glass, weighed with the ratio formed of each embodiment shown in table and uniformly mixed, then Put into platinum crucible, the melting difficulty formed according to glass, entered using electric furnace within the temperature range of 1100~1500 DEG C Row 2~5 hours melts, and then stirring homogenizes, and then casts into mould etc., Slow cooling, is thus made.
Herein, the refractive index (n of the glass of embodiment and comparative exampled) and Abbe number (νd) it is based on the industrial emblem of Japanese Optical nitre Quasi- JOGIS01-2003 measure.Herein, refractive index (nd), Abbe number (νd) by making Slow cooling cooling rate be -25 DEG C/glass obtained from hr is measured and obtains.
In addition, the glass transition temperature (Tg) of the glass of embodiment and comparative example has used horizontal type dilatometer by carrying out (Japanese：Horizontal type Peng Zhang Measuring determine device) measure obtain.Herein, sample when being measured usesLong by 50~ 55mm sample, it is 4 DEG C/min to make programming rate.
In addition, the transmissivity of the glass of embodiment and comparative example can standard JOGIS02 measure according to the industry of Japanese Optical nitre.Need It is noted that in the present invention, by determining the transmissivity of glass, so as to obtain paneless coloring and its degree.Specifically For, for 10 ± 0.1mm of the thickness parallel grinding object in opposite, according to JISZ8722,200~800nm spectral-transmission favtor is determined, Obtain λ5(wavelength during transmissivity 5%), λ70(wavelength during transmissivity 70%).
In addition, the liquidus temperature of the glass of embodiment and comparative example is obtained as follows：Load into the platinum crucible of 50ml capacity The glass specimen of 30cc cullet shape, it is fitted into platinum crucible and complete molten condition is made at 1250 DEG C, be cooled to 1180 DEG C to 800 DEG C of certain temperature every 10 DEG C of ground settings, kept for 12 hours, take out to outside stove, be cooled to, observe immediately after There is nodeless mesh in glass surface and glass, obtain the minimum temperature for not finding crystallization.
In addition, the proportion of the glass of embodiment and comparative example is based on Japanese Optical nitre industry meeting standard JOGIS05-1975 " light Learn the assay method of the proportion of glass " measure.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
[table 11]
[table 12]
[table 13]
[table 14]
[table 15]
[table 16]
[table 17]
[table 18]
[table 19]
[table 20]
As seen from table, for the optical glass of embodiments of the invention, the high Gd of material cost can be reduced2O3Composition, Ta2O5 The content of composition, therefore, can more inexpensively it obtain.
Especially, for embodiments of the invention (No.A1~No.A75) optical glass, mole and (Gd2O3+Ta2O5) small In 5.0%, in more detail, less than 0.3%, therefore, can more inexpensively obtain.
In addition, especially, for embodiments of the invention (No.B1~No.B71) optical glass, by containing more than 0%, it is the Y of more than 3.0% lower cost for material in more detail2O3Composition, the high Gd of material cost can be reduced2O3Composition And Ta2O5The content of composition.In more detail, due to can will mole and (Gd2O3+Ta2O5) 5.0% is decreased below, in more detail Ground is said, decreases below 0.3%, therefore, can more inexpensively obtain the optical glass with desired optical constant.
On the other hand, the glass of comparative example is free of the Y of lower cost for material2O3Composition, mole and (Gd2O3+Ta2O5) be 16.455%, more contain Gd2O3Or Ta2O5, therefore, material cost uprises.
The glass transition temperature (Tg) of the optical glass of embodiments of the invention is all higher than 580 DEG C and for less than 630 DEG C, more in detail Carefully say, be less than more than 583 DEG C 630 DEG C, in desired scope.On the other hand, the vitrifying of the glass of comparative example turns Temperature (Tg) is more than 630 DEG C.
In addition, the liquidus temperature of the optical glass of embodiments of the invention is less than 1100 DEG C, in desired scope.Separately On the one hand, the liquidus temperature of the glass of comparative example is more than 1100 DEG C.
Thus, it can be known that for the optical glass of embodiments of the invention, even in the composition for contributing to high index of refraction high dispersive In, the Y containing lower cost for material2O3During composition, without using Gd2O3Composition, Ta2O5During the high composition of the material costs such as composition, Even if with the glass of the comparative example optical glass that to be in a ratio of glass transition temperature low, devitrification when glass makes can be also reduced.
In addition, the λ of the optical glass of embodiments of the invention70(wavelength during transmissivity 70%) is below 450nm, more in detail Carefully say, be below 440nm.In addition, the λ of the optical glass of embodiments of the invention5(wavelength during transmissivity 5%) is Below 400nm, it is below 370nm in more detail.Thus, it can be known that the optical glass of embodiments of the invention, short in visible ray Transmissivity under wavelength is high, it is difficult to colours.
In addition, refractive index (the n of the optical glass of embodiments of the inventiond) be more than 1.80, in more detail, be 1.81 with On, and the refractive index (nd) it is less than 1.95, it is less than 1.92, in desired scope in more detail.
In addition, Abbe number (the ν of the optical glass of embodiments of the inventiond) it is more than 30, it is more than 33 in more detail, And the Abbe number (νd) it is less than 45, it is less than 43, in desired scope in more detail.
In addition, the proportion of the optical glass of embodiments of the invention is less than 5.50, it is less than 5.21 in more detail.Cause This understands that the proportion of the optical glass of embodiments of the invention is small.
Thus, it can be known that refractive index (the n of the optical glass of embodiments of the inventiond) and Abbe number (νd) in desired scope It is interior, and the transmissivity under visible ray short wavelength is high, and devitrification resistance is high, easily carries out the extrusion forming based on heating and softening, and And proportion is small.
And then using the optical glass of embodiments of the invention, after progress reheating is molded, it is ground and is ground, processed Into the shape of lens and prism.In addition, using the optical glass of embodiments of the invention, precision press formation is formed with preforming Product, precision press formation is processed into the shape of lens and prism with preform precision press formation.In all cases, exist The problems such as opalization and devitrification does not occur in glass after heating and softening, it can stably be processed into the shape of a variety of lens and prism Shape.
The present invention above is described in detail by illustrate purpose, but the present embodiment is only to illustrate purpose, it will be appreciated that not In the case of the thought and scope of the present invention, those skilled in the art can be variously changed.

Claims (33)

1. a kind of optical glass, in terms of mole %, contain the B below more than 10.0% 50.0%2O3Composition, more than 5.0% Less than 30.0% La2O3Composition, and with more than 1.80 refractive index (nd), with less than more than 30 45 Abbe number (νd)。
2. optical glass as claimed in claim 1, in terms of mole %, Y2O3The content of composition is less than 20.0%.
3. optical glass as claimed in claim 1, in terms of mole %, contain the Y more than 0% and for less than 20.0%2O3Into Point.
4. optical glass as claimed in claim 1, in terms of mole %, Y2O3The content of composition is less than 10.0%.
5. optical glass as claimed in claim 1, in terms of mole %,
Gd2O3Composition is 0~10.0%,
Yb2O3Composition is 0~10.0%,
Lu2O3Composition is 0~10.0%.
6. optical glass as claimed in claim 1, in terms of mole %, Ta2O5The content of composition is less than 10.0%.
7. optical glass as claimed in claim 1, Gd2O3+Yb2O3+Ta2O5Mole and for less than 10.0%.
8. optical glass as claimed in claim 1, Gd2O3+Ta2O5Mole and less than 5.0%.
9. optical glass as claimed in claim 1, in terms of mole %, Ta2O5The content of composition is less than 1.0%.
10. optical glass as claimed in claim 1, in terms of mole %, Gd2O3The content of composition is less than 1.0%.
11. optical glass as claimed in claim 1, Ln2O3Composition mole and for less than more than 10.0% 40.0%, Ln2O3 In, Ln is selected from one or more of La, Gd, Y, Yb, Lu.
12. optical glass as claimed in claim 1, contain above-mentioned Ln2O3Two or more composition in composition.
13. optical glass as claimed in claim 1, in terms of mole %,
TiO2Composition is 0~20.0%,
Nb2O5Composition is 0~10.0%.
14. optical glass as claimed in claim 1, in terms of mole %, WO3The content of composition is less than 20.0%.
15. optical glass as claimed in claim 1, in terms of mole %, contain the WO below more than 1.0% 20.0%3Composition.
16. optical glass as claimed in claim 1, TiO2+WO3+Nb2O5Mole and for 1.0~30.0%.
17. optical glass as claimed in claim 1, in terms of mole %, containing less than more than 10.0% 38.0% ZnO into Point.
18. optical glass as claimed in claim 1, in terms of mole %, ZrO2The content of composition is less than 10.0%.
19. optical glass as claimed in claim 1, in terms of mole %, SiO2The content of composition is less than 15.0%.
20. optical glass as claimed in claim 1, in terms of mole %, Li2The content of O compositions is less than 8.0%.
21. optical glass as claimed in claim 1, in terms of mole %,
Na2O compositions are 0~15.0%,
K2O compositions are 0~10.0%,
Cs2O compositions are 0~10.0%.
22. optical glass as claimed in claim 1, Rn2O compositions mole and be less than 20.0%, Rn2In O, Rn be selected from One or more of Li, Na, K, Cs.
23. optical glass as claimed in claim 1, in terms of mole %,
MgO compositions are 0~10.0%,
CaO compositions are 0~10.0%,
SrO compositions are 0~10.0%,
BaO compositions are 0~10.0%.
24. optical glass as claimed in claim 1, RO compositions mole and in less than 11.0%, RO, R be selected from Mg, One or more of Ca, Sr, Ba.
25. optical glass as claimed in claim 1, in terms of mole %,
GeO2Composition is 0~10.0%,
P2O5Composition is 0~10.0%,
Bi2O3Composition is 0~15.0%,
TeO2Composition is 0~15.0%,
Al2O3Composition is 0~15.0%,
Ga2O3Composition is 0~15.0%,
Sb2O3Composition is 0~1.0%,
Had instead of part or all and the fluoride that contains of one or more kinds of oxides of above-mentioned each element The content of fluorine atom be 0~15.0 mole of %.
26. optical glass as claimed in claim 1, there is less than more than 1.80 1.95 refractive index (nd), have more than 30 45 Following Abbe number (νd)。
27. optical glass as claimed in claim 1, glass transition temperature Tg is more than 580 DEG C and for less than 630 DEG C.
28. optical glass as claimed in claim 1, there is less than 1100 DEG C of liquidus temperature.
29. a kind of preforming material, formed as the optical glass described in claim 1.
30. a kind of optical element, it is to make the preforming material extrusion forming described in claim 29.
A kind of 31. optical element, using the optical glass any one of claim 1~28 as main material.
32. a kind of optical device, possesses the optical element described in claim 30.
33. a kind of optical device, possesses the optical element described in claim 31.
CN201711008789.5A 2013-04-05 2014-04-03 Optical glass, preforming material and optical element Pending CN107721160A (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2013079981 2013-04-05
JP2013079982 2013-04-05
JP2013-079982 2013-04-05
JP2013-079981 2013-04-05
JP2013239213A JP5875572B2 (en) 2013-04-05 2013-11-19 Optical glass, preform material and optical element
JP2013-239213 2013-11-19
JP2013-241228 2013-11-21
JP2013241228A JP6014573B2 (en) 2013-04-05 2013-11-21 Optical glass, preform material and optical element
CN201410133778.XA CN104098267A (en) 2013-04-05 2014-04-03 Optical Glass, Preforming Material And Optical Element

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201410133778.XA Division CN104098267A (en) 2013-04-05 2014-04-03 Optical Glass, Preforming Material And Optical Element

Publications (1)

Publication Number Publication Date
CN107721160A true CN107721160A (en) 2018-02-23

Family

ID=51666859

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201711008789.5A Pending CN107721160A (en) 2013-04-05 2014-04-03 Optical glass, preforming material and optical element
CN201410133778.XA Pending CN104098267A (en) 2013-04-05 2014-04-03 Optical Glass, Preforming Material And Optical Element

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201410133778.XA Pending CN104098267A (en) 2013-04-05 2014-04-03 Optical Glass, Preforming Material And Optical Element

Country Status (1)

Country Link
CN (2) CN107721160A (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117486484A (en) * 2014-12-24 2024-02-02 株式会社小原 Optical glass, prefabricated member and optical element
WO2017006998A1 (en) * 2015-07-07 2017-01-12 Hoya株式会社 Glass, optical glass, phosphate optical glass, polishing glass, glass material for press molding, and optical element
CN105198207A (en) * 2015-09-16 2015-12-30 深圳市森维德电子科技有限公司 High-refraction-index low-chromatic-dispersion optical glass suitable for precise mold pressing
CN105271715B (en) * 2015-10-14 2018-05-25 成都光明光电股份有限公司 Optical glass
TWI731991B (en) * 2016-06-29 2021-07-01 日商小原股份有限公司 Optical glass, preforms and optical components
JP7203008B2 (en) * 2017-02-21 2023-01-12 株式会社オハラ Optical glass, preform materials and optical elements
KR102642282B1 (en) * 2017-07-12 2024-02-28 호야 가부시키가이샤 Light guide plate and image display device
CN109264989B (en) * 2018-09-28 2022-02-18 成都光明光电股份有限公司 Optical glass, preform thereof, optical element and optical instrument
JP2021178765A (en) * 2020-05-15 2021-11-18 日本電気硝子株式会社 Glass material
CN111943502B (en) * 2020-08-03 2022-03-22 成都光明光电股份有限公司 Optical glass, glass preform and optical element

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55116641A (en) * 1979-02-28 1980-09-08 Minolta Camera Co Ltd Optical glass
JPS60131845A (en) * 1983-12-01 1985-07-13 シヨツト、グラスヴエルケ Optical glass having refractive index of more than 1.90, abbe's number of more than 25 and high chemical stability
JPS60221338A (en) * 1984-04-12 1985-11-06 Ohara Inc Optical glass
JPH08217484A (en) * 1995-02-13 1996-08-27 Ohara Inc Optical glass
JP2002284542A (en) * 2001-03-27 2002-10-03 Hoya Corp Optical glass and optical part using the same
JP2004175632A (en) * 2002-11-28 2004-06-24 Hikari Glass Co Ltd Optical glass
CN101367611A (en) * 2008-09-25 2009-02-18 成都光明光电股份有限公司 High-refractive index environment friendly weight lanthanum flint optical glass
WO2012046833A1 (en) * 2010-10-08 2012-04-12 株式会社オハラ Optical glass, preform material, and optical element

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55116641A (en) * 1979-02-28 1980-09-08 Minolta Camera Co Ltd Optical glass
JPS60131845A (en) * 1983-12-01 1985-07-13 シヨツト、グラスヴエルケ Optical glass having refractive index of more than 1.90, abbe's number of more than 25 and high chemical stability
JPS60221338A (en) * 1984-04-12 1985-11-06 Ohara Inc Optical glass
JPH08217484A (en) * 1995-02-13 1996-08-27 Ohara Inc Optical glass
JP2002284542A (en) * 2001-03-27 2002-10-03 Hoya Corp Optical glass and optical part using the same
JP2004175632A (en) * 2002-11-28 2004-06-24 Hikari Glass Co Ltd Optical glass
CN101367611A (en) * 2008-09-25 2009-02-18 成都光明光电股份有限公司 High-refractive index environment friendly weight lanthanum flint optical glass
WO2012046833A1 (en) * 2010-10-08 2012-04-12 株式会社オハラ Optical glass, preform material, and optical element

Also Published As

Publication number Publication date
CN104098267A (en) 2014-10-15

Similar Documents

Publication Publication Date Title
CN104341102B (en) Optical glass and optical element
CN107721160A (en) Optical glass, preforming material and optical element
CN103168013A (en) Optical glass, preform material, and optical element
CN104010982A (en) Optical glass and optical element
CN107986616A (en) Optical glass and optical element
CN107879621A (en) Optical glass, preform and optical element
JP2017039640A (en) Optical glass and optical element
CN108117257B (en) Optical glass, preform and optical element
CN104341101A (en) Optical glass, preform material and optical element
CN102712523B (en) Optical glass, preform and optical element
CN101935164B (en) Optical glass, preforming material and optical element
CN106167354B (en) Optical glass and optical element
CN102910816A (en) Optical glass, preform, and optical element
JP6188553B2 (en) Optical glass, preform material and optical element
CN103958427A (en) Optical glass, preform, and optical element
CN103864293A (en) Optical glass, preformed blank and optical element
CN104445922A (en) Optical glass and optical element
JP6363141B2 (en) Optical glass, preform material and optical element
JP5875572B2 (en) Optical glass, preform material and optical element
CN106927675A (en) A kind of optical glass, prefabricated component and optical element
TWI621599B (en) Optical glass, preforms and optical components
CN107867799A (en) A kind of optical glass, prefabricated component and optical element
CN104926101B (en) Optical glass, lens preform, and optical element
CN110642512A (en) Optical glass, prefabricated member and optical element
CN108863048A (en) Optical glass, preform and optical element

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination