CN104176933A - Phosphate optical glass, prefabricated member used for precision press forming and optical element - Google Patents

Phosphate optical glass, prefabricated member used for precision press forming and optical element Download PDF

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Publication number
CN104176933A
CN104176933A CN201310195041.6A CN201310195041A CN104176933A CN 104176933 A CN104176933 A CN 104176933A CN 201310195041 A CN201310195041 A CN 201310195041A CN 104176933 A CN104176933 A CN 104176933A
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Prior art keywords
glass
optical glass
arbitrary
phosphate optical
phosphate
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CN201310195041.6A
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Chinese (zh)
Inventor
匡波
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Priority to CN201310195041.6A priority Critical patent/CN104176933A/en
Priority to CN201710890917.7A priority patent/CN107540213A/en
Priority to JP2014105014A priority patent/JP5972310B2/en
Publication of CN104176933A publication Critical patent/CN104176933A/en
Pending legal-status Critical Current

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Abstract

The invention provides phosphate optical glass having the refractive index of 1.57-1.62 and the abbe number of 65-70. The optical glass has a small coefficient of thermal expansion and is suitable for precision press forming. The phosphate optical glass comprises following components by mole: 32-50% of P2O5, 3-20% of B2O3, 12-25% of BaO, 0-20% of SrO, 0-8% of Al2O3, more than 0 and not more than 15% of Li2O, more than 0 and not more than 11% of MgO, 0-15% of CaO, 0-5% of Gd2O3, 0-5% of La2O3, and 0-0.5% of Sb2O3, and is free of ZnO. By reasonable distribution of the contents of the components, the coefficient of thermal expansion that is alpha of the optical glass is lower than 110*10<-7> /DEG C, and the transformation temperature is lower than 520 DEG C.

Description

Phosphate optical glass, preform for precise press molding and optical element
Technical field
The present invention relates to a kind of precise press molding phosphate optical glass, and the preform for precise press molding being formed by above-mentioned glass and optical element.
Background technology
Along with popularizing of the photovoltaic such as digital camera, mobile telephone capable of taking pictures, optical system is more and more toward miniaturization, light-weighted future development, the non-spherical lens being formed by opticglass precise compression molding can be simplified lens arrangement, and can reduce lens number of packages, so also grow to even greater heights to the demand of non-spherical lens in market.
The opticglass with medium refractive index, low dispersiveness is the class opticglass that the optical system demand of photovoltaic is larger, particularly specific refractory power (nd) scope is 1.57～1.62, the opticglass that Abbe number (Vd) scope is 65～70, can be become prefabricated component and optical element and be applied in optical system by precise compression molding.But the past, this type of thermal expansion coefficient of glass was larger, and in precise compression molding process, glass deformation is larger, easily bursts.
Summary of the invention
Technical problem to be solved by this invention is to provide the phosphate optical glass that a kind of specific refractory power is 1.57～1.62, Abbe number is 65～70, and this opticglass has less thermal expansivity, is suitable for precise press molding.
The present invention also will provide a kind of preform for precise press molding consisting of above-mentioned phosphate optical glass, and the optical element with above-mentioned optical characteristics and excellent weatherability.
The technical scheme that technical solution problem of the present invention adopts is: phosphate optical glass, contains the following component representing with mol%: P 2o 5: 32～50%, B 2o 3: 3～20%, BaO:12～25%, SrO:0～20%, Al 2o 3: 0～8%, Li 2o: be greater than 0 but be less than or equal to 15%, MgO: be greater than 0 but be less than or equal to 11%, CaO:0～15%, Gd 2o 3: 0～5%, La 2o 3: 0-5%, Sb 2o 3: 0～0.5%, and do not contain ZnO.
Further, its composition by mol% is: P 2o 5: 32～50%, B 2o 3: 3～20%, BaO:12～25%, SrO:0～20%, Al 2o 3: 0～8%, Li 2o: be greater than 0 but be less than or equal to 15%, MgO: be greater than 0 but be less than or equal to 11%, CaO:0～15%, Gd 2o 3: 0～5%, La 2o 3: 0-5%, Sb 2o 3: 0～0.5%, Na 2o:0～10%, K 2o:0～5%.
Further, wherein, P 2o 5: 35～40%.
Further, wherein, BaO:15～20%.
Further, wherein, MgO:5～11%.
Further, wherein, CaO:0～8%.
Further, wherein, MgO+CaO < 11%.
Further, wherein, B 2o 3: 5～15%.
Further, wherein, La 2o 5: 0-2%.
Further, wherein, Li 2o:5～15%.
Further, wherein, Gd 2o 3: 0.1～3%.
Further, its ranges of indices of refraction is 1.57-1.62, and Abbe number scope is 65-70.
Further, its thermal expansivity (20～300 ℃) is 110 * 10 -7/ ℃ below.
Further, its transition temperature is less than 520 ℃.
Preform for precise press molding, consists of above-mentioned phosphate optical glass.
Optical element, is made by above-mentioned phosphate optical glass.
The invention has the beneficial effects as follows: the present invention is by the content of each component of properly distributed, and the ranges of indices of refraction of the opticglass obtaining is 1.57～1.62, and Abbe number scope is 65～70, and thermalexpansioncoefficientα (20～300 ℃) is 110 * 10 -7/ ℃ below, transition temperature is less than 520 ℃.
Embodiment
The present invention is that the setting of each compositional range of glass be the reasons are as follows in order to obtain ranges of indices of refraction 1.57～1.62, Abbe number scope 65～70, the good opticglass of the coefficient of expansion.It should be noted that, in this specification sheets, except as otherwise noted, the content of each component is to represent with mol%.
P 2o 5be that glass of the present invention forms the cancellated necessary component of glass, can improve stability, glass and viscosity.But when its content is 50% when above, glass refraction declines; And when containing quantity not sufficient 32%, vitrified tendency enhancing makes glass unstable.Therefore, in glass of the present invention, P 2o 5content be 32～50%, be preferably 35～40%.
B 2o 3be the necessary component of glass of the present invention, can improve stability and the melting behaviour of glass, when its content is too low, can affect the low dispersiveness of glass, in order to reach above-mentioned effect, B 2o 3content, preferably more than 3%, still adds too much B 2o 3, can affect the thermostability of glass.Therefore, B 2o 3content is 3～20%, is preferably 5～15%, more preferably 10～15%.
In glass of the present invention, Li 2o is necessary component, has the transition temperature and the press forming temperature that reduce glass.But if add-on is too much, the weathering resistance of glass and stability worsen, and glass dispersion is increased, so its add-on is greater than 0 but be less than or equal to 15%, be preferably 5～15%, more preferably 9～14%.
Na 2o and K 2although O also can improve resistance to vitrifying performance, reduce second-order transition temperature, yield-point and liquidus temperature, can be used as any composition that improves the high-temperature fusion performance of glass and add.But when adding when excessive, not only the stability of glass worsens, and weathering resistance also worsens significantly, and specific refractory power declines.Therefore, in glass of the present invention, Na 2the add-on of O is 0～10%, K 2the add-on of O is 0～5%, does not preferably introduce Na 2o, K 2o.
BaO is the necessary component of glass of the present invention, can effectively improve the specific refractory power of glass and the stability of glass, as the composition that improves weathering resistance, is particularly the most effective.But, excessively add BaO can damage significantly the devitrification stability of glass, make the transition temperature of glass increase, and there is the shortcoming of destroying low dispersiveness.Therefore,, in glass of the present invention, its add-on is 12～25%, is preferably 15～20%.
SrO is also the effective constituent that improves glass refraction, can improve the weathering resistance of glass simultaneously, and still, when adding SrO excessive, the stability of glass worsens, and liquidus temperature also can raise.Therefore, in glass of the present invention, the add-on of SrO is 0～20%, is preferably 5～15%, more preferably 7～12%.
The present invention is in order to realize low dispersion glass, introduces the component that BaO, SrO, MgO, CaO etc. are conducive to low dispersiveness, if the BaO and/or the SrO that only introduce are not easy not reach the object of low dispersiveness.But in glass component of the present invention, do not introduce ZnO, because ZnO has the detrimental action that increases glass dispersion.
Contriver finds by research, introduces in right amount at least one in MgO and CaO, can reach the object of low dispersiveness as the divalent component beyond BaO or SrO.Particularly, using MgO as necessary component, in low dispersiveness, can also effectively improve stability and the weathering resistance of glass.But, when the content of MgO surpasses 11%, the thermostability variation of glass, therefore, the content range of MgO is for being greater than 0 but be less than or equal to 11%, and preferred content is 5～11%.
CaO can be used as any component and introduces, and for improving the melt stability of glass, but content surpasses 15%, glass refraction step-down, and chemical stability variation, and therefore, the content range of CaO is 0～15%, preferable range is 0～8%.
Contriver also studies discovery, and during the present invention fills a prescription and forms, the total amount of MgO and CaO should be controlled in the scope that is less than 11%, to guarantee low dispersiveness and the weather resisteant of glass, does not preferably introduce CaO.
Al 2o 3not the necessary component of glass of the present invention, but can be used as the effective constituent of the weathering resistance that improves glass.But when its add-on surpasses 8%, the transition temperature of glass or yield-point can raise, the stability of glass, high-temperature fusion performance can worsen, and glass refraction reduces, so its add-on is 0～8%, is preferably 0～6%, more preferably 0～5%.
Gd in the present invention 2o 3be as any component that improves specific refractory power, but excessively introduce Gd 2o 3, the tendency towards devitrification of glass increases, and it is unstable that glass becomes.So Gd 2o 3content is 0～5%, is preferably Gd 2o 30.1～3%.
In glass of the present invention, Sb 2o 3finings while can be used as glass melting adds, and its content range is 0～0.5%, is preferably 0～0.1%, and more preferably 0～0.05%.
Glass of the present invention, preferably substantially by P 2o 5, B 2o 3, Al 2o 3, Li 2o, MgO, BaO, SrO, Gd 2o 3and Sb 2o 3form, in glass of the present invention, the content summation of above-mentioned each component preferably surpasses 95%, more preferably surpasses 98%, particularly preferably surpasses 99%, most preferably is 100%.
In the scope of harmless the object of the invention, also can add and be selected from Na 2o, K 2o, CaO, La 2o 3, Y 2o 3, Yb 2o 3, ZrO 2, Ta 2o 5, Bi 2o 3, WO 3, TiO 2in one or more components.Wherein, La 2o 3be the component of introducing arbitrarily, because it can make the stability of glass, worsen sharp, melting behaviour also can reduce simultaneously, therefore, and La 2o 3content range be 0～8%, preferable range is 0～2%, does not more preferably add.
Glass of the present invention, its specific refractory power (nd) scope is 1.57～1.62, preferable range is 1.58～1.61, more preferably 1.59～1.60; Abbe number (Vd) scope is 65～70, and preferable range is 66～69, and more preferably scope is 67～68.The composition of glass of the present invention can suitably be set, to meet its characteristic in above-mentioned scope.By introducing each composition in above-mentioned preferable range, in demonstrating the scope of low dispersing characteristic, can access the glass that refractive index ratio is higher.
The present invention measures specific refractory power (nd), Abbe number (ν d), transition temperature (Tg), the coefficient of expansion and the proportion that obtains opticglass by following method.
(1) specific refractory power (nd) and Abbe number (ν d)
Specific refractory power and Abbe number are according to < < GB/T 7962.11-2010 colouless optical glass testing method specific refractory power and abbe number > > test.
(2) transition temperature (Tg)
Opticglass can be gradually by the solid-state plastic stage that becomes in a certain temperature range.Its transition temperature Tg refers to that glass specimen is warming up to the temperature T s that hangs down that speeds, the corresponding temperature of intersection point that its low-temperature region and high-temperature area straight line portion extended line are crossing from room temperature.Method according to GB/T 7962.16-2010 regulation is measured.
(3) thermalexpansioncoefficientα
Thermalexpansioncoefficientα refers in certain temperature range that temperature raises 1 ℃ time, the elongation of glass unit length.The present invention is the mean value of 20～300 ℃ according to the method measurement temperature of GB/T7962.16-2010 regulation.
(4) density
The density of opticglass refers to, the quality of unit volume when temperature is 20 ℃.The density of opticglass is measured by the method for GB/T7962.20-2010 regulation.Unit is with g/cm 3represent.
Glass of the present invention, its transition temperature (Tg) is preferably below 520 ℃, more preferably below 510 ℃, most preferably below 500 ℃.Due to such softening temperature, in the time of can be by precise press molding, temperature be compressed on lower temperature.In glass of the present invention, can suitably in above-mentioned scope, set it and form, make its transition temperature (Tg) for as mentioned above.
Glass of the present invention, its thermalexpansioncoefficientα (20～300 ℃) is 110 * 10 -7/ ℃ below, be preferably 107 * 10 -7/ ℃ below, more preferably 104 * 10 -7/ ℃ below.In glass of the present invention, can suitably in above-mentioned scope, set it and form, make its coefficient of expansion for as mentioned above.
Glass of the present invention, its density is 3.45 (g/cm 3) below, be preferably 3.36 (g/cm 3) below, 3.32 (g/cm more preferably 3) below.
The prefabricated component that precise press molding of the present invention is used consists of the invention described above phosphate optical glass, is that the glass that has a same quality with precise press molding goods is made body.Different according to the shape of goods, prefabricated component is shaped as suitable shape, can be the shapes such as spherical, ellipsoid of revolution.Prefabricated component is heated to the viscosity that can carry out precise press molding, then carries out precise press molding.
Optical element of the present invention is the optical element of being manufactured by the phosphate optical glass of the invention described above.Owing to forming the glass of optical element, there is above-mentioned various characteristics, so optical element of the present invention has effectively utilized required optical constant and excellent thermal expansivity, can the high reliability of long term maintenance.
As optical element of the present invention, can be the various lens such as spherical lens, non-spherical lens, micro lens, or diffraction grating, the lens that diffraction grating is housed, lens arra, prism etc.As above-mentioned optical element, hope is by prefabricated component of the present invention being heated, softened the element obtaining by precise press molding.
As required, antireflection film, total reflection film, part reflectance coating can be set on this optical element, there is the optical thin films such as film of dichroism.
Embodiment
Below by embodiment, further illustrate the present invention.
In table 1～table 3, demonstrate composition, specific refractory power (nd), Abbe number (ν d), transition temperature (Tg), thermal expansivity (α), the proportion (ρ) of each embodiment glass.Various glass has been used each corresponding oxide compound, oxyhydroxide, phosphoric acid salt, metaphosphate, carbonate and nitrate as the raw material of each composition, above-mentioned raw materials is weighed, after fully mixing, put into platinum crucible the temperature range melting of 1050～1200 ℃, stirring homogenizes accomplishing, through clarification, cooling, be cast to again in the mold that is preheating to proper temperature, the glass cools of casting is directly put into annealing furnace after transition temperature, and Slow cooling just obtains phosphate optical glass of the present invention to room temperature.
Table 1
Table 2
Table 3

Claims (16)

1. phosphate optical glass, is characterized in that, contains the following component representing with mol%: P 2o 5: 32～50%, B 2o 3: 3～20%, BaO:12～25%, SrO:0～20%, Al 2o 3: 0～8%, Li 2o: be greater than 0 but be less than or equal to 15%, MgO: be greater than 0 but be less than or equal to 11%, CaO:0～15%, Gd 2o 3: 0～5%, La 2o 3: 0-5%, Sb 2o 3: 0～0.5%, and do not contain ZnO.
2. phosphate optical glass as claimed in claim 1, is characterized in that, its composition by mol% is: P 2o 5: 32～50%, B 2o 3: 3～20%, BaO:12～25%, SrO:0～20%, Al 2o 3: 0～8%, Li 2o: be greater than 0 but be less than or equal to 15%, MgO: be greater than 0 but be less than or equal to 11%, CaO:0～15%, Gd 2o 3: 0～5%, La 2o 3: 0-5%, Sb 2o 3: 0～0.5%, Na 2o:0～10%, K 2o:0～5%.
3. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and P 2o 5: 35～40%.
4. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and BaO:15～20%.
5. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and MgO:5～11%.
6. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and CaO:0～8%.
7. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and MgO+CaO < 11%.
8. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and B 2o 3: 5～15%.
9. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and La 2o 5: 0-2%.
10. the phosphate optical glass as described in claim as arbitrary in claim 1～2, is characterized in that, wherein, and Li 2o:5～15%.
Phosphate optical glass as described in 11. claims as arbitrary in claim 1～2, is characterized in that, wherein, and Gd 2o 3: 0.1～3%.
Phosphate optical glass as described in 12. claims as arbitrary in claim 1～11, is characterized in that, its ranges of indices of refraction is 1.57-1.62, and Abbe number scope is 65-70.
Phosphate optical glass as described in 13. claims as arbitrary in claim 1～11, is characterized in that, its thermal expansivity (20～300 ℃) is 110 * 10 -7/ ℃ below.
Phosphate optical glass as described in 14. claims as arbitrary in claim 1～11, is characterized in that, its transition temperature is less than 520 ℃.
15. preform for precise press molding, consist of the phosphate optical glass described in the arbitrary claim of claim 1～14.
16. optical elements, are made by the phosphate optical glass described in the arbitrary claim of claim 1～14.
CN201310195041.6A 2013-05-21 2013-05-21 Phosphate optical glass, prefabricated member used for precision press forming and optical element Pending CN104176933A (en)

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CN201710890917.7A CN107540213A (en) 2013-05-21 2013-05-21 Phosphate optical glass, preform for precise press molding and optical element
JP2014105014A JP5972310B2 (en) 2013-05-21 2014-05-21 Phosphate optical glass, precast for precision press molding, and optical element

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN114644455A (en) * 2020-12-18 2022-06-21 成都光明光电股份有限公司 Optical glass

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Publication number Priority date Publication date Assignee Title
CN106536436B (en) * 2014-09-05 2019-07-26 株式会社尼康 Optical glass, the optical element using there is optical glass, Optical devices
JP2018030736A (en) * 2016-08-22 2018-03-01 日本電気硝子株式会社 Production method of optical glass element
WO2018105279A1 (en) * 2016-12-07 2018-06-14 株式会社 オハラ Optical glass, preform, and optical element

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CN1974453A (en) * 2005-09-30 2007-06-06 Hoya株式会社 Optical glass, precision press molding preform and manufacturing method of the same, optical element and manufacturing method of the same
CN102372429A (en) * 2010-08-06 2012-03-14 旭硝子株式会社 Optical glass

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JP5690505B2 (en) * 2010-05-20 2015-03-25 株式会社住田光学ガラス Optical glass, mold press molding preform and optical element

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Publication number Priority date Publication date Assignee Title
CN1974453A (en) * 2005-09-30 2007-06-06 Hoya株式会社 Optical glass, precision press molding preform and manufacturing method of the same, optical element and manufacturing method of the same
CN102372429A (en) * 2010-08-06 2012-03-14 旭硝子株式会社 Optical glass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114644455A (en) * 2020-12-18 2022-06-21 成都光明光电股份有限公司 Optical glass
CN114644455B (en) * 2020-12-18 2023-12-05 成都光明光电股份有限公司 Optical glass

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