CN101746953B - High refractive index optical phosphate glass - Google Patents

High refractive index optical phosphate glass Download PDF

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CN101746953B
CN101746953B CN 200810236829 CN200810236829A CN101746953B CN 101746953 B CN101746953 B CN 101746953B CN 200810236829 CN200810236829 CN 200810236829 CN 200810236829 A CN200810236829 A CN 200810236829A CN 101746953 B CN101746953 B CN 101746953B
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CN101746953A (en
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邓和平
黄少林
张卫
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Hubei New Huaguang Information Materials Co Ltd
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Abstract

The invention provides high refractive index optical phosphate glass, belonging to the technical field of optical glass. The invention mainly aims at solving the problems as follows: the current phosphate glass of the same kind contains Bi2O3, is complex in the melting process, is not suitable for volume production, and introduces the oxides which should not be introduced, thus making melting difficult. The glass contains the following materials according to the weight percent of the oxides: 15-30% of P2O5, 35-60% of Nb2O5, 0.5-25% of BaO, 0-10% of B2O3, 1-20% of TiO2, 0-1% of Li2O, 0-11% of Na2O, 1-16% of K2O, 0.5-8% of WO3, 0-5% of fluorides, 0-5% of Ta2O5, 0-5% of CaO, 0-3% of ZrO2 and 0-3% of ZnO. The glass has the characteristics of refractive index (nd) between 1.91 and 1.96, the Abbe number (upsilond) between 17.5 and 21, the transmittance in the visible region not less than 83% and the negative anomalous dispersion, and is mainly used for the sensing and projecting lenses in the digital cameras, video cameras and LCD projectors.

Description

High refractive index optical phosphate glass
Technical field
Invention belongs to the opticglass technical field, is specifically related to a kind of specific refractory power (n d) 1.91～1.96 and Abbe number (υ d) in 17.5～21 scopes, do not contain poisonous objectionable constituent PbO, As 2O 3Deng and diminish the composition Bi of platinum 2O 3, have high visible light transmissivity, and can be suitable for the phosphate optical glass that secondary mould pressing is processed the high refractive index of optical element, low Abbe number.
Background technology
In the optical system design, people promote digital camera, pick up camera, mobile phone camera to the development of miniaturized, ultra-thinization and the realization of wide-angleization with glass of high refractive index usually in recent years.And when design special optical system, more hope aberration is reduced to minimum.And the glass of the high refraction of this type, low Abbe number can remedy and correcting chromatic aberration, and aberration is decreased in the lower scope.
The early stage glass (like H-ZF847/238) of making high refractive index, high chromatic dispersion is with SiO 2Generate body as glass, introduce more a large amount of TiO 2, Nb 2O 5Form as host glass, but, will introduce more Nb along with the increase of specific refractory power and chromatic dispersion 2O 5Or TiO 2Be achieved, but this will make the stability of the glass extreme difference that becomes, painted also more serious.
At present known have Chinese patent publication number CN1704369A to disclose P 2O 5, Nb 2O 5, TiO 2Phosphate glass as staple.But the composition Bi that contains easy damaged platinum container in this glass 2O 3With introduced the oxide compound that should not introduce at phosphate glass, thereby melting technology will be tending towards complicated, the increase with causing production cost is difficult to mass production.
Summary of the invention
The object of the invention provides a kind of specific refractory power (n to above-mentioned weak point exactly d) 1.91～1.96 and Abbe number (υ d) in 17.5～21 scopes, do not contain poisonous objectionable constituent PbO, As 2O 3Deng and diminish the composition Bi of platinum 2O 3, have high visible light transmissivity, also have favorable manufacturability ability and stability simultaneously, and can be suitable for the phosphate optical glass that secondary mould pressing is processed the high refractive index of optical element, low Abbe number.
For eliminating the shortcomings and deficiencies of known glass, technical solution of the present invention is: a kind of high refractive index optical phosphate glass is characterized in that: its compositional range contains in oxide compound by weight percentage:
P 2O 5 15～30％；
Nb 2O 5 35～60％；
BaO 0.5～25％；
B 2O 3 0～10％；
TiO 2 1～20％；
Li 2O 0～1％；
Na 2O 0～11％；
K 2O 1～16％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜23％；
WO 3 0.5～8％；
RF 0～5％；
Ta 2O 5 0～5％；
CaO 0～5％；
ZrO 2 0～3％；
ZnO 0～3％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜10％。
The preferred technical solution of the present invention is: a kind of high refractive index optical phosphate glass is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 15～28％；
Nb 2O 5 37～58％；
BaO 0.5～23％；
B 2O 3 0～7％；
TiO 2 2～18％；
Li 2O 0～1.0％；
Na 2O 0～10％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜21％；
WO 3 0.5～6％；
RF 0～4％；
Ta 2O 5 0～4％；
CaO 0～5％；
ZrO 2 0～3％；
ZnO 0～3％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜9％。
The another kind of preferred technical solution of the present invention is: a kind of high refractive index optical phosphate glass is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 16～28％；
Nb 2O 5 37～58％；
BaO 0.5～21％；
B 2O 3 0～7％；
TiO 2 3～18％；
Li 2O 0～1.0％；
Na 2O 0～9.5％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜19％；
WO 3 0.5～6％；
RF 0～3％；
Ta 2O 5 0～3％；
CaO 0～5％；
ZrO 2 0～2％；
ZnO 0～2％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜7％。
The most preferred technical solution of the present invention is: a kind of high refractive index optical phosphate glass is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 16～28％；
Nb 2O 5 37～55％；
BaO 0.5～21％；
B 2O 3 0～7％；
TiO 2 3～18％；
Li 2O 0～0.5％；
Na 2O 0～9.5％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜18％；
WO 3 0.5～6％；
RF 0～3％；
Ta 2O 5 0～3％；
CaO 0～5％；
ZrO 2 0～1.5％；
ZnO 0～1.5％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜6％。
Described in the technical solution of the present invention be: ∑ (Li 2O, Na 2O, K 2O) following is limited to 2.0%, wherein Li 2O is an optional member, and its introducing amount can be zero.
Sb described in the technical solution of the present invention 2O 3The introducing amount greater than 0.1%, but less than 0.5%.
∑ described in the technical solution of the present invention (CaO, ZrO 2, ZnO) higher limit be 7.0%, ZrO wherein 2, ZnO is as optional member, its introducing amount also can be zero.
For realizing above-mentioned purpose, find among the result of the present invention through prolonged and repeated research and experiment, do not containing Bi 2O 3, SiO 2Composition, and contain WO 3And the above-described particular glass component of fluorochemical composition solves.
With opticglass of the present invention is with P 2O 5, Nb 2O 5, BaO, TiO 2As the staple of glass, and introduce essential alkalimetal oxide, WO 3Deng as the host glass system.
P 2O 5Be the basis that constitutes phosphate glass, compare with silicate glass that phosphate glass more can dissolve refractory oxide, temperature of fusion is lower, and transmitance is higher.Therefore, P 2O 5Content can not be less than 15%, and content surpasses at 30% o'clock, glass is difficult to the optical constant that reaches required.Therefore, P 2O 5Content select 15～30%, more preferably in 16～28% scope.
Nb 2O 5Be the essential composition that is used to obtain high refractive index and high chromatic dispersion, and significantly the improvement stability is stable with raising.Like Nb 2O 5Content is less than 35%, can not obtain the performance of high refractive index and high chromatic dispersion, surpasses 60% like content, and the glass melting degradation also will increase the glass increased devitrification resistance simultaneously, for obtaining stable glass, preferably in 37～55% scope.
TiO 2Also be the essential composition that obtains high refractive index and high chromatic dispersion, and also can significantly improving stability and increase negative anomalous dispersion.Work as TiO 2Content surpass at 20% o'clock, the not only painted intensification of glass, and devitrification behavior degenerates.Therefore, TiO 2The upper content limit value is preferably 18% or lower.
B 2O 3In phosphate glass, can improve the glass devitrification behavior and improve melting properties.B 2O 3Content surpass at 8% o'clock, be difficult to obtain the performance of high refraction, high chromatic dispersion.The present invention finds, surpasses this content and also is prone to make glass coloring to deepen.So B 2O 3The upper limit of introducing amount is preferably in 7.0%.In another kind was preferably formed, its lower limit can be zero.
BaO is a kind of devitrification behavior and essential composition that alleviates glass coloring of improving.Surpass 25% like content, will be difficult to obtain the performance of high chromatic dispersion.Therefore, the upper limit of BaO introducing amount is preferably 21%, and more preferably 20%, lower limit is preferably 0.5%.
Introduce alkalimetal oxide Li 2O, Na 2O, K 2O, particularly 0～10%Na2O and 1～15%K 2O is as reducing liquidus temperature (L T), improve transmitance and improve the essential composition of melting properties.Work as Na 2O, K 2The total content of O surpasses at 22% o'clock, will be difficult to obtain required optical constant, and stability, glass is also with variation simultaneously.Therefore, Na 2O, K 2The upper limit of O introducing amount always preferred 20% or lower.And Li 2O is as optional components, and its introducing amount can be zero fully.
WO 3It is the essential composition that improves specific refractory power and chromatic dispersion, reduces tendency towards devitrification.When its content surpassed 8%, glass coloring was deepened.Therefore the higher limit of its introducing amount is preferably in 8%, more preferably 6% or lower.
Ta 2O 5In glass of the present invention, to improving specific refractory power and alleviating tendency towards devitrification obvious effects is arranged, but the introducing amount surpasses 5%, does not then reach the dispersion values that needs.Therefore for reaching above-mentioned effect, the introducing amount upper limit is preferred 5%, and more preferably 3%.
When an amount of introducing RF (fluorochemical), can effectively obtain required specific refractory power and dispersion values, remarkable to the transmitance effect that improves visible region simultaneously.When the introducing amount surpassed 5%, the stability, glass variation was difficult to obtain desirable optical constant.Therefore, be limited in 4% on this composition introducing amount, more preferably in 3%.
CaO, ZrO as optional member 2, ZnO introducing (optional amount be 5% and each 3%), in the little introducing of maintenance dose and reach under the prerequisite of required optical constant the effect that helps to reduce tendency towards devitrification He alleviate glass coloring.But the content of these compositions also can be zero fully.In preferred a composition, the following of its each composition is limited to 1.0%.Find that three's total amount surpasses 10% can increase tendency towards devitrification greatly, does not also reach required specific refractory power and dispersion values simultaneously.
The preferred Sb of glass of the present invention 2O 3As finings, add-on is in 0.5%.
Specific refractory power (n of the present invention d) between 1.91～1.96 and Abbe number (υ d) in 17.5～21, have transmitance>=83% at visible region, have the characteristic of negative anomalous dispersion.The present invention is mainly used in sensing and the projecting lens in digital camera, pick up camera, the liquid crystal projection apparatus.
Embodiment
To opticglass of the present invention exemplarily be described with embodiment below.
In table 1～3, be included in 9 embodiment in the preferred compositing range, these are comparative embodiment, compare with these different physicochemical characteristics with described high refractive index optical phosphate glass of the present invention, comprise that simultaneously 2 typical comparative examples compare.
Opticglass of the present invention removes and does not contain PbO, As 2O 3Outside objectionable constituent, also do not contain the oxide compound Bi that is prone to infringement platinum container 2O 3Preferred WO 3And fluorochemical is as the composition that improves performance.
The invention still further relates to a kind of special melting method for preparing opticglass of the present invention.This method is mixed with compound with the component of known formation glass with oxide compound, nitrate salt, carbonate and fluorochemical and is heated to molten mass.This molten mass contains 16～30%P 2O 5, 30～60%Nb 2O 5, 0.5～25%BaO, 0～10%B 2O 3, 1～20%TiO 2, 0～11%Na 2O, 1～16%K 2O.Can add 0～1%Li by the present invention as optional components 2O, preferred≤0.5%, wherein ∑ (Li 2O, Na 2O, K 2O) 1＜X＜23.In vitreum, must introduce 0～8%WO 3, 0～5% fluorochemical, optional each 0～5%CaO, Ta 2O 5, each 0～3%ZrO 2, ZnO, wherein ∑ (CaO, ZrO 2, ZnO) the upper limit preferred 7% in.
The preparation embodiment of opticglass of the present invention comprises as follows: take by weighing various oxide compounds, the raw material of preferably nitrate, carbonate and RF (fluorochemical) adds Trace Sb 2O 3, its thorough mixing is even, and this opticglass compound is changed material under 1100～1300 ℃ in a kind of special smelting apparatus, stirs clarification and homogenizing, being suitable for leaking material and moulding under the temperature of moulding, can obtain opticglass of the present invention thus.
Table 1: the embodiment of host glass H-ZF92 (amount is represented with weight %)
Figure GSB00000780318600061
Table 2: the embodiment of host glass H-ZF94 (amount is represented with weight %)
Figure GSB00000780318600071
Table 3: the embodiment of host glass H-ZF95 (amount is represented with weight %)
Figure GSB00000780318600072
Figure GSB00000780318600081
Can find out that from table 1,2 glass of the embodiment of the invention (1～9) not only has the specific refractory power (n in institute's claimed range d) and Abbe number (υ d), also have the characteristic of negative anomalous dispersion.Glass transmitance under 450nm or shorter wavelength can reach more than 83%, and glass also has low liquidus temperature and favorable manufacturability ability simultaneously, is suitable for mass production.
Said by above performance, such glass also can be suitable for once shaped or secondary press and process different size optical element blank.
Though reached desired optical characteristics, glass coloring is dark for table 3 comparative example (a, b), see through to the displacement of long wave direction, and the glass tendency towards devitrification is big, can't produce specification product.
The present invention adopts phosphate system as the host glass possibility that will become.This glass is with P 2O 5Generate body as glass, and introduce a large amount of Nb 2O 5, TiO 2P 2O 5-Nb 2O 5-BaO-TiO 2-R 2The O system can obtain the glass of favorable and stable as host glass, and glass can produce painted hardly, but along with Nb 2O 5, TiO 2The increasing of introducing amount, glass will produce painted.

Claims (4)

1. high refractive index optical phosphate glass, it is characterized in that: its compositional range contains in oxide compound by weight percentage:
P 2O 5 15～30％；
Nb 2O 5 35～60％；
BaO 0.5～25％；
B 2O 3 0～10％；
TiO 2 1～20％；
Li 2O 0～1％；
Na 2O 0～11％；
K 2O 1～16％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜23％；
WO 3 0.5～8％；
RF 0～5％；
Ta 2O 5 0～5％；
CaO 0～5％；
ZrO 2 0～3％；
ZnO 0～3％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜10％；
Sb 2O 3 0.1～0.5％。
2. according to the described a kind of high refractive index optical phosphate glass of claim 1, it is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 15～28％；
Nb 2O 5 37～58％；
BaO 0.5～23％；
B 2O 3 0～7％；
TiO 2 2～18％；
Li 2O 0～1.0％；
Na 2O 0～10％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜21％；
WO 3 0.5～6％；
RF 0～4％；
Ta 2O 5 0～4％；
CaO 0～5％；
ZrO 2 0～3％；
ZnO 0～3％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜9％；
Sb 2O 3 0.1～0.5％。
3. according to the described a kind of high refractive index optical phosphate glass of claim 1, it is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 16～28％；
Nb 2O 5 37～58％；
BaO 0.5～21％；
B 2O 3 0～7％；
TiO 2 3～18％；
Li 2O 0～1.0％；
Na 2O 0～9.5％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜19％；
WO 3 0.5～6％；
RF 0～3％；
Ta 2O 5 0～3％；
CaO 0～5％；
ZrO 2 0～2％；
ZnO 0～2％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜7％；
Sb 2O 3 0.1～0.5％。
4. according to the described a kind of high refractive index optical phosphate glass of claim 1, it is characterized in that: described compositional range in oxide compound is by weight percentage:
P 2O 5 16～28％；
Nb 2O 5 37～55％；
BaO 0.5～21％；
B 2O 3 0～7％；
TiO 2 3～18％；
Li 2O 0～0.5％；
Na 2O 0～9.5％；
K 2O 1～15％；
∑(Li 2O、Na 2O、K 2O) 1％＜X＜18％；
WO 3 0.5～6％；
RF 0～3％；
Ta 2O 5 0～3％；
CaO 0～5％；
ZrO 2 0～1.5％；
ZnO 0～1.5％；
∑(CaO、ZrO 2、ZnO) 1％≤X＜6％；
Sb 2O 3 0.1～0.5％。
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CN102320745B (en) * 2011-09-02 2013-05-08 湖北新华光信息材料有限公司 Optical glass and preparation method thereof
CN102515527B (en) * 2011-12-08 2014-11-05 成都光明光电股份有限公司 Phosphate optical glass
CN104445930B (en) * 2014-11-10 2017-02-15 湖北新华光信息材料有限公司 Optical glass
CN104944770B (en) * 2015-06-17 2017-12-08 成都光明光电股份有限公司 Especial dispersion optical glass
CN110204198B (en) * 2018-02-28 2022-04-05 成都尤利特光电科技股份有限公司 Phosphate optical glass
CN114853334A (en) * 2018-12-03 2022-08-05 成都光明光电股份有限公司 Optical glass, optical preform, optical element and optical instrument
CN109399916B (en) * 2018-12-03 2022-06-17 成都光明光电股份有限公司 Optical glass, optical preform, optical element and optical instrument
CN113603360B (en) * 2021-09-14 2022-12-13 成都光明光电股份有限公司 High-refraction high-dispersion optical glass and optical element
CN115028353B (en) * 2022-06-22 2023-08-08 成都光明光电有限责任公司 Optical glass with negative anomalous dispersion
CN117800594A (en) * 2023-06-28 2024-04-02 湖南旗滨新材料有限公司 Lithium aluminosilicate glass composition, lithium aluminosilicate reinforced glass and preparation method

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