JP6402138B2 - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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JP6402138B2
JP6402138B2 JP2016105141A JP2016105141A JP6402138B2 JP 6402138 B2 JP6402138 B2 JP 6402138B2 JP 2016105141 A JP2016105141 A JP 2016105141A JP 2016105141 A JP2016105141 A JP 2016105141A JP 6402138 B2 JP6402138 B2 JP 6402138B2
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optical glass
glass
optical
fluorescence
performance
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JP2017007933A (en
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偉 袁
偉 袁
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成都光明光▲電▼股▲分▼有限公司
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Description

The present invention relates to an optical glass and an optical element. In particular, it is an optical glass having a refractive index (n d ) of 1.61-1.75 and an Abbe number (υ d ) of 35-45, has negative anomalous dispersion performance, has low fluorescence, and has chemical stability. Relates to a good optical glass and optical element.

  Optical glass is an indispensable and important component in optical equipment and photoelectric products, and in recent years, optical glass performance is most demanded by the widespread trend of photoelectric products such as digital cameras and digital single lens reflex cameras. For example, it is required to have the performance of removing or removing residual chromatic aberration of the secondary spectrum as much as possible. For this purpose, the optical glass is required to have negative anomalous dispersion performance. Glass with negative anomalous dispersion performance has a small relative chromatic dispersion, and when used in combination with a glass with a large relative partial dispersion, it removes residual chromatic aberration in the secondary spectrum relatively well and improves the image quality of the optical lens. can do.

  Moreover, low optical performance is required for optical glass used for optical instruments such as fluorescent microscopes currently used. In the biology and medical fields, the observation target (specimen) such as a biological tissue, cell, or bacteria is irradiated with ultraviolet light and irradiated, and the fluorescence emitted from the observation target is measured. In recent years, weak fluorescence emitted from a very small amount of bacteria and cells has been measured using a fluorescence microscope. By irradiating the observation target with excitation light using a fluorescence microscope, the optical system (objective lens) using the fluorescence microscope can also emit weak fluorescence, and noise is observed when observing and measuring such weak fluorescence. Is a problem. Therefore, a decrease in fluorescence intensity obtained by excitation of optical glass used in an optical system (particularly an objective lens) of a fluorescence microscope is required.

At present, optical glass having negative anomalous dispersion performance employing a B 2 O 3 —Al 2 O 3 —PbO system is known. For example, in Japanese Patent Publication Nos. 45-2311 and 48-74516, since the PbO content of the glass system is relatively large, not only the chemical stability of the glass is bad, but also the environmental requirements are not met. Regarding a glass system that does not contain PbO, Japanese Patent Publication No. 51-34407 contains a large amount of expensive GeO 2 and / or Ta 2 O 5 and is not suitable for actual production. The glass disclosed in JP1222593, DE4032566 may possibly incorporate an element that destroys anomalous dispersion performance such as Ti or F.

The glass of low fluorescence efficiency, in JP-A 10-158029 has disclosed a highly dispersed low fluorescence optical glass of B 2 O 3 -P 2 O 5 -R 2 O-Nb 2 O 5 and / or Ta 2 O 5 system However, the glass has a drawback of insufficient chemical stability. Japanese Patent Application Laid-Open No. 10-231140 discloses another type of B 2 O 3 —P 2 O 5 —R 2 O—Ta 2 O 5 -based high dispersion low fluorescence optical glass, but this type of glass has durability and translucency. In addition to the shortage problem, a large amount of expensive Ta 2 O 5 raw material is used, so that the manufacturing cost is high. Japanese Patent Laid-Open No. 10-3 1 6449 discloses a Ge 2 O 3 —Ta 2 O 5 —R 2 O-based high dispersion low fluorescence optical glass. However, this type of glass is also insufficient in chemical durability. Including a large amount of expensive Ge 2 O 3 component, the production cost is very high and lacks practicality.

The problem to be solved by the invention is to provide an optical glass and an optical element which have negative anomalous dispersion performance, low fluorescence performance, and good chemical stability.

In order to solve the above problems, the present invention is the mass percentage composition SiO 2: 31~55%; Nb 2 O 5: 15~29%; ZrO 2: 0.5~9%; La 2 O 3: 0 0.5 to 10%; R 2 O: An optical glass containing 12 to 30% is provided, and the R 2 O includes one or several of Na 2 O, Li 2 O, and K 2 O.

The optical glass of the present invention preferably further contains B 2 O 3 : 0 to 5%; Sb 2 O 3 : 0 to 0.5%; RO: 0 to 10%. The RO includes one kind or several kinds of BaO, SrO, and CaO.

Further, B 2 O 3: 0.5~5% and / or RO: is preferably 1 to 9%.

Further, SiO 2: is preferably 35 to 50%.

Furthermore, Nb 2 O 5: is preferably 18 to 29%.

Further, ZrO 2: is preferably 0.5 to 8%.

Moreover, La 2 O 3: is preferably 0.5 to 8%.

Furthermore, R 2 O: is preferably 13 to 25%.

Further, the mass ratio of La 2 O 3 / Nb 2 O 5 is preferably 0.01-0.45.

  Further, the refractive index of the optical glass is preferably 1.61 to 1.75, and the Abbe number is preferably 35 to 45.

  Further, it is preferable that negative anomalous dispersion ΔPg, F <−0.0008 of the optical glass.

  Furthermore, it measures based on prescription | regulation of Japanese standard JOGIS 03-1975, and it is preferable that the fluorescence of the said optical glass is 1st grade, and is a low fluorescence performance.

  Moreover, this invention provides the optical element manufactured with one of the said optical glasses.

  In the optical glass of the present invention, it is not necessary to add any element that harms the environment, the refractive index is 1.61 to 1.75, the Abbe number is 35 to 45, negative anomalous dispersion ΔPg, F <−0.0008. Therefore, the fluorescence of the optical glass is first grade as measured by the method defined in Japanese Standard JOGIS 03-1975. Since the optical glass of the present invention has low fluorescence performance and is environmentally friendly, it is widely applicable to devices such as digital cameras, digital video cameras, camera phones, and fluorescence microscopes.

Each composition of the optical glass of the present invention will be described as follows. Unless otherwise described, the characteristic value of each composition content is expressed in mass %.

It is a SiO 2 glass-forming substance and an essential oxide component that becomes glass. A certain amount of SiO 2 gives relatively good chemical stability to the optical glass and improves the transparency of the glass. The content of SiO 2 is lower than 31%, and the refractive index of the glass does not fall within the required range. However, when the content of SiO 2 is higher than 55%, the high-temperature viscosity of the glass becomes too high, and the engineering performance in production deteriorates. Therefore, the content of SiO 2 is limited to 31 to 55%, preferably 35 to 50%.

Nb 2 O 5 effectively improves the refractive index of the glass and increases the dispersion in the middle wave portion, while not significantly increasing the dispersion in the short wave portion, thereby increasing the negative anomalous dispersion performance of the optical glass. However, if the Nb 2 O 5 content is too high, the negative anomalous dispersion performance will be destroyed. Therefore, the content of Nb 2 O 5 is limited to 15 to 29%, preferably 18 to 29%.

The refractive index and negative anomalous dispersion performance of the ZrO 2 optical glass can be improved. However, if the ZrO 2 content is lower than 0.5%, the desired effect cannot be achieved. When the content of ZrO 2 is higher than 9%, this hardly soluble oxide deteriorates the melting performance of the glass, and a glass with good uniformity cannot be obtained. Therefore, the content of ZrO 2 is 0.5 to 9%, preferably 0.5 to 8%.

La 2 O 3 is an effective component that improves the refractive index of glass, and does not emit fluorescence in the visible light zone. The chemical stability and devitrification resistance improvement effect of glass is remarkable. However, when the content is less than 0.5%, a necessary engineering constant cannot be obtained. When the content is higher than 10%, the devitrification tendency is increased. Therefore, the content of La 2 O 3 is limited to 0.5 to 10%, preferably 0.5 to 8%.

In addition, in order to obtain stable glass (good devitrification) at the same time with relatively low fluorescence and further reduce the cost of the glass, in the present invention, the mass ratio of La 2 O 3 / Nb 2 O 5 is set to 0.01−. It has been discovered that it should be controlled within the 0.45 range, preferably within the 0.03-0.43 range.

R 2 O is one or several kinds of alkali metal oxides Na 2 O, Li 2 O, and K 2 O, and is a relatively good cosolvent, and an appropriate amount of R 2 O is an optical glass with relatively good uniformity. Is obtained. However, when the content of R 2 O is lower than 12%, the flux action cannot be achieved, and the high temperature viscosity of the glass becomes relatively large. When the total amount of R 2 O is higher than 30%, the chemical stability of the optical glass is deteriorated. Therefore, the content of R 2 O is 12 to 30%, preferably 13 to 25%.

B 2 O 3 is also a network-generating material, has a relatively good flux action, reduces the short wave dispersion of the glass, and has a relatively good negative anomalous dispersion performance. Therefore, the content of B 2 O 3 is set to 0 to 5%, preferably 0.5 to 5%.

  RO is one or several kinds of alkaline earth metal oxides BaO, SrO, and CaO, and can effectively improve the refractive index and Abbe number of glass. The RO content is 0 to 10%, preferably 1 to 9%.

Sb 2 O 3 is used as a fining agent in the present invention, and its content is 0 to 0.5%.

  The optical glass of the present invention is manufactured by a manufacturing method familiar to those skilled in the art. That is, the raw materials are dissolved, clarified and uniformly mixed, then cooled to an appropriate temperature and molded. The refractive index provided by the present invention is 1.61-1.75, Abbe number is 35-45, negative Optical glass with anomalous dispersion ΔPg of F <−0.0008, low fluorescence performance (measured by the method specified in Japanese Standard JOGIS 03-1975, and the fluorescence grade is first grade) and chemical stability Make up.

  The measuring method of the performance parameter of the optical glass provided by the present invention is as follows.

  The refractive index, Abbe number, and Pg and F are measured according to “GB / T 7962.1-2010 Colorless Optical Glass Measuring Method Refractive Index and Dispersion Coefficient”.

It has the performance below the optical glass of this invention obtained through said measurement. The refractive index (nd) is 1.61-1.75, the Abbe number is (ν d ) 35-45, and negative anomalous dispersion ΔPg, F <−0.0008.

  The fluorescence for judging low-fluorescence performance of glass is measured based on the Japanese standard “Optical Glass Fluorescence Measurement Method (JOGIS03-1975)”. The master sample is the flint glass specification specified by the Japan Optical Glass Industry Association. The sample is irradiated with ultraviolet excitation light having a wavelength of 365 nm, the fluorescence spectrum in the 400-700 nm wavelength range is measured, the peak value of the spectrum curve is defined as the fluorescence intensity, and the fluorescence, that is, the fluorescence of the glass sample is measured. It is the ratio between the intensity and the fluorescence intensity of the master sample. When the ratio exceeds 1.5, the grade is 3, and when the strength ratio is 0.7-1.5, the grade is 2, and when the strength ratio is less than 0.7, the grade is 1. In the case of the fluorescent grade 1st grade, the low fluorescence optical glass has a very low fluorescence intensity obtained by exciting ultraviolet rays, and is excellent in low fluorescence performance. The glass fluorescence grade of the present invention is first grade and has low fluorescence performance.

The water resistance DW of the glass powder method is measured according to GB / T17129 measurement standard.

Glass powder method acid stability D A is measured by GB / T17129 metric.

  The present invention further provides an optical element. The optical element is made of the optical glass of the present invention. Therefore, the optical element has all the characteristics of the optical glass of the present invention. The optical glass of the present invention also has negative anomalous dispersion performance, low fluorescence performance, no need to add any element harmful to the environment, refractive index (nd) is 1.61-1.75, The Abbe number (vd) is 35 to 45. The optical element provided by the present invention is applicable to devices such as a digital camera, a digital video camera, a camera phone, and a fluorescence microscope.

  As means for solving the problems of the present invention, the precision compression-molded optical glass of the present invention will be described in more detail with reference to examples. However, the scope of rights of the present invention is not limited to these examples.

  Optical glass Examples 1 to 30 displayed in Tables 1 to 3 are shown in Tables 1 to 3. After weighing and mixing uniformly based on the characteristic values of the individual examples, placing in an optical glass melting furnace, melting, clarifying, homogenizing at an appropriate process temperature, and then setting an appropriate temperature After cooling, the molten glass is cast in a preheated mold and annealed to produce the necessary optical glass.

In the present invention, the optical glass component having negative anomalous dispersion performance and corresponding to the optical glass component of low fluorescence performance, refractive index (nd), dispersion (nF-nC), Abbe number (vd), relative partial dispersion ratio (Pg, F) , Negative anomalous dispersion (ΔPg, F), fluorescence, powder water resistance stability D W , powder acid resistance stability D A , and results are collectively shown in Examples 1 to 30 in Tables 1 to 3. Therefore, the origin of Pg, F and ΔPg, F is explained by the following formula.

  In the above formula, the relative partial variance is calculated by formula (1). For many “normal glasses”, the linear correlation of equation (2) holds. When “normal glass” NSL7 and PBM2 are used as the reference glass, the deviation rate of the special dispersion in the inclination rate mx, y and the intercept bx, y, equation (3) when compared with ΔPx, y many “normal glass” Represents the characteristic, and finally, the detailed value of ΔPg, F is calculated in the equation (4).

From the above examples, it is not necessary for the optical glass provided by the present invention to add any element that harms the environment. Optical glass refractive index (n d ) is 1.61-1.75, Abbe number (ν d ) is 35-45, negative anomalous dispersion is ΔPg, F <−0.0008, low fluorescence performance (Japanese standard JOGIS Measured by the method defined in 03-1975, the fluorescence grade is first grade.), Has good chemical stability, and is applicable to devices such as digital cameras, digital video cameras, camera phones, and fluorescence microscopes.

Claims (12)

  1. Mass percentage composition ratio SiO 2: 31~55%; Nb 2 O 5: 15~29%; ZrO 2: 4.13~9%; La 2 O 3: 0.5~10%; R 2 O: 12 was 30%, the R 2 O is Na 2 O, Li 2 O, 1 type of K 2 O is or viewing contains several, refractive index of 1.61 to 1.75, and the Abbe number of 35 to 45 those having an optical glass (except Ti, F, PbO, an optical glass containing Ta 2 O 5, P 2 O 5 or Ge 2 O 3).
  2. The mass percentage composition is B 2 O 3 : 0 to 5%; Sb 2 O 3 : 0 to 0.5%; RO: 0 to 10%, and the above RO is one kind or several kinds of BaO, SrO and CaO. The optical glass according to claim 1, which is included.
  3. B 2 O 3: 0.5~5% and / or RO: is 1 to 9% optical glass according to claim 2.
  4. SiO 2: a 35% to 50%, the optical glass according to claim 1 or claim 2.
  5. Nb 2 O 5: a 18 to 29%, the optical glass according to claim 1 or claim 2.
  6. The optical glass according to claim 1 or 2, wherein ZrO2 is 4.13% to 8%.
  7. La 2 O 3: 0.5 to 8% optical glass according to claim 1 or claim 2.
  8. R 2 O: a 13 to 25%, the optical glass according to claim 1 or claim 2.
  9. La weight ratio of 2 O 3 / Nb 2 O 5 is 0.01 to 0.45, the optical glass according to claim 1 or claim 2.
  10.   The optical glass according to claim 1, wherein the optical glass has a negative abnormal color dispersion of ΔPg, F <−0.0008.
  11. The optical glass according to any one of claims 1 to 10 , which is measured by a method defined in Japanese Standard JOGIS 03-1975, and the fluorescence degree of the optical glass is first grade and has low fluorescence performance.
  12. Optical element manufactured from the optical glass according to any one of claims 1 to 11.
JP2016105141A 2015-06-23 2016-05-26 Optical glass and optical element Active JP6402138B2 (en)

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JP2017088483A (en) * 2015-11-06 2017-05-25 株式会社オハラ Optical glass, preform and optical element
US10370289B2 (en) 2015-11-11 2019-08-06 Ohara Inc. Optical glass, preform, and optical element
CN106830677A (en) * 2015-12-07 2017-06-13 株式会社小原 A kind of optical glass, prefabricated component and optical element
CN106915901A (en) * 2015-12-25 2017-07-04 株式会社小原 A kind of optical glass, prefabricated component and optical element
CN106938887B (en) * 2017-03-30 2019-07-09 湖北新华光信息材料有限公司 Optical glass with negative anomalous dispersion and preparation method thereof and optical element

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JPS5342331B2 (en) * 1975-12-10 1978-11-10
JPH0424298B2 (en) * 1985-07-09 1992-04-24 Hoya Corp
US5007948A (en) * 1990-03-19 1991-04-16 Corning Incorporated Essentially colorless silver-containing glasses through ion exchange
JP3302892B2 (en) * 1996-10-23 2002-07-15 株式会社オハラ Optical glass
AU7772901A (en) * 2000-08-15 2002-02-25 Ohara Kk Low fluorescent optical glass
JP4034589B2 (en) * 2001-06-06 2008-01-16 株式会社オハラ Optical glass
DE102007025601B4 (en) * 2007-05-31 2009-04-30 Schott Ag Barium heavy-duty optical glasses, their use and method of making an optical element
JP6573781B2 (en) * 2015-06-02 2019-09-11 光ガラス株式会社 Optical glass, optical element using optical glass, optical device

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