WO2016114274A1 - Glass, glass material for press molding, optical element blank, and optical element - Google Patents
Glass, glass material for press molding, optical element blank, and optical element Download PDFInfo
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- WO2016114274A1 WO2016114274A1 PCT/JP2016/050753 JP2016050753W WO2016114274A1 WO 2016114274 A1 WO2016114274 A1 WO 2016114274A1 JP 2016050753 W JP2016050753 W JP 2016050753W WO 2016114274 A1 WO2016114274 A1 WO 2016114274A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- 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
Definitions
- the present invention relates to glass, a glass material for press molding, an optical element blank, and an optical element.
- Patent Documents 1 to 18 Glass having a high refractive index and low dispersion (high refractive index and low dispersion glass) having a refractive index nd in the range of 1.800 to 1.850 and an Abbe number ⁇ d in the range of 41.5 to 44 are described in Patent Documents 1 to 18, for example.
- Patent Document 1 JP 2002-12443
- Patent Document 2 JP 2003-267748
- Patent Document 3 JP 2005-281124
- Patent Document 4 JP 2005-298262
- Patent Document 5 JP Japanese Patent Application Laid-Open No. 55-121925
- Patent Document 6 Japanese Patent Application Laid-Open No. 2009-203083
- Patent Document 7 Japanese Patent Application Laid-Open No.
- Patent Document 8 Japanese Patent Application Laid-Open No. 56-160340 Patent Document 9: Japanese Patent Application Laid-Open No. 2009-167080 Patent Document 10: Japanese Patent Application Laid-Open No. 2009-167081 Patent Document 11: Japanese Patent Application Laid-Open No. 2009-298646 Patent Document 12: Japanese Patent Application Laid-Open No. 2010-111527 Patent Document 13: Japanese Patent Application Laid-Open No. 2010-111528 Patent Document 14: Japanese Patent Application Laid-Open No. 2010-111530 Patent Document 15: Japanese Patent Application Laid-Open No. 57-056344 Document 16: JP 61-163138 JP Patent Document 17: JP 2002-284542 JP Patent Document 18: JP 2007-269584 JP
- Glass with a refractive index nd in the range of 1.800 to 1.850 and an Abbe number ⁇ d in the range of 41.5 to 44 is useful for correcting chromatic aberration, increasing the functionality of the optical system, and making it more compact. It is a material for an optical element.
- the refractive index means the refractive index nd at the d-line (helium wavelength 587.56 nm) unless otherwise specified.
- the Abbe number means ⁇ d unless otherwise specified.
- the glass described in Patent Document 7 contains a large amount of Ta.
- the glasses described in Patent Documents 8 to 14 and the glass having a refractive index and an Abbe number in the above-described ranges described in Patent Document 17 contain a large amount of Gd.
- the proportion of Yb in the glass composition is low. This is due to the following reason. Yb has absorption in the near infrared region. Therefore, glass containing a large amount of Yb (for example, glass described in Patent Document 16) is used for applications that require high transmittance from the visible range to the near-infrared range, such as surveillance cameras, night vision cameras, and in-vehicle camera lenses. It is not suitable as a material for optical elements. Yb belongs to a heavy rare earth element, has a large atomic weight as a glass component, and increases the specific gravity of the glass. As the specific gravity of the glass increases, the lens becomes heavier. As a result, when such a lens is incorporated into an autofocus camera lens, the power consumption increases and the battery consumption becomes severe. From the above points, it is desirable to reduce the proportion of Yb in the glass composition.
- the refractive index nd is in the range of 1.800 to 1.850
- the Abbe number ⁇ d is in the range of 41.5 to 44
- the glass composition has Gd
- a glass having a reduced proportion of Ta and Yb and excellent thermal stability is provided.
- the glass further satisfy one or more of the following points.
- an ultraviolet curable adhesive is usually used to bond the lenses together. Details are as follows. An ultraviolet curable adhesive is applied to the surface where the lenses are bonded together, and the lenses are bonded together. At this time, an extremely thin coating layer of an ultraviolet curable adhesive is usually formed between the lenses. Next, the coating layer is irradiated with ultraviolet rays through a lens to cure the ultraviolet curable adhesive.
- the transmittance of the ultraviolet ray of the lens is low, a sufficient amount of ultraviolet ray does not reach the coating layer through the lens, resulting in insufficient curing. Or it takes a long time to cure.
- an ultraviolet curable adhesive is used to adhere and fix a lens to a lens barrel or the like, if the lens has a low ultraviolet transmittance, curing may be insufficient or long. It takes time. Therefore, in order to obtain a glass having transmittance characteristics suitable for the production of an optical system, it is necessary to increase the transmittance in the ultraviolet region of the glass, in other words, to increase the wavelength of the light absorption edge on the short wavelength side of the glass. It is desirable to suppress this.
- the light absorption edge on the short wavelength side of the glass has a longer wavelength, and the transmittance in the ultraviolet region is reduced.
- the glass composition of the conventional high refractive index and low dispersion glass when trying to maintain both the high refractive index and low dispersion characteristics and the thermal stability while reducing the content of Gd and Ta, There was a tendency that the wavelength of the light absorption edge became longer and the transmittance of ultraviolet rays was greatly reduced.
- Suitable for machining Details are as follows.
- a method for obtaining an optical element from glass in addition to a precision press molding method (see, for example, Patent Documents 1 to 4), an optical element blank is formed from glass, and mechanical processing such as grinding and polishing is performed on the optical element blank.
- mechanical processing such as grinding and polishing
- glass for precision press molding has a low glass transition temperature, but a glass having a low glass transition temperature tends to be easily broken during machining. Therefore, in order to obtain a glass suitable for machining, it is desirable that the glass transition temperature is higher than that of the glass for precision press molding.
- One embodiment of the present invention is represented by mass%,
- the total content of B 2 O 3 and SiO 2 is 15 to 35% by mass,
- the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 is 45 to 65% by mass, provided that the Yb 2 O 3 content is 3% by mass or less, ZrO 2 content is 3 to 11% by mass, Ta 2 O 5 content is 5% by mass or less
- the mass ratio of B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4-0.900
- Mass ratio of the total content of B 2 O 3 and SiO 2 to the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.
- one embodiment of the present invention is represented by cation% display.
- the total content of B 3+ and Si 4+ is 45 to 65%, The total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 25-35%, provided that the Yb 3+ content is less than 2%; Zr 4+ content is 2-8 %, Ta 5+ content is 3% or less,
- the cation ratio of the B 3+ content to the total content of B 3+ and Si 4+ (B 3+ / (B 3+ + Si 4+ )) is 0.65 or more and less than 0.94
- Cation ratio of the total content of B 3+ and Si 4+ to the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 1.65 to 2.60
- the glass 1 is a glass having a refractive index nd and an Abbe number ⁇ d in the above range, and includes various components including Gd 2 O 3 (that is, La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Yb 2 O 3). ) Satisfies the above mass ratio with the Gd 2 O 3 content as the numerator and the total content of the various components as the denominator. Therefore, the proportion of Gd in the glass composition is reduced. Furthermore, the Ta 2 O 5 content and the Yb 2 O 3 content are as described above, and the proportion of Ta and Yb in the glass composition is also reduced.
- Gd 2 O 3 that is, La 2 O 3 , Y 2 O 3 , Gd 2 O 3 , Yb 2 O 3
- the above glass has a high thermal stability by adjusting the composition satisfying the above-mentioned content, total content and mass ratio in the composition in which the proportion of Gd, Ta and Yb is thus reduced. Can be realized. Further, it is possible to suppress the increase in the wavelength of the light absorption edge on the short wavelength side and to increase the glass transition temperature (Tg) (to increase the glass transition temperature).
- the glass 2 is a glass having a refractive index nd and an Abbe number ⁇ d in the above range, and is a total content of various components including Gd 3+ (ie, La 3+ , Y 3+ , Gd 3+ , Yb 3+ ). Within the above range, the cation ratio is satisfied with the Gd 3+ content as the numerator and the total content of the various components as the denominator. Therefore, the proportion of Gd in the glass composition is reduced. Further, the Ta 5+ content and the Yb 3+ content are as described above, and the proportion of Ta and Yb in the glass composition is also reduced.
- Gd 3+ ie, La 3+ , Y 3+ , Gd 3+ , Yb 3+
- the above glass has a high thermal stability by adjusting the composition satisfying the above-mentioned content, total content and cation ratio in the composition in which the proportion of Gd, Ta and Yb is reduced. Can be realized. Further, it is possible to suppress the increase in the wavelength of the light absorption edge on the short wavelength side and to increase the glass transition temperature (Tg) (to increase the glass transition temperature).
- a glass that has high refractive index and low dispersion characteristics useful in an optical system, can be stably supplied, and is excellent in thermal stability. Furthermore, according to one embodiment of the present invention, it is possible to provide a glass material for press molding, an optical element blank, and an optical element made of the glass.
- the spectral transmittance curve in the thickness 10.0mm of the glass A mentioned later is shown.
- the spectral transmittance curve in the thickness 10.0mm of the glass B mentioned later is shown.
- the glass composition in the present invention can be quantified by a method such as ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry).
- the analysis value obtained by ICP-AES may include a measurement error of about ⁇ 5% of the analysis value, for example.
- that the content of the constituent component is 0% or does not contain or is not introduced means that the constituent component is substantially not contained, and the content of the constituent component is an impurity level. It means less than or equal to.
- a (more) preferable lower limit and a (more) preferable upper limit may be shown in a table.
- the numerical value described below is more preferable, and the numerical value described most downward is most preferable.
- the (more) preferred lower limit means that it is (more) preferred to be greater than or equal to the stated value, and the (more) preferred upper limit is less than the stated value. (More) It is preferable.
- the numerical value range can be defined by arbitrarily combining the numerical values described in the (more) preferable lower limit column and the (more) preferable upper limit column in the table.
- Glass 1 and glass 2 according to one embodiment of the present invention have the above-described glass composition, have an index of refraction nd of 1.800 to 1.850, and an Abbe number ⁇ d of 41.5 to 44. It is a physical glass. Hereinafter, the details of the glass 1 and the glass 2 will be described.
- the glass composition of the glass 1 is displayed on an oxide basis.
- the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed at the time of melting and existing as oxides in the glass. Unless otherwise specified, the glass composition of the glass 1 is expressed on a mass basis (mass%, mass ratio).
- B 2 O 3 and SiO 2 are glass network forming components.
- the thermal stability of the glass is improved, and the crystallization of the glass during production is suppressed. it can.
- the total content of B 2 O 3 and SiO 2 is 35% or less, a decrease in the refractive index nd can be suppressed, so that the glass having the above-described optical characteristics, that is, the refractive index nd is 1
- the total content of B 2 O 3 and SiO 2 in the glass 1 is in the range of 15 to 35%.
- the preferable lower limit and preferable upper limit of the total content of B 2 O 3 and SiO 2 are as shown in the following table.
- the content ratio of each component of B 2 O 3 and SiO 2 is related to the thermal stability, meltability, formability, chemical durability, weather resistance, machinability, etc. of glass. Influence. B 2 O 3 is more excellent in improving the meltability than SiO 2 , but easily volatilizes during melting. On the other hand, SiO 2 has a function of improving the chemical durability, weather resistance, and machinability of glass and increasing the viscosity of glass during melting. In general, in a high refractive index low dispersion glass containing rare earth elements such as B 2 O 3 and La 2 O 3 , the viscosity of the glass at the time of melting is low.
- the glass having excellent formability corresponds to a glass having a relatively high viscosity when a molten glass is poured into a mold among high refractive index and low dispersion glass containing rare earth elements.
- the mass ratio of the B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.900 or less, the viscosity at the time of melting Decline can be suppressed, thereby improving the thermal stability of the glass and suppressing volatilization during melting. Volatilization at the time of melting causes a large variation in glass composition and characteristics. As a result, it becomes difficult to form optically homogeneous glass. Therefore, it is preferable that the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) be 0.900 or less to suppress volatilization at the time of melting from the viewpoint of mass-producing glass with little variation in composition and characteristics.
- the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2)) is equal to 0.900 or less, the chemical durability of the glass, weather resistance, it is also possible to suppress a decrease in machinability.
- the B 2 O 3 content is 28 to 30% by mass, and the SiO 2 content is 1 to 3%. It is mass% (refer the claim of patent document 15).
- the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) calculated from the contents of these components is a large value of 0.903 to 0.968.
- the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4 or more, it is possible to prevent unmelted glass raw material at the time of melting, thereby improving the meltability. it can. From the above points, in the glass 1, the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is set in the range of 0.4 to 0.900.
- the preferable lower limit and the preferable upper limit of the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) in the glass 1 are as shown in the following table.
- La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 are components having a function of increasing the refractive index while suppressing a decrease in the Abbe number. These components also have the function of improving the chemical durability and weather resistance of the glass and increasing the glass transition temperature. Refraction when the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 ) is 45% or more Since the reduction in the rate can be suppressed, the glass having the above-described optical characteristics can be produced. Furthermore, it is possible to suppress a decrease in chemical durability and weather resistance of the glass.
- the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 in the glass 1 is in the range of 45 to 65%.
- the preferable lower limit and the preferable upper limit of the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 are shown in the following table.
- ZrO 2 is a component having a function of increasing the refractive index, and also has a function of improving the thermal stability of the glass by containing an appropriate amount. ZrO 2 also has a function of increasing the glass transition temperature and making it difficult for the glass to break during mechanical processing. In order to obtain these effects satisfactorily, the glass 1 has a ZrO 2 content of 3% or more. On the other hand, if the content of ZrO 2 is 11% or less, the thermal stability of the glass can be improved, so that crystallization during glass production and generation of unmelted glass during glass melting can be suppressed. . Therefore, the content of ZrO 2 in the glass 1 is in the range of 3 to 11%. The preferable lower limit and the preferable upper limit of the ZrO 2 content are shown in the following table.
- Ta 2 O 5 is a component that desirably reduces the proportion of the glass composition from the viewpoint of stable glass supply.
- Ta 2 O 5 is a component having a function of increasing the refractive index, but is also a component that increases the specific gravity of the glass and decreases the meltability. Therefore, the Ta 2 O 5 content in the glass 1 is set to 5% or less.
- the preferable lower limit and the preferable upper limit of the content of Ta 2 O 5 are shown in the following table.
- La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 are used.
- the mass ratio of the total content of B 2 O 3 and SiO 2 to the total content of ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0
- the range is from 42 to 0.53. If the mass ratio ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.42 or more, the thermal stability of the glass should be improved.
- the increase in specific gravity of glass can also be suppressed.
- an optical element manufactured using the glass becomes heavy.
- an optical system incorporating this optical element becomes heavy. For example, if a heavy optical element is incorporated in an autofocus camera, the power consumption when driving the autofocus increases, and the battery is quickly consumed.
- the ability to suppress an increase in the specific gravity of glass is preferable from the viewpoint of reducing the weight of an optical element produced using the glass and an optical system incorporating the optical element.
- the mass ratio ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.53 or less, the above optical characteristics can be realized. Can do.
- the fact that the mass ratio ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.53 or less indicates the chemical durability of the glass. It is also preferable from the viewpoint of improvement and high glass transition temperature (Tg).
- Tg glass transition temperature
- the preferred lower limit and preferred upper limit of the mass ratio ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) are shown in the following table.
- Yb 2 O 3 is a desirable component for reducing the proportion of the glass composition for the reason described above. . Therefore, in the glass 1, the Yb 2 O 3 content is 3% or less.
- the preferable lower limit and the preferable upper limit of the Yb 2 O 3 content are shown in the following table.
- Y 2 O 3 is a component that functions to improve the thermal stability of the glass without significantly reducing the light transmittance in the near infrared region. Moreover, since the atomic weight is small, it is a preferable component for suppressing an increase in the specific gravity of the glass. However, if the content of Y 2 O 3 is too large, the thermal stability of the glass is remarkably lowered and crystallization is likely to occur. Moreover, meltability falls.
- the mass ratio of Y 2 O 3 content to the total content (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is in the range of 0.05 to 0.45.
- the preferable lower limit and the preferable upper limit of the mass ratio (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) are shown in the following table.
- Gd 2 O 3 is a component that desirably reduces the proportion of the glass composition for the reasons described above.
- Gd belongs to heavy rare earth elements like Yb, has a large atomic weight as a glass component, and increases the specific gravity of glass. Also from this point, it is desirable to reduce the proportion of Gd in the glass composition.
- the content of Gd 2 O 3 depends on the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 and the Gd 2 O 3 content relative to this total content. Determined.
- La 2 O 3 and Y 2 O are used in order to stably supply the high refractive index and low dispersion glass having the above-mentioned optical characteristics, and further to make a glass having a small specific gravity as the high refractive index and low dispersion glass.
- the mass ratio of Gd 2 O 3 content to the total content of Gd 2 O 3 and Yb 2 O 3 (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) Is in the range of 0 to 0.05.
- the preferable lower limit and preferable upper limit of the mass ratio (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) are shown in the following table.
- La 2 O 3 is useful for providing a high refractive index and low dispersion glass without significantly lowering the light transmittance in the near infrared region, improving the thermal stability and suppressing an increase in specific gravity. Is an essential ingredient. Therefore, in the glass 1, the mass ratio of La 2 O 3 content to the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (La 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is preferably in the range of 0.55 to 0.95. More preferable lower limits and more preferable upper limits of the mass ratio (La 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) are shown in the following table.
- Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 are components that have a function of increasing the refractive index, and also have a function of improving the thermal stability of the glass by containing an appropriate amount.
- the above optical characteristics are that the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 ) is in the range of 3 to 15%. It is preferable for further improving the thermal stability of the glass while realizing it.
- the more preferable lower limit and the more preferable upper limit of the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 are shown in the following table.
- ZnO has a function of promoting melting of a raw material of glass when melting glass, that is, a function of improving meltability. It also has functions of adjusting the refractive index and Abbe number and lowering the glass transition temperature.
- the value obtained by dividing the ZnO content by the total content of B 2 O 3 and SiO 2 , that is, the mass ratio (ZnO / (B 2 O 3 + SiO 2 )) is 0.04 or more. It is preferable for improvement.
- the mass ratio (ZnO / (B 2 O 3 + SiO 2 )) is 0.4 or less in order to suppress the decrease in Abbe number (high dispersion) and realize the above optical characteristics.
- the thermal stability and improved high glass transition temperature (Tg) of the glass mass ratio (ZnO / (B 2 O 3 + SiO 2)) is 0.4 or less. Therefore, the content of ZnO is set to 0.04 to 0.4 times the total content of B 2 O 3 and SiO 2 by mass ratio, that is, mass ratio (ZnO / (B 2 O 3 + SiO 2 )) Is preferably 0.04 to 0.4. More preferable lower limits and more preferable upper limits of the mass ratio (ZnO / (B 2 O 3 + SiO 2 )) are shown in the following table.
- the preferred lower limit and preferred upper limit of the ZnO content are as shown in the following table.
- Mass ratio of the total content of B 2 O 3 and SiO 2 to the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 ((B 2 O 3 + SiO 2 ) / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is in the range of 2.65 to 10 in order to increase the ultraviolet transmittance of the glass while suppressing the increase in the coloring degree ⁇ 5 described later while realizing the above optical characteristics. It is preferable.
- the mass ratio ((B 2 O 3 + SiO 2 ) / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) should be 2.65 or more. preferable. More preferable lower limits and more preferable upper limits of the mass ratio ((B 2 O 3 + SiO 2 ) / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) are shown in the following table.
- Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 serve to improve the thermal stability of the glass by containing appropriate amounts.
- TiO 2 increases, the transmittance of the visible region of the glass tends to decrease, and the coloration of the glass tends to increase.
- the action of Ta 2 O 5 is as described above.
- WO 3 when the content thereof increases, the transmittance in the visible region of the glass tends to decrease and the coloration of the glass tends to increase, and the specific gravity tends to increase.
- Nb 2 O 5 has a function of hardly increasing the specific gravity, coloring, and production cost of the glass, increasing the refractive index, and improving the thermal stability of the glass.
- the ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is set in the range of 0.5 to 1.
- the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is increased from the viewpoint of reducing the coloring degree ⁇ 5 and promoting the curing of the ultraviolet curable adhesive by ultraviolet irradiation. It is preferable. More preferable lower limit and more preferable upper limit of the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) are shown in the following table.
- the content of Nb 2 O 5 with respect to the total content of Nb 2 O 5 , TiO 2 and WO 3 excluding Ta 2 O 5 among Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 The preferable range of the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + WO 3 )) will be described.
- the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + WO 3 )) must be in the range of 0.50 to 1 in order to produce a glass with excellent thermal stability and low coloration. Is preferred. More preferable lower limit and more preferable upper limit of the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + WO 3 )) are shown in the following table.
- the mass ratio of ZnO content to the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 improves the meltability. From the viewpoint of the above, it is preferably 0.1 or more.
- it is preferably 0.1 or more.
- the glass with low meltability when the melting temperature of glass is raised or the melting time is lengthened so that there is no unmelted glass raw material, the coloring of the glass tends to increase.
- the mass ratio (ZnO / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is 0.1 or more from the viewpoint of suppressing the coloring of the glass. .
- the mass ratio (ZnO / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is preferably 3 or less. More preferable lower limits and more preferable upper limits of the mass ratio (ZnO / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) are shown in the following table.
- the Li 2 O content is 1% from the viewpoint of further improving the thermal stability of the glass, suppressing the lowering of the glass transition temperature (improvement of machinability by this), and improving the chemical durability and weather resistance.
- the following is preferable.
- the preferable lower limit and the more preferable upper limit of the Li 2 O content are shown in the following table.
- Na 2 O, K 2 O, Rb 2 O, and Cs 2 O all have a function of improving the meltability of the glass.
- the content thereof increases, the thermal stability and chemical durability of the glass are increased. Property, weather resistance, and machinability tend to decrease. Therefore, it is preferable that the lower limit and the upper limit of each content of Na 2 O, K 2 O, Rb 2 O, and Cs 2 O are as shown in the following table.
- Rb 2 O and Cs 2 O are expensive components and are not suitable for general-purpose glass compared to Li 2 O, Na 2 O, and K 2 O. Therefore, in order to improve the meltability of the glass while maintaining the thermal stability, chemical durability, weather resistance, and machinability of the glass, the total content of Li 2 O, Na 2 O and K 2 O
- the lower limit and the upper limit of (Li 2 O + Na 2 O + K 2 O) are preferably as shown in the following table, respectively.
- MgO, CaO, SrO, and BaO are all components that have a function of improving the meltability of glass. However, if the content of these components is increased, the thermal stability of the glass is lowered and a tendency to devitrification is exhibited. Accordingly, the content of each of these components is preferably set to be equal to or higher than the lower limit shown below, and is preferably set to be lower than the upper limit.
- the total content of MgO, CaO, SrO and BaO is preferably not less than the lower limit shown in the following table, and preferably not more than the upper limit. .
- Al 2 O 3 is a component having a function of improving the chemical durability and weather resistance of glass.
- the content of Al 2 O 3 increases, a refractive index decreasing tendency, a glass thermal stability decreasing tendency, and a meltability decreasing tendency may be observed.
- the Al 2 O 3 content is preferably not less than the lower limit shown in the following table, and preferably not more than the upper limit.
- Ga 2 O 3 , In 2 O 3 , Sc 2 O 3 , and HfO 2 all have a function of increasing the refractive index nd. However, these components are expensive and are not essential components for obtaining the glass 1. Therefore, the contents of Ga 2 O 3 , In 2 O 3 , Sc 2 O 3 , and HfO 2 are preferably not less than the lower limit shown in the following table, and preferably not more than the upper limit.
- Lu 2 O 3 functions to increase the refractive index nd, but is also a component that increases the specific gravity of the glass. It is also an expensive component. From the above points, the preferred lower limit and the preferred upper limit of the content of Lu 2 O 3 are as shown in the following table.
- GeO 2 has a function of increasing the refractive index nd, but is a prominent and expensive component among commonly used glass components. From the viewpoint of reducing the production cost of glass, the preferred lower limit and preferred upper limit of the GeO 2 content are as shown in the following table.
- Bi 2 O 3 is a component that increases the refractive index nd and decreases the Abbe number. It is also a component that tends to increase the coloration of the glass.
- the preferred lower and preferred upper limits for the Bi 2 O 3 content are as shown in the following table from the viewpoint of producing a glass having the above-mentioned optical properties and little coloration.
- the total content (total content) of the glass components described above is preferably more than 95%, more than 98%. More preferably, it is more preferably more than 99%, and still more preferably more than 99.5%.
- P 2 O 5 is a component that lowers the refractive index and is also a component that lowers the thermal stability of the glass. May improve stability.
- the preferred lower limit and preferred upper limit of the P 2 O 5 content are as shown in the following table for producing a glass having the above-mentioned optical characteristics and excellent thermal stability.
- TeO 2 is a component that increases the refractive index, but since it is a toxic component, it is preferable to reduce the content of TeO 2 .
- the preferable lower limit and preferable upper limit of the TeO 2 content are as shown in the following table.
- the content of (more) a preferred lower limit or 0% in each of the above tables is 0%.
- Pb, As, Cd, Tl, Be, and Se each have toxicity. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- U, Th, and Ra are all radioactive elements. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- V, Cr, Mn, Fe, Co, Ni, Cu, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Ce increase the coloration of the glass and become a source of fluorescence.
- the element contained in the glass for optical elements is not preferable. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- Sb and Sn are arbitrarily addable elements that function as fining agents.
- the amount of Sb added is 0 to 0.11% by mass when converted to Sb 2 O 3 and the total content of glass components other than Sb 2 O 3 is 100% by mass in the oxide-based glass composition.
- the range is preferably 0.01 to 0.08% by mass, more preferably 0.02 to 0.05% by mass.
- the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed during melting and existing as oxides in the glass.
- the Sb 2 O 3 content in the glass composition shown in the table described later is also the content calculated by the above method.
- the addition amount of Sn should be in the range of 0 to 1.0% by mass when converted to SnO 2 and the total content of glass components other than SnO 2 is 100% by mass in the oxide-based glass composition.
- the range is 0 to 0.5% by mass, more preferably 0 to 0.2% by mass, and still more preferably 0% by mass.
- the glass composition of the glass 2 is expressed in terms of cation% with respect to the cation component.
- the cation% is a percentage in which the total content of all cation components contained in the glass is 100%.
- the cation component is expressed as B 3+ , Si 4+ , La 3+ , for example, but the valence of the cation component (for example, the valence of B 3+ is +3 and the valence of Si 4+ is +4).
- the valence of La 3+ is a value determined by convention, and is the same as expressing B, Si, La as B 2 O 3 , SiO 2 , La 2 O 3 on the oxide basis. .
- the content of the cation component and the total content (total content) of the plurality of types of cation components are expressed in cation%. Furthermore, in the cation% display, the ratio of the contents of cation components (including the total content of plural kinds of cation components) is referred to as a cation ratio.
- B 3+ and Si 4+ are glass network forming components.
- the thermal stability of the glass is improved, and the crystallization of the glass during production is suppressed. it can.
- the total content of B 3+ and Si 4+ is 65% or less, a decrease in the refractive index can be suppressed, so that the glass having the above-described optical characteristics, that is, the refractive index nd is 1. It is possible to produce a glass having a range of 800 to 1.850 and an Abbe number ⁇ d of 41.5 to 44. Therefore, the total content of B 3+ and Si 4+ in the glass 2 is in the range of 45 to 65%.
- the preferable lower limit and the preferable upper limit of the total content of B 3+ and Si 4+ are as shown in the following table.
- the ratio of the content of B 3+ and Si 4+ which are glass network forming components, is related to the thermal stability, meltability, formability, chemical durability, weather resistance, machinability, etc. of glass. Influence. B 3+ is superior to Si 4+ in improving the meltability, but tends to volatilize during melting. On the other hand, Si 4+ has a function of improving the chemical durability, weather resistance, and machinability of glass and increasing the viscosity of glass during melting. Generally, in a high refractive index and low dispersion glass containing rare earth elements such as B 3+ and La 3+ , the viscosity of the glass at the time of melting is low.
- the glass having excellent formability corresponds to a glass having a relatively high viscosity when a molten glass is poured into a mold among high refractive index and low dispersion glass containing rare earth elements. If the cation ratio of the content of B 3+ to the total content of B 3+ and Si 4+ (B 3+ / (B 3+ + Si 4+ )) is less than 0.94, viscosity reduction during melting can be reduced.
- the thermal stability of the glass can be improved, and volatilization during melting can be suppressed.
- Volatilization at the time of melting causes a large variation in glass composition and characteristics.
- the cation ratio (B 3+ / (B 3+ + Si 4+ )) is less than 0.94, it is possible to suppress the deterioration of the chemical durability, weather resistance, and machinability of the glass.
- Patent Document 15 Japanese Patent Laid-Open No. 57-056344
- the B 2 O 3 content is 28 to 30% by mass
- the SiO 2 content is 1 to 3%. It is mass% (refer the claim of patent document 15).
- the cation ratio (B 3+ / (B 3+ + Si 4+ )) calculated from the contents of these components is as large as 0.942 to 0.981.
- the cation ratio (B 3+ / (B 3+ + Si 4+ )) is 0.65 or more, it is possible to prevent melting of the glass raw material at the time of melting, so that the meltability can be improved. .
- the cation ratio (B 3+ / (B 3+ + Si 4+ )) is set to 0.65 or more and less than 0.94.
- the preferable lower limit and preferable upper limit of the cation ratio (B 3+ / (B 3+ + Si 4+ )) in the glass 2 are as shown in the following table.
- the lower limit and preferable for improving the thermal stability, meltability, formability, chemical durability, weather resistance, machining, etc. of the glass is shown in the table below.
- La 3+ , Y 3+ , Gd 3+ and Yb 3+ are components having a function of increasing the refractive index while suppressing a decrease in the Abbe number. These components also have the function of improving the chemical durability and weather resistance of the glass and increasing the glass transition temperature. If the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ (La 3+ + Y 3+ + Gd 3+ + Yb 3+ ) is 25% or more, the decrease in refractive index can be suppressed. Therefore, it is possible to produce a glass having the above optical characteristics. Furthermore, it is possible to suppress a decrease in chemical durability and weather resistance of the glass.
- the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is in the range of 25 to 35%.
- the preferable lower limit and preferable upper limit of the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ are shown in the following table.
- Zr 4+ is a component having a function of increasing the refractive index, and also has a function of improving the thermal stability of the glass by containing an appropriate amount.
- Zr 4+ also has a function of increasing the glass transition temperature and making it difficult for the glass to break during mechanical processing.
- the glass 2 has a Zr 4+ content of 2% or more.
- the content of Zr 4+ is 8% or less, the thermal stability of the glass can be improved, so that crystallization during glass production and generation of unmelted residue during glass melting can be suppressed. it can. Therefore, the Zr 4+ content in the glass 2 is set in the range of 2 to 8%.
- the preferable lower limit and the preferable upper limit of the Zr 4+ content are shown in the following table.
- Ta 5+ is a component that desirably reduces the proportion of the glass composition from the viewpoint of stable glass supply.
- Ta 5+ is a component having a function of increasing the refractive index, but is also a component that increases the specific gravity of the glass and decreases the meltability. Therefore, the Ta 5+ content in the glass 2 is 3% or less.
- the preferable lower limit and the preferable upper limit of the content of Ta 5+ are shown in the following table.
- the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ in the glass 2 The cation ratio ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) of the total content of B 3+ and Si 4+ with respect to 1.65 to 2.60 Range. If the cation ratio ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 1.65 or more, the thermal stability of the glass can be improved. Glass devitrification can be suppressed.
- the increase in specific gravity of glass can also be suppressed.
- an optical element manufactured using the glass becomes heavy.
- an optical system incorporating this optical element becomes heavy.
- the ability to suppress an increase in the specific gravity of glass is preferable from the viewpoint of reducing the weight of an optical element produced using the glass and an optical system incorporating the optical element.
- the cation ratio ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 2.60 or less, the above optical characteristics can be realized.
- the cation ratio ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) of 2.60 or less means that the chemical durability of the glass is improved and the high glass It is also preferable from the viewpoint of transition temperature (Tg).
- Tg transition temperature
- the preferable lower limit and the preferable upper limit of the cation ratio ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) are shown in the following table.
- Yb 3+ is a component that desirably reduces the proportion of the glass composition for the reasons described above. Therefore, in the glass 2, the Yb 3+ content is less than 2%.
- the preferable lower limit and the preferable upper limit of the Yb 3+ content are shown in the following table.
- Y 3+ is a component that functions to improve the thermal stability of the glass without significantly reducing the light transmittance in the near infrared region. Moreover, since the atomic weight is small, it is a preferable component for suppressing an increase in the specific gravity of the glass. However, if the content of Y 3+ is too large, the thermal stability of the glass is remarkably lowered and crystallization is likely to occur. Moreover, meltability falls.
- La 3+ In order to improve the thermal stability and suppress the increase in specific gravity without significantly reducing the light transmittance in the near-infrared region and to make a glass having the above optical properties, in the glass 2, La 3+ , The cation ratio of the content of Y 3+ to the total content of Y 3+ , Gd 3+ and Yb 3+ (Y 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 0.05 The range is to 0.45.
- the preferable lower limit and the preferable upper limit of the cation ratio (Y 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) are shown in the following table.
- Gd 3+ is a component that desirably reduces the proportion of the glass composition for the reasons described above.
- Gd belongs to heavy rare earth elements like Yb, has a large atomic weight as a glass component, and increases the specific gravity of glass. Also from this point, it is desirable to reduce the proportion of Gd in the glass composition.
- La 3+ , Y 3+ , Y 3+ , Y 2 The cation ratio of the Gd 3+ content to the total content of Gd 3+ and Yb 3+ (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is in the range of 0 to 0.05. .
- the preferable lower limit and the preferable upper limit of the cation ratio (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) are shown in the following table.
- La 3+ does not significantly reduce the light transmittance in the near infrared region, improves thermal stability, suppresses an increase in specific gravity, and is useful for providing a high refractive index and low dispersion glass. It is an ingredient. Therefore, in the glass 2, the cation ratio of La 3+ content to the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ (La 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3) + )) Is preferably in the range of 0.55 to 0.95. More preferable lower limits and more preferable upper limits of the cation ratio (La 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) are shown in the following table.
- Nb 5+ , Ti 4+ , Ta 5+ and W 6+ are components having a function of increasing the refractive index, and also have a function of improving the thermal stability of the glass by containing an appropriate amount.
- the total optical content of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ ) is in the range of 2 to 10%. It is preferable for further improving the thermal stability of the glass while realizing it.
- the more preferable lower limit and the more preferable upper limit of the total content of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ are shown in the following table.
- Zn 2+ has a function of accelerating melting of the glass raw material when the glass is melted, that is, a function of improving the meltability. It also has functions of adjusting the refractive index and Abbe number and lowering the glass transition temperature.
- a value obtained by dividing the Zn 2+ content by the total content of B 3+ and Si 4+ , that is, the cation ratio (Zn 2+ / (B 3+ + Si 4+ )) is 0.01 or more. It is preferable for improving the meltability.
- the cation ratio (Zn 2+ / (B 3+ + Si 4+ )) is preferably 0.22 or less in order to suppress the decrease in Abbe number (high dispersion) and realize the above optical characteristics. .
- the cation ratio (Zn 2+ / (B 3+ + Si 4+ )) is preferably 0.22 or less from the viewpoint of improving the thermal stability of the glass and increasing the glass transition temperature (Tg). Accordingly, the Zn 2+ content is set to 0.01 to 0.22 times the total cation ratio of B 3+ and Si 4+ , that is, the cation ratio (Zn 2+ / (B 3 + + Si 4+ )) is preferably 0.01 to 0.22. More preferable lower limit and more preferable upper limit of the cation ratio (Zn 2+ / (B 3+ + Si 4+ )) are shown in the following table.
- the preferred lower limit and preferred upper limit of the Zn 2+ content are as shown in the following table. is there.
- Cation ratio of the total content of B 3+ and Si 4+ to the total content of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ ((B 3+ + Si 4+ ) / (Nb 5+ + Ti 4 + + Ta 5+ + W 6+ )) is in the range of 9.0 to 32 in order to increase the ultraviolet transmittance of the glass by suppressing the increase in the coloring degree ⁇ 5 described later while realizing the above optical characteristics. It is preferable.
- the cation ratio ((B 3+ + Si 4+ ) / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) should be 9.0 or more in order to improve the thermal stability of the glass.
- More preferable lower limit and more preferable upper limit of the cation ratio ((B 3+ + Si 4+ ) / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) are shown in the following table.
- Nb 5+ , Ti 4+ , Ta 5+ and W 6+ serve to improve the thermal stability of the glass by containing appropriate amounts.
- Ti 4+ increases, the transmittance in the visible region of the glass tends to decrease and the coloration of the glass tends to increase.
- the action of Ta 5+ is as described above.
- W 6+ when the content thereof increases, the transmittance in the visible range of the glass tends to decrease and the coloration of the glass tends to increase, and the specific gravity tends to increase.
- Nb 5+ has a function of hardly increasing the specific gravity, coloring, and production cost of the glass, increasing the refractive index, and improving the thermal stability of the glass.
- the glass 2 an excellent effect of Nb 5+, in order to utilize the effect, Nb 5+, Ti 4+, Ta 5+, and W 6+ content of the cation ratio of Nb 5+ to the total content of ( Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) is set in the range of 0.4 to 1.
- the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) should be increased. Is preferred. More preferable lower limits and more preferable upper limits of the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) are shown in the following table.
- Nb 5+ with respect to the total content of Nb 5+ , Ti 4+ and W 6+ excluding Ta 5+ in Nb 5+ , Ti 4+ , Ta 5+ and W 6+
- the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + W 6+ )) should be in the range of 0.4 to 1 in order to produce a glass with excellent thermal stability and low coloration. Is preferred. More preferable lower limit and more preferable upper limit of the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + W 6+ )) are shown in the following table.
- the cation ratio of Zn 2+ content to the total content of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ is From the viewpoint of improving meltability, it is preferably 0.1 or more.
- the glass with low meltability when the melting temperature of glass is raised or the melting time is lengthened so that there is no unmelted glass raw material, the coloring of the glass tends to increase.
- the cation ratio (Zn 2+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) can prevent the coloring of the glass.
- the cation ratio (Zn 2+ / (Nb 5 + + Ti 4+ + Ta 5+ + W 6+ )) is preferably 5 or less. More preferable lower limit and more preferable upper limit of the cation ratio (Zn 2+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) are shown in the following table.
- Nb 5+ content Ti 4+ content
- W 6+ content Preferred lower limits and preferred upper limits for each of Nb 5+ content, Ti 4+ content, and W 6+ content are shown in the following table.
- Li + content is 3% or less from the viewpoint of further improving the thermal stability of glass, suppressing the decrease in glass transition temperature (improvement of machinability), and improving chemical durability and weather resistance. It is preferable that The preferable lower limit and the more preferable upper limit of the Li + content are shown in the following table.
- Na + , K + , Rb + , and Cs + all have a function of improving the meltability of the glass.
- the thermal stability, chemical durability, and weather resistance of the glass are increased.
- the machinability tends to decrease. Therefore, it is preferable that the lower limit and the upper limit of each content of Na + , K + , Rb + and Cs + are as shown in the following table.
- Rb + and Cs + are expensive components, and are not suitable for general-purpose glass compared to Li + , Na + and K + . Therefore, in order to improve the meltability of the glass while maintaining the thermal stability, chemical durability, weather resistance, and machinability of the glass, the total content of Li + , Na + and K + (Li + The lower limit and the upper limit of (+ Na + + K + ) are each preferably as shown in the following table.
- Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ are all components having a function of improving the meltability of glass. However, if the content of these components is increased, the thermal stability of the glass is lowered and a tendency to devitrification is exhibited. Accordingly, the content of each of these components is preferably set to be equal to or higher than the lower limit shown below, and is preferably set to be lower than the upper limit.
- the total content of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ is: It is preferable to be not less than the lower limit shown in the following table, and preferably not more than the upper limit.
- Al 3+ is a component having a function of improving the chemical durability and weather resistance of glass.
- the content of Al 3+ increases, a refractive index decreasing tendency, a glass thermal stability decreasing tendency, and a meltability decreasing tendency may be observed.
- the Al 3+ content is preferably not less than the lower limit shown in the following table, and preferably not more than the upper limit.
- Ga 3+ , In 3+ , Sc 3+ , and Hf 4+ all have a function of increasing the refractive index. However, these components are expensive and are not essential components for obtaining the glass 2. Accordingly, the contents of Ga 3+ , In 3+ , Sc 3+ , and Hf 4+ are preferably set to the lower limit or more shown in the following table, and preferably set to the upper limit or less.
- Lu 3+ has a function of increasing the refractive index, but is also a component that increases the specific gravity of the glass. It is also an expensive component. From the above points, the preferred lower limit and the preferred upper limit of the Lu 3+ content are as shown in the following table.
- Ge 4+ has a function of increasing the refractive index, but is a prominently expensive component among commonly used glass components. From the viewpoint of reducing the production cost of glass, the preferred lower limit and the preferred upper limit of the Ge 4+ content are as shown in the following table.
- Bi 3+ is a component that increases the refractive index and decreases the Abbe number. It is also a component that tends to increase the coloration of the glass.
- the preferred lower and preferred upper limits for the Bi 3+ content are as shown in the following table from the viewpoint of producing a glass having the above optical properties and little coloration.
- the total content (total content) of the cation components described above is preferably more than 95%, more than 98%. More preferably, it is more preferably more than 99%, and still more preferably more than 99.5%.
- P 5+ is a component that lowers the refractive index and is a component that lowers the thermal stability of the glass. May improve thermal stability.
- the preferred lower limit and preferred upper limit of the P 5+ content are as shown in the following table for producing a glass having the above-described optical properties and excellent thermal stability.
- Te 4+ is a component that increases the refractive index, but since it is a toxic component, it is preferable to reduce the Te 4+ content.
- the preferable lower limit and preferable upper limit of the Te 4+ content are as shown in the following table.
- the content of (more) a preferred lower limit or 0% in each of the above tables is 0%.
- Pb, As, Cd, Tl, Be, and Se each have toxicity. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- U, Th, and Ra are all radioactive elements. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- V, Cr, Mn, Fe, Co, Ni, Cu, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Ce increase the coloration of the glass and become a source of fluorescence.
- the element contained in the glass for optical elements is not preferable. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
- Sb and Sn are arbitrarily addable elements that function as fining agents.
- the amount of Sb added is 0 to 0.11% by mass when converted to Sb 2 O 3 and the total content of glass components other than Sb 2 O 3 is 100% by mass in the oxide-based glass composition.
- the range is preferably 0.01 to 0.08% by mass, more preferably 0.02 to 0.05% by mass.
- the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed during melting and existing as oxides in the glass.
- the Sb 2 O 3 content in the glass composition shown in the table described later is also the content calculated by the above method.
- the addition amount of Sn should be in the range of 0 to 1.0% by mass when converted to SnO 2 and the total content of glass components other than SnO 2 is 100% by mass in the oxide-based glass composition.
- the range is 0 to 0.5% by mass, more preferably 0 to 0.2% by mass, and still more preferably 0% by mass.
- the cationic component has been described above. Next, the anion component will be described.
- glass 2 is an oxide glass, it contains O 2 ⁇ as an anion component.
- the content of O 2 ⁇ is preferably in the range of 98 to 100 anion%, more preferably in the range of 99 to 100 anion%, still more preferably 99.5 to 100 anion%, It is more preferable that it is% anion.
- the anion component other than O 2 ⁇ include F ⁇ , Cl ⁇ , Br ⁇ and I ⁇ .
- F ⁇ , Cl ⁇ , Br ⁇ and I ⁇ are easily volatilized during melting of the glass. Due to volatilization of these components, the characteristics of the glass fluctuate and the homogeneity of the glass tends to decrease, or the melting equipment tends to be consumed significantly.
- the anion% is a percentage with the total content of all anion components contained in the glass being 100%.
- the glass has a refractive index nd in the range of 1.800 to 1.850, and an Abbe number ⁇ d of 41.5 to 44.
- Glass having a refractive index of 1.800 or more is suitable as a material for optical elements such as lenses having a large refractive power.
- the refractive index is higher than 1.850, the Abbe number tends to decrease, the thermal stability of the glass tends to decrease, and the coloring tends to increase.
- the preferable lower limit and preferable upper limit of the refractive index are shown in the following table.
- the glass is preferably a glass having a small partial dispersion ratio when the Abbe number is fixed.
- the partial dispersion ratios Pg and F are (ng ⁇ nF) / (nF ⁇ nC) using the refractive indexes ng, nF and nC in the g-line (mercury wavelength 435.84 nm), F-line and C-line. ).
- preferred lower limits and preferred upper limits of the partial dispersion ratios Pg, F of the glass are as shown in the following table.
- the glass preferably has a glass transition temperature of 640 ° C. or higher from the viewpoint of improving machinability.
- a glass transition temperature of 640 ° C. or higher from the viewpoint of improving machinability.
- the glass transition temperature is too high, the glass must be annealed at a high temperature, and the annealing furnace is significantly consumed. Further, when glass is molded, it must be molded at a high temperature, and the consumption of the mold used for molding becomes significant. From the viewpoint of improving machinability and reducing the burden on the annealing furnace and the mold, more preferable lower limit and preferable upper limit of the glass transition temperature are as shown in the following table.
- the coloring degree ⁇ 5 is a wavelength at which the spectral transmittance (including surface reflection loss) of a glass having a thickness of 10 mm is 5% from the ultraviolet region to the visible region.
- ⁇ 5 shown in the examples described later is a value measured in a wavelength region of 250 to 700 nm.
- the spectral transmittance is, for example, more specifically, glass samples having mutually parallel planes optically polished to a thickness of 10.0 ⁇ 0.1 mm, and light from a direction perpendicular to the optically polished surface.
- the coloring degree ⁇ 5 the absorption edge on the short wavelength side of the spectral transmittance can be quantitatively evaluated.
- the adhesive is cured by irradiating the adhesive with ultraviolet rays through an optical element.
- the absorption edge on the short wavelength side of the spectral transmittance is in a short wavelength region.
- the coloring degree ⁇ 5 can be used as an index for quantitatively evaluating the absorption edge on the short wavelength side.
- the glass can exhibit a ⁇ 5 of preferably 335 nm or less, more preferably 332 nm or less, still more preferably 330 nm or less, more preferably 328 nm or less, and even more preferably 326 nm or less, by adjusting the composition described above.
- the lower limit of ⁇ 5 can be 315 nm, but it is not particularly limited as it is lower.
- coloring degree ⁇ 70 is a wavelength at which the spectral transmittance measured by the method described for ⁇ 5 is 70%. From the viewpoint of making the glass with little coloration, a preferable range of ⁇ 70 is 420 nm or less, a more preferable range is 400 nm or less, a more preferable range is 390 nm or less, and a still more preferable range is 380 nm or less. A guideline for the lower limit of ⁇ 70 is 340 nm, but the lower limit is preferably not particularly limited. Further, as an index of the coloring degree of the glass, a coloring degree ⁇ 80 is also mentioned.
- ⁇ 80 is a wavelength at which the spectral transmittance measured by the method described for ⁇ 5 is 80%.
- the preferable range of ⁇ 80 is 480 nm or less, the more preferable range is 460 nm or less, the more preferable range is 440 nm or less, and the still more preferable range is 420 nm or less.
- a guideline for the lower limit of ⁇ 80 is 350 nm, but the lower limit is preferably not particularly limited.
- the refractive power is determined by the refractive index of the glass constituting the lens and the curvature of the optical functional surface of the lens (the surface on which light to be controlled is incident and emitted). If the curvature of the optical function surface is increased, the thickness of the lens also increases. As a result, the lens becomes heavy. On the other hand, if a glass having a high refractive index is used, a large refractive power can be obtained without increasing the curvature of the optical function surface. As described above, if the refractive index can be increased while suppressing an increase in the specific gravity of the glass, it is possible to reduce the weight of the optical element having a certain refractive power.
- d / (nd-1) is used as an index for reducing the weight of the optical element, and by reducing this value, the lens can be reduced in weight. Since the glass has a small proportion of Gd, Ta, and Yb that cause an increase in specific gravity, it is possible to reduce the specific gravity while being a high refractive index and low dispersion glass. Therefore, d / (nd-1) of the glass can be, for example, 5.70 or less.
- d / (nd-1) is preferably set to 5.00 or more. More preferable lower limit and more preferable upper limit of d / (nd-1) are shown in the following table.
- preferred lower limits and preferred upper limits of the specific gravity d of the glass are shown in the following table. Setting the specific gravity d to be equal to or higher than the upper limit shown in the following table is preferable from the viewpoint of reducing the weight of the optical element made of this glass. Moreover, it is preferable to make specific gravity more than the lower limit shown in the following table
- the liquidus temperature LT is preferably 1300 ° C. or lower, more preferably 1250 ° C. or lower, and further preferably 1200 ° C. or lower, 1150 It is still more preferable that it is below °C.
- the lower limit of the liquidus temperature LT is 1100 ° C. or more as an example, but is preferably not low and is not particularly limited.
- the glass (glass 1 and glass 2) according to one embodiment of the present invention described above is a high refractive index and low dispersion glass and is useful as a glass material for an optical element. Furthermore, it is possible to homogenize the glass and reduce coloring by adjusting the composition described above. In addition, the glass is easy to mold and mechanically work. Therefore, the above glass is suitable as an optical glass.
- the glass is weighed and prepared as raw materials such as oxides, carbonates, sulfates, nitrates and hydroxides, and mixed well to form a mixed batch. It can be obtained by heating, melting, defoaming and stirring to make a molten glass free of bubbles and molding it. Specifically, it can be made using a known melting method.
- the above glass is a high refractive index low dispersion glass having the above-mentioned optical properties, it is excellent in thermal stability, and therefore can be stably produced using a known melting method and molding method.
- a glass material for press molding comprising the glass 1 or glass 2 described above;
- An optical element blank made of the glass 1 or glass 2 described above, about.
- a method for producing a glass material for press molding comprising the step of forming the glass 1 or glass 2 described above into a glass material for press molding;
- a method for producing an optical element blank comprising a step of producing an optical element blank by press-molding the above-described press-molding glass material using a press mold;
- a method for producing an optical element blank comprising the step of forming the glass 1 or glass 2 described above into an optical element blank, Is also provided. Since the glass material for press molding and the optical element blank are made of the glass 1 or glass 2 described above, the glass material for press molding and the optical element blank naturally correspond to the glass described above.
- the optical element blank approximates the shape of the target optical element, and is polished to the shape of the optical element (surface layer to be removed by polishing) or ground as necessary (to be removed by grinding).
- the optical element is finished by polishing the surface of the optical element blank or by grinding and polishing.
- an optical element blank can be produced by a method of pressing a molten glass obtained by melting an appropriate amount of the glass (referred to as a direct press method).
- an optical element blank can be produced by solidifying and further processing a molten glass obtained by melting an appropriate amount of the glass.
- an optical element blank can be produced by producing a press-molding glass material and press-molding the produced press-molding glass material.
- Press molding of the glass material for press molding can be performed by a known method of pressing the glass material for press molding in a softened state by heating with a press mold. Both heating and press molding can be performed in the atmosphere.
- a uniform optical element blank can be obtained by annealing after press molding to reduce strain inside the glass.
- the glass material for press molding is subjected to mechanical processing such as cutting, grinding, polishing, etc. in addition to what is called glass gob for press molding used for press molding for optical element blank production as it is. It includes those that are subjected to press molding via
- a cutting method a groove is formed in a portion of the surface of the glass plate to be cut by a method called scribing, and a local pressure is applied to the groove portion from the back surface of the surface on which the groove is formed.
- a method of breaking a plate and a method of cutting a glass plate with a cutting blade.
- known processing methods such as barrel polishing can be mentioned.
- the glass material for press molding is produced, for example, by casting molten glass into a mold to form a glass plate and cutting the glass plate into a plurality of glass pieces, or barrel-polishing these glass pieces. Can do.
- a glass gob for press molding can be produced by molding an appropriate amount of molten glass.
- An optical element blank can also be produced by repressing and softening a glass gob for press molding and press forming it.
- a method of producing an optical element blank by press-molding glass by reheating and softening is called a reheat press method as opposed to a direct press method.
- the present invention relates to an optical element made of the glass 1 or the glass 2 described above.
- the optical element is manufactured using the glass 1 or the glass 2 described above.
- one or more coatings such as a multilayer film such as an antireflection film may be formed on the glass surface. Since the optical element is made of the glass 1 or glass 2 described above, it naturally corresponds to the glass described above. When a coating is formed on the glass surface of the optical element, the glass portion excluding the coating corresponds to the glass described above.
- a method for producing an optical element comprising a step of producing an optical element by polishing at least the optical element blank described above, Is also provided.
- the manufacturing method of the optical element a known method may be applied for grinding and polishing, and an optical element having high internal quality and surface quality can be obtained by sufficiently washing and drying the surface of the optical element after processing. it can. In this way, an optical element made of the glass can be obtained.
- the optical element include various lenses such as a spherical lens, an aspheric lens, and a micro lens, a prism, and the like.
- the optical element made of the glass 1 or the glass 2 is also suitable as a lens constituting the cemented optical element.
- the cemented optical element include those in which lenses are cemented (a cemented lens), and in which lenses and a prism are cemented.
- the bonding optical element the bonding surface of two optical elements to be bonded is precisely processed so that the shape is inverted (for example, spherical polishing), and an ultraviolet curable adhesive is applied to the bonding surface. It can be produced by bonding the bonding surfaces to each other and then irradiating the adhesive on the bonding surface with ultraviolet rays through the optical element to cure the adhesive.
- the glass is preferable.
- a plurality of optical elements to be bonded are manufactured using a plurality of types of glasses having different Abbe numbers, and bonded to each other, whereby an element suitable for correcting chromatic aberration can be obtained.
- the glass component may be expressed on an oxide basis, and the content of the glass component may be displayed in mass%.
- the composition represented by mass% on the basis of oxide can be converted into the composition represented by cation% and anion%, for example, by the following method.
- an oxide consisting of cations A and oxygen is expressed as A m O n.
- m and n are integers determined stoichiometrically.
- the total value of P is ⁇ P
- the value obtained by standardizing the P value of each cation component so that ⁇ P is 100% is the content of As + in the cation% display.
- s is 2 n / m.
- a trace amount of additive for example, a clarifying agent such as Sb 2 O 3 may not be included in ⁇ P. In that case, the Sb content may be the externally divided content (mass%) converted to Sb 2 O 3 as described above.
- the total content of the glass components excluding the Sb 2 O 3 content is 100% by mass, and the Sb 2 O 3 content is expressed as a value with respect to 100% by mass.
- the molecular weight may be calculated using, for example, a value obtained by rounding off the fourth decimal place to the third decimal place.
- the molecular weight of the oxide A m O n is the values and atomic weight of oxygen atom amount was multiplied by m elements A is the sum of the n-fold value.
- the following table shows the molecular weight of some glass components and additives in terms of oxide standards.
- Example 1 In order to obtain a glass having the composition shown in the table below, compounds such as oxide and boric acid were weighed as raw materials and mixed sufficiently to prepare batch raw materials. This batch raw material was put in a platinum crucible, and the whole crucible was heated to a temperature of 1350 to 1450 ° C., and the glass was melted and refined over 2 to 3 hours. After the molten glass was agitated and homogenized, the molten glass was cast into a preheated mold and allowed to cool to near the glass transition temperature, and then the glass together with the mold was placed in an annealing furnace. Then, annealing was performed for about 1 hour near the glass transition temperature.
- the glass characteristic of the obtained glass was measured by the method shown below.
- the measurement results are shown in the following table.
- (1) Refractive index nd, nF, nC, ng, Abbe number ⁇ d Refractive indexes nd, nF, nC, and ng were measured for the glass obtained by lowering the temperature at a temperature drop rate of ⁇ 30 ° C./hour by the refractive index measurement method of the Japan Optical Glass Industry Association standard.
- the Abbe number ⁇ d was calculated using the measured values of the refractive indexes nd, nF, and nC.
- a spectrophotometer is used to inject light having an intensity Iin from the direction perpendicular to the polished surface.
- the spectral transmittance Iout / Iin is calculated by measuring the intensity Iout of the light that has passed through ⁇ 5, the wavelength at which the spectral transmittance is 5% is ⁇ 5, the wavelength at which the spectral transmittance is 70% is ⁇ 70, and the spectral transmittance is 80 The wavelength at which% is obtained is ⁇ 80.
- Partial dispersion ratio Pg, F It calculated from the value of nF, nC, and ng measured by said (1).
- Liquidus temperature The glass was placed in a furnace heated to a predetermined temperature and held for 2 hours. After cooling, the inside of the glass was observed with a 100-fold optical microscope, and the liquidus temperature was determined from the presence or absence of crystals.
- Example 2 Various glasses obtained in Example 1 were used to produce a press-molding glass lump (glass gob). This glass lump was heated and softened in the atmosphere, and press-molded with a press mold to produce a lens blank (optical element blank). The produced lens blank was taken out from the press mold, annealed, and machined including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
- Example 3 A desired amount of the molten glass produced in Example 1 was obtained, and while the obtained glass was in a softened state, it was press-molded with a press mold and cooled to produce a lens blank (optical element blank). The produced lens blank was taken out from the press mold, annealed, and machined including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
- Example 4 A glass lump (optical element blank) produced by solidifying the molten glass produced in Example 1 was annealed and subjected to mechanical processing including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
- Example 5 The spherical lens produced in Examples 2 to 4 was bonded to a spherical lens made of another type of glass to produce a cemented lens.
- the cemented surfaces of the spherical lenses produced in Examples 2 to 4 were convex spherical surfaces, and the cemented surfaces of spherical lenses made of other types of optical glass were concave spherical surfaces.
- the two joint surfaces were produced so that the absolute values of the curvature radii were equal to each other.
- An ultraviolet curable adhesive for optical element bonding was applied to the bonding surface, and the two lenses were bonded to each other at the bonding surfaces.
- the adhesive applied to the joint surface was irradiated with ultraviolet rays through the spherical lenses prepared in Examples 2 to 4, and the adhesive was solidified.
- a cemented lens was produced as described above. The cemented lens had a sufficiently high bonding strength and a sufficient level of optical performance.
- a glass having a composition shown in Table 102 below (hereinafter referred to as “glass A”) and a glass having a composition shown in Table 103 (hereinafter referred to as “glass B”) were respectively melted and molded. And processed into a plate shape. These glass plates have two opposing flat surfaces. The two planes are parallel to each other and are optically polished. The distance between the two planes was 10.0 mm. Using such a glass plate, the spectral transmittance was measured.
- the glass B does not contain Y 2 O 3 in the glass composition expressed by mass%, the mass ratio (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is as described above. The glass is out of range. Further, since glass B does not contain Y 3+ in the glass composition represented by cation%, the cation ratio (Y 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is outside the above range. It is glass.
- the glass B is does not correspond to the glass 2 in the glass 1 according to one embodiment of the present invention described above, increase or decrease the absorption of near-infrared region according to the magnitude of the Yb content, Y 2 O 3 And does not depend on the presence or absence of Y 3+ . Therefore, by comparing the glass A and the glass B, it is possible to confirm the influence of Yb on the transmittance in the near infrared region. As shown in FIG.
- Example 2 The glass of Example 28 (hereinafter referred to as “glass C”) in Patent Document 5 (Japanese Patent Laid-Open No. 55-121925) was reproduced, and ⁇ 5 was measured by the above method to be 348 nm. A spherical lens was produced using glass C. Next, using the convex spherical surface of this spherical lens and the concave spherical surface of a spherical lens made of another type of optical glass as a bonding surface, an ultraviolet curable adhesive for optical element bonding was applied and the same as in Example 5 An attempt was made to produce a cemented lens. However, when the ultraviolet curable adhesive applied to the bonding surface was irradiated with ultraviolet rays through a lens made of glass C, the adhesive could not be sufficiently cured because the ultraviolet transmittance of glass C was low.
- Example 3 The glass of Example 7 of Patent Document 17 (Japanese Patent Laid-Open No. 2002-284542) has a mass ratio (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) of 0. 09 and the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.92.
- composition a This composition is hereinafter referred to as “composition a”.
- Gd 2 O 3 contained in 5.15% by mass is reduced to 3% by mass, and the decrease in Gd 2 O 3 content is 2.15% by mass with the content of La 2 O 3 and Y 2 O. respectively in accordance with the content of 3 it was allocated to La 2 O 3 and Y 2 O 3.
- composition b This composition is hereinafter referred to as “composition b”.
- Table 104 shows the composition, “Composition a”, and “Composition b” of Example 7 of Patent Document 17.
- a glass was produced according to the method described in the example of Patent Document 17, and the molten glass was poured into a mold to form a peripheral part of the glass, that is, by contact with the mold. Although no crystal deposition was observed in the rapidly cooled portion, a large number of crystals were deposited in the central portion of the glass, that is, in the portion where the cooling speed was lower than that in the peripheral portion. In addition, when the glass of the Example described previously was produced by the same method, the precipitation of the crystal
- Example 4 The glass of Example 7 of Patent Document 17 (Japanese Patent Laid-Open No. 2002-284542) has a cation ratio (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) of 0.08 and a cation ratio ( B 3+ / (B 3+ + Si 4+ )) is 0.95.
- Gd 3+ contained in 2.31 cation% is set to 0%, and the decrease in Gd 3+ content is 2.31 cation% according to La 3+ content and Y 3+ content, respectively. Allocated to La 3+ and Y 3+ . Specifically, 1.31 cation% calculated as 2.31 cation% ⁇ ((La 3+ content / (La 3+ content and Y 3+ content)) ”. Is replaced by Gd 3+ to La 3+ and calculated as 2.31 cation% ⁇ ((Y 3+ content / (La 3+ content and Y 3+ and total content)). 63 cation% was replaced from Gd 3+ to Y 3+ , and this composition is referred to as “Composition c” below.
- composition d ((0.59 cations% calculated as content / (La 3+ content and total content of Y 3+)) of La 3+ La 3 substituted to +
- 0.81 cations% ⁇ ((Y 3+ content / (0.22 cations% calculated as the total amount)) of the content of La 3+ and Y 3+ Y 3 of + was replaced to.
- composition d Table 105 shows the composition, “composition c”, and “composition d” of Example 7 of Patent Document 17.
- the total content of B 2 O 3 and SiO 2 is 15 to 35% by mass, La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 in terms of mass%.
- the mass ratio of B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4 to 0.900
- La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 in total mass ratio of total content of B 2 O 3 and SiO 2 ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3)) is 0.42 ⁇ 0.53, La 2 O 3 ,
- the total content of B 3+ and Si 4+ is 45 to 65% in terms of cation%, and the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 25 to 35%, however, the Yb 3+ content is less than 2%, the Zr 4+ content is 2 to 8%, the Ta 5+ content is 3% or less, the total of B 3+ and Si 4+
- the cation ratio of the B 3+ content to the content (B 3+ / (B 3+ + Si 4+ )) is 0.65 or more and less than 0.94, La 3+ , Y 3+ , Gd 3+ and Yb 3+
- the cation ratio of the total content of B 3+ and Si 4+ to the total content of ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 1.65 to 2.60, cation ratio of Y 3+ content to total content of La 3+
- Glass 1 and glass 2 are high-refractive index, low-dispersion optical glasses having a refractive index nd and an Abbe number ⁇ d in the above ranges and useful as materials for optical elements constituting an optical system.
- the glass is a glass in which the contents of Gd, Ta, and Yb are reduced, and can exhibit high thermal stability.
- the glass 1 is from the viewpoint of improving the meltability, further improving the thermal stability of the glass, suppressing the decrease in the glass transition temperature (improvement of machinability thereby), and improving the chemical durability.
- the mass ratio (ZnO / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is preferably in the range of 0.1 to 3.
- the glass 2 is from the viewpoint of improving the meltability, further improving the thermal stability of the glass, suppressing the decrease in the glass transition temperature (thereby improving the machinability), and improving the chemical durability.
- the cation ratio (Zn 2+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) is preferably in the range of 0.1 to 5.
- the glass 1 and the glass 2 have a suppressed light absorption edge on the short wavelength side of the glass so that the coloring degree ⁇ 5 is 335 nm or less.
- the specific gravity d and the refractive index nd of the glass 1 and the glass 2 satisfy the above-described formula (A) from the viewpoint of enabling the weight reduction of an optical element having a constant refractive power.
- the glass 1 and the glass 2 preferably have a glass transition temperature of 640 ° C. or higher from the viewpoint of improving machinability.
- a glass material for press molding, an optical element blank, and an optical element can be produced. That is, according to another aspect, a glass material for press molding made of glass 1 or glass 2, an optical element blank, and an optical element are provided.
- a method for producing a press-molding glass material comprising a step of molding glass 1 or glass 2 into a press-molding glass material.
- an optical element blank manufacturing method including a step of manufacturing an optical element blank by press-molding the press-molding glass material using a press mold.
- an optical element blank manufacturing method including a step of forming glass 1 or glass 2 into an optical element blank.
- an optical element manufacturing method including a step of manufacturing an optical element by polishing at least the optical element blank.
- the embodiment disclosed this time should be considered as illustrative in all points and not restrictive.
- the scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
- the glass concerning 1 aspect of this invention can be obtained by performing the composition adjustment as described in the specification with respect to the glass composition illustrated above.
- a certain glass may correspond to both the glass 1 and the glass 2.
- the present invention is useful in the field of manufacturing various optical elements.
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Abstract
Description
特許文献1:特開2002-12443号公報
特許文献2:特開2003-267748号公報
特許文献3:特開2005-281124号公報
特許文献4:特開2005-298262号公報
特許文献5:特開昭55-121925号公報
特許文献6:特開2009-203083号公報
特許文献7:特開昭54-090218号公報
特許文献8:特開昭56-160340号公報
特許文献9:特開2009-167080号公報
特許文献10:特開2009-167081号公報
特許文献11:特開2009-298646号公報
特許文献12:特開2010-111527号公報
特許文献13:特開2010-111528号公報
特許文献14:特開2010-111530号公報
特許文献15:特開昭57-056344号公報
特許文献16:特開昭61-163138号公報
特許文献17:特開2002-284542号公報
特許文献18:特開2007-269584号公報 Glass having a high refractive index and low dispersion (high refractive index and low dispersion glass) having a refractive index nd in the range of 1.800 to 1.850 and an Abbe number νd in the range of 41.5 to 44 Are described in Patent Documents 1 to 18, for example. The entire description of Patent Documents 1 to 18 is specifically incorporated herein by reference.
Patent Document 1: JP 2002-12443 A Patent Document 2: JP 2003-267748 A Patent Document 3: JP 2005-281124 A Patent Document 4: JP 2005-298262 A Patent Document 5: JP Japanese Patent Application Laid-Open No. 55-121925 Patent Document 6: Japanese Patent Application Laid-Open No. 2009-203083 Patent Document 7: Japanese Patent Application Laid-Open No. 54-090218 Patent Document 8: Japanese Patent Application Laid-Open No. 56-160340 Patent Document 9: Japanese Patent Application Laid-Open No. 2009-167080 Patent Document 10: Japanese Patent Application Laid-Open No. 2009-167081 Patent Document 11: Japanese Patent Application Laid-Open No. 2009-298646 Patent Document 12: Japanese Patent Application Laid-Open No. 2010-111527 Patent Document 13: Japanese Patent Application Laid-Open No. 2010-111528 Patent Document 14: Japanese Patent Application Laid-Open No. 2010-111530 Patent Document 15: Japanese Patent Application Laid-Open No. 57-056344 Document 16: JP 61-163138 JP Patent Document 17: JP 2002-284542 JP Patent Document 18: JP 2007-269584 JP
Ybは近赤外域に吸収を有する。そのため、Ybを多く含むガラス(例えば特許文献16に記載のガラス)は、可視域から近赤外域にわたって高い透過率が必要とされる用途、例えば、監視カメラ、暗視カメラ、車載カメラのレンズ等の光学素子用の材料には適していない。また、Ybは重希土類元素に属し、ガラスの成分としては原子量が大きく、ガラスの比重を増大させる。ガラスの比重が増大すると、レンズが重くなる。その結果、そのようなレンズをオートフォーカス式のカメラレンズに組み込むと、消費電力が大きくなり、電池の消耗が激しくなってしまう。以上の点から、ガラス組成においてYbが占める割合を低減することが望ましい。 The proportion of Yb in the glass composition is low. This is due to the following reason.
Yb has absorption in the near infrared region. Therefore, glass containing a large amount of Yb (for example, glass described in Patent Document 16) is used for applications that require high transmittance from the visible range to the near-infrared range, such as surveillance cameras, night vision cameras, and in-vehicle camera lenses. It is not suitable as a material for optical elements. Yb belongs to a heavy rare earth element, has a large atomic weight as a glass component, and increases the specific gravity of the glass. As the specific gravity of the glass increases, the lens becomes heavier. As a result, when such a lens is incorporated into an autofocus camera lens, the power consumption increases and the battery consumption becomes severe. From the above points, it is desirable to reduce the proportion of Yb in the glass composition.
色収差の補正のために、それぞれ異なる光学特性を有するガラスを用いて複数のレンズを作り、これらのレンズを貼り合わせ、接合レンズを作る方法が知られている。接合レンズを作る過程で、レンズ同士を貼り合わせるために、通常、紫外線硬化型接着剤が用いられる。詳しくは、次の通りである。レンズ同士を貼り合せる面に紫外線硬化型接着剤を塗布し、レンズを貼り合わせる。このとき、通常、レンズ間に紫外線硬化型接着剤の極めて薄い塗布層が形成される。次いで、上記塗布層に対して、レンズを通して紫外線を照射し紫外線硬化型接着剤を硬化する。したがって、レンズの紫外線の透過率が低いと、レンズを通して上記塗布層に十分な光量の紫外線が届かず、硬化が不十分になってしまう。または硬化に長時間を要してしまう。また、紫外線硬化型接着剤を用いて、レンズ鏡筒等にレンズを接着し固定する場合にも、同様に、レンズの紫外線透過率が低いと、硬化が不十分になるか、または硬化に長時間を要してしまう。
したがって、光学系の作製に好適な透過率特性を有するガラスとするためには、ガラスの紫外域の透過率を高くすること、換言すれば、ガラスの短波長側の光吸収端の長波長化を抑制することが望ましい。
しかるに、本発明者の検討によれば、例えば特許文献5に記載のガラスは、ガラスの短波長側の光吸収端が長波長化し、紫外域の透過率が低下していた。また、従来の高屈折率低分散ガラスのガラス組成において、GdやTaの含有量を低減しつつ、高屈折率低分散特性と熱的安定性をともに維持しようとすると、ガラスの短波長側の光吸収端が長波長化し、紫外線の透過率が大きく低下する傾向があった。 The increase in the wavelength of the light absorption edge on the short wavelength side of the glass is suppressed. This is due to the following reason.
In order to correct chromatic aberration, a method is known in which a plurality of lenses are made using glass having different optical characteristics, and these lenses are bonded to form a cemented lens. In the process of making a cemented lens, an ultraviolet curable adhesive is usually used to bond the lenses together. Details are as follows. An ultraviolet curable adhesive is applied to the surface where the lenses are bonded together, and the lenses are bonded together. At this time, an extremely thin coating layer of an ultraviolet curable adhesive is usually formed between the lenses. Next, the coating layer is irradiated with ultraviolet rays through a lens to cure the ultraviolet curable adhesive. Therefore, when the transmittance of the ultraviolet ray of the lens is low, a sufficient amount of ultraviolet ray does not reach the coating layer through the lens, resulting in insufficient curing. Or it takes a long time to cure. Similarly, when an ultraviolet curable adhesive is used to adhere and fix a lens to a lens barrel or the like, if the lens has a low ultraviolet transmittance, curing may be insufficient or long. It takes time.
Therefore, in order to obtain a glass having transmittance characteristics suitable for the production of an optical system, it is necessary to increase the transmittance in the ultraviolet region of the glass, in other words, to increase the wavelength of the light absorption edge on the short wavelength side of the glass. It is desirable to suppress this.
However, according to the study of the present inventor, for example, in the glass described in Patent Document 5, the light absorption edge on the short wavelength side of the glass has a longer wavelength, and the transmittance in the ultraviolet region is reduced. In addition, in the glass composition of the conventional high refractive index and low dispersion glass, when trying to maintain both the high refractive index and low dispersion characteristics and the thermal stability while reducing the content of Gd and Ta, There was a tendency that the wavelength of the light absorption edge became longer and the transmittance of ultraviolet rays was greatly reduced.
B2O3とSiO2との合計含有量が15~35質量%、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量が45~65質量%、但し、Yb2O3含有量が3質量%以下であり、
ZrO2含有量が3~11質量%、
Ta2O5含有量が5質量%以下、
B2O3とSiO2との合計含有量に対するB2O3含有量の質量比(B2O3/(B2O3+SiO2))が0.4~0.900、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するB2O3およびSiO2の合計含有量の質量比((B2O3+SiO2)/(La2O3+Y2O3+Gd2O3+Yb2O3))が0.42~0.53、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するY2O3含有量の質量比(Y2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))が0.05~0.45、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するGd2O3含有量の質量比(Gd2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))が0~0.05、
Nb2O5、TiO2、Ta2O5およびWO3の合計含有量に対するNb2O5含有量の質量比(Nb2O5/(Nb2O5+TiO2+Ta2O5+WO3))が0.5~1、
であり、屈折率ndが1.800~1.850の範囲であり、かつアッベ数νdが41.5~44である酸化物ガラスであるガラス(以下、「ガラス1」という。)、
に関する。 One embodiment of the present invention is represented by mass%,
The total content of B 2 O 3 and SiO 2 is 15 to 35% by mass,
The total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 is 45 to 65% by mass, provided that the Yb 2 O 3 content is 3% by mass or less,
ZrO 2 content is 3 to 11% by mass,
Ta 2 O 5 content is 5% by mass or less,
The mass ratio of B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4-0.900,
Mass ratio of the total content of B 2 O 3 and SiO 2 to the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.42 to 0.53,
Mass ratio of Y 2 O 3 content to total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.05 to 0.45,
Mass ratio of Gd 2 O 3 content to total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0 to 0.05,
Mass ratio of Nb 2 O 5 content to the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) 0.5-1
A glass which is an oxide glass having a refractive index nd in the range of 1.800 to 1.850 and an Abbe number νd of 41.5 to 44 (hereinafter referred to as “glass 1”),
About.
B3+とSi4+との合計含有量が45~65%、
La3+、Y3+、Gd3+およびYb3+の合計含有量が25~35%、但し、Yb 3+有量が2%未満であり、
Zr4+含有量が2~8%、
Ta5+含有量が3%以下、
B3+とSi4+との合計含有量に対するB3+含有量のカチオン比(B3+/(B3++Si4+))が0.65以上0.94未満、
La3+、Y3+、Gd3+およびYb3+の合計含有量に対するB3+とSi4+との合計含有量のカチオン比((B3++Si4+)/(La3++Y3++Gd3++Yb3+))が1.65~2.60、
La3+、Y3+、Gd3+およびYb3+の合計含有量に対するY3+含有量のカチオン比(Y3+/(La3++Y3++Gd3++Yb3+))が0.05~0.45、
La3+、Y3+、Gd3+およびYb3+の合計含有量に対するGd3+含有量のカチオン比(Gd3+/(La3++Y3++Gd3++Yb3+))が0~0.05、
Nb5+、Ti4+、Ta5+およびW6+の合計含有量に対するNb5+含有量のカチオン比(Nb5+/(Nb5++Ti4++Ta5++W6+))が0.4~1、
であり、屈折率ndが1.800~1.850の範囲であり、かつアッベ数νdが41.5~44である酸化物ガラスであるガラス(以下、「ガラス2」という。)、
に関する。 Further, one embodiment of the present invention is represented by cation% display.
The total content of B 3+ and Si 4+ is 45 to 65%,
The total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 25-35%, provided that the Yb 3+ content is less than 2%;
Zr 4+ content is 2-8 %,
Ta 5+ content is 3% or less,
The cation ratio of the B 3+ content to the total content of B 3+ and Si 4+ (B 3+ / (B 3+ + Si 4+ )) is 0.65 or more and less than 0.94,
Cation ratio of the total content of B 3+ and Si 4+ to the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ ((B 3+ + Si 4+ ) / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 1.65 to 2.60,
The cation ratio of Y 3+ content to the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ (Y 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 0 .05 to 0.45,
The cation ratio of Gd 3+ content to the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is 0 ~ 0.05,
Cation ratio of Nb 5+ content to the total content of Nb 5+ , Ti 4+ , Ta 5+ and W 6+ (Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) is 0 .4 to 1,
A glass which is an oxide glass having a refractive index nd in the range of 1.800 to 1.850 and an Abbe number νd of 41.5 to 44 (hereinafter referred to as “glass 2”),
About.
本発明の一態様にかかるガラス1およびガラス2は、上記ガラス組成を有し、屈折率ndが1.800~1.850の範囲であり、かつアッベ数νdが41.5~44である酸化物ガラスである。以下、ガラス1およびガラス2の詳細について説明する。 [Glass]
Glass 1 and glass 2 according to one embodiment of the present invention have the above-described glass composition, have an index of refraction nd of 1.800 to 1.850, and an Abbe number νd of 41.5 to 44. It is a physical glass. Hereinafter, the details of the glass 1 and the glass 2 will be described.
本発明では、ガラス1のガラス組成を、酸化物基準で表示する。ここで「酸化物基準のガラス組成」とは、ガラス原料が熔融時にすべて分解されてガラス中で酸化物として存在するものとして換算することにより得られるガラス組成をいうものとする。また、特記しない限り、ガラス1のガラス組成は、質量基準(質量%、質量比)で表示するものとする。 <Glass composition of glass 1>
In this invention, the glass composition of the glass 1 is displayed on an oxide basis. Here, the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed at the time of melting and existing as oxides in the glass. Unless otherwise specified, the glass composition of the glass 1 is expressed on a mass basis (mass%, mass ratio).
一般に、B2O3とLa2O3等の希土類元素を含む高屈折率低分散ガラスでは、熔融時のガラスの粘性が低い。しかし、熔融時のガラスの粘性が低いと熱的安定性が低下する(結晶化しやすくなる)。ガラス製造時の結晶化は、アモルファス状態(非晶質状態)よりも結晶化したほうが安定であり、ガラスを構成するイオンがガラス中を移動して結晶構造をもつように配列することにより生じる。したがって、熔融時の粘性が高くなるようにB2O3とSiO2の各成分の含有量の比率を調整することにより、上記イオンを結晶構造をもつように配列しにくくして、ガラスの結晶化を更に抑制しガラスの熱的安定性を改善することができる。
鋳型に熔融ガラスを流し込んで成形する時、熔融ガラスの粘度が低いと、鋳型内に流し込んだガラスの固化した表面部が依然として熔融状態にあるガラスの内部に巻き込まれて脈理となり、ガラスの光学的な均質性が低下してしまう。成形性の優れたガラスとは、希土類元素を含む高屈折率低分散ガラスの中でも、熔融状態のガラスを鋳型に流し込む時の粘度が比較的高いガラスに相当する。
B2O3とSiO2との合計含有量に対するB2O3含有量の質量比(B2O3/(B2O3+SiO2))が0.900以下であれば、熔融時の粘性低下を抑制することができ、これによりガラスの熱的安定性を改善したり、熔融時の揮発を抑制することができる。熔融時の揮発は、ガラス組成の変動、特性の変動を大きくする原因となる。そしてその結果、光学的に均質なガラスを成形することを難しくする。したがって、質量比(B2O3/(B2O3+SiO2))を0.900以下として熔融時の揮発を抑制できることは、組成や特性のばらつきの少ないガラスを量産する観点から好ましい。更に、質量比(B2O3/(B2O3+SiO2))が0.900以下であれば、ガラスの化学的耐久性、耐候性、機械加工性の低下を抑制することもできる。これに対し、前述の特許文献15(特開昭57-056344号公報)に記載されているガラス組成では、B2O3含有量は28~30質量%、SiO2の含有量は1~3質量%である(特許文献15の特許請求の範囲参照)。これら成分の含有量から算出される質量比(B2O3/(B2O3+SiO2))は、0.903~0.968と大きい値になる。
一方、質量比(B2O3/(B2O3+SiO2))が0.4以上であれば、熔融時のガラス原料の熔け残りを防ぐことができるため、熔融性を向上することができる。
以上の点から、ガラス1において、質量比(B2O3/(B2O3+SiO2))を0.4~0.900の範囲とする。ガラス1における質量比(B2O3/(B2O3+SiO2))の好ましい下限および好ましい上限は、下記表に示す通りである。 The content ratio of each component of B 2 O 3 and SiO 2 , which are glass network forming components, is related to the thermal stability, meltability, formability, chemical durability, weather resistance, machinability, etc. of glass. Influence. B 2 O 3 is more excellent in improving the meltability than SiO 2 , but easily volatilizes during melting. On the other hand, SiO 2 has a function of improving the chemical durability, weather resistance, and machinability of glass and increasing the viscosity of glass during melting.
In general, in a high refractive index low dispersion glass containing rare earth elements such as B 2 O 3 and La 2 O 3 , the viscosity of the glass at the time of melting is low. However, when the viscosity of the glass at the time of melting is low, the thermal stability is lowered (it becomes easier to crystallize). Crystallization during glass production is more stable when crystallized than when it is in an amorphous state (amorphous state), and occurs when ions constituting the glass move in the glass and are arranged so as to have a crystal structure. Therefore, by adjusting the content ratio of each component of B 2 O 3 and SiO 2 so as to increase the viscosity at the time of melting, it becomes difficult to arrange the ions so as to have a crystal structure, and the crystal of the glass The glass can be further suppressed and the thermal stability of the glass can be improved.
When the molten glass is poured into the mold and molded, if the viscosity of the molten glass is low, the solidified surface portion of the glass poured into the mold is entangled inside the glass that is still in the molten state, which causes striae. Homogeneity is reduced. The glass having excellent formability corresponds to a glass having a relatively high viscosity when a molten glass is poured into a mold among high refractive index and low dispersion glass containing rare earth elements.
If the mass ratio of the B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.900 or less, the viscosity at the time of melting Decline can be suppressed, thereby improving the thermal stability of the glass and suppressing volatilization during melting. Volatilization at the time of melting causes a large variation in glass composition and characteristics. As a result, it becomes difficult to form optically homogeneous glass. Therefore, it is preferable that the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) be 0.900 or less to suppress volatilization at the time of melting from the viewpoint of mass-producing glass with little variation in composition and characteristics. Further, the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2)) is equal to 0.900 or less, the chemical durability of the glass, weather resistance, it is also possible to suppress a decrease in machinability. On the other hand, in the glass composition described in Patent Document 15 (Japanese Patent Laid-Open No. 57-056344), the B 2 O 3 content is 28 to 30% by mass, and the SiO 2 content is 1 to 3%. It is mass% (refer the claim of patent document 15). The mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) calculated from the contents of these components is a large value of 0.903 to 0.968.
On the other hand, if the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4 or more, it is possible to prevent unmelted glass raw material at the time of melting, thereby improving the meltability. it can.
From the above points, in the glass 1, the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is set in the range of 0.4 to 0.900. The preferable lower limit and the preferable upper limit of the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) in the glass 1 are as shown in the following table.
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量(La2O3+Y2O3+Gd2O3+Yb2O3)が45%以上であると、屈折率の低下を抑制することができるため、上記した光学特性を有するガラスの作製が可能となる。更に、ガラスの化学的耐久性や耐候性の低下を抑制することもできる。なお、ガラス転移温度が低下すると、ガラスを機械的に加工(切断、切削、研削、研磨など)するときにガラスが破損しやすくなる(機械加工性の低下)が、La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量が45%以上であると、ガラス転移温度の低下を抑制することができるため、機械加工性を高めることもできる。一方、La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量が65%以下であれば、ガラスの熱的安定性を高めることができるため、ガラスを製造するときの結晶化の抑制や、ガラスを熔融するときの原料の熔け残りを低減することもできる。したがって、ガラス1において、La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量は、45~65%の範囲とする。La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量の好ましい下限および好ましい上限を、下記表に示す。 La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 are components having a function of increasing the refractive index while suppressing a decrease in the Abbe number. These components also have the function of improving the chemical durability and weather resistance of the glass and increasing the glass transition temperature.
Refraction when the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 ) is 45% or more Since the reduction in the rate can be suppressed, the glass having the above-described optical characteristics can be produced. Furthermore, it is possible to suppress a decrease in chemical durability and weather resistance of the glass. Note that when the glass transition temperature is lowered, the glass is likely to be damaged when mechanically processing the glass (cutting, cutting, grinding, polishing, etc.) (decrease in machinability), but La 2 O 3 , Y 2 When the total content of O 3 , Gd 2 O 3 and Yb 2 O 3 is 45% or more, a decrease in glass transition temperature can be suppressed, so that machinability can also be improved. On the other hand, if the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 is 65% or less, the thermal stability of the glass can be increased, and thus glass is produced. It is also possible to suppress crystallization at the time, and to reduce the unmelted raw material when the glass is melted. Therefore, the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 in the glass 1 is in the range of 45 to 65%. The preferable lower limit and the preferable upper limit of the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 are shown in the following table.
ガラス1において、Gd2O3の含有量は、La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量と、この合計含有量に対するGd2O3含有量により定まる。ガラス1では、上記した光学特性を有する高屈折率低分散ガラスを安定供給する上から、更には高屈折率低分散ガラスとしては比重が小さいガラスを作る上から、La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するGd2O3含有量の質量比(Gd2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))を0~0.05の範囲とする。質量比(Gd2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))の好ましい下限および好ましい上限を、下記表に示す。 Gd 2 O 3 is a component that desirably reduces the proportion of the glass composition for the reasons described above. Gd belongs to heavy rare earth elements like Yb, has a large atomic weight as a glass component, and increases the specific gravity of glass. Also from this point, it is desirable to reduce the proportion of Gd in the glass composition.
In glass 1, the content of Gd 2 O 3 depends on the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 and the Gd 2 O 3 content relative to this total content. Determined. In the glass 1, La 2 O 3 and Y 2 O are used in order to stably supply the high refractive index and low dispersion glass having the above-mentioned optical characteristics, and further to make a glass having a small specific gravity as the high refractive index and low dispersion glass. 3 , the mass ratio of Gd 2 O 3 content to the total content of Gd 2 O 3 and Yb 2 O 3 (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) Is in the range of 0 to 0.05. The preferable lower limit and preferable upper limit of the mass ratio (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) are shown in the following table.
これら成分のうち、TiO2の含有量が多くなると、ガラスの可視域の透過率が低下して、ガラスの着色が増大する傾向がある。
Ta2O5の作用については、前述の通りである。
WO3については、その含有量が増加すると、ガラスの可視域の透過率が低下してガラスの着色が増大する傾向があり、また比重が増大する傾向がある。
これに対し、Nb2O5は、ガラスの比重、着色、製造コストを増大させにくく、屈折率を高め、ガラスの熱的安定性を改善する働きがある。そこで、ガラス1では、Nb2O5の優れた作用、効果を活かすために、Nb2O5、TiO2、Ta2O5およびWO3の合計含有量に対するNb2O5の含有量の質量比(Nb2O5/(Nb2O5+TiO2+Ta2O5+WO3))を0.5~1の範囲とする。着色度λ5を低下させ、紫外線照射による紫外線硬化型接着剤の硬化を促進させる上からは、質量比(Nb2O5/(Nb2O5+TiO2+Ta2O5+WO3))を大きくすることが好ましい。質量比(Nb2O5/(Nb2O5+TiO2+Ta2O5+WO3))のより好ましい下限およびより好ましい上限を、下記表に示す。 Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 serve to improve the thermal stability of the glass by containing appropriate amounts.
Among these components, when the content of TiO 2 increases, the transmittance of the visible region of the glass tends to decrease, and the coloration of the glass tends to increase.
The action of Ta 2 O 5 is as described above.
As for the content of WO 3 , when the content thereof increases, the transmittance in the visible region of the glass tends to decrease and the coloration of the glass tends to increase, and the specific gravity tends to increase.
On the other hand, Nb 2 O 5 has a function of hardly increasing the specific gravity, coloring, and production cost of the glass, increasing the refractive index, and improving the thermal stability of the glass. Therefore, the glass 1, excellent effect of Nb 2 O 5, in order to utilize the effect, Nb 2 O 5, by weight of the content of TiO 2, Ta 2 O 5 and WO Nb 2 O 5 to the total content of 3 The ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is set in the range of 0.5 to 1. The mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is increased from the viewpoint of reducing the coloring degree λ5 and promoting the curing of the ultraviolet curable adhesive by ultraviolet irradiation. It is preferable. More preferable lower limit and more preferable upper limit of the mass ratio (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) are shown in the following table.
U、Th、Raはいずれも放射性元素である。そのため、これらの元素を含有させないこと、すなわち、これら元素をガラス成分としてガラス中に導入しないことが好ましい。
V、Cr、Mn、Fe、Co、Ni、Cu、Pr,Nd、Pm、Sm、Eu、Tb、Dy、Ho、Er、Tm、Ceは、ガラスの着色を増大させたり、蛍光の発生源となり、光学素子用のガラスに含有させる元素としては好ましくない。そのため、これらの元素を含有させないこと、すなわち、これら元素をガラス成分としてガラス中に導入しないことが好ましい。 Pb, As, Cd, Tl, Be, and Se each have toxicity. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
U, Th, and Ra are all radioactive elements. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
V, Cr, Mn, Fe, Co, Ni, Cu, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Ce increase the coloration of the glass and become a source of fluorescence. The element contained in the glass for optical elements is not preferable. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
Sbの添加量は、Sb2O3に換算し、酸化物基準のガラス組成において、Sb2O3以外のガラス成分の合計含有量を100質量%としたとき、0~0.11質量%の範囲にすることが好ましく、0.01~0.08質量%の範囲にすることがより好ましく、0.02~0.05質量%の範囲にすることがさらに好ましい。ここで、「酸化物基準のガラス組成」とは、ガラス原料が熔融時にすべて分解されてガラス中で酸化物として存在するものとして換算することにより得られるガラス組成をいうものとする。後述の表に示すガラス組成におけるSb2O3含有量も、上記の方法により算出される含有量である。
Snの添加量は、SnO2に換算し、酸化物基準のガラス組成において、SnO2以外のガラス成分の合計含有量を100質量%としたとき、0~1.0質量%の範囲にすることが好ましく、0~0.5質量%の範囲にすることがより好ましく、0~0.2質量%の範囲にすることがさらに好ましく、0質量%が一層好ましい。 Sb and Sn are arbitrarily addable elements that function as fining agents.
The amount of Sb added is 0 to 0.11% by mass when converted to Sb 2 O 3 and the total content of glass components other than Sb 2 O 3 is 100% by mass in the oxide-based glass composition. The range is preferably 0.01 to 0.08% by mass, more preferably 0.02 to 0.05% by mass. Here, the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed during melting and existing as oxides in the glass. The Sb 2 O 3 content in the glass composition shown in the table described later is also the content calculated by the above method.
The addition amount of Sn should be in the range of 0 to 1.0% by mass when converted to SnO 2 and the total content of glass components other than SnO 2 is 100% by mass in the oxide-based glass composition. Preferably, the range is 0 to 0.5% by mass, more preferably 0 to 0.2% by mass, and still more preferably 0% by mass.
本発明では、ガラス2のガラス組成を、カチオン成分についてカチオン%で表記する。カチオン%とは、周知のように、ガラスに含まれるすべてのカチオン成分の合計含有量を100%とした百分率である。
カチオン成分については、例えば、B3+、Si4+、La3+のように表示するが、カチオン成分の価数(例えば、B3+の価数は+3、Si4+の価数は+4、La3+の価数は+3)は、慣習により定まった値であり、B、Si、Laを酸化物基準でB2O3、SiO2、La2O3と表記することと同様である。酸化物基準でAmOn(Aはカチオンを表し、Oは酸素を表し、mおよびnは化学量論的に定まる整数である。)と表記される成分について、カチオンAはAs+と表記される。ここで、s=2n/mである。したがって、例えば、ガラス組成を分析、定量する際に、カチオン成分の価数まで分析しなくてもよい。以下、特記しない限り、カチオン成分の含有量、複数種のカチオン成分の含有量の合計(合計含有量)をカチオン%で表示する。更に、カチオン%表示において、カチオン成分同士の含有量(複数種のカチオン成分の合計含有量も含む)の比をカチオン比という。 <Glass composition of glass 2>
In the present invention, the glass composition of the glass 2 is expressed in terms of cation% with respect to the cation component. As is well known, the cation% is a percentage in which the total content of all cation components contained in the glass is 100%.
The cation component is expressed as B 3+ , Si 4+ , La 3+ , for example, but the valence of the cation component (for example, the valence of B 3+ is +3 and the valence of Si 4+ is +4). The valence of La 3+ is a value determined by convention, and is the same as expressing B, Si, La as B 2 O 3 , SiO 2 , La 2 O 3 on the oxide basis. . Cation A is expressed as A s + for a component expressed as A m O n on the oxide basis (A represents a cation, O represents oxygen, and m and n are stoichiometric integers). Is done. Here, s = 2n / m. Therefore, for example, when analyzing and quantifying the glass composition, it is not necessary to analyze the valence of the cation component. Hereinafter, unless otherwise specified, the content of the cation component and the total content (total content) of the plurality of types of cation components are expressed in cation%. Furthermore, in the cation% display, the ratio of the contents of cation components (including the total content of plural kinds of cation components) is referred to as a cation ratio.
一般に、B3+とLa3+等の希土類元素を含む高屈折率低分散ガラスでは、熔融時のガラスの粘性が低い。しかし、熔融時のガラスの粘性が低いと熱的安定性が低下する(結晶化しやすくなる)。ガラス製造時の結晶化は、アモルファス状態(非晶質状態)よりも結晶化したほうが安定であり、ガラスを構成するイオンがガラス中を移動して結晶構造をもつように配列することにより生じる。したがって、熔融時の粘性が高くなるようにB3+とSi4+の各成分の含有量の比率を調整することにより、上記イオンが結晶構造をもつように配列しにくくして、ガラスの結晶化を更に抑制しガラスの熱的安定性を改善することができる。
鋳型に熔融ガラスを流し込んで成形する時、熔融ガラスの粘度が低いと、鋳型内に流し込んだガラスの固化した表面部が依然として熔融状態にあるガラスの内部に巻き込まれて脈理となり、ガラスの光学的な均質性が低下してしまう。成形性の優れたガラスとは、希土類元素を含む高屈折率低分散ガラスの中でも、熔融状態のガラスを鋳型に流し込む時の粘度が比較的高いガラスに相当する。
B3+およびSi4+の合計含有量に対するB3+の含有量のカチオン比(B3+/(B3++Si4+))が0.94未満であれば、熔融時の粘性低下を抑制することができ、これによりガラスの熱的安定性を改善したり、熔融時の揮発を抑制することができる。熔融時の揮発は、ガラス組成の変動、特性の変動を大きくする原因となる。そしてその結果、光学的に均質なガラスを成形することを難しくする。したがって、カチオン比(B3+/(B3++Si4+))を0.94未満として熔融時の揮発を抑制できることは、組成や特性のばらつきの少ないガラスを量産する観点から好ましい。更に、カチオン比(B3+/(B3++Si4+))が0.94未満であれば、ガラスの化学的耐久性、耐候性、機械加工性の低下を抑制することもできる。これに対し、前述の特許文献15(特開昭57-056344号公報)に記載されているガラス組成では、B2O3含有量は28~30質量%、SiO2の含有量は1~3質量%である(特許文献15の特許請求の範囲参照)。これら成分の含有量から算出されるカチオン比(B3+/(B3++Si4+))は、0.942~0.981と大きい値になる。
一方、カチオン比(B3+/(B3++Si4+))が0.65以上であれば、熔融時のガラス原料の熔け残りを防ぐことができるため、熔融性を向上することができる。
以上の点から、ガラス2において、カチオン比(B3+/(B3++Si4+))を0.65以上0.94未満とする。ガラス2におけるカチオン比(B3+/(B3++Si4+))の好ましい下限および好ましい上限は、下記表に示す通りである。 The ratio of the content of B 3+ and Si 4+ , which are glass network forming components, is related to the thermal stability, meltability, formability, chemical durability, weather resistance, machinability, etc. of glass. Influence. B 3+ is superior to Si 4+ in improving the meltability, but tends to volatilize during melting. On the other hand, Si 4+ has a function of improving the chemical durability, weather resistance, and machinability of glass and increasing the viscosity of glass during melting.
Generally, in a high refractive index and low dispersion glass containing rare earth elements such as B 3+ and La 3+ , the viscosity of the glass at the time of melting is low. However, when the viscosity of the glass at the time of melting is low, the thermal stability is lowered (it becomes easier to crystallize). Crystallization during glass production is more stable when crystallized than when it is in an amorphous state (amorphous state), and occurs when ions constituting the glass move in the glass and are arranged so as to have a crystal structure. Therefore, by adjusting the content ratio of each component of B 3+ and Si 4+ so as to increase the viscosity at the time of melting, it becomes difficult for the above ions to be arranged so as to have a crystal structure. The glass can be further suppressed and the thermal stability of the glass can be improved.
When the molten glass is poured into the mold and molded, if the viscosity of the molten glass is low, the solidified surface portion of the glass poured into the mold is entangled inside the glass that is still in the molten state, which causes striae. Homogeneity is reduced. The glass having excellent formability corresponds to a glass having a relatively high viscosity when a molten glass is poured into a mold among high refractive index and low dispersion glass containing rare earth elements.
If the cation ratio of the content of B 3+ to the total content of B 3+ and Si 4+ (B 3+ / (B 3+ + Si 4+ )) is less than 0.94, viscosity reduction during melting can be reduced. Thus, the thermal stability of the glass can be improved, and volatilization during melting can be suppressed. Volatilization at the time of melting causes a large variation in glass composition and characteristics. As a result, it becomes difficult to form optically homogeneous glass. Therefore, it is preferable that the cation ratio (B 3+ / (B 3+ + Si 4+ )) be less than 0.94 to suppress volatilization at the time of melting from the viewpoint of mass-producing glass with little variation in composition and characteristics. Furthermore, if the cation ratio (B 3+ / (B 3+ + Si 4+ )) is less than 0.94, it is possible to suppress the deterioration of the chemical durability, weather resistance, and machinability of the glass. On the other hand, in the glass composition described in Patent Document 15 (Japanese Patent Laid-Open No. 57-056344), the B 2 O 3 content is 28 to 30% by mass, and the SiO 2 content is 1 to 3%. It is mass% (refer the claim of patent document 15). The cation ratio (B 3+ / (B 3+ + Si 4+ )) calculated from the contents of these components is as large as 0.942 to 0.981.
On the other hand, if the cation ratio (B 3+ / (B 3+ + Si 4+ )) is 0.65 or more, it is possible to prevent melting of the glass raw material at the time of melting, so that the meltability can be improved. .
From the above points, in the glass 2, the cation ratio (B 3+ / (B 3+ + Si 4+ )) is set to 0.65 or more and less than 0.94. The preferable lower limit and preferable upper limit of the cation ratio (B 3+ / (B 3+ + Si 4+ )) in the glass 2 are as shown in the following table.
La3+、Y3+、Gd3+およびYb3+の合計含有量(La3++Y3++Gd3++Yb3+)が25%以上であると、屈折率の低下を抑制することができるため、上記した光学特性を有するガラスの作製が可能となる。更に、ガラスの化学的耐久性や耐候性の低下を抑制することもできる。なお、ガラス転移温度が低下すると、ガラスを機械的に加工(切断、切削、研削、研磨など)するときにガラスが破損しやすくなる(機械加工性の低下)が、La3+、Y3+、Gd3+およびYb3+の合計含有量が25%以上であると、ガラス転移温度の低下を抑制することができるため、機械加工性を高めることもできる。一方、La3+、Y3+、Gd3+およびYb3+の合計含有量が35%以下であれば、ガラスの熱的安定性を高めることができるため、ガラスを製造するときの結晶化の抑制や、ガラスを熔融するときの原料の熔け残りを低減することもできる。したがって、ガラス2において、La3+、Y3+、Gd3+およびYb3+の合計含有量は、25~35%の範囲とする。La3+、Y3+、Gd3+およびYb3+の合計含有量の好ましい下限および好ましい上限を、下記表に示す。 La 3+ , Y 3+ , Gd 3+ and Yb 3+ are components having a function of increasing the refractive index while suppressing a decrease in the Abbe number. These components also have the function of improving the chemical durability and weather resistance of the glass and increasing the glass transition temperature.
If the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ (La 3+ + Y 3+ + Gd 3+ + Yb 3+ ) is 25% or more, the decrease in refractive index can be suppressed. Therefore, it is possible to produce a glass having the above optical characteristics. Furthermore, it is possible to suppress a decrease in chemical durability and weather resistance of the glass. Note that when the glass transition temperature is lowered, the glass is likely to be damaged when mechanically processing the glass (cutting, cutting, grinding, polishing, etc.) (decrease in machinability), but La 3+ , Y 3+ When the total content of Gd 3+ and Yb 3+ is 25% or more, a decrease in glass transition temperature can be suppressed, so that machinability can also be improved. On the other hand, if the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is 35% or less, the thermal stability of the glass can be increased. In addition, it is possible to reduce the remaining amount of raw materials when glass is melted or when melting glass. Therefore, in the glass 2, the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ is in the range of 25 to 35%. The preferable lower limit and preferable upper limit of the total content of La 3+ , Y 3+ , Gd 3+ and Yb 3+ are shown in the following table.
ガラス2において、Gd3+の含有量は、La3+、Y3+、Gd3+およびYb3+の合計含有量と、この合計含有量に対するGd3+含有量により定まる。ガラス2では、上記した光学特性を有する高屈折率低分散ガラスを安定供給する上から、更には高屈折率低分散ガラスとしては比重が小さいガラスを作る上から、La3+、Y3+、Gd3+およびYb3+の合計含有量に対するGd3+含有量のカチオン比(Gd3+/(La3++Y3++Gd3++Yb3+))を0~0.05の範囲とする。カチオン比(Gd3+/(La3++Y3++Gd3++Yb3+))の好ましい下限および好ましい上限を、下記表に示す。 Gd 3+ is a component that desirably reduces the proportion of the glass composition for the reasons described above. Gd belongs to heavy rare earth elements like Yb, has a large atomic weight as a glass component, and increases the specific gravity of glass. Also from this point, it is desirable to reduce the proportion of Gd in the glass composition.
In the glass 2, the Gd 3+ content, La 3+, Y 3+, and the total content of Gd 3+ and Yb 3+, determined by Gd 3+ content for this total content. In the glass 2, La 3+ , Y 3+ , Y 3+ , Y 2 The cation ratio of the Gd 3+ content to the total content of Gd 3+ and Yb 3+ (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is in the range of 0 to 0.05. . The preferable lower limit and the preferable upper limit of the cation ratio (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) are shown in the following table.
これら成分のうち、Ti4+の含有量が多くなると、ガラスの可視域の透過率が低下して、ガラスの着色が増大する傾向がある。
Ta5+の作用については、前述の通りである。
W6+については、その含有量が増加すると、ガラスの可視域の透過率が低下してガラスの着色が増大する傾向があり、また比重が増大する傾向がある。
これに対し、Nb5+は、ガラスの比重、着色、製造コストを増大させにくく、屈折率を高め、ガラスの熱的安定性を改善する働きがある。そこで、ガラス2では、Nb5+の優れた作用、効果を活かすために、Nb5+、Ti4+、Ta5+およびW6+の合計含有量に対するNb5+の含有量のカチオン比(Nb5+/(Nb5++Ti4++Ta5++W6+))を0.4~1の範囲とする。着色度λ5を低下させ、紫外線照射による紫外線硬化型接着剤の硬化を促進させる上からは、カチオン比(Nb5+/(Nb5++Ti4++Ta5++W6+))を大きくすることが好ましい。カチオン比(Nb5+/(Nb5++Ti4++Ta5++W6+))のより好ましい下限およびより好ましい上限を、下記表に示す。 Nb 5+ , Ti 4+ , Ta 5+ and W 6+ serve to improve the thermal stability of the glass by containing appropriate amounts.
Among these components, when the content of Ti 4+ increases, the transmittance in the visible region of the glass tends to decrease and the coloration of the glass tends to increase.
The action of Ta 5+ is as described above.
With regard to W 6+ , when the content thereof increases, the transmittance in the visible range of the glass tends to decrease and the coloration of the glass tends to increase, and the specific gravity tends to increase.
On the other hand, Nb 5+ has a function of hardly increasing the specific gravity, coloring, and production cost of the glass, increasing the refractive index, and improving the thermal stability of the glass. Therefore, the glass 2, an excellent effect of Nb 5+, in order to utilize the effect, Nb 5+, Ti 4+, Ta 5+, and W 6+ content of the cation ratio of Nb 5+ to the total content of ( Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) is set in the range of 0.4 to 1. In order to reduce the coloring degree λ5 and promote the curing of the ultraviolet curable adhesive by ultraviolet irradiation, the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) should be increased. Is preferred. More preferable lower limits and more preferable upper limits of the cation ratio (Nb 5+ / (Nb 5+ + Ti 4+ + Ta 5+ + W 6+ )) are shown in the following table.
U、Th、Raはいずれも放射性元素である。そのため、これらの元素を含有させないこと、すなわち、これら元素をガラス成分としてガラス中に導入しないことが好ましい。
V、Cr、Mn、Fe、Co、Ni、Cu、Pr,Nd、Pm、Sm、Eu、Tb、Dy、Ho、Er、Tm、Ceは、ガラスの着色を増大させたり、蛍光の発生源となり、光学素子用のガラスに含有させる元素としては好ましくない。そのため、これらの元素を含有させないこと、すなわち、これら元素をガラス成分としてガラス中に導入しないことが好ましい。 Pb, As, Cd, Tl, Be, and Se each have toxicity. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
U, Th, and Ra are all radioactive elements. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
V, Cr, Mn, Fe, Co, Ni, Cu, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Ce increase the coloration of the glass and become a source of fluorescence. The element contained in the glass for optical elements is not preferable. Therefore, it is preferable not to contain these elements, that is, not to introduce these elements into the glass as glass components.
Sbの添加量は、Sb2O3に換算し、酸化物基準のガラス組成において、Sb2O3以外のガラス成分の合計含有量を100質量%としたとき、0~0.11質量%の範囲にすることが好ましく、0.01~0.08質量%の範囲にすることがより好ましく、0.02~0.05質量%の範囲にすることがさらに好ましい。ここで、「酸化物基準のガラス組成」とは、ガラス原料が熔融時にすべて分解されてガラス中で酸化物として存在するものとして換算することにより得られるガラス組成をいうものとする。後述の表に示すガラス組成におけるSb2O3含有量も、上記の方法により算出される含有量である。
Snの添加量は、SnO2に換算し、酸化物基準のガラス組成において、SnO2以外のガラス成分の合計含有量を100質量%としたとき、0~1.0質量%の範囲にすることが好ましく、0~0.5質量%の範囲にすることがより好ましく、0~0.2質量%の範囲にすることがさらに好ましく、0質量%が一層好ましい。 Sb and Sn are arbitrarily addable elements that function as fining agents.
The amount of Sb added is 0 to 0.11% by mass when converted to Sb 2 O 3 and the total content of glass components other than Sb 2 O 3 is 100% by mass in the oxide-based glass composition. The range is preferably 0.01 to 0.08% by mass, more preferably 0.02 to 0.05% by mass. Here, the “oxide-based glass composition” refers to a glass composition obtained by converting all glass raw materials to be decomposed during melting and existing as oxides in the glass. The Sb 2 O 3 content in the glass composition shown in the table described later is also the content calculated by the above method.
The addition amount of Sn should be in the range of 0 to 1.0% by mass when converted to SnO 2 and the total content of glass components other than SnO 2 is 100% by mass in the oxide-based glass composition. Preferably, the range is 0 to 0.5% by mass, more preferably 0 to 0.2% by mass, and still more preferably 0% by mass.
O2-以外のアニオン成分としては、F-、Cl-、Br-、I-を例示することができる。ただし、F-、Cl-、Br-、I-は、いずれもガラスの熔融中に揮発しやすい。これらの成分の揮発によって、ガラスの特性が変動しガラスの均質性が低下したり、熔融設備の消耗が著しくなる傾向がある。したがって、F-、Cl-、Br-およびI-の合計含有量を、100アニオン%から、O2-の含有量を差し引いた量に抑えることが好ましい。
なお、アニオン%とは周知のように、ガラスに含まれるすべてのアニオン成分の合計含有量を100%とした百分率である。 Since glass 2 is an oxide glass, it contains O 2− as an anion component. The content of O 2− is preferably in the range of 98 to 100 anion%, more preferably in the range of 99 to 100 anion%, still more preferably 99.5 to 100 anion%, It is more preferable that it is% anion.
Examples of the anion component other than O 2− include F − , Cl − , Br − and I − . However, all of F − , Cl − , Br − and I − are easily volatilized during melting of the glass. Due to volatilization of these components, the characteristics of the glass fluctuate and the homogeneity of the glass tends to decrease, or the melting equipment tends to be consumed significantly. Therefore, it is preferable to suppress the total content of F − , Cl − , Br − and I − to an amount obtained by subtracting the content of O 2− from 100 anion%.
As well known, the anion% is a percentage with the total content of all anion components contained in the glass being 100%.
次に、ガラス1およびガラス2に共通するガラス特性について説明する。以下に記載するガラスは、ガラス1およびガラス2を指すものとする。 <Glass characteristics>
Next, glass characteristics common to the glass 1 and the glass 2 will be described. The glass described below refers to glass 1 and glass 2.
上記ガラスは、屈折率ndが1.800~1.850の範囲であり、かつアッベ数νdが41.5~44である。 (Optical properties of glass)
The glass has a refractive index nd in the range of 1.800 to 1.850, and an Abbe number νd of 41.5 to 44.
色収差補正の観点から、上記ガラスは、アッベ数を固定したとき、部分分散比が小さいガラスであることが好ましい。
ここで、部分分散比Pg,Fは、g線(水銀の波長435.84nm)、F線、C線における各屈折率ng、nF、nCを用いて、(ng-nF)/(nF-nC)と表される。
高次の色収差補正に好適なガラスを提供する上から、上記ガラスの部分分散比Pg,Fの好ましい下限および好ましい上限は、下記表に示す通りである。 (Partial dispersion characteristics)
From the viewpoint of correcting chromatic aberration, the glass is preferably a glass having a small partial dispersion ratio when the Abbe number is fixed.
Here, the partial dispersion ratios Pg and F are (ng−nF) / (nF−nC) using the refractive indexes ng, nF and nC in the g-line (mercury wavelength 435.84 nm), F-line and C-line. ).
From the viewpoint of providing a glass suitable for high-order chromatic aberration correction, preferred lower limits and preferred upper limits of the partial dispersion ratios Pg, F of the glass are as shown in the following table.
上記ガラスは、機械加工性改善の観点から、ガラス転移温度が640℃以上であることが好ましい。ガラス転移温度を640℃以上にすることにより、切断、切削、研削、研磨などガラスを機械的に加工する時に、ガラスを破損しにくくすることができる。
一方、ガラス転移温度を高くし過ぎると、ガラスを高温でアニールしなければならなくなり、アニール炉が著しく消耗する。また、ガラスを成形するときに、高い温度で成形を行わなければならず、成形に使用する型の消耗が著しくなる。
機械加工性の改善、アニール炉や成形型への負担軽減から、ガラス転移温度のより好ましい下限および好ましい上限は、下記表に示す通りである。 (Glass-transition temperature)
The glass preferably has a glass transition temperature of 640 ° C. or higher from the viewpoint of improving machinability. By setting the glass transition temperature to 640 ° C. or higher, it is possible to make the glass difficult to break when mechanically processing the glass, such as cutting, cutting, grinding, and polishing.
On the other hand, if the glass transition temperature is too high, the glass must be annealed at a high temperature, and the annealing furnace is significantly consumed. Further, when glass is molded, it must be molded at a high temperature, and the consumption of the mold used for molding becomes significant.
From the viewpoint of improving machinability and reducing the burden on the annealing furnace and the mold, more preferable lower limit and preferable upper limit of the glass transition temperature are as shown in the following table.
ガラスの光線透過性、詳しくは、短波長側の光吸収端の長波長化が抑制されていることは、着色度λ5により評価することができる。着色度λ5とは、紫外域から可視域にかけて、厚さ10mmのガラスの分光透過率(表面反射損失を含む)が5%となる波長である。後述の実施例に示すλ5は、250~700nmの波長域において測定された値である。分光透過率とは、例えばより詳しくは、10.0±0.1mmの厚さに光学研磨された互いに平行な平面を有するガラス試料を用い、上記光学研磨された面に対して垂直方向から光を入射して得られる分光透過率、すなわち、上記ガラス試料に入射する光の強度をIin、上記ガラス試料を透過した光の強度をIoutとしたときの強度比Iout/Iinのことである。
着色度λ5によれば、分光透過率の短波長側の吸収端を定量的に評価することができる。前述の通り、接合レンズ作製のためにレンズ同士を紫外線硬化型接着剤により接合する際など、光学素子を通して接着剤に紫外線を照射し接着剤を硬化させることが行われる。効率よく紫外線硬化型接着剤の硬化を行う上から、分光透過率の短波長側の吸収端が短い波長域にあることが好ましい。この短波長側の吸収端を定量的に評価する指標として、着色度λ5を用いることができる。上記ガラスは、先に記載した組成調整により、好ましくは335nm以下、より好ましくは332nm以下、更に好ましくは330nm以下、一層好ましくは328nm以下、より一層好ましくは326nm以下のλ5を示すことができる。λ5の下限は、一例として、315nmを目安とすることができるが、低いほど好ましく特に限定されるものではない。 (Light transmittance of glass)
It is possible to evaluate the light transmittance of glass, specifically, that the increase in the wavelength of the light absorption edge on the short wavelength side is suppressed by the coloring degree λ5. The coloring degree λ5 is a wavelength at which the spectral transmittance (including surface reflection loss) of a glass having a thickness of 10 mm is 5% from the ultraviolet region to the visible region. Λ5 shown in the examples described later is a value measured in a wavelength region of 250 to 700 nm. The spectral transmittance is, for example, more specifically, glass samples having mutually parallel planes optically polished to a thickness of 10.0 ± 0.1 mm, and light from a direction perpendicular to the optically polished surface. Is an intensity ratio Iout / Iin where Iin is the intensity of light incident on the glass sample and Iout is the intensity of light transmitted through the glass sample.
According to the coloring degree λ5, the absorption edge on the short wavelength side of the spectral transmittance can be quantitatively evaluated. As described above, when the lenses are bonded with an ultraviolet curable adhesive to produce a bonded lens, the adhesive is cured by irradiating the adhesive with ultraviolet rays through an optical element. In order to efficiently cure the ultraviolet curable adhesive, it is preferable that the absorption edge on the short wavelength side of the spectral transmittance is in a short wavelength region. As an index for quantitatively evaluating the absorption edge on the short wavelength side, the coloring degree λ5 can be used. The glass can exhibit a λ5 of preferably 335 nm or less, more preferably 332 nm or less, still more preferably 330 nm or less, more preferably 328 nm or less, and even more preferably 326 nm or less, by adjusting the composition described above. As an example, the lower limit of λ5 can be 315 nm, but it is not particularly limited as it is lower.
また、ガラスの着色度の指標としては、着色度λ80も挙げられる。λ80は、λ5について記載した方法で測定される分光透過率が80%となる波長である。着色の少ないガラスとする上から、λ80の好ましい範囲は480nm以下、より好ましい範囲は460nm以下、一層好ましい範囲は440nm以下、より一層好ましい範囲は420nm以下である。λ80の下限の目安は350nmであるが、低いほど好ましく特に限定されるものではない。 On the other hand, as an index of the coloring degree of glass, coloring degree λ70 is mentioned. λ70 is a wavelength at which the spectral transmittance measured by the method described for λ5 is 70%. From the viewpoint of making the glass with little coloration, a preferable range of λ70 is 420 nm or less, a more preferable range is 400 nm or less, a more preferable range is 390 nm or less, and a still more preferable range is 380 nm or less. A guideline for the lower limit of λ70 is 340 nm, but the lower limit is preferably not particularly limited.
Further, as an index of the coloring degree of the glass, a coloring degree λ80 is also mentioned. λ80 is a wavelength at which the spectral transmittance measured by the method described for λ5 is 80%. From the viewpoint of making the glass with little coloring, the preferable range of λ80 is 480 nm or less, the more preferable range is 460 nm or less, the more preferable range is 440 nm or less, and the still more preferable range is 420 nm or less. A guideline for the lower limit of λ80 is 350 nm, but the lower limit is preferably not particularly limited.
光学系を構成する光学素子(レンズ)では、レンズを構成するガラスの屈折率とレンズの光学機能面(制御しようとする光線が入射、出射する面)の曲率によって、屈折力が決まる。光学機能面の曲率を大きくしようとすると、レンズの厚みも増加する。その結果、レンズが重くなる。これに対し、屈折率の高いガラスを使用すれば、光学機能面の曲率を大きくしなくても大きな屈折力を得ることができる。
以上より、ガラスの比重の増加を抑えつつ、屈折率を高めることができれば、一定の屈折力を有する光学素子の軽量化が可能となる。
屈折率ndの屈折力への寄与に関しては、ガラスの屈折率ndから真空中の屈折率である1を引いた値(nd―1)に対するガラスの比重dの比を取ることにより、光学素子の軽量化を図る際の指標とすることができる。すなわち、d/(nd-1)を光学素子の軽量化を図る際の指標とし、この値を低減することにより、レンズの軽量化を図ることができる。
上記ガラスは、比重の増加を招くGd、Ta、Ybの占める比率が少ないため、高屈折率低分散ガラスでありながら、低比重化が可能である。したがって、上記ガラスのd/(nd-1)は、例えば5.70以下であることができる。ただし、d/(nd-1)を過剰に減少させると、ガラスの熱的安定性が低下傾向を示す。そのため、d/(nd-1)は、5.00以上とすることが好ましい。d/(nd-1)のより好ましい下限およびより好ましい上限を、下記表に示す。 (Specific gravity of glass)
In the optical element (lens) constituting the optical system, the refractive power is determined by the refractive index of the glass constituting the lens and the curvature of the optical functional surface of the lens (the surface on which light to be controlled is incident and emitted). If the curvature of the optical function surface is increased, the thickness of the lens also increases. As a result, the lens becomes heavy. On the other hand, if a glass having a high refractive index is used, a large refractive power can be obtained without increasing the curvature of the optical function surface.
As described above, if the refractive index can be increased while suppressing an increase in the specific gravity of the glass, it is possible to reduce the weight of the optical element having a certain refractive power.
Regarding the contribution of the refractive index nd to the refractive power, by taking the ratio of the specific gravity d of the glass to the value obtained by subtracting 1 which is the refractive index in vacuum (nd-1) from the refractive index nd of the glass, It can be used as an index for weight reduction. That is, d / (nd-1) is used as an index for reducing the weight of the optical element, and by reducing this value, the lens can be reduced in weight.
Since the glass has a small proportion of Gd, Ta, and Yb that cause an increase in specific gravity, it is possible to reduce the specific gravity while being a high refractive index and low dispersion glass. Therefore, d / (nd-1) of the glass can be, for example, 5.70 or less. However, if d / (nd-1) is excessively decreased, the thermal stability of the glass tends to decrease. Therefore, d / (nd-1) is preferably set to 5.00 or more. More preferable lower limit and more preferable upper limit of d / (nd-1) are shown in the following table.
ガラスの熱的安定性の指標の一つに液相温度がある。ガラス製造時の結晶化、失透を抑制する上から、液相温度LTが1300℃以下であることが好ましく、1250℃以下であることがより好ましく、1200℃以下であることが一層好ましく、1150℃以下であることがより一層好ましい。液相温度LTの下限は、一例として1100℃以上であるが、低いことが好ましく特に限定されるものではない。 (Liquid phase temperature)
One indicator of the thermal stability of glass is the liquidus temperature. In order to suppress crystallization and devitrification during glass production, the liquidus temperature LT is preferably 1300 ° C. or lower, more preferably 1250 ° C. or lower, and further preferably 1200 ° C. or lower, 1150 It is still more preferable that it is below ℃. The lower limit of the liquidus temperature LT is 1100 ° C. or more as an example, but is preferably not low and is not particularly limited.
上記ガラスは、目的のガラス組成が得られるように、原料である酸化物、炭酸塩、硫酸塩、硝酸塩、水酸化物などを秤量、調合し、十分に混合して混合バッチとし、熔融容器内で加熱、熔融し、脱泡、攪拌を行い均質かつ泡を含まない熔融ガラスを作り、これを成形することによって得ることができる。具体的には公知の熔融法を用いて作ることができる。上記ガラスは、上記した光学特性を有する高屈折率低分散ガラスでありながら、熱的安定性が優れているため、公知の熔融法、成形法を用いて、安定的に製造することができる。 <Glass manufacturing method>
In order to obtain the desired glass composition, the glass is weighed and prepared as raw materials such as oxides, carbonates, sulfates, nitrates and hydroxides, and mixed well to form a mixed batch. It can be obtained by heating, melting, defoaming and stirring to make a molten glass free of bubbles and molding it. Specifically, it can be made using a known melting method. Although the above glass is a high refractive index low dispersion glass having the above-mentioned optical properties, it is excellent in thermal stability, and therefore can be stably produced using a known melting method and molding method.
本発明の他の一態様は、
上述のガラス1またはガラス2からなるプレス成形用ガラス素材;
上述のガラス1またはガラス2からなる光学素子ブランク、
に関する。 [Press-molding glass material, optical element blank, and manufacturing method thereof]
Another aspect of the present invention is:
A glass material for press molding comprising the glass 1 or glass 2 described above;
An optical element blank made of the glass 1 or glass 2 described above,
About.
上述のガラス1またはガラス2をプレス成形用ガラス素材に成形する工程を備えるプレス成形用ガラス素材の製造方法;
上述のプレス成形用ガラス素材を、プレス成形型を用いてプレス成形することにより光学素子ブランクを作製する工程を備える光学素子ブランクの製造方法;
上述のガラス1またはガラス2を光学素子ブランクに成形する工程を備える光学素子ブランクの製造方法、
も提供される。
プレス成形用ガラス素材、光学素子ブランクが上述のガラス1またはガラス2で作られているため、当然のことながら、プレス成形用ガラス素材、光学素子ブランクも上述のガラスに相当する。 According to another aspect of the invention,
A method for producing a glass material for press molding comprising the step of forming the glass 1 or glass 2 described above into a glass material for press molding;
A method for producing an optical element blank comprising a step of producing an optical element blank by press-molding the above-described press-molding glass material using a press mold;
A method for producing an optical element blank, comprising the step of forming the glass 1 or glass 2 described above into an optical element blank,
Is also provided.
Since the glass material for press molding and the optical element blank are made of the glass 1 or glass 2 described above, the glass material for press molding and the optical element blank naturally correspond to the glass described above.
本発明の他の一態様は、
上述のガラス1またはガラス2からなる光学素子
に関する。
上記光学素子は、上述のガラス1またはガラス2を用いて作製される。上記光学素子において、ガラス表面には、例えば、反射防止膜等の多層膜等、一層以上のコーティングが形成されていてもよい。
光学素子は上述のガラス1またはガラス2により作られているので、当然のことながら、上述のガラスに相当する。また光学素子のガラス表面にコーティングが形成されている場合は、コーティングを除いたガラスの部分が上述のガラスに相当する。 [Optical element and manufacturing method thereof]
Another aspect of the present invention is:
The present invention relates to an optical element made of the glass 1 or the glass 2 described above.
The optical element is manufactured using the glass 1 or the glass 2 described above. In the optical element, one or more coatings such as a multilayer film such as an antireflection film may be formed on the glass surface.
Since the optical element is made of the glass 1 or glass 2 described above, it naturally corresponds to the glass described above. When a coating is formed on the glass surface of the optical element, the glass portion excluding the coating corresponds to the glass described above.
上述の光学素子ブランクを少なくとも研磨することにより光学素子を作製する工程を備える光学素子の製造方法、
も提供される。 According to one embodiment of the present invention,
A method for producing an optical element comprising a step of producing an optical element by polishing at least the optical element blank described above,
Is also provided.
例えば、カチオンAと酸素からなる酸化物はAmOnと表記される。mとnはそれぞれ化学量論的に定まる整数である。例えば、B3+では酸化物基準による表記がB2O3となり、m=2、n=3となり、Si4+ではSiO2となり、m=1、n=2となる。
まず、質量%表示におけるAmOnの含有量をAmOnの分子量で割り、さらにmを乗じる。この値をPとする。そして、カチオン成分のすべてについてPを合計する。Pを合計した値をΣPとすると、ΣPが100%になるように各カチオン成分のPの値を規格した値が、カチオン%表示におけるAs+の含有量となる。ここで、sは2n/mである。
なお、微量の添加剤、例えばSb2O3のような清澄剤については、ΣPの中に含めなくてもよい。その場合、Sbの含有量は、上述のようにSb2O3に換算した外割りの含有量(質量%)とすればよい。すなわち、Sb2O3の含有量を除くガラス成分の含有量の合計を100質量%とし、Sb2O3の含有量を100質量%に対する値として表す。
また、上記の分子量は、例えば、小数点以下4桁目を四捨五入し、小数点以下3桁目までの表示とした値を用いて計算すればよい。なお、例えば、酸化物AmOnの分子量は、元素Aの原子量をm倍した値と酸素の原子量をn倍した値の合計である。幾つかのガラス成分、添加剤について、酸化物基準による表記における分子量を、下記の表に示す。 As a result of the quantitative analysis of the glass composition, the glass component may be expressed on an oxide basis, and the content of the glass component may be displayed in mass%. Thus, the composition represented by mass% on the basis of oxide can be converted into the composition represented by cation% and anion%, for example, by the following method.
For example, an oxide consisting of cations A and oxygen is expressed as A m O n. m and n are integers determined stoichiometrically. For example, for B 3+ , the oxide standard is B 2 O 3 , m = 2 and n = 3, and for Si 4+ , SiO 2 , m = 1 and n = 2.
First, the content of A m O n in mass percentage divided by the molecular weight of A m O n, further multiplied by m. Let this value be P. And P is totaled about all the cation components. When the total value of P is ΣP, the value obtained by standardizing the P value of each cation component so that ΣP is 100% is the content of As + in the cation% display. Here, s is 2 n / m.
Note that a trace amount of additive, for example, a clarifying agent such as Sb 2 O 3 may not be included in ΣP. In that case, the Sb content may be the externally divided content (mass%) converted to Sb 2 O 3 as described above. That is, the total content of the glass components excluding the Sb 2 O 3 content is 100% by mass, and the Sb 2 O 3 content is expressed as a value with respect to 100% by mass.
In addition, the molecular weight may be calculated using, for example, a value obtained by rounding off the fourth decimal place to the third decimal place. Incidentally, for example, the molecular weight of the oxide A m O n is the values and atomic weight of oxygen atom amount was multiplied by m elements A is the sum of the n-fold value. The following table shows the molecular weight of some glass components and additives in terms of oxide standards.
下記の表に示す組成を有するガラスが得られるように、原料として酸化物、ホウ酸などの化合物を秤量し、充分、混合してバッチ原料を作製した。
このバッチ原料を白金坩堝中に入れ、1350~1450℃の温度に坩堝ごと加熱し、2~3時間かけてガラスを熔融、清澄した。熔融ガラスを攪拌して均質化した後、予熱した成形型に熔融ガラスを鋳込み、ガラス転移温度付近まで放冷してから直ちに、成形型ごとガラスをアニール炉内に入れた。それから、ガラス転移温度付近で約1時間アニールした。アニールした後、アニール炉内で室温まで放冷した。
このようにして作製したガラスを観察したところ、結晶の析出、泡、脈理、原料の熔け残りは認められなかった。このようにして、均質性の高いガラスを作ることができた。
表100(表100-1~100-7)中のNo.1~33は、ガラス1、表101(表101-1~101-6)中のNo.1~33は、ガラス2である。 (Example 1)
In order to obtain a glass having the composition shown in the table below, compounds such as oxide and boric acid were weighed as raw materials and mixed sufficiently to prepare batch raw materials.
This batch raw material was put in a platinum crucible, and the whole crucible was heated to a temperature of 1350 to 1450 ° C., and the glass was melted and refined over 2 to 3 hours. After the molten glass was agitated and homogenized, the molten glass was cast into a preheated mold and allowed to cool to near the glass transition temperature, and then the glass together with the mold was placed in an annealing furnace. Then, annealing was performed for about 1 hour near the glass transition temperature. After annealing, it was allowed to cool to room temperature in an annealing furnace.
Observation of the glass thus prepared revealed no crystal precipitation, bubbles, striae, or unmelted raw material. In this way, highly homogenous glass could be made.
No. in Table 100 (Tables 100-1 to 100-7). Nos. 1-33 are Nos. 1 in Glass 1, Table 101 (Tables 101-1 to 101-6). 1 to 33 are the glass 2.
(1)屈折率nd、nF、nC、ng、アッベ数νd
降温速度-30℃/時間で降温して得たガラスについて、日本光学硝子工業会規格の屈折率測定法により、屈折率nd、nF、nC、ngを測定した。屈折率nd、nF、nCの各測定値を用いて、アッベ数νdを算出した。
(2)ガラス転移温度Tg
示差走査熱量分析装置(DSC)を用いて、昇温速度を10℃/分にして測定した。
(3)比重
アルキメデス法により測定した。
(4)着色度λ5、λ70、λ80
互いに対向する2つの光学研磨された平面を有する厚さ10±0.1mmのガラス試料を用い、分光光度計により、研磨された面に対して垂直方向から強度Iinの光を入射し、ガラス試料を透過した光の強度Ioutを測定し、分光透過率Iout/Iinを算出し、分光透過率が5%になる波長をλ5、分光透過率が70%になる波長をλ70、分光透過率が80%になる波長をλ80とした。
(5)部分分散比Pg,F
上記(1)で測定したnF、nC、ngの値から算出した。
(6)液相温度
ガラスを所定温度に加熱された炉内に入れて2時間保持し、冷却後、ガラス内部を100倍の光学顕微鏡で観察し、結晶の有無から液相温度を決定した。 The glass characteristic of the obtained glass was measured by the method shown below. The measurement results are shown in the following table.
(1) Refractive index nd, nF, nC, ng, Abbe number νd
Refractive indexes nd, nF, nC, and ng were measured for the glass obtained by lowering the temperature at a temperature drop rate of −30 ° C./hour by the refractive index measurement method of the Japan Optical Glass Industry Association standard. The Abbe number νd was calculated using the measured values of the refractive indexes nd, nF, and nC.
(2) Glass transition temperature Tg
Using a differential scanning calorimeter (DSC), the heating rate was 10 ° C./min.
(3) Specific gravity Measured by Archimedes method.
(4) Degree of coloring λ5, λ70, λ80
Using a glass sample having a thickness of 10 ± 0.1 mm having two optically polished planes facing each other, a spectrophotometer is used to inject light having an intensity Iin from the direction perpendicular to the polished surface. The spectral transmittance Iout / Iin is calculated by measuring the intensity Iout of the light that has passed through λ5, the wavelength at which the spectral transmittance is 5% is λ5, the wavelength at which the spectral transmittance is 70% is λ70, and the spectral transmittance is 80 The wavelength at which% is obtained is λ80.
(5) Partial dispersion ratio Pg, F
It calculated from the value of nF, nC, and ng measured by said (1).
(6) Liquidus temperature The glass was placed in a furnace heated to a predetermined temperature and held for 2 hours. After cooling, the inside of the glass was observed with a 100-fold optical microscope, and the liquidus temperature was determined from the presence or absence of crystals.
実施例1で得られた各種ガラスを使用し、プレス成形用ガラス塊(ガラスゴブ)を作製した。このガラス塊を大気中で加熱、軟化し、プレス成形型でプレス成形し、レンズブランク(光学素子ブランク)を作製した。作製したレンズブランクをプレス成形型から取り出し、アニールし、研磨を含む機械加工を行い、実施例1で作製した各種ガラスからなる球面レンズを作製した。 (Example 2)
Various glasses obtained in Example 1 were used to produce a press-molding glass lump (glass gob). This glass lump was heated and softened in the atmosphere, and press-molded with a press mold to produce a lens blank (optical element blank). The produced lens blank was taken out from the press mold, annealed, and machined including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
実施例1において作製した熔融ガラスを所望量取得し、取得したガラスが軟化状態にある間にプレス成形型でプレス成形し、冷却してレンズブランク(光学素子ブランク)を作製した。作製したレンズブランクをプレス成形型から取り出し、アニールし、研磨を含む機械加工を行い、実施例1で作製した各種ガラスからなる球面レンズを作製した。 (Example 3)
A desired amount of the molten glass produced in Example 1 was obtained, and while the obtained glass was in a softened state, it was press-molded with a press mold and cooled to produce a lens blank (optical element blank). The produced lens blank was taken out from the press mold, annealed, and machined including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
実施例1において作製した熔融ガラスを固化して作製したガラス塊(光学素子ブランク)をアニールし、研磨を含む機械加工を行い、実施例1で作製した各種ガラスからなる球面レンズを作製した。 Example 4
A glass lump (optical element blank) produced by solidifying the molten glass produced in Example 1 was annealed and subjected to mechanical processing including polishing, and spherical lenses made of various glasses produced in Example 1 were produced.
実施例2~4において作製した球面レンズを、他種のガラスからなる球面レンズと貼り合せ、接合レンズを作製した。実施例2~4において作製した球面レンズの接合面は凸状の球面、他種の光学ガラスからなる球面レンズの接合面は凹状の球面であった。上記2つの接合面は、互いに曲率半径の絶対値が等しくなるように作製した。接合面に光学素子接合用の紫外線硬化型接着剤を塗布し、2つのレンズを接合面同士で貼り合せた。その後、実施例2~4において作製した球面レンズを通して、接合面に塗布した接着剤に紫外線を照射し、接着剤を固化させた。
上記のようにして接合レンズを作製した。接合レンズの接合強度は充分高く、光学性能も充分なレベルのものであった。 (Example 5)
The spherical lens produced in Examples 2 to 4 was bonded to a spherical lens made of another type of glass to produce a cemented lens. The cemented surfaces of the spherical lenses produced in Examples 2 to 4 were convex spherical surfaces, and the cemented surfaces of spherical lenses made of other types of optical glass were concave spherical surfaces. The two joint surfaces were produced so that the absolute values of the curvature radii were equal to each other. An ultraviolet curable adhesive for optical element bonding was applied to the bonding surface, and the two lenses were bonded to each other at the bonding surfaces. Thereafter, the adhesive applied to the joint surface was irradiated with ultraviolet rays through the spherical lenses prepared in Examples 2 to 4, and the adhesive was solidified.
A cemented lens was produced as described above. The cemented lens had a sufficiently high bonding strength and a sufficient level of optical performance.
下記の表102に示す組成を有するガラス(以下、「ガラスA」と記載する。)、表103に示す組成を有するガラス(以下、「ガラスB」と記載する。)を、それぞれ熔融、成形し、板状に加工した。これらガラス板は、対向する2つの平面を有する。2つの平面は互いに平行であり、光学研磨されている。2つの平面の間隔は10.0mmとした。
このようなガラス板を使用し、分光透過率を測定した。上記の対向する2つの平面に垂直に光を入射し、波長をスキャンしながら、ガラス板に入射する入射光の強度とガラス板を透過した透過光の強度の比(透過光の強度/入射光の強度)を算出し、ガラス板の分光透過率曲線を得た。これら2種類のガラスの厚さ10.0mmにおける分光透過率曲線を図1、図2にそれぞれ示す(図1:ガラスA、図2:ガラスB)。 (Examination of the influence of Yb on the transmittance in the near infrared region)
A glass having a composition shown in Table 102 below (hereinafter referred to as “glass A”) and a glass having a composition shown in Table 103 (hereinafter referred to as “glass B”) were respectively melted and molded. And processed into a plate shape. These glass plates have two opposing flat surfaces. The two planes are parallel to each other and are optically polished. The distance between the two planes was 10.0 mm.
Using such a glass plate, the spectral transmittance was measured. The ratio of the intensity of the incident light incident on the glass plate and the intensity of the transmitted light transmitted through the glass plate while scanning the wavelength while vertically incident light on the two opposing planes (transmitted light intensity / incident light Intensity) was obtained, and a spectral transmittance curve of the glass plate was obtained. Spectral transmittance curves of these two types of glass at a thickness of 10.0 mm are shown in FIGS. 1 and 2, respectively (FIG. 1: glass A, FIG. 2: glass B).
図1に示されているように、質量%表示のガラス組成においてYb2O3を0.1質量%含み、カチオン%表示のガラス組成においてYb3+を0.04カチオン%含むガラスAでは、波長950nm付近を中心とするYbの光吸収により、この付近の透過率が低下している。
また、図2に示されているように、質量%表示のガラス組成においてYb2O3を3.68質量%含み、カチオン%表示のガラス組成においてYb3+を2.00カチオン%含むガラスBでは、波長960nm付近を中心とするYbの光吸収により、この付近の透過率が大幅に低下する。
このように、Ybの含有量の増加に伴い、ガラスの近赤外域における透過率は大幅に低下するため、可視域から近赤外域にわたり高い透過率を求められる用途に用いられるガラスとしては、Ybを多く含むガラスは適していない。 Since the glass B does not contain Y 2 O 3 in the glass composition expressed by mass%, the mass ratio (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is as described above. The glass is out of range. Further, since glass B does not contain Y 3+ in the glass composition represented by cation%, the cation ratio (Y 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) is outside the above range. It is glass. Accordingly, the glass B is does not correspond to the glass 2 in the glass 1 according to one embodiment of the present invention described above, increase or decrease the absorption of near-infrared region according to the magnitude of the Yb content, Y 2 O 3 And does not depend on the presence or absence of Y 3+ . Therefore, by comparing the glass A and the glass B, it is possible to confirm the influence of Yb on the transmittance in the near infrared region.
As shown in FIG. 1, in a glass A containing 0.1% by mass of Yb 2 O 3 in a glass composition represented by mass% and containing 0.04 cation% Yb 3+ in a glass composition represented by cation%, Due to the light absorption of Yb centered around the wavelength of 950 nm, the transmittance in the vicinity thereof is lowered.
Further, as shown in FIG. 2, glass B containing 3.68% by mass of Yb 2 O 3 in the glass composition represented by mass% and glass composition containing 2.00% cation Yb 3+ in the glass composition represented by cation%. Then, due to the light absorption of Yb centered around the wavelength of 960 nm, the transmittance in the vicinity thereof is greatly reduced.
As described above, as the Yb content increases, the transmittance in the near infrared region of the glass is greatly reduced. Therefore, as a glass used for applications requiring high transmittance from the visible region to the near infrared region, Yb Glass that contains a lot of is not suitable.
特許文献6(特開2009-203083号公報)の実施例4のガラスを再現することを試みたが、ガラス作製中に結晶化した。これは、このガラスは、質量%表示のガラス組成において質量比(B2O3/(B2O3+SiO2))が1であり、カチオン%表示のガラス組成においてカチオン比(B3+/(B3++Si4+))が1であるため熱的安定性が低いことに起因するものと考えられる。 (Comparative Example 1)
An attempt was made to reproduce the glass of Example 4 of Patent Document 6 (Japanese Patent Application Laid-Open No. 2009-203083), but it crystallized during glass production. This is because the glass has a mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) of 1 in the glass composition of mass%, and the cation ratio (B 3+ / Since (B 3+ + Si 4+ )) is 1, it is considered that the thermal stability is low.
特許文献5(特開昭55-121925号公報)の実施例28のガラス(以下、「ガラスC」と記載する。)を再現し、上記方法によりλ5を測定したところ、348nmであった。
ガラスCを用いて球面レンズを作製した。次に、この球面レンズの凸状の球面と他種の光学ガラスからなる球面レンズの凹状の球面とを接合面として、光学素子接合用の紫外線硬化型接着剤を塗布し、実施例5と同様に接合レンズの作製を試みた。しかし、接合面に塗布した紫外線硬化型接着剤に、ガラスCからなるレンズを通して紫外線を照射したところ、ガラスCの紫外線透過率が低いため、接着剤を充分に硬化することができなかった。 (Comparative Example 2)
The glass of Example 28 (hereinafter referred to as “glass C”) in Patent Document 5 (Japanese Patent Laid-Open No. 55-121925) was reproduced, and λ5 was measured by the above method to be 348 nm.
A spherical lens was produced using glass C. Next, using the convex spherical surface of this spherical lens and the concave spherical surface of a spherical lens made of another type of optical glass as a bonding surface, an ultraviolet curable adhesive for optical element bonding was applied and the same as in Example 5 An attempt was made to produce a cemented lens. However, when the ultraviolet curable adhesive applied to the bonding surface was irradiated with ultraviolet rays through a lens made of glass C, the adhesive could not be sufficiently cured because the ultraviolet transmittance of glass C was low.
特許文献17(特開2002-284542号公報)の実施例7のガラスは、質量比(Gd2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))が0.09、質量比(B2O3/(B2O3+SiO2))が0.92である。このガラスについて、La2O3、Y2O3、Gd2O3以外の成分の含有量を一定とし、Gd2O3の一部または全部をLa2O3とY2O3へ置換したときの、ガラスの熱的安定性の変化を検証した。
まず、酸化物基準のガラス組成として、5.15質量%含まれているGd2O3を0%とし、Gd2O3含有量の減少量5.15質量%をLa2O3の含有量とY2O3の含有量に応じてLa2O3とY2O3へそれぞれ配分した。具体的には、5.15質量%×((La2O3の含有量/(La2O3の含有量とY2O3の含有量との合計含有量))として算出される4.09質量%をGd2O3からLa2O3へ置換し、5.15質量%×((Y2O3の含有量/(La2O3の含有量とY2O3と合計含有量))として算出される1.06質量%をGd2O3からY2O3へ置換した。この組成を、以下において「組成a」と記載する。
次に、5.15質量%含まれているGd2O3を3質量%に減量し、Gd2O3含有量の減少量2.15質量%をLa2O3の含有量とY2O3の含有量に応じてそれぞれLa2O3とY2O3へ配分した。具体的には、2.15質量%×((La2O3の含有量/(La2O3の含有量とY2O3との合計含有量))として算出される1.71質量%をGd2O3からLa2O3へ置換し、5.15質量%×((Y2O3の含有量/(La2O3の含有量とY2O3との合計含有量))として算出される0.44質量%をGd2O3からY2O3へ置換した。この組成を、以下において「組成b」と記載する。
特許文献17の実施例7の組成、「組成a」および「組成b」を表104に示す。 (Comparative Example 3)
The glass of Example 7 of Patent Document 17 (Japanese Patent Laid-Open No. 2002-284542) has a mass ratio (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) of 0. 09 and the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.92. This glass, La 2 O 3, Y 2 O 3, Gd 2 O 3 other than the content of the component constant, by substituting a part or all of Gd 2 O 3 to La 2 O 3 and Y 2 O 3 The change in the thermal stability of the glass was verified.
First, as an oxide-based glass composition, 5.15% by mass of Gd 2 O 3 is 0%, and the decrease in Gd 2 O 3 content is 5.15% by mass of La 2 O 3 . And Y 2 O 3 were distributed to La 2 O 3 and Y 2 O 3 , respectively. Specifically, it is calculated as 5.15% by mass × ((La 2 O 3 content / (La 2 O 3 content and Y 2 O 3 content)) ”. 09 wt% was replaced by Gd 2 O 3 to La 2 O 3, 5.15 wt% × ((amount of Y 2 O 3 / (content of La 2 O 3 and Y 2 O 3 and the total content )) Was replaced by 1.06% by mass from Gd 2 O 3 to Y 2 O 3. This composition is hereinafter referred to as “composition a”.
Next, Gd 2 O 3 contained in 5.15% by mass is reduced to 3% by mass, and the decrease in Gd 2 O 3 content is 2.15% by mass with the content of La 2 O 3 and Y 2 O. respectively in accordance with the content of 3 it was allocated to La 2 O 3 and Y 2 O 3. Specifically, 2.15 wt% × ((amount of La 2 O 3 / (total content of the content and the Y 2 O 3 of La 2 O 3)) 1.71 mass% calculated as was replaced from Gd 2 O 3 to La 2 O 3, 5.15 wt% × ((amount of Y 2 O 3 / (total content of the content and the Y 2 O 3 of La 2 O 3)) As a result, 0.44% by mass was substituted from Gd 2 O 3 to Y 2 O 3. This composition is hereinafter referred to as “composition b”.
Table 104 shows the composition, “Composition a”, and “Composition b” of Example 7 of Patent Document 17.
以上の結果は、質量比(B2O3/(B2O3+SiO2))が先に記載した範囲を超えるガラス組成において、Gd2O3含有量を低下させると熱的安定性が低下することを示す結果と考えられる。 Using 150 g of glass having the compositions a and b, a glass was produced according to the method described in the example of Patent Document 17, and the molten glass was poured into a mold to form a peripheral part of the glass, that is, by contact with the mold. Although no crystal deposition was observed in the rapidly cooled portion, a large number of crystals were deposited in the central portion of the glass, that is, in the portion where the cooling speed was lower than that in the peripheral portion. In addition, when the glass of the Example described previously was produced by the same method, the precipitation of the crystal | crystallization was not recognized not only the periphery part of glass but the whole.
The above results show that in the glass composition where the mass ratio (B 2 O 3 / (B 2 O 3 + SiO 2 )) exceeds the previously described range, the thermal stability decreases when the Gd 2 O 3 content is decreased. It is thought that it is the result which shows doing.
特許文献17(特開2002-284542号公報)の実施例7のガラスは、カチオン比(Gd3+/(La3++Y3++Gd3++Yb3+))が0.08、カチオン比(B3+/(B3++Si4+))が0.95である。このガラスについて、La3+、Y3+、Gd3+以外の成分の含有量を一定とし、Gd3+の一部または全部をLa3+とY3+へ置換したときの、ガラスの熱的安定性の変化を検証した。
まず、2.31カチオン%含まれているGd3+を0%とし、Gd3+含有量の減少量2.31カチオン%をLa3+の含有量とY3+の含有量に応じてそれぞれLa3+とY3+へ配分した。具体的には、2.31カチオン%×((La3+の含有量/(La3+の含有量とY3+の含有量との合計含有量))として算出される1.68カチオン%をGd3+からLa3+へ置換し、2.31カチオン%×((Y3+の含有量/(La3+の含有量とY3+と合計含有量))として算出される0.63カチオン%をGd3+からY3+へ置換した。この組成を、以下において「組成c」と記載する。
次に、2.31カチオン%含まれているGd3+を1.5カチオン%に減量し、Gd3+含有量の減少量0.81カチオン%をLa3+の含有量とY3+の含有量に応じてLa3+とY3+へそれぞれ配分した。具体的には、0.81カチオン%×((La3+の含有量/(La3+の含有量とY3+との合計含有量))として算出される0.59カチオン%をLa3+へ置換し、0.81カチオン%×((Y3+の含有量/(La3+の含有量とY3+との合計含有量))として算出される0.22カチオン%をY3+へ置換した。この組成を、以下において「組成d」と記載する。
特許文献17の実施例7の組成、「組成c」および「組成d」を表105に示す。 (Comparative Example 4)
The glass of Example 7 of Patent Document 17 (Japanese Patent Laid-Open No. 2002-284542) has a cation ratio (Gd 3+ / (La 3+ + Y 3+ + Gd 3+ + Yb 3+ )) of 0.08 and a cation ratio ( B 3+ / (B 3+ + Si 4+ )) is 0.95. This glass, La 3+, Y 3+, and a constant content of components other than Gd 3+, when replacing a part or all of Gd 3+ into La 3+ and Y 3+, glass heat The change of mechanical stability was verified.
First, Gd 3+ contained in 2.31 cation% is set to 0%, and the decrease in Gd 3+ content is 2.31 cation% according to La 3+ content and Y 3+ content, respectively. Allocated to La 3+ and Y 3+ . Specifically, 1.31 cation% calculated as 2.31 cation% × ((La 3+ content / (La 3+ content and Y 3+ content)) ”. Is replaced by Gd 3+ to La 3+ and calculated as 2.31 cation% × ((Y 3+ content / (La 3+ content and Y 3+ and total content)). 63 cation% was replaced from Gd 3+ to Y 3+ , and this composition is referred to as “Composition c” below.
Then it reduced the Gd 3+ contained 2.31 cations% to 1.5 cation%, the content of La 3+ the decrease 0.81 cations% of Gd 3+ content and the Y 3+ It distributed to La3 + and Y3 + according to content. Specifically, 0.81 cationic% × ((0.59 cations% calculated as content / (La 3+ content and total content of Y 3+)) of La 3+ La 3 substituted to +, 0.81 cations% × ((Y 3+ content / (0.22 cations% calculated as the total amount)) of the content of La 3+ and Y 3+ Y 3 of + was replaced to. the composition, referred to as "composition d" in the following.
Table 105 shows the composition, “composition c”, and “composition d” of Example 7 of Patent Document 17.
以上の結果は、カチオン比(B3+/(B3++Si4+))が先に記載した範囲を超えるガラス組成において、Gd3+含有量を低下させると熱的安定性が低下することを示す結果と考えられる。 Using 150 g of glass having compositions c and d, a glass was produced according to the method described in the example of Patent Document 17, and the molten glass was poured into a mold to form a peripheral part of the glass, that is, by contact with the mold. Although no crystal deposition was observed in the rapidly cooled portion, a large number of crystals were deposited in the central portion of the glass, that is, in the portion where the cooling speed was lower than that in the peripheral portion. In addition, when the glass of the Example described previously was produced by the same method, the precipitation of the crystal | crystallization was not recognized not only the periphery part of glass but the whole.
The above results show that the thermal stability decreases when the Gd 3+ content is decreased in a glass composition whose cation ratio (B 3+ / (B 3+ + Si 4+ )) exceeds the range described above. This is considered to be a result.
例えば、上述の例示されたガラス組成に対し、明細書に記載の組成調整を行うことにより、本発明の一態様にかかるガラスを得ることができる。
また、明細書に例示または好ましい範囲として記載した事項の2つ以上を任意に組み合わせることは、もちろん可能である。
また、あるガラスが、ガラス1およびガラス2の両方に該当することもある。 The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
For example, the glass concerning 1 aspect of this invention can be obtained by performing the composition adjustment as described in the specification with respect to the glass composition illustrated above.
Of course, it is possible to arbitrarily combine two or more of the matters described as examples or preferred ranges in the specification.
A certain glass may correspond to both the glass 1 and the glass 2.
Claims (8)
- 質量%表示にて、
B2O3とSiO2との合計含有量が15~35質量%、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量が45~65質量%、但し、Yb2O3含有量が3質量%以下であり、
ZrO2含有量が3~11質量%、
Ta2O5含有量が5質量%以下、
B2O3とSiO2との合計含有量に対するB2O3含有量の質量比(B2O3/(B2O3+SiO2))が0.4~0.900、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するB2O3およびSiO2の合計含有量の質量比((B2O3+SiO2)/(La2O3+Y2O3+Gd2O3+Yb2O3))が0.42~0.53、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するY2O3含有量の質量比(Y2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))が0.05~0.45、
La2O3、Y2O3、Gd2O3およびYb2O3の合計含有量に対するGd2O3含有量の質量比(Gd2O3/(La2O3+Y2O3+Gd2O3+Yb2O3))が0~0.05、
Nb2O5、TiO2、Ta2O5およびWO3の合計含有量に対するNb2O5含有量の質量比(Nb2O5/(Nb2O5+TiO2+Ta2O5+WO3))が0.5~1、
であり、屈折率ndが1.800~1.850の範囲であり、かつアッベ数νdが41.5~44である酸化物ガラスであるガラス。 In mass% display
The total content of B 2 O 3 and SiO 2 is 15 to 35% by mass,
The total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 is 45 to 65% by mass, provided that the Yb 2 O 3 content is 3% by mass or less,
ZrO 2 content is 3 to 11% by mass,
Ta 2 O 5 content is 5% by mass or less,
The mass ratio of B 2 O 3 content to the total content of B 2 O 3 and SiO 2 (B 2 O 3 / (B 2 O 3 + SiO 2 )) is 0.4-0.900,
Mass ratio of the total content of B 2 O 3 and SiO 2 to the total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 ((B 2 O 3 + SiO 2 ) / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.42 to 0.53,
Mass ratio of Y 2 O 3 content to total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (Y 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0.05 to 0.45,
Mass ratio of Gd 2 O 3 content to total content of La 2 O 3 , Y 2 O 3 , Gd 2 O 3 and Yb 2 O 3 (Gd 2 O 3 / (La 2 O 3 + Y 2 O 3 + Gd 2 O 3 + Yb 2 O 3 )) is 0 to 0.05,
Mass ratio of Nb 2 O 5 content to the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 (Nb 2 O 5 / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) 0.5-1
A glass which is an oxide glass having a refractive index nd of 1.800 to 1.850 and an Abbe number νd of 41.5 to 44. - Nb2O5、TiO2、Ta2O5およびWO3の合計含有量に対するZnO含有量の質量比(ZnO/(Nb2O5+TiO2+Ta2O5+WO3))が0.1~3の範囲である請求項1に記載のガラス。 The mass ratio of ZnO content to the total content of Nb 2 O 5 , TiO 2 , Ta 2 O 5 and WO 3 (ZnO / (Nb 2 O 5 + TiO 2 + Ta 2 O 5 + WO 3 )) is 0.1 to 3 The glass according to claim 1, which is in the range of
- 着色度λ5が335nm以下である請求項1または2に記載のガラス。 The glass according to claim 1 or 2, wherein the coloring degree λ5 is 335 nm or less.
- 比重dと屈折率ndとが、下記(A)式:
d/(nd-1)≦5.70 …(A)
を満たす請求項1~3のいずれか1項に記載のガラス。 Specific gravity d and refractive index nd are expressed by the following formula (A):
d / (nd-1) ≦ 5.70 (A)
The glass according to any one of claims 1 to 3, which satisfies: - ガラス転移温度が640℃以上である請求項1~4のいずれか1項に記載のガラス。 The glass according to any one of claims 1 to 4, which has a glass transition temperature of 640 ° C or higher.
- 請求項1~5のいずれか1項に記載のガラスからなるプレス成形用ガラス素材。 A glass material for press molding comprising the glass according to any one of claims 1 to 5.
- 請求項1~5のいずれか1項に記載のガラスからなる光学素子ブランク。 An optical element blank made of the glass according to any one of claims 1 to 5.
- 請求項1~5のいずれか1項に記載のガラスからなる光学素子。 An optical element made of the glass according to any one of claims 1 to 5.
Priority Applications (2)
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CN (2) | CN108715512B (en) |
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CN109956666B (en) * | 2017-12-22 | 2023-01-06 | Hoya株式会社 | Optical glass and optical element |
CN109734304B (en) * | 2019-03-28 | 2021-12-07 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
CN115304269A (en) * | 2022-08-26 | 2022-11-08 | 成都光明光电股份有限公司 | Optical glass |
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JP4017832B2 (en) * | 2001-03-27 | 2007-12-05 | Hoya株式会社 | Optical glass and optical components |
JP2006111482A (en) * | 2004-10-14 | 2006-04-27 | Konica Minolta Opto Inc | Optical glass and optical element |
JP5180758B2 (en) * | 2008-09-30 | 2013-04-10 | Hoya株式会社 | Optical glass, glass gob for press molding, optical element, manufacturing method thereof, and manufacturing method of optical element blank |
US8661853B2 (en) * | 2008-11-10 | 2014-03-04 | Hoya Corporation | Method for producing glass, optical glass, glass material for press molding, optical element and methods for producing same |
CN101935164B (en) * | 2009-06-30 | 2014-12-10 | 株式会社小原 | Optical glass, preforming material and optical element |
DE102009047511A1 (en) * | 2009-12-04 | 2011-06-09 | Schott Ag | High-refractive and highly transparent optical glass |
JP5827067B2 (en) * | 2010-08-23 | 2015-12-02 | 株式会社オハラ | Optical glass and optical element |
CN107285622A (en) * | 2011-12-20 | 2017-10-24 | 株式会社小原 | Optical glass and optical element |
TWI659004B (en) * | 2013-04-05 | 2019-05-11 | 日商小原股份有限公司 | Optical glass, preforms and optical components |
JP6086804B2 (en) * | 2013-04-30 | 2017-03-01 | 株式会社オハラ | Optical glass, preform and optical element |
JP5979723B2 (en) * | 2013-07-31 | 2016-08-31 | 株式会社オハラ | Optical glass and optical element |
CN104341101A (en) * | 2013-07-31 | 2015-02-11 | 株式会社小原 | Optical glass, preform material and optical element |
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JPS56100151A (en) * | 1980-01-08 | 1981-08-11 | Fuji Photo Film Co Ltd | Tantalum oxide-free optical glass of high refraction |
JPS5756344A (en) * | 1980-09-18 | 1982-04-03 | Ohara Inc | Optical glass |
JP2014088321A (en) * | 2007-04-09 | 2014-05-15 | Olympus Corp | Optical glass and optical device using the same |
JP2015127276A (en) * | 2013-12-27 | 2015-07-09 | 株式会社オハラ | Optical glass |
JP2015127277A (en) * | 2013-12-27 | 2015-07-09 | 株式会社オハラ | Manufacturing method for optical glass |
Also Published As
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JP2023085359A (en) | 2023-06-20 |
CN107207320B (en) | 2018-08-07 |
JP6291598B2 (en) | 2018-03-14 |
JP2021008397A (en) | 2021-01-28 |
JP2022050507A (en) | 2022-03-30 |
CN108715512B (en) | 2021-05-04 |
TWI671270B (en) | 2019-09-11 |
TWI641572B (en) | 2018-11-21 |
JP6812382B2 (en) | 2021-01-13 |
JP7250106B2 (en) | 2023-03-31 |
JP7514351B2 (en) | 2024-07-10 |
JP2018104283A (en) | 2018-07-05 |
JPWO2016114274A1 (en) | 2017-12-14 |
CN107207320A (en) | 2017-09-26 |
TW201904900A (en) | 2019-02-01 |
TW201641456A (en) | 2016-12-01 |
JP7003198B2 (en) | 2022-01-20 |
CN108715512A (en) | 2018-10-30 |
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