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CN103313947A - Optical glass, preform, and optical element - Google Patents

Optical glass, preform, and optical element Download PDF

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Publication number
CN103313947A
CN103313947A CN2012800055094A CN201280005509A CN103313947A CN 103313947 A CN103313947 A CN 103313947A CN 2012800055094 A CN2012800055094 A CN 2012800055094A CN 201280005509 A CN201280005509 A CN 201280005509A CN 103313947 A CN103313947 A CN 103313947A
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Prior art keywords
composition
glass
opticglass
oxide compound
converts
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Chinese (zh)
Inventor
巴广明
桃野净行
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Ohara Inc
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Ohara Inc
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Application filed by Ohara Inc filed Critical Ohara Inc
Priority to CN201711159798.4A priority Critical patent/CN107879621A/en
Publication of CN103313947A publication Critical patent/CN103313947A/en
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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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Provided are an optical glass which has a refractive index (nd) and an Abbe number (vd) in respective desired ranges and, despite this, is suitable for use in correcting chromatic aberration and a lens preform obtained using the optical glass. The optical glass comprises, with respect to the total mass of the glass in terms of oxide composition in mass%, 1.0-31.0% B2O3 component, 40.0-65.0% Ln2O3 component, up to 30.0% TiO2 component, and up to 30.0% Nb2O5 component. The lens preform comprises this optical glass as the base material.

Description

Opticglass, preform and optical element
Technical field
The present invention relates to opticglass, preform and optical element.
Background technology
Optics such as digital camera, pick up camera system comprises the bleeding that is called as aberration that varies in size.This aberration is classified as monochromatic aberration and chromatic aberation, and especially the material behavior of the lens that use in chromatic aberation and the optics system is closely related.Here, in order to improve chromatic aberation, wish the high-refractivity and low-dispersion zone opticglass partial dispersion than (θ g, F) little.
Partial dispersion is than (θ g is F) with following formula (1) expression.
θg，F＝（n g-n F）/（n F-n C）······（1）
For opticglass, the partial dispersion of the partial dispersion in expression short wavelength zone than (θ g, F) and Abbe number (ν d) between have the relation of substantial linear.The straight line of representing this relation be used in partial dispersion than (θ g, F) be the longitudinal axis, with Abbe number (ν d) for partial dispersion that connect to mark and draw NSL7 and PBM2 on the rectangular coordinates of transverse axis when 2 straight lines that obtain of Abbe number represent that this straight line is called as standard lines (Fig. 1 with reference to).According to the difference of opticglass manufacturers and difference, but each company all defines with about equally slope and intercept as the normal glass of the benchmark of standard lines.(NSL7 and PBM2 are the opticglass that Kabushiki Kaisya Ohara makes, the Abbe number (ν of PBM2 d) be 36.3, partial dispersion is than (θ g F) is the Abbe number (ν of 0.5828, NSL7 d) be 60.5, partial dispersion is than (θ g is 0.5436 F).）
Here, as the high refractive index (n that has more than 1.80 d) and 30 following low Abbe number (ν d) glass, for example known to the more La that contains shown in the patent documentation 1～6 2O 3Become the opticglass of the rare earth elements that grades.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 60-033229 communique
Patent documentation 2: TOHKEMY 2005-179142 communique
Patent documentation 3: Japanese kokai publication sho 60-131845 communique
Patent documentation 4: TOHKEMY 2006-137645 communique
Patent documentation 5: TOHKEMY 2007-022846 communique
Patent documentation 6: TOHKEMY 2007-112697 communique
Summary of the invention
The problem that invention will solve
Yet for the opticglass of patent documentation 1～6, in having the glass of high refractive index, although have low chromatic dispersion, partial dispersion is than big, and it is inadequate using as the lens of proofreading and correct aforementioned secondary spectrum.That is, need have high refractive index (n d) and big Abbe number (ν d) and partial dispersion than (θ g, F) little opticglass.
The present invention makes in view of the above problems, and its purpose is, obtains specific refractory power (n d) and Abbe number (ν d) in target zone, can be preferred for chromatic aberation correction opticglass and use its lens preform.
For the scheme of dealing with problems
The inventor etc. have carried out deep experimental study repeatedly in order to solve above-mentioned problem, found that, by at B 2O 3Composition and rare earth elements (are used Ln 2O 3Composition is represented) in be used in combination TiO 2Composition and Nb 2O 5Composition, can obtain to have high refractive index and low chromatic dispersion and partial dispersion than little, to the high and low glass of liquidus temperature of the transparency of visible light, thereby finished the present invention.Particularly, the invention provides following technical scheme.
(1) a kind of opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains 1.0～31.0% B 2O 3Composition and 18.0～65.0% Ln 2O 3Composition, TiO 2The content of composition is below 30.0%, Nb 2O 5The content of composition is below 30.0%.
(2) according to (1) described opticglass, wherein, the mass ratio Ln of the composition that converts with oxide compound 2O 3/ TiO 2Be (in the formula, Ln is more than one elements that are selected from the group that is made of La, Gd, Y, Yb, Lu) more than 3.00.
(3) according to (1) or (2) described opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains 18.0～60.0% La 2O 3Composition.
(4) according to each the described opticglass in (1)～(3), wherein, with respect to the glass total mass of the composition that converts with oxide compound, quality and (TiO 2+ Nb 2O 5) be more than 8.0% and below 35.0%.
(5) according to each the described opticglass in (1)～(4), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
SiO 2Composition be 0～20.0% and/or
ZrO 2Composition is 0～15.0%.
(6) according to (5) described opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains the SiO more than 1.0% 2Composition.
(7) according to (5) or (6) described opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains the ZrO more than 3.0% 2Composition.
(8) according to each the described opticglass in (1)～(7), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
GeO 2Composition be 0～10.0% and/or
Ta 2O 5Composition is 0～20.0%.
(9) according to (8) described opticglass, wherein, with the mass ratio (GeO in the composition of oxide compound conversion 2+ Ta 2O 5)/(TiO 2+ Nb 2O 5) be below 1.00.
(10) according to each the described opticglass in (1)～(9), wherein, with respect to the glass total mass of the composition that converts with oxide compound, quality and (Nb 2O 5+ Ta 2O 5) be more than 3.0% and below 30.0%.
(11) according to each the described opticglass in (1)～(10), wherein, with the mass ratio TiO in the composition of oxide compound conversion 2/ (Nb 2O 5+ Ta 2O 5) be more than 0.80.
(12) according to each the described opticglass in (1)～(11), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
WO 3Composition be 0～10.0% and/or
SnO 2Composition is 0～5.0%.
(13) according to (12) described opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound contains the WO greater than 0.5% 3Composition.
(14) according to each the described opticglass in (1)～(13), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
Gd 2O 3Composition be 0～30.0% and/or
Y 2O 3Composition be 0～20.0% and/or
Yb 2O 3Composition be 0～6.0% and/or
Lu 2O 3Composition is 0～6.0%.
(15) according to each the described opticglass in (1)～(14), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
The MgO composition be 0～15.0% and/or
The CaO composition be 0～15.0% and/or
The SrO composition be 0～15.0% and/or
The BaO composition be 0～35.0% and/or
The ZnO composition is 0～15.0%.
(16) according to (15) described opticglass, wherein, with respect to the glass total mass of the composition that converts with oxide compound, the quality of RO composition (in the formula, R is more than one elements that are selected from the group of being made up of Mg, Ca, Sr, Ba) and be below 35.0%.
(17) according to each the described opticglass in (1)～(16), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
Li 2The O composition be 0～15.0% and/or
Na 2The O composition be 0～15.0% and/or
K 2The O composition is 0～15.0%.
(18) according to (17) described opticglass, wherein, with respect to the glass total mass of the composition that converts with oxide compound, Rn 2The quality of O composition (in the formula, Rn is more than one elements that are selected from the group of being made up of Li, Na, K) and be below 10.0%.
(19) according to each the described opticglass in (1)～(18), wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
P 2O 5Composition be 0～10.0% and/or
Bi 2O 3Composition be 0～10.0% and/or
TeO 2Composition be 0～10.0% and/or
Al 2O 3Composition be 0～10.0% and/or
Ga 2O 3Composition be 0～10.0% and/or
Sb 2O 3Composition is 0～1.0%.
(20) according to each the described opticglass in (1)～(19), it has the specific refractory power (n more than 1.80 d), and have more than 22 and 30 following Abbe number (ν d).
(21) according to each the described opticglass in (1)～(20), its have below 0.615 partial dispersion than (θ g, F).
(22) a kind of preform material, it is formed by each the described opticglass in (1)～(21).
(23) a kind of optical element, it makes (22) described preform material compression moulding.
(24) a kind of optical element, it is mother metal with each the described opticglass in (1)～(21).
(25) a kind of opticinstrument, it possesses each the described optical element in (23) or (24).
The effect of invention
According to the present invention, can access specific refractory power (n d) and Abbe number (ν d) in target zone, can be preferred for correction and the high opticglass of devitrification resistance of chromatic aberation and the preform and the optical element that use this opticglass.
Description of drawings
Fig. 1 illustrates with partial dispersion than (θ g is that the longitudinal axis, Abbe number (ν d) are the figure of the represented standard lines of the rectangular coordinates of transverse axis F).
Embodiment
About opticglass of the present invention, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains 1.0～31.0% B 2O 3Composition and 40.0～65.0% Ln 2O 3Composition, TiO 2The content of composition is below 30.0%, Nb 2O 5The content of composition is below 30.0%.Contain B by the scope of content with regulation 2O 3Composition and rare earth elements (Ln 2O 3Composition), the partial dispersion of glass ratio diminishes, and the transparency of visible light is improved.In addition, containing the TiO with the effect that increases chromatic dispersion 2Composition and Nb 2O 5Under the situation of composition, by containing the strong rare earth elements of effect that reduces chromatic dispersion, also can obtain having the opticglass of high refractive index and low chromatic dispersion, and the liquidus temperature step-down of glass.Therefore, can access specific refractory power (n d) and Abbe number (ν d) within the limits prescribed, can be preferred for correction and the high opticglass of devitrification resistance of chromatic aberation and the preform and the optical element that use this opticglass.
Below, the embodiment of opticglass of the present invention is elaborated.The present invention is not subjected to any restriction of following embodiment, can suitably change in the scope of purpose of the present invention and implement.Need to prove, for the place that explanation repeats, suitably omit explanation sometimes, but be not the purport that limits invention.
[glass ingredient]
Below explanation constitutes the compositing range of each composition of opticglass of the present invention.In this manual, do not having under the situation about specifying, the content of each composition all uses the quality % with respect to the glass total mass of the composition that converts with oxide compound to represent.Here, the oxide compound that " composition that converts with oxide compound " refers to use as the raw material of glass constituent of the present invention in hypothesis, composite salt, metal fluoride etc. all decompose during in fusion and are changed under the situation of oxide compound, are the composition that each composition that 100 quality % represent in the glass to be contained obtains with the total mass of the oxide compound of this generation.
＜about neccessary composition, arbitrarily composition＞
B 2O 3Composition is at the inner composition that forms network structure, promotes stable glass formation of glass.Particularly by making B 2O 3The content of composition is more than 1.0%, has reduced the liquidus temperature of glass, is difficult to devitrification, can easily obtain stable glass.On the other hand, by making B 2O 3The content of composition is below 31.0%, and specific refractory power becomes and is difficult to reduce, and therefore, can easily obtain targeted refractive index.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, B 2O 3The lower limit of the content of composition is preferably 1.0%, more preferably 3.0%, most preferably is 5.0%, and its upper limit is preferably 31.0%, more preferably 25.0%, more preferably 20.0%, most preferably is 14.0%.B 2O 3Composition can use for example H 3BO 3, Na 2B 4O 7, Na 2B 4O 710H 2O, BPO 4Deng being included in the glass as raw material.
The preferred Ln of opticglass of the present invention 2O 3The quality of the content of composition (in the formula, Ln is more than one elements that are selected from the group of being made up of La, Gd, Y, Yb, Lu) and be more than 18.0% and below 65.0%.Here, by making this quality and being more than 18.0%, can easily obtain high refractive index and the lower part chromatic dispersion ratio of target, and can reduce painted.On the other hand, by making this quality and being below 65.0%, can suppress glass chromatic dispersion reduction and can reduce the devitrification that contains the glass that these compositions cause because of excessive.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Ln 2O 3The quality of the content of composition and lower limit be preferably 18.0%, more preferably 30.0%, more preferably 40.0%, most preferably be 45.0%, its upper limit is preferably 65.0%, more preferably 62.0%, most preferably is 60.0%.
TiO 2Composition is the composition that improves specific refractory power and the chromatic dispersion of glass and improve the devitrification resistance of glass.Particularly by making TiO 2The content of composition is below 30.0%, can suppress glass the partial dispersion ratio rising and make visible light short wavelength's (500nm following) transmittance be difficult for variation.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, TiO 2The upper limit of the content of composition is preferably 30.0%, more preferably 25.0%, more preferably 22.0%, most preferably is 20.0%.TiO 2Composition can use for example TiO 2Deng being included in the glass as raw material.On the other hand, by containing TiO 2Composition can access optical constant and the devitrification resistance of target.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, TiO 2The lower limit of the content of composition is preferably 5.0%, more preferably 6.6%, more preferably 8.0%, most preferably is 10.0%.
Nb 2O 5Composition is the composition that improves specific refractory power and the chromatic dispersion of glass and improve the devitrification resistance of glass.Particularly by making Nb 2O 5The content of composition is below 30.0%, can suppress because of the excessive Nb of containing 2O 5The rising of composition and the devitrification that causes and the partial dispersion ratio that can suppress glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Nb 2O 5The upper limit of the content of composition is preferably 30.0%, more preferably 25.0%, more preferably 20.0%, most preferably is 15.0%.On the other hand, by containing Nb 2O 5Composition can access optical constant and the devitrification resistance of target.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Nb 2O 5The lower limit of the content of composition is preferably 1.0%, more preferably 2.0%, more preferably 3.0%, most preferably is 3.8%.Nb 2O 5Composition can use for example Nb 2O 5Deng being included in the glass as raw material.
For opticglass of the present invention, preferably, Ln 2O 3The content of composition is with respect to TiO 2The ratio of the content of composition is more than 3.00.Thus, can keep liquidus temperature and raising stability and the minimizing glass coloring of high refractive index, reduction glass.Therefore, the mass ratio Ln of the composition that converts with oxide compound 2O 3/ TiO 2Lower limit be preferably 3.00, more preferably 3.20, most preferably be 3.40.On the other hand, the upper limit of this mass ratio for example mostly is below 10.00, more specifically, mostly is below 8.00, more particularly, mostly is below 6.00.
La 2O 3Composition is the composition that improves the specific refractory power of glass and reduce chromatic dispersion.Particularly by making La 2O 3The content of composition is more than 18.0%, can easily obtain having high refractive index and lower part chromatic dispersion ratio and the glass high to the transmitance of visible light.On the other hand, by making La 2O 3The content of composition is below 60.0%, and the chromatic dispersion that can suppress glass exceeds needs ground and reduces, also suppresses because of the excessive La of containing 2O 3Composition and the rising of the liquidus temperature that causes.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, La 2O 3The lower limit of the content of composition is preferably 18.0%, more preferably 25.0%, lower limit more preferably 28.0%, most preferably be 31.0%, its upper limit is preferably 60.0%, more preferably 58.0%, most preferably is 55.0%.La 2O 3Composition can use for example La 2O 3, La(NO 3) 3XH 2O(X is integer arbitrarily) etc. be included in the glass as raw material.
In addition, for opticglass of the present invention, preferably, TiO 2Composition and Nb 2O 5The quality of composition and be more than 8.0% and below 35.0%.Particularly by making this quality and being more than 3.0%, can easily obtain the high refractive index of target.On the other hand, by making this quality and being below 35.0%, can suppress because of the excessive rising that contains the chromatic dispersion that these compositions cause, and can suppress the reduction of the stability of glass, further improve the devitrification resistance of glass.In addition, because the rising of the partial dispersion ratio of glass is suppressed, therefore, can access the glass of the lower part chromatic dispersion ratio with target.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, quality and (TiO 2+ Nb 2O 5) lower limit be preferably 8.0%, more preferably 11.5%, most preferably be 15.0%, its upper limit is preferably 35.0%, more preferably 30.0%, most preferably is 25.0%.
SiO 2Composition is to improve the viscosity of melten glass and reduce the liquidus temperature of glass, the composition of inhibition devitrification (generation of crystallisate), is any composition in the opticglass of the present invention.Particularly by making SiO 2The content of composition is below 20.0%, can avoid the fusion under the high temperature, and can suppress the reduction of the specific refractory power of glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, SiO 2The upper limit of the content of composition is preferably 20.0%, more preferably 14.0%, more preferably 10.0%, most preferably is 7.0%.Need to prove, also can not contain SiO 2Composition, but by containing SiO 2Composition can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, SiO 2The lower limit of the content of composition is preferably greater than 0%, and more preferably 1.0%, more preferably 3.0%, most preferably greater than 4.0%.SiO 2Composition can use for example SiO 2, K 2SiF 6, Na 2SiF 6Deng being included in the glass as raw material.
ZrO 2Composition is the specific refractory power that improves glass, reduce the liquidus temperature of glass and improve the composition of devitrification resistance, is any composition in the opticglass of the present invention.Particularly by making ZrO 2The content of composition is below 15.0%, can suppress the reduction of Abbe number of glass and the fusion under the high temperature when avoiding glass to make, the energy waste when reducing glass and making.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, ZrO 2The upper limit of the content of composition is preferably 15.0%, more preferably 10.0%, most preferably is 8.0%.Need to prove ZrO 2The content of composition also can be 0%, by containing ZrO 2Composition, the liquidus temperature step-down of glass thus, can easily improve devitrification resistance.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, ZrO 2The lower limit of the content of composition is preferably greater than 0%, more preferably 1.0%, more preferably 3.0%, most preferably be 4.2%.ZrO 2Composition can use for example ZrO 2, ZrF 4Deng being included in the glass as raw material.
GeO 2Composition is to have the specific refractory power that improves glass, the composition that improves the effect of devitrification resistance, is any composition in the opticglass of the present invention.But, GeO 2The cost of material height of composition, therefore, it is measured for a long time, and material cost uprises, and therefore, the glass that obtains becomes impracticable.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, GeO 2The upper limit of the content of composition is preferably 10.0%, more preferably 5.0%, more preferably 3.0%, most preferably is 2.0%.GeO 2Composition can use for example GeO 2Deng being included in the glass as raw material.
Ta 2O 5Composition is to improve the specific refractory power of glass and reduce the liquidus temperature of glass, the composition of raising devitrification resistance, is any composition in the opticglass of the present invention.Particularly by making Ta 2O 5The content of composition is below 20.0%, can reduce the material cost of glass and avoid fusion, the energy waste when reducing glass and making under the high temperature.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Ta 2O 5The upper limit of the content of composition is preferably 20.0%, more preferably 15.0%, more preferably 10.0%, most preferably is 5.0%.Ta 2O 5Composition can use for example Ta 2O 5Deng being included in the glass as raw material.
In addition, for opticglass of the present invention, preferably, GeO 2Composition and Ta 2O 5The quality of composition and with respect to TiO 2Composition and Nb 2O 5The quality of composition and ratio be below 1.00.Thus, can reduce the especially GeO of costliness in the composition that improves specific refractory power 2Composition and Ta 2O 5Therefore the content of composition, can reduce the material cost of opticglass.Therefore, with the mass ratio (GeO in the composition of oxide compound conversion 2+ Ta 2O 5)/(TiO 2+ Nb 2O 5) the upper limit be preferably 1.00, more preferably 0.80, most preferably be 0.50.
In addition, for opticglass of the present invention, preferably, Nb 2O 5Composition and Ta 2O 5The quality of composition and be more than 3.0% and below 30.0%.Quality by making these compositions and in the scope more than 3.0% and below 30.0%, therefore the liquidus temperature step-down of glass, can easily obtain the higher opticglass of devitrification resistance.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, quality and (Nb 2O 5+ Ta 2O 5) lower limit be preferably 3.0%, more preferably 3.5%, most preferably be 3.8%, its upper limit is preferably 30.0%, more preferably 20.0%, most preferably is 15.0%.
In addition, for opticglass of the present invention, preferably, TiO 2The content of composition is with respect to Nb 2O 5Composition and Ta 2O 5The ratio of the content sum of composition is more than 0.80.Thus, can improve the stability of glass, and, can access higher specific refractory power.Therefore, the mass ratio TiO of the composition that converts with oxide compound 2/ (Nb 2O 5+ Ta 2O 5) lower limit be preferably 0.80, more preferably 1.20, more preferably 1.78.Particularly from can easily realizing the low liquidus temperature aspect consideration below 1160 ℃, more preferably be limited to 2.05 down.On the other hand, the upper limit of this mass ratio for example mostly is below 10.00, more specifically, mostly is below 8.00, more particularly, mostly is below 5.00.
WO 3Composition is the liquidus temperature that reduces glass, the composition that improves devitrification resistance, and is to improve the specific refractory power of glass and the composition of chromatic dispersion, is any composition in the opticglass of the present invention.Particularly by making WO 3The content of composition is below 10.0%, can suppress glass the partial dispersion ratio rising and can make visible light short wavelength's (500nm following) transmittance be difficult for variation.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, WO 3The upper limit of the content of composition is preferably 10.0%, more preferably 7.0%, more preferably 5.0%, most preferably is 3.0%.On the other hand, preferably, with respect to the glass total mass of the composition that converts with oxide compound, WO 3The lower limit of the content of composition is preferably greater than 0%, more preferably 0.1%, more preferably 0.5%, most preferably be 0.6%.WO 3Composition can use for example WO 3Deng being included in the glass as raw material.
SnO 2Composition is to reduce the oxidation of melten glass and the composition that makes the melten glass clarification, is any composition in the opticglass of the present invention.Particularly by making SnO 2The content of composition is below 5.0%, can be difficult for taking place the devitrification of painted, the glass of glass that the reduction because of melten glass causes.In addition, because SnO 2The alloying of composition and fusion equipment (particularly precious metal such as Pt) is reduced, and therefore, can realize the long lifetime of the equipment that fuses.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, SnO 2The upper limit of the content of composition is preferably 5.0%, more preferably 3.0%, most preferably is 1.5%.Need to prove SnO 2The content of composition also can be 0%, but by containing the SnO more than 0.1% 2Composition can make glass that the transmitance of visible light is difficult for variation.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, SnO 2The lower limit of the content of composition is preferably 0.1%, more preferably 0.3%, and further preferred content is greater than 0.5%.SnO 2Composition can use for example SnO, SnO 2, SnF 2, SnF 4Deng being included in the glass as raw material.
For opticglass of the present invention, preferably, WO 3The content of composition is with respect to SnO 2The ratio of the content of composition is more than 0.1 and below 3.0.By this ratio is set within the limits prescribed, can access the liquidus temperature of low glass, and can suppress the perviousness of the painted of glass and raising visible light.Therefore, with the mass ratio WO in the composition of oxide compound conversion 3/ SnO 2Lower limit be preferably 0.1, more preferably 0.3, most preferably be 0.5, its upper limit is preferably 3.0, more preferably 2.5, most preferably is 2.0.
Gd 2O 3Composition is the specific refractory power that improves glass, the composition that reduces chromatic dispersion.Particularly by making Gd 2O 3The content of composition is below 30.0%, can suppress the phase-splitting of glass, and can make glass be difficult for devitrification when making glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Gd 2O 3The upper limit of the content of composition is preferably 30.0%, more preferably 28.0%, most preferably is 25.0%.Gd 2O 3Composition can use for example Gd 2O 3, GdF 3Deng being included in the glass as raw material.
Y 2O 3Composition, Yb 2O 3Composition and Lu 2O 3Composition is the specific refractory power that improves glass, the composition that reduces chromatic dispersion.Here, by making Y 2O 3The content of composition is below 20.0% or makes Yb 2O 3Composition or Lu 2O 3The content of composition is below 6.0%, can make glass be difficult for devitrification.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Y 2O 3The upper limit of the content of composition is preferably 20.0%, more preferably 15.0%, more preferably 10.0%, more preferably 9.0%, more preferably 8.0%, more preferably 4.0%, most preferably less than 2.0%.In addition, with respect to the glass total mass of the composition that converts with oxide compound, Yb 2O 3Composition and Lu 2O 3The upper limit of the content of composition is preferably 6.0%, more preferably 2.0%, more preferably 1.5% respectively, most preferably is 1.0%.Y 2O 3Composition, Yb 2O 3Composition and Lu 2O 3Composition can use for example Y 2O 3, YF 3, Yb 2O 3, Lu 2O 3Deng being included in the glass as raw material.
MgO composition, CaO composition, SrO composition and BaO composition are the compositions that improves glass melting and improve devitrification resistance, are any compositions in the opticglass of the present invention.Be below 35.0% by making more than one content in MgO composition, CaO composition or the SrO composition be respectively below 15.0% and/or make the content of BaO composition particularly, can make the specific refractory power of glass be difficult for reducing and make the liquidus temperature of glass be difficult for raising.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, the upper limit of the content of MgO composition, CaO composition and SrO composition is preferably 15.0%, more preferably 10.0% respectively, most preferably is 6.0%.In addition, with respect to the glass total mass of the composition that converts with oxide compound, the upper limit of the content of BaO composition is preferably 35.0%, more preferably 20.0%, more preferably 10.0%, most preferably is 6.0%.MgO composition, CaO composition, SrO composition and BaO composition can use for example MgCO 3, MgF 2, CaCO 3, CaF 2, Sr(NO 3) 2, SrF 2, BaCO 3, Ba(NO 3) 2Deng being included in the glass as raw material.
The ZnO composition is chemical durability, the reduction second-order transition temperature that improves glass and the composition that forms stable glass easily, is any composition in the opticglass of the present invention.Be below 15.0% by the content that makes the ZnO composition particularly, can suppress rising, the raising devitrification resistance of the liquidus temperature of glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, the upper limit of the content of ZnO composition is preferably 15.0%, more preferably 10.0%, more preferably 5.5%.Under the situation of the glass that particularly suppress the photoelastic constant of opticglass lower in desire, the color rendering when obtaining for optical element is high, with respect to the glass total mass of the composition that converts with oxide compound, the content of ZnO composition can be for below 0.08%.The ZnO composition can use for example ZnO, ZnF 2Deng being included in the glass as raw material.
For opticglass of the present invention, preferably, the quality of the content of RO composition (in the formula, R is more than one elements that are selected from the group of being made up of Mg, Ca, Sr, Ba and Zn) and be below 35.0%.Thus, can reduce the devitrification of the glass that causes because of the excessive RO of containing composition and the specific refractory power of glass be difficult for to be reduced.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, the quality of the content of RO composition and the upper limit be preferably 35.0%, more preferably 25.0%, more preferably 15.0%, further be preferably 8.0%, most preferably be 4.7%.
Li 2The O composition is the composition that reduces the partial dispersion ratio of glass, and is the composition that improves glass melting and reduce second-order transition temperature, is any composition in the opticglass of the present invention.Particularly by making Li 2The content of O composition is below 15.0%, can suppress glass specific refractory power reduction and make because of the excessive Li of containing 2O composition and the difficult generations such as devitrification that cause.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Li 2The upper limit of the content of O composition is preferably 15.0%, more preferably 5.0%, more preferably 3.0%, further is preferably 2.0%.Li 2The O composition can use for example Li 2CO 3, LiNO 3, LiF etc. is included in the glass as raw material.
Na 2The O composition is the composition that improves glass melting and reduce second-order transition temperature, is any composition in the opticglass of the present invention.Particularly by making Na 2The content of O composition is below 15.0%, can make the specific refractory power of glass be difficult for to reduce and improve glass stability, make difficult generation such as devitrification.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Na 2The upper limit of the content of O composition is preferably 15.0%, more preferably 5.0%, more preferably 3.0%, most preferably is 2.0%.Na 2The O composition can use for example Na 2CO 3, NaNO 3, NaF, Na 2SiF 6Deng being included in the glass as raw material.
K 2The O composition is the composition that improves glass melting and reduce second-order transition temperature, is any composition in the opticglass of the present invention.Be 15.0% by the content that makes the K2O composition particularly, can suppress the rising of the partial dispersion ratio of glass.In addition, by making K 2The content of O composition is below 15.0%, can make the specific refractory power of glass be difficult for to reduce and improve glass stability, make difficult generation such as devitrification.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, K 2The upper limit of the content of O composition is preferably 15.0%, more preferably 5.0%, more preferably 3.0%, most preferably is 2.0%.K 2The O composition can use for example K 2CO 3, KNO 3, KF, KHF 2, K 2SiF 6Deng being included in the glass as raw material.
In opticglass of the present invention, by making Rn 2The total content of O composition (in the formula, Rn is more than one elements that are selected from the group of being made up of Li, Na, K) is below 10.0%, can make the specific refractory power of glass be difficult for to reduce and improve glass stability, reduce the generation of devitrification etc.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Rn 2The quality of O composition and the upper limit be preferably 10.0%, more preferably 5.0%, most preferably be 3.0%.
In addition, for opticglass of the present invention, preferably, B 2O 3Composition, ZnO composition, WO 3Composition and Li 2The quality of O composition and be more than 3.0% and below 30.0%.Quality by making them and be more than 3.0%, therefore the second-order transition temperature step-down, can access the glass that is pressed easily.On the other hand, by making this quality and being below 30.0%, the rising of the liquidus temperature of glass can be suppressed, therefore, the higher glass of devitrification resistance can be easily obtained.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, quality and (B 2O 3+ ZnO+WO 3+ Li 2O) lower limit is preferably 3.0%, more preferably 5.0%, most preferably is 7.0%, and its upper limit is preferably 30.0%, more preferably 20.0%, most preferably is 18.0%.
In addition, in opticglass of the present invention, preferably, B 2O 3Composition, ZnO composition, WO 3Composition and Li 2The quality of O composition and with respect to SiO 2Composition, GeO 2Composition, Ta 2O 5Composition and Nb 2O 5The quality of composition and ratio be more than 0.50 and below 5.00.Be more than 0.5 by making this ratio, with respect to the composition that improves second-order transition temperature, the content that reduces the composition of second-order transition temperature increases, and therefore, can easily obtain the lower glass of second-order transition temperature.On the other hand, be below 5.00 by making this ratio, can easily improve the devitrification resistance of glass.Therefore, with the mass ratio (B in the composition of oxide compound conversion 2O 3+ ZnO+WO 3+ Li 2O)/(SiO 2+ GeO 2+ Ta 2O 5+ Nb 2O 5) lower limit be preferably 0.50, more preferably 0.55, most preferably be 0.60, its upper limit is preferably 5.00, more preferably 4.00, more preferably 3.00, most preferably is 2.00.
P 2O 5Composition is to have the liquidus temperature that reduces glass and the composition that improves the effect of devitrification resistance, is any composition in the opticglass of the present invention.Particularly by making P 2O 5The content of composition is below 10.0%, can suppress the reduction of the chemical durability of glass, particularly water tolerance.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, P 2O 5The upper limit of the content of composition is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.P 2O 5Composition can use for example Al(PO 3) 3, Ca(PO 3) 2, Ba(PO 3) 2, BPO 4, H 3PO 4Deng being included in the glass as raw material.
Bi 2O 3Composition is the composition that improves the specific refractory power of glass and reduce second-order transition temperature, is any composition in the opticglass of the present invention.Particularly by making Bi 2O 3The content of composition is below 10.0%, can suppress the deterioration of the devitrification resistance of glass, the rising of partial dispersion ratio, and can make visible light short wavelength's (500nm is following) transmittance be difficult for variation.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Bi 2O 3The upper limit of the content of composition is preferably 10.0%, more preferably 5.0%, most preferably is 3.0%.Bi 2O 3Composition can use for example Bi 2O 3Deng being included in the glass as raw material.
TeO 2Composition is the composition that improves specific refractory power, is any composition in the opticglass of the present invention.But, TeO 2Have following problem: when in the fusion tank that the crucible of platinum system, the part that contacts with melten glass are formed by platinum, making the frit fusion, can with platinum alloyization, thus, the intensity of crucible, fusion tank, the easy variation of thermotolerance.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, TeO 2The upper limit of the containing ratio of composition is preferably 10.0%, more preferably is limited to 8.0% on this, most preferably is 5.0%.TeO 2Composition can use for example TeO 2Deng being included in the glass as raw material.
Al 2O 3Composition is the composition that forms stable glass easily and improve the chemical durability of glass.Particularly by making Al 2O 3The content of composition is below 10.0%, can suppress the deterioration of the devitrification resistance of glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Al 2O 3The upper limit of the content of composition is preferably 10.0%, more preferably 5.0%, most preferably is 2.0%.Al 2O 3Composition can use for example Al 2O 3, Al(OH) 3, AlF 3Deng being included in the glass as raw material.
Ga 2O 3Composition is the composition that forms stable glass easily and improve specific refractory power, is any composition in the opticglass of the present invention.Particularly by making Ga 2O 3The content of composition is respectively below 10.0%, and the Abbe number that can suppress glass reduces and reduce the material cost of glass.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Ga 2O 3The upper limit of the content of composition is preferably 10.0%, more preferably 5.0% respectively, most preferably is 2.0%.Ga 2O 3Composition can use for example Ga 2O 3, Ga(OH) 3Deng being included in the glass as raw material.
Sb 2O 3Composition is the composition that makes the melten glass froth breaking, is any composition in the opticglass of the present invention.Particularly by making Sb 2O 3The content of composition is below 1.0%, and the excess foaming in the time of can making glass melting is difficult for Sb takes place 2O 3Composition is difficult for and fusion equipment precious metals such as (particularly) Pt alloying.Therefore, with respect to the glass total mass of the composition that converts with oxide compound, Sb 2O 3The upper limit of the content of composition is preferably 1.0%, more preferably 0.8%, most preferably is 0.5%.Sb 2O 3Composition can use for example Sb 2O 3, Sb 2O 5, Na 2H 2Sb 2O 75H 2O etc. are included in the glass as raw material.
Need to prove, make the composition of glass clarifying and froth breaking be not limited to above-mentioned Sb 2O 3Composition can use known finings in the glass manufacturing area, defoamer or their combination.At this moment, Sb 2O 3Composition, CeO 2Become the upper limit of summation of the content of the defoamer that grades to be preferably 1.0%, more preferably 0.8%, most preferably to be 0.5%.Particularly the viewpoint of the few glass of the load of environment is considered from can easily obtaining, can be made the summation of content of defoamer less than 0.1%.
＜about the composition that should not contain＞
Then, to the composition that should not contain in the opticglass of the present invention, and the composition that does not preferably contain describe.
In opticglass of the present invention, can in the scope of the characteristic of the glass that does not diminish the present application, add other composition as required.Wherein, GeO 2Become branch to improve the dispersivity of glass, therefore, preferably do not contain in fact.
In addition, even each transiting metal component such as the V except Ti, Zr, Nb, W, La, Gd, Y, Yb, Lu, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo has in the independent or compound character that also can make glass coloring under a spot of situation, produce absorption at the certain wavelengths place of visible region that contains, therefore, particularly in the opticglass of the wavelength that uses the visible region, preferably do not comprise them in fact.
And then, lead compound and As such as PbO 2O 3Each composition Deng arsenic compound and Th, Cd, Tl, Os, Be, Se has the tendency that will control use as harmful chemical substance in recent years, the manufacturing process of glass not only, manufacturing procedure, and goodsization after processing also need disposal on the environmental cure.Therefore, under the situation of paying attention to the influence on the environment, except inevitably sneaking into, preferably do not contain them in fact.Thus, the material that in opticglass, does not contain contaminate environment in fact.Therefore, even do not take disposal on the special environmental cure, also can make this opticglass and process, and discarded.
For glass composition of the present invention, its composition uses the quality % with respect to the glass total mass of the composition that converts with oxide compound to represent, therefore, it is not the composition of directly representing with the record of mole %, but by mole % forming of representing of each composition that in satisfying the glass composition of various characteristics of the presently claimed invention, exists forming meter in order to what oxide compound converted, be roughly following value.
B 2O 3Composition 2.0～55.0mol%,
TiO 2Composition greater than 0mol%～55.0mol%, and
Nb 2O 5Composition greater than 0mol%～20.0mol% and
La 2O 3Composition 0～30.0mol% and/or
SiO 2Composition 0～50.0mol% and/or
ZrO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～10.0mol% and/or
Ta 2O 5Composition 0～7.0mol% and/or
WO 3 Composition 0～7.0mol% and/or
SnO 2Composition 0～5.0mol% and/or
Gd 2O 3Composition 0～12.0mol% and/or
Y 2O 3Composition 0～20.0mol% and/or
Yb 2O 3Composition 0～3.0mol% and/or
Lu 2O 3Composition 0～3.0mol% and/or
MgO composition 0～45.0mol% and/or
CaO composition 0～35.0mol% and/or
SrO composition 0～30.0mol% and/or
BaO composition 0～50.0mol% and/or
ZnO composition 0～30.0mol% and/or
Li 2O composition 0～55.0mol% and/or
Na 2O composition 0～40.0mol% and/or
K 2O composition 0～30.0mol% and/or
P 2O 5Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～3.0mol% and/or
TeO 2Composition 0～10.0mol% and/or
Al 2O 3Composition 0～20.0mol% and/or
Ga 2O 3Composition 0～10.0mol% and/or
Sb 2O 3Composition 0～0.5mol%
[manufacture method]
Opticglass of the present invention for example following operation is made.That is, in the mode of each composition in the scope of the content of regulation above-mentioned raw materials is mixed, after carrying out thick fusion in the mixture input platinum crucible, quartz crucible or the alumina crucible that make, drop in golden crucible, platinum crucible, platinum alloy crucible or the iridium crucible, 1200～1500 ℃ temperature range fusions 3～5 hours, stirring, carry out froth breaking etc. after, be down to the temperature below 1200 ℃, then, carry out post-treatment and stir, remove striped, the use shaping dies is shaped, and makes thus.
[rerum natura]
Opticglass of the present invention preferably has the high refractive index of regulation and has low chromatic dispersion (high Abbe number).More specifically, the specific refractory power (n of opticglass of the present invention d) lower limit be preferably 1.80, more preferably 1.85, more preferably 1.90, most preferably be 1.95.On the other hand, to the specific refractory power (n of opticglass of the present invention d) the upper limit be not particularly limited, mostly be roughly below 2.20, more specifically, mostly be below 2.10, more particularly, mostly be below 2.05.In addition, the Abbe number (ν of opticglass of the present invention d) lower limit be preferably 22, more preferably 24, most preferably be 26.On the other hand, to the Abbe number (ν of opticglass of the present invention d) the upper limit be not particularly limited, mostly be roughly below 30.Thus, the degree of freedom of optical design is widened, and then, even seek the amount of refraction that the slimming of element also can obtain big light.
In addition, opticglass of the present invention have the lower part chromatic dispersion than (θ g, F).More specifically, opticglass of the present invention have below 0.615 partial dispersion than (θ g, F).Thus, can access in the zone of high-refractivity and low-dispersion and partial dispersion than little opticglass, therefore, can reduce the chromatic aberation of the optical element that formed by this opticglass.Here, the partial dispersion of opticglass is than (θ g, upper limit F) is preferably 0.615, more preferably 0.610, most preferably is 0.605.On the other hand, to the partial dispersion of opticglass of the present invention than (θ g, lower limit F) is not particularly limited, and mostly is roughly more than 0.585, more specifically, mostly is more than 0.588, more particularly, mostly is more than 0.590.
The partial dispersion of opticglass of the present invention is than (θ g F) is based on that the industry of Japanese optics nitre can standard JOGIS01-2003 measures.Need to prove that the glass that uses in this mensuration uses the slow cooling cooling rate is made as-25 ℃/hr, has carried out the glass of handling with leer.
In addition, opticglass of the present invention is preferred painted few.Particularly for opticglass of the present invention, when representing with the transmitance of glass, represent the wavelength (λ of spectrophotometric transmittance 70% in the sample of thickness 10mm 70) be below the 520nm, more preferably below the 500nm, most preferably be below the 480nm.In addition, for opticglass of the present invention, the wavelength (λ of expression spectrophotometric transmittance 5% in the sample of thickness 10mm 5) be below the 420nm, more preferably below the 400nm, most preferably be below the 380nm.Thus, the absorption limit of glass be positioned at the UV-light zone near, the transparency of the glass of visible region is improved, therefore, can be with the material of this opticglass as optical element such as lens.
The transmitance of opticglass of the present invention can be measured by standard JOGIS02 based on Japanese optics nitre industry.Particularly, measure the spectrophotometric transmittance of 200～800nm based on the opposed parallel grinding object of the thickness 10 ± 0.1mm of JISZ8722, obtain λ 70(wavelength during transmitance 70%) and λ 5(wavelength during transmitance 5%).
In addition, the preferred devitrification resistance height of opticglass of the present invention.Particularly opticglass of the present invention preferably has the low liquidus temperature below 1240 ℃.More specifically, the upper limit of the liquidus temperature of opticglass of the present invention is preferably 1240 ℃, more preferably 1200 ℃, more preferably 1180 ℃, most preferably is 1160 ℃.Thus, the stability of glass is improved, and crystallization reduces, and therefore, can improve the devitrification resistance when forming glass by molten state, can reduce the influence to the optical characteristics of the optical element of use glass.On the other hand, the lower limit of the liquidus temperature of opticglass of the present invention is not particularly limited, the liquidus temperature of the glass that is obtained by the present invention mostly is roughly more than 500 ℃, particularly, mostly is more than 550 ℃, more specifically, mostly is more than 600 ℃.
The liquidus temperature of opticglass of the present invention is following obtaining: in the platinum of 50ml capacity crucible processed, the glass specimen of the glass cullet shape of 30cc is added in the platinum crucible, under 1350 ℃, make it become molten state fully, the arbitrary temps of setting with 10 ℃ of intervals being cooled to from 1300 ℃ to 1000 ℃, kept 12 hours, and be taken out to outside the stove, after cooling off, immediately having or not of the crystallization in sight glass surface and the glass, do not find during by this observation that the minimum temperature of crystallization is obtained.
Need to prove, the devitrification resistance of opticglass of the present invention is except obtaining by above-mentioned liquidus temperature, can also obtain by following insulation test: frit is added in the platinum crucible processed of 50cc, fusion is about 120 minutes in 1200 ℃～1400 ℃ stove, after the stirring, the glass that obtains was kept 10 hours in being set at 1000～1150 ℃ stove, the surface of sight glass and inner and with face that the inwall of crucible contacts on the crystallization of separating out.
[preform and optical element]
The means that can use for example hot repressing to make die formings such as shape, precise press molding are made glass shaping body by the opticglass that makes.That is, can make the preform that die forming is used by opticglass, after this preform is carried out hot repressing and makes shape, carry out attrition process, make glass shaping body, perhaps, for example the preform that makes carrying out attrition process carries out precise press molding, makes glass shaping body.Need to prove that the means of making glass shaping body are not limited to these means.
The glass shaping body of Zhi Zuoing is useful to various optical elements thus, wherein, especially is preferred for the purposes of optical elements such as lens, prism.Thus, can reduce the bleeding of the color that causes because of chromatic aberation that sees through light of the optics system that is provided with optical element.Therefore, when this optical element is used for photographic camera, can show the photography target thing more accurately, when this optical element is used for projector, can the high more reflection of projection target subtly.
Embodiment
Embodiments of the invention (No.1～No.63) and reference example (No.1～composition No.3) and the specific refractory power (n of these glass d) and Abbe number (ν d), partial dispersion than (θ g, F), the wavelength (λ during transmitance 70% 70) wavelength (λ when [nm], transmitance 5% 5) [nm] and liquidus temperature [and ℃] value be shown in table 1～table 9.Need to prove that following embodiment only enumerates for illustrative purposes, the present invention is not subjected to any restriction of these embodiment.
((glass of No.1～No.3) all is following making to embodiments of the invention: as the raw material of each composition for No.1～No.63) and reference example, select corresponding oxide compound separately, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, metaphosphoric acid compound etc. is generally used for the high-purity raw of opticglass, mode weighing with the proportion of composing that becomes each embodiment shown in table 1～table 9 and reference example, after evenly mixing, drop in the platinum crucible, fusion difficulty according to the glass composition, fused 3～5 hours 1200～1500 ℃ temperature range with electric furnace, stirring, carry out froth breaking etc., then, be cast in mould, glass is made in slowly cooling.
Here, embodiment (No.1～No.63) and the reference example (specific refractory power (n of the glass of No.1～No.3) d) and Abbe number (ν d) and partial dispersion than (θ g F) can measure by standard JOGIS01-2003 based on the industry of Japanese optics nitre.Need to prove that the glass that uses in this mensuration uses the slow cooling cooling rate is made as-25 ℃/hr, has carried out the glass of handling with leer.
In addition, ((transmitance of the glass of No.1～No.3) can be measured by standard JOGIS02 based on Japanese optics nitre industry for No.1～No.63) and reference example about embodiment.Need to prove, in the present invention, by measuring the transmitance of glass, obtain having or not and degree of glass coloring.Particularly, based on JISZ8722, the opposed parallel grinding object of thickness 10 ± 0.1mm is measured the spectrophotometric transmittance of 200～800nm, the wavelength (λ when obtaining transmitance 70% 70) and λ 5(wavelength during transmitance 5%).
In addition, embodiment (No.1～No.63) and reference example (following the obtaining of liquidus temperature of the glass of No.1～No.3): in the platinum of 50ml capacity crucible processed, the glass specimen of the glass cullet shape of 30cc is added platinum crucible, under 1350 ℃, make it become molten state fully, be cooled between 1300 ℃～1000 ℃ with 10 ℃ of arbitrary temps of setting at interval, kept 12 hours, be taken out to outside the stove, after cooling off, immediately having or not of the crystallization in sight glass surface and the glass, do not find during by this observation that the minimum temperature of crystallization is obtained.
[table 1]
Figure BDA00003518769000241
[table 2]
Figure BDA00003518769000251
[table 3]
Figure BDA00003518769000261
[table 4]
Figure BDA00003518769000271
[table 5]
Figure BDA00003518769000281
[table 6]
Figure BDA00003518769000291
[table 7]
Figure BDA00003518769000301
[table 8]
[table 9]
Figure BDA00003518769000321
Abbe number (the ν of the opticglass of embodiments of the invention d) be below 30, and, this Abbe number (ν d) be more than 22, more specifically be more than 28, in target zone.
In addition, the partial dispersion of the opticglass of embodiments of the invention is than (θ g is below 0.615 F), more specifically is below 0.604.Therefore as can be known, the opticglass of embodiments of the invention has low chromatic dispersion, and partial dispersion is than (θ g, F) little, the chromatic aberation in the time of making the formation optical element is little.
In addition, the specific refractory power (n of the opticglass of embodiments of the invention d) be more than 1.90, more specifically, be more than 1.98, and, this specific refractory power (n d) be below 2.20, more specifically, be below 2.01, in target zone.
In addition, the λ of the opticglass of embodiments of the invention 70(wavelength during transmitance 70%) is below the 520nm, more specifically, is below the 487nm.In addition, the λ of the opticglass of embodiments of the invention 5(wavelength during transmitance 5%) is below the 420nm, more specifically, is below the 379nm, in target zone.And the λ of the glass of reference example (No.1) 70Be 501nm.Therefore as can be known, the glassy phase ratio of the opticglass of embodiments of the invention and reference example (No.1) is to the transmitance height of visible light, painted also few.
In addition, the liquidus temperature of the opticglass of embodiments of the invention is below 1240 ℃, more specifically, be below 1220 ℃, and this liquidus temperature is more than 500 ℃, in target zone.And reference example (liquidus temperature of the glass of No.2～No.3) is 1300 ℃, and particularly devitrification has taken place the glass of reference example (No.2).Therefore as can be known, the opticglass of embodiments of the invention and reference example (the glassy phase ratio of No.2～No.3), devitrification resistance height.
Therefore as can be known, the specific refractory power (n of the opticglass of embodiments of the invention d) and Abbe number (ν d) in target zone, chromatic aberation is little, and is high to the transparency of the light of the wavelength of visible region, and the devitrification resistance height.
And then, use the opticglass that obtains in the embodiments of the invention to carry out hot repressing and make shape, then, carried out grinding and cut and grind, be processed into the shape of lens and prism.In addition, use the opticglass of embodiments of the invention, formed the precise press molding preform, precise press molding has been carried out precise press molding processing with preform.In any case, problems such as opacification and devitrification all do not take place in the glass after the thermoplastic, can stably be processed into the shape of various lens and prism.
More than with illustrative purpose the present invention is had been described in detail, but present embodiment only enumerates for illustrative purposes, those skilled in the art can carry out various changes under the situation that does not break away from thought of the present invention and scope.

Claims (25)

1. opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains 1.0～31.0% B 2O 3Composition and 40.0～65.0% Ln 2O 3Composition, TiO 2The content of composition is below 30.0%, Nb 2O 5The content of composition is below 30.0%.
2. opticglass according to claim 1, wherein, the mass ratio Ln of the composition that converts with oxide compound 2O 3/ TiO 2Be more than 3.00, in the formula, Ln is more than one elements that are selected from the group of being made up of La, Gd, Y, Yb, Lu.
3. opticglass according to claim 1 and 2, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains 18.0～60.0% La 2O 3Composition.
4. according to each the described opticglass in the claim 1～3, wherein, with respect to the glass total mass of the composition that converts with oxide compound, quality and (TiO 2+ Nb 2O 5) be more than 8.0% and below 35.0%.
5. according to each the described opticglass in the claim 1～4, wherein, the glass total mass with respect to the composition that converts with oxide compound, in quality %, also contain following each composition:
0～20.0% SiO 2Composition and/or
0～15.0% ZrO 2Composition.
6. opticglass according to claim 5, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains the SiO more than 1.0% 2Composition.
7. according to claim 5 or 6 described opticglass, wherein, the glass total mass with respect to the composition that converts with oxide compound in quality %, contains the ZrO more than 3.0% 2Composition.
8. according to each the described opticglass in the claim 1～7, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
GeO 2Composition be 0～10.0% and/or
Ta 2O 5Composition is 0～20.0%.
9. opticglass according to claim 8, wherein, the mass ratio (GeO in the composition that converts with oxide compound 2+ Ta 2O 5)/(TiO 2+ Nb 2O 5) be below 1.00.
10. according to each the described opticglass in the claim 1～9, wherein, with respect to the glass total mass of the composition that converts with oxide compound, quality and (Nb 2O 5+ Ta 2O 5) be more than 3.0% and below 30.0%.
11. according to each the described opticglass in the claim 1～10, wherein, with the mass ratio TiO in the composition of oxide compound conversion 2/ (Nb 2O 5+ Ta 2O 5) be more than 0.80.
12. according to each the described opticglass in the claim 1～11, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
WO 3Composition be 0～10.0% and/or
SnO 2Composition is 0～5.0%.
13. opticglass according to claim 12, wherein, the glass total mass with respect to the composition that converts with oxide compound contains the WO greater than 0.5% 3Composition.
14. according to each the described opticglass in the claim 1～13, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
Gd 2O 3Composition be 0～30.0% and/or
Y 2O 3Composition be 0～20.0% and/or
Yb 2O 3Composition be 0～6.0% and/or
Lu 2O 3Composition is 0～6.0%.
15. according to each the described opticglass in the claim 1～14, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
The MgO composition be 0～15.0% and/or
The CaO composition be 0～15.0% and/or
The SrO composition be 0～15.0% and/or
The BaO composition be 0～35.0% and/or
The ZnO composition is 0～15.0%.
16. opticglass according to claim 15, wherein, with respect to the glass total mass of the composition that converts with oxide compound, the quality of RO composition and be below 35.0%, in the formula, R is more than one elements that are selected from the group of being made up of Mg, Ca, Sr, Ba.
17. according to each the described opticglass in the claim 1～16, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
Li 2The O composition be 0～15.0% and/or
Na 2The O composition be 0～15.0% and/or
K 2The O composition is 0～15.0%.
18. opticglass according to claim 17, wherein, with respect to the glass total mass of the composition that converts with oxide compound, Rn 2The quality of O composition and be below 10.0%, in the formula, Rn is more than one elements that are selected from the group of being made up of Li, Na, K.
19. according to each the described opticglass in the claim 1～18, wherein, with respect to the glass total mass of the composition that converts with oxide compound, in quality %,
P 2O 5Composition be 0～10.0% and/or
Bi 2O 3Composition be 0～10.0% and/or
TeO 2Composition be 0～10.0% and/or
Al 2O 3Composition be 0～10.0% and/or
Ga 2O 3Composition be 0～10.0% and/or
Sb 2O 3Composition is 0～1.0%.
20. according to each the described opticglass in the claim 1～19, it has the specific refractory power (n more than 1.80 d), and have more than 22 and 30 following Abbe number (ν d).
21. according to each the described opticglass in the claim 1～20, its have below 0.615 partial dispersion than (θ g, F).
22. a preform material, it is formed by each the described opticglass in the claim 1～21.
23. an optical element, it makes claim 22 described preform material compression moulding.
24. an optical element, it is mother metal with each the described opticglass in the claim 1～21.
25. an opticinstrument, it possesses each the described optical element in claim 23 or 24.
CN2012800055094A 2011-01-18 2012-01-18 Optical glass, preform, and optical element Pending CN103313947A (en)

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WO2012099168A1 (en) 2012-07-26
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JP2017145192A (en) 2017-08-24
JP2012162448A (en) 2012-08-30

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