CN102159512A - Optical glass, optical element, and preform for precision press molding - Google Patents

Optical glass, optical element, and preform for precision press molding Download PDF

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Publication number
CN102159512A
CN102159512A CN2010800026088A CN201080002608A CN102159512A CN 102159512 A CN102159512 A CN 102159512A CN 2010800026088 A CN2010800026088 A CN 2010800026088A CN 201080002608 A CN201080002608 A CN 201080002608A CN 102159512 A CN102159512 A CN 102159512A
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China
Prior art keywords
composition
glass
opticglass
oxide compound
quality
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CN2010800026088A
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Chinese (zh)
Inventor
土渊菜那
荻野道子
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Ohara Inc
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Ohara Inc
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Priority claimed from JP2009111384A external-priority patent/JP5694647B2/en
Priority claimed from JP2009111386A external-priority patent/JP5630968B2/en
Priority claimed from JP2009111301A external-priority patent/JP2010260739A/en
Priority claimed from JP2009111313A external-priority patent/JP2010260742A/en
Priority claimed from JP2009111308A external-priority patent/JP2010260740A/en
Priority claimed from JP2009111405A external-priority patent/JP5698442B2/en
Application filed by Ohara Inc filed Critical Ohara Inc
Priority to CN201610959882.3A priority Critical patent/CN107082562B/en
Publication of CN102159512A publication Critical patent/CN102159512A/en
Pending legal-status Critical Current

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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
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • 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
    • 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
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

Provided is optical glass which has a low Abbe number (nu d) even though the refractive index (nd) thereof is within a desired range, and which is highly transparent to visible light. Also disclosed are an optical element and a preform for precision press molding. The optical glass contains, in mass% relative to the total mass of the glass in terms of oxides, 5.0-40.0% of a P2O5 component and 10.0%-60.0% of an Nb2O5 component. The optical element and the preform for precision press molding are composed of the optical glass.

Description

Opticglass, optical element and preformed articles for precise pressurization shaping
Technical field
The present invention relates to opticglass, optical element and preformed articles for precise pressurization shaping.
Background technology
In recent years, along with the instrument that uses optical system to digitizing and the high development rapidly that becomes more meticulous, be representative, more and more higher with photographic goods such as digital camera and pick up cameras to the requirement of high precision int, lightweight and the miniaturization of the optical elements such as lens that are used for optical system.
In making the opticglass of optical element, particularly to the lightweight and the miniaturization that can realize optical element, have the high refractive index (n below 2.20 more than 1.70 d), have the Abbe number (ν below 25 more than 10 d), the requirement of glass with high refractive index and high chromatic dispersion is very high.As this high refractive index high-dispersion glass, for example as specific refractory power (n d) be more than 1.91, have the opticglass of the Abbe number below 21, the glass of known patent document 1 representative.And, as specific refractory power (n d) be more than 1.65, have the opticglass of the Abbe number below 33.1 more than 17.2, the glass of known patent document 2 representatives.
Patent documentation 1: TOHKEMY 2005-206433 communique
Patent documentation 2: Japanese kokai publication hei 06-345481 communique
Summary of the invention
When using this glass to make optical element, can use following method: the thermoplastic glass material also carries out press molding (reheat press molding) and obtains glass molded article (molding glass), this glass molded article is ground cut and abrasive method again; Thermoplastic preliminary shaping material, and in mould, this preliminary shaping material being carried out the method (precise pressurization shaping) of press molding with high degree of accuracy forming face, above-mentioned preliminary shaping material can be the glass gob (gob) that cuts off or glass block (block) are ground the preliminary shaping material cutting and grind and obtain or for by the known floating preliminary shaping material that is shaped etc. and forms of going up.
Yet, patent documentation 1 disclosed glass, its Abbe number (ν d) low more then to the low more (λ of the transparency of visible light 70Value big), and Abbe number (ν d) low glass can be coloured to yellow or orange.Therefore, even patent documentation 1 disclosed glass has the high chromatic dispersion of expectation, also can't realize making the purposes of visible transmission.
And patent documentation 1 and 2 disclosed glass have the problem that devitrification takes place easily when making glass.And the glass that devitrification does not take place when making glass has following problem: carry out attrition process when making the preliminary shaping material when the glass of press molding carries out attrition process by the reheat pressurization or to glass, be easy to generate muddiness.Particularly, in case devitrification or muddy glass have taken place, then be difficult to control the optical element of visible light by its making.
In addition, patent documentation 1 and 2 disclosed glass, most for being difficult to carry out the glass of attrition process and press molding.Particularly, the glass molded article behind the press molding is carried out attrition process when carrying out attrition process when obtaining optical element or to glass gob or glass block, damage glass easily.And, carry out press molding when making glass become the shape of optical element or its preformed articles at mould internal heating glass and to it, in most cases, in the glass impression or crack can take place.
In addition, in patent documentation 1 and the 2 disclosed glass, majority is the high glass of vitrifying point (Tg), even thereby these glass are heated also be difficult for making it softening.Therefore, if make the preliminary shaping material by the glass of patent documentation 1, and the preliminary shaping material carried out thermoplastic and press molding when making optical element, then need to raise and the preliminary shaping material is carried out the temperature of thermoplastic and press molding, therefore can cause being used for the mould and the preliminary shaping material generation fusion adhesion of press molding, perhaps can the optical characteristics of optical element be exerted an influence.
In addition, patent documentation 1 and 2 disclosed glass have following problem: for example to by reheat pressurization and the glass of press molding carries out after the attrition process it is washed when making the preliminary shaping material when carrying out glass being washed after the attrition process or to glass again again, be easy to generate muddiness.Particularly, in case devitrification or muddy glass have taken place, then be difficult to control the optical element of visible light by its making.
The present invention puts in view of the above problems and finishes, and purpose is to provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d) and to the transparent high opticglass and the optical element of visible light.
In addition, the present invention also aims to provide and have above-mentioned specific refractory power (n d), Abbe number (ν d) with to the transparency of visible light, making and be difficult to take place devitrification or muddiness and easy opticglass and the optical element that carries out the manufacturing of preliminary shaping material and optical element by attrition process during processed glass simultaneously.
In addition, the present invention also aims to provide and have above-mentioned specific refractory power (n d), Abbe number (ν d) and to the transparency of visible light and easily carry out the opticglass and the optical element of attrition process and press molding.
In addition, the present invention also aims to provide and have above-mentioned specific refractory power (n d), Abbe number (ν d) and to the transparency of visible light and easily carry out opticglass, optical element and the preformed articles for precise pressurization shaping of low temperature softening.
The present invention also aims to provide and have above-mentioned specific refractory power (n d), Abbe number (ν d) and to the transparency of visible light and opticglass and the optical element that when making preliminary shaping material and optical element, easily washs.
The contriver has carried out deep repeatedly experimental study in order to solve above-mentioned problem, found that by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can be realized the high refractive indexization of glass, can improve chromatic dispersion simultaneously and obtains low Abbe number, and can improve the transparency of glass to visible light, thereby finish the present invention.
And the inventor also finds by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can improve specific refractory power (n d), chromatic dispersion and to the transparency of visible light, the liquidus temperature of glass reduces simultaneously, and can improve acid resistance.
In addition, the inventor also finds by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can improve specific refractory power (n d), chromatic dispersion and to the transparency of visible light, can give suitable wear intensity simultaneously, and average coefficient of linear expansion (α) diminishes.
In addition, the inventor also find by and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition, Nb 2O 5Composition and TiO 2The containing ratio of composition is controlled in the specified range, can improve specific refractory power (n d), chromatic dispersion and to the transparency of visible light, vitrifying point (Tg) reduces simultaneously.
In addition, the inventor also find by and use P 2O 5Composition and Nb 2O 5Composition, and contain Li 2O composition, Na 2O composition, K 2At least a as neccessary composition in the O composition can be improved specific refractory power (n d), chromatic dispersion and to the transparency of visible light, vitrifying point (Tg) step-down simultaneously.
In addition, the inventor also finds by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can improve specific refractory power (n d), chromatic dispersion and to the transparency of visible light, can improve liquidus temperature simultaneously, and can improve the resistance to detergents of glass.Particularly the invention provides following content.
(1) a kind of opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, in quality %, it contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition.
(2) as (1) described opticglass, its spectral transmittance is shown as 70% o'clock wavelength (λ 70) be below the 500nm, have the liquidus temperature below 1200 ℃ more than 500 ℃.
(3) as (1) described opticglass, it has the wear intensity below 400 more than 100.
(4) as (1) described opticglass, its resistance to detergents that draws by the ISO test method(s) (PR) is 1～3 grade.
(5) as (1) described opticglass, it contains Li 2O composition, Na 2O composition, K 2In the O composition any has the vitrifying point (Tg) below 700 ℃ as neccessary composition at least.
(6) as each described opticglass in (1) to (5), wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, TiO 2The content of composition is below 30.0%.
(7) as (6) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, TiO 2The content of composition is below 12.0%.
(8) as (6) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, TiO 2Composition contain quantity not sufficient 10.0%.
(9) as (1) described opticglass, wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, TiO 2Composition contain quantity not sufficient 10.0%, have the vitrifying point (Tg) below 700 ℃.
(10) as (1) described opticglass, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the TiO below 30.0% more than 10.0% 2Composition has the vitrifying point (Tg) below 700 ℃.
(11) as each described opticglass in (1) to (10), wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
WO 3Composition 0～20.0% and/or
BaO composition 0～30.0% and/or
SiO 2Composition 0～10.0%.
(12) as (11) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
WO 3Composition is greater than 0% and be below 20.0%, and
The BaO composition is greater than 0% and be below 30.0%.
(13) as (11) or (12) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, in quality %, the content of BaO composition is below 13.0%.
(14) as (11) or (12) described opticglass, wherein, the glass total mass of convert forming with respect to oxide compound, in quality %, the BaO composition contain quantity not sufficient 7.0%.
(15) as (11) or (12) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, in quality %, the content of BaO composition is below 4.5%.
(16) as (11) or (12) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, in quality %, the content of BaO composition is more than 1.0% and less than 17.0%.
(17) as (11) or (12) described opticglass, wherein, the glass total mass of convert forming with respect to oxide compound, in quality %, the content of BaO composition is more than 2.0% below 15.0%.
(18) as (11) or (12) described opticglass, wherein, the glass total mass of convert forming with respect to oxide compound, in quality %, the content of BaO composition is greater than 7.0% and be below 30.0%.
(19) as each described opticglass in (11) to (18), wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, SiO 2The content of composition is below 2.0%.
(20) as each described opticglass in (11) to (18), wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the SiO greater than 2.0% 2Composition.
(21) as each described opticglass in (11) to (20), wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, WO 3The content of composition is below 10.0%.
(22) as each described opticglass in (1) to (21), wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
Li 2O composition 0～20.0% and/or
Na 2O composition 0～35.0% and/or
K 2O composition 0～20.0%.
(23) as (22) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
Li 2O composition 0～10.0% and/or
Na 2O composition 0～15.0% and/or
K 2O composition less than 0～10.0%.
(24) as (22) or (23) described opticglass, it contains Li 2The O composition is as neccessary composition.
(25) as each described opticglass in (22) to (24), wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, K 2The content of O composition is more than 0.1%.
(26) as each described opticglass in (22) to (25), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is below 35.0%.
(27) as each described opticglass in (22) to (26), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is more than 5.0% below 35.0%.
(28) as each described opticglass in (22) to (27), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is greater than 7.0% and be below 35.0%.
(29) as each described opticglass in (22) to (28), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is greater than 8.0%.
(30) as each described opticglass in (22) to (29), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is greater than 10.0%.
(31) as each described opticglass in (22) to (30), wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is below 15.0%.
(32) as each described opticglass in (22) to (31), wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the BaO composition more than 15.0%, quality and Li 2O+Na 2O+K 2O is greater than 10.0%.
(33) as (22) to (32) described opticglass, it contains Li 2O composition, Na 2O composition and K 2Composition more than 2 kinds in the O composition.
(34) as each described opticglass in (1) to (33), wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
MgO composition 0～5.0% and/or
CaO composition 0～10.0% and/or
SrO composition 0～10.0%.
(35) as (34) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and MgO+CaO+SrO+BaO are below 30.0%.
(36) as each described opticglass in (1) to (35), wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
Y 2O 3Composition 0～10.0% and/or
La 2O 3Composition 0～10.0% and/or
Gd 2O 3Composition 0～10.0%.
(37) as (36) described opticglass, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Y 2O 3+ La 2O 3+ Gd 2O 3Be below 20.0%.
(38) as each described opticglass in (1) to (37), wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
B 2O 3Composition 0～10.0% and/or
GeO 2Composition 0～10.0% and/or
Bi 2O 3Composition 0～20.0% and/or
ZrO 2Composition 0～10.0% and/or
ZnO composition 0～10.0% and/or
Al 2O 3Composition 0～10.0% and/or
Ta 2O 5Composition 0～10.0% and/or
Sb 2O 3Composition 0～1.0%.
(39) as each described opticglass in (1) to (38), it has the specific refractory power below 2.20 (nd) more than 1.70, has the Abbe number below 25 more than 10 (ν d).
(40) as each described opticglass in (1) to (39), its chemical durability that draws by powder method (acid resistance) is 1～5 grade.
(41) as each described opticglass in (1) to (40), its spectral transmittance is shown as 70% o'clock wavelength (λ 70) be below the 500nm.
(42) as each described opticglass in (1) to (41), the average coefficient of linear expansion (α) in the time of its-30～+ 70 ℃ is 150 * 10 -7K -1Below.
(43) a kind of optical element, it is made by each described opticglass in (1) to (42).
(44) a kind of preformed articles for precise pressurization shaping, it is made by each described opticglass in (1) to (42).
(45) a kind of optical element, it is that (44) described preformed articles for precise pressurization shaping is carried out precise pressurization shaping and gets.
According to the present invention, can realize the high refractive indexization of glass, the chromatic dispersion that can improve glass simultaneously improves the transparency of glass to visible light.Therefore can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d) and to the transparent high opticglass and the optical element of visible light.
Especially, according to the present invention, by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can provide (the n of the specific refractory power with expectation d), Abbe number (ν d) and to the transparency of visible light, simultaneously at opticglass and the optical element making and be difficult to take place devitrification or muddiness during processed glass and carry out the manufacturing of preliminary shaping material and optical element by attrition process easily.
And, according to the present invention, by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can provide (the n of the specific refractory power with expectation d), Abbe number (ν d) and to the transparency of visible light, easily carry out the opticglass and the optical element of attrition process and press molding.
In addition, according to the present invention, by and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition, Nb 2O 5Composition and TiO 2The containing ratio of composition is controlled in the specified range, and (the n of the specific refractory power with expectation can be provided d), Abbe number (ν d) and to the transparency of visible light, carry out the opticglass of low temperature softening, the optical element that uses this opticglass and preformed articles for precise pressurization shaping simultaneously easily.
In addition, according to the present invention, by and use P 2O 5Composition and Nb 2O 5Composition, and contain Li 2O composition, Na 2O composition, K 2At least a as neccessary composition in the O composition can provide (the n of the specific refractory power with expectation d), Abbe number (ν d) and to the transparency of visible light, carry out the opticglass of low temperature softening, the optical element that uses this opticglass and preformed articles for precise pressurization shaping simultaneously easily.
In addition, according to the present invention, by containing the P of specified quantitative 2O 5Composition and Nb 2O 5Composition can provide (the n of the specific refractory power with expectation d), Abbe number (ν d) and to opticglass and the optical element transparency of visible light, that when making preliminary shaping material and optical element, easily wash simultaneously.
Embodiment
Opticglass of the present invention, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition.By and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition and Nb 2O 5The containing ratio of composition is controlled in the specified range, can realize the high refractive indexization of glass, can improve chromatic dispersion simultaneously, and can improve the transparency of glass to visible light.Therefore, can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d) and to the transparent high opticglass and the optical element of visible light.
At this, the opticglass of first embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition, its spectral transmittance are shown as 70% o'clock wavelength (λ 70) be below the 500nm, and have the liquidus temperature below 1200 ℃ more than 500 ℃.By and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition and Nb 2O 5The containing ratio of composition is controlled in the specified range, the high refractive indexization of glass can be realized and chromatic dispersion can be improved, can improve the transparency of glass to visible light, reduce the liquidus temperature of glass, thereby even and the acid resistance glass that can improve glass contact also not easy damaged glass with lapping liquid or washings.Therefore, can provide specific refractory power (n d) be in the expected range, have low Abbe number (ν simultaneously d), high and to the transparency of visible light at opticglass and the optical element making and be difficult to take place devitrification or muddiness during processed glass and carry out the making of preliminary shaping material and optical element by attrition process easily.
In addition, the opticglass of second embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition has the wear intensity below 400 more than 100.By and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition and Nb 2O 5The containing ratio of composition is controlled in the specified range, can realize the high refractive indexization of glass, and the while can be improved chromatic dispersion and be obtained low Abbe number, can improve the transparency of glass to visible light, can give suitable wear intensity, and average coefficient of linear expansion (α) reduces.Therefore, can provide specific refractory power (n d) be in the expected range, have simultaneously high chromatic dispersion (low Abbe number), to visible light transparent high, easily carry out attrition process and can reduce impression (depression) and fissured opticglass and the optical element that press molding causes lens.
In addition, the opticglass of third embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition, and TiO 2Composition contain quantity not sufficient 10.0%, have the vitrifying point (Tg) below 700 ℃.By and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition, Nb 2O 5Composition and TiO 2The containing ratio of composition is controlled in the specified range, can realize the high refractive indexization of glass, and the while can be improved chromatic dispersion and be obtained low Abbe number, can improve the transparency of glass to visible light, and vitrifying point (Tg) reduces.Therefore, can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d), high and easily carry out low temperature softening and easily carry out the opticglass of press molding and use the optical element and the preformed articles for precise pressurization shaping of this opticglass to the transparency of visible light.
In addition, the opticglass of four embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition, the resistance to detergents (PR) that draws by the ISO test method(s) is 1～3 grade.By and use P 2O 5Composition and Nb 2O 5Composition, and with P 2O 5Composition and Nb 2O 5The containing ratio of composition is controlled in the specified range, can realize the high refractive indexization of glass, simultaneously can improve chromatic dispersion, can improve the transparency of glass visible light, thereby even and the resistance to detergents glass that can improve glass contact also not easy damaged glass with lapping liquid or washings.Therefore, can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d), high and when the glass after the attrition process is washed, be difficult for taking place opticglass and optical element muddy, that when making preliminary shaping material or optical element, wash easily to the transparency of visible light.
In addition, the opticglass of fifth embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition and 10.0% above TiO below 30.0% 2Composition has the vitrifying point (Tg) below 700 ℃.By and use P 2O 5Composition, Nb 2O 5Composition and TiO 2Composition, and with P 2O 5Composition, Nb 2O 5Composition and TiO 2The containing ratio of composition is controlled in the specified range, can realize the high refractive indexization of glass, and the while can be improved chromatic dispersion and be obtained low Abbe number, can improve the transparency of glass to visible light, and vitrifying point (Tg) reduces.Therefore, can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d), high and easily carry out low temperature softening and easily carry out the opticglass of press molding, the optical element that uses this opticglass and preformed articles for precise pressurization shaping to the transparency of visible light.
In addition, the opticglass of sixth embodiment of the invention, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition, and contain Li 2O composition, Na 2O composition, K 2At least a as neccessary composition in the O composition has the vitrifying point (Tg) below 700 ℃.By and use P 2O 5Composition and Nb 2O 5Composition, and contain Li 2O composition, Na 2O composition, K 2At least a as neccessary composition in the O composition can be realized the high refractive indexization of glass, can improve chromatic dispersion simultaneously and obtains low Abbe number, can improve the transparency of glass to visible light, and vitrifying point (Tg) reduces.Therefore, can provide specific refractory power (n d) be in the expected range and have low Abbe number (ν d), high and easily carry out low temperature softening and easily carry out the opticglass of press molding, the optical element that uses this opticglass and preformed articles for precise pressurization shaping to the transparency of visible light.
Below, the embodiment of opticglass of the present invention is elaborated, but the present invention is not subjected to any qualification of following embodiment, can be carried out appropriate change in the scope of the object of the invention and implement.In addition, for the repeat specification part, suitably omit explanation sometimes, but purport of the present invention is unrestricted.
[glass ingredient]
The compositing range that constitutes each composition of opticglass of the present invention is as described below.Unless otherwise specified, the containing ratio of each composition all uses the quality % of the glass total mass of forming with respect to the oxide compound conversion to represent in this specification sheets.Wherein, " oxide compound converts and forms " is meant, oxide compound, composite salt and the metal fluoride etc. that use as the raw material of glass moiety of the present invention in hypothesis during in fusion whole decomposition and inversion become under the situation of oxide compound, total mass with this generation oxide compound is 100 quality %, the composition of each contained composition in the glass.
＜about neccessary composition, optional member 〉
P 2O 5Composition is that glass forms composition, is the composition that makes the melting temperature (Tm) reduction of glass.Especially, by making P 2O 5The containing ratio of composition is more than 5.0%, can improve the transmissivity of glass in the visible region, is difficult for simultaneously the wear intensity of glass is risen to more than the specified range, thereby can reduces the damage that attrition process causes.On the other hand, by making P 2O 5The containing ratio of composition is below 40.0%, and the high refractive index that can obtain expecting is difficult for the wear intensity of glass is reduced to more than the specified range simultaneously, thereby can improve the working (machining) efficiency of attrition process.Therefore, with respect to the glass total mass that oxide compound converts and forms, P 2O 5The lower value of composition containing ratio is preferably 5.0%, more preferably 8.0%, most preferably is 10.0%, and higher limit is preferably 40.0%, more preferably 35.0%, more preferably 33.0%, most preferably is 30.0%.Can use for example Al (PO 3) 3, Ca (PO 3) 2, Ba (PO 3) 2, BPO 4, H 3PO 4Deng as raw material, make glass contain P 2O 5Composition.
Nb 2O 5Composition is to improve the specific refractory power of glass and the composition of chromatic dispersion.Especially, by making Nb 2O 5The containing ratio of composition is more than 10.0%, high refractive index that can obtain expecting and high chromatic dispersion.On the other hand, by making Nb 2O 5The containing ratio of composition is below 60.0%, and the rising that can suppress the liquidus temperature of glass improves the stability of glass, thereby can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Nb 2O 5The lower value of composition containing ratio is preferably 10.0%, more preferably 20.0%, most preferably is 30.0%, and higher limit is preferably 60.0%, more preferably 58.0%, more preferably 57.0%, more preferably 56.0%, most preferably is 55.0%.Particularly in the opticglass of the 6th embodiment, above-mentioned Nb 2O 5The higher limit of composition containing ratio is preferably 60.0%, more preferably 50.0%, most preferably is 45.0%.Can use for example Nb 2O 5Deng as raw material, make glass contain Nb 2O 5Composition.
TiO 2Composition is to improve the specific refractory power of glass and the composition of chromatic dispersion, is chemical durability, particularly resistance to detergents and the acid proof composition that improves glass, is the optional member in the opticglass of the present invention.Especially, by making TiO 2The containing ratio of composition is below 30.0%, can obtain high refractive index and high chromatic dispersion, and the rising that can suppress the glass liquidus temperature simultaneously improves the stability of glass, thereby can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, TiO 2The higher limit of composition containing ratio is preferably 30.0%, more preferably 28.0%, more preferably 25.0%, most preferably is 20.0%.Wherein, in the opticglass of first and second embodiments, by making TiO 2The containing ratio of composition is below 12.0%, can obtain high refractive index and chromatic dispersion, especially can improve the transparency of glass to visible light.At this moment, above-mentioned TiO 2The higher limit of composition containing ratio is preferably 12.0%, more preferably 11.0%, most preferably is less than 10.0%.And, in the opticglass of the 3rd embodiment, by making TiO 2The containing ratio less than 10.0% of composition can obtain high refractive index and high chromatic dispersion, and can improve the transparency of glass to visible light.At this moment, above-mentioned TiO 2The higher limit of composition containing ratio be preferably less than 10.0%, more preferably 9.8%, most preferably be 9.5%.In the opticglass of the present invention,, also can make TiO in particular for obtaining transparent high glass to visible light 2The containing ratio less than 5.0% of composition.On the other hand, in the opticglass of the 5th embodiment, by making TiO 2The containing ratio of composition is more than 10.0%, can further improve the chromatic dispersion of glass.Therefore, under the situation of the high chromatic dispersionization that further realizes glass, above-mentioned TiO 2The lower value of composition containing ratio is preferably 10.0%, more preferably 12.0%, more preferably 13.0%, most preferably is 14.0%.
In addition, even do not contain TiO 2Composition also can access the opticglass with desired characteristic, but by containing the TiO more than 0.1% 2Composition can improve the acid resistance of glass, thereby can reduce glass and variable color takes place adding man-hour.Therefore, with respect to the glass total mass of oxide compound conversion composition, TiO at this moment 2The lower value of composition containing ratio is preferably 0.1%, more preferably 1.0%, most preferably is 2.0%.At this, realizing under the higher acid proof situation above-mentioned TiO 2The lower value of composition containing ratio is preferably 5.0%, more preferably 11.0%, most preferably is 12.0%.Can use for example TiO 2Deng as raw material, make glass contain TiO 2Composition.
The BaO composition is the composition that improves the specific refractory power of glass, and is the composition that improves devitrification resistance by the liquidus temperature that reduces glass, is the optional member in the opticglass of the present invention.Wherein, be below 30.0% by the containing ratio that makes the BaO composition, can obtain the high refractive index expected easily, the reduction of devitrification resistance can be suppressed simultaneously, and the reduction of chemical durabilities such as acid resistance can be suppressed.Especially, be below 20.0% by the containing ratio that makes the BaO composition, can suppress the increase of the average coefficient of linear expansion (α) of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, the higher limit of BaO composition containing ratio is preferably 30.0%, more preferably 28.0%, more preferably 25.0%, most preferably is 20.0%.Wherein, in the opticglass of first and second embodiments, the higher limit of above-mentioned BaO composition containing ratio is preferably 20.0%, more preferably 18.0%, most preferably is 15.0%.And in the opticglass of the 3rd embodiment, the higher limit of above-mentioned BaO composition containing ratio is preferably 20.0%, more preferably 19.0%, most preferably is 18.0%.
Wherein, consider from the aspect that can obtain big (Abbe number the is little) glass of chromatic dispersion particularly that with respect to the glass total mass that oxide compound converts and forms, the higher limit of BaO composition containing ratio is preferably less than 17.0%, more preferably 13.0%, most preferably be 4.5%.Wherein, in the opticglass of first and second embodiments, the higher limit of above-mentioned BaO composition containing ratio is preferably 13.0%, more preferably less than 10.0%, most preferably be 4.5%.And, in the opticglass of the 3rd embodiment, the containing ratio of above-mentioned BaO composition be preferably less than 17.0%, more preferably less than 15.0%, most preferably be less than 13.0%.In addition, in the opticglass of the 5th embodiment, the higher limit of above-mentioned BaO composition containing ratio is preferably 15.0%, more preferably 13.0%, most preferably is less than 10.0%.And, in the opticglass of the 6th embodiment, above-mentioned BaO composition containing ratio be preferably less than 7.0%, more preferably less than 5.0%, most preferably be less than 4.0%.
In addition, may not obtain having the high chromatic dispersion of expectation and the opticglass of high-transmission rate even do not contain the BaO composition yet, but, can reduce the liquidus temperature of glass, thereby can obtain the high and easily stable glass of making of devitrification resistance by containing BaO composition greater than 0%.Therefore, under the situation that obtains the high glass of devitrification resistance, with respect to the glass total mass that oxide compound converts and forms, the lower value of BaO composition containing ratio is preferably more than 0%, more preferably 1.0%, most preferably is 3.0%.Wherein, in the opticglass of the 3rd embodiment, the lower value of above-mentioned BaO composition containing ratio is preferably 1.0%, more preferably 3.0%, most preferably is 4.5%.And in the opticglass of the 5th embodiment, the lower value of above-mentioned BaO composition containing ratio is preferably more than 0%, more preferably 1.0%, most preferably is 2.0%.In addition, in the opticglass of the 6th embodiment, the lower value of above-mentioned BaO composition containing ratio is preferably 0.1%, more preferably 0.5%, most preferably is 1.0%.On the other hand, by containing BaO composition, can reduce the liquidus temperature of glass, and can improve the resistance to detergents of glass greater than 7.0%.Therefore, under the situation that obtains the high glass of resistance to detergents, the lower value of above-mentioned BaO composition containing ratio is preferably 7.0%, more preferably 10.0%, most preferably is 15.0%.Can use for example BaCO 3, Ba (NO 3) 2, BaF 2Deng as raw material, make glass contain the BaO composition.
SiO 2Composition be reduce painted, improve transmissivity to short-wavelength visible light, promote the composition that forms stabilized glass and improve the devitrification resistance of glass simultaneously, be the optional member in the opticglass of the present invention.Especially, by making SiO 2The containing ratio of composition is below 10.0%, can suppress SiO 2The reduction of the specific refractory power that composition causes, thereby can obtain the high refractive index expected easily.Therefore, with respect to the glass total mass that oxide compound converts and forms, SiO 2The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, more preferably 6.0%, most preferably is 5.0%.Wherein, particularly consider above-mentioned SiO from the aspect that can obtain big (Abbe number the is little) glass of chromatic dispersion easily 2The higher limit of composition containing ratio is preferably 2.0%, more preferably 1.5%, most preferably is 1.0%.
Therefore, even reduce SiO 2The content of composition or do not contain SiO 2Composition also might obtain having the high chromatic dispersion of expectation and the opticglass of high-transmission rate.On the other hand, particularly in the 2nd the opticglass, by containing SiO greater than 2.0% 2Composition can improve the wear intensity of glass, thereby can obtain the easy glass that forms by attrition process.Therefore, with respect to the glass total mass of oxide compound conversion composition, SiO at this moment 2The lower value of composition containing ratio is preferably more than 2.0%, more preferably 3.0%, most preferably is 4.0%.Can use for example SiO 2, K 2SiF 6, Na 2SiF 6Deng as raw material, make glass contain SiO 2Composition.
WO 3Composition is the composition that improves glass refraction and improve the glass chromatic dispersion, is the optional member in the opticglass of the present invention.Especially, by making WO 3The containing ratio of composition is below 20.0%, can improve the devitrification resistance of glass, and can reduce vitrifying point (Tg), can suppress the transmissivity of glass to short-wavelength visible light simultaneously.Therefore, with respect to the glass total mass that oxide compound converts and forms, WO 3The higher limit of composition containing ratio is preferably 20.0%, more preferably 17.0%, more preferably 15.0%, most preferably is 10.0%.Wherein, particularly consider WO from the glass aspect that can obtain easily having the high chromatic dispersion of expectation and having reduced TG point (Tg) 3The containing ratio of composition is preferably below 10.0%.Therefore, this moment above-mentioned WO 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, more preferably 7.0%, most preferably is 5.0%.
In addition, even do not contain WO 3Composition also can access the high chromatic dispersion with expectation and the opticglass of high-transmission rate, but by containing the WO greater than 0% 3Composition, the chromatic dispersion that can improve glass, thereby make glass have high chromatic dispersion concurrently easily and to the transparency of visible light.Therefore, with respect to the glass total mass of oxide compound conversion composition, WO at this moment 3The lower value of composition containing ratio is preferably more than 0%, more preferably 1.0%, more preferably 3.0%, most preferably is 4.0%.Can use for example WO 3Deng as raw material, make glass contain WO 3Composition.
Li 2The O composition is to reduce the melting temperature (Tm) of glass and the composition of vitrifying point (Tg), and is the composition of the devitrification resistance when improving glass formation, is the optional member in the opticglass of the present invention.Wherein, by making Li 2The containing ratio of O composition is below 20.0%, can obtain the high refractive index expected easily, can reduce the liquidus temperature of glass simultaneously and improves the stability of glass, thereby can reduce glass generation devitrification etc.Especially, by making Li 2The containing ratio of O composition is below 10.0%, can suppress the increase of the average coefficient of linear expansion (α) of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Li 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 10.0%, most preferably is 5.0%.Especially, in the opticglass of first and second embodiments, above-mentioned Li 2The higher limit of O composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.And, in the opticglass of third and fourth embodiment, above-mentioned Li 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 15.0%, most preferably is 10.0%.In addition, in the opticglass of the 5th and the 6th embodiment, above-mentioned Li 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 18.0%, more preferably 15.0%, most preferably is 10.0%.
In addition, even do not contain Li 2The O composition also may obtain having the high chromatic dispersion of expectation and the opticglass of high-transmission rate, but by containing the Li greater than 0% 2The O composition can reduce vitrifying point (Tg), thereby the glass that can obtain having high chromatic dispersion and easily carry out low temperature softening.Therefore, with respect to the glass total mass of oxide compound conversion composition, Li at this moment 2The lower value of O composition containing ratio is preferably more than 0%, more preferably greater than 0.3%, most preferably be 0.5%.Can use for example Li 2CO 3, LiNO 3, LiF etc. is as raw material, makes glass contain Li 2The O composition.
Na 2The O composition is to reduce the melting temperature (Tm) of glass and the composition of vitrifying point (Tg), and is the composition of the devitrification resistance when improving glass formation, is the optional member in the opticglass of the present invention.Especially, by making Na 2The containing ratio of O composition is below 35.0%, can obtain the high refractive index expected easily, thereby the liquidus temperature that can reduce glass improves the stability of glass, reduces glass generation devitrification etc.Therefore, with respect to the glass total mass that oxide compound converts and forms, Na 2The higher limit of O composition containing ratio is preferably 35.0%, more preferably 25.0%, most preferably is 15.0%.Especially, in the opticglass of first embodiment, above-mentioned Na 2The higher limit of O composition containing ratio is preferably 15.0%, more preferably 12.0%, most preferably is 10.0%.And, in the 2nd the opticglass, above-mentioned Na 2The higher limit of O composition containing ratio is preferably 15.0%, more preferably 13.0%, most preferably is 12.0%.And, in the opticglass of third and fourth embodiment, above-mentioned Na 2The higher limit of O composition containing ratio is preferably 35.0%, more preferably 30.0%, more preferably 25.0%, most preferably is 15.0%.And, in the opticglass of the 5th and the 6th embodiment, above-mentioned Na 2The higher limit of O composition containing ratio is preferably 35.0%, more preferably 30.0%, more preferably 25.0%, most preferably is 20.0%.
In addition, even do not contain Na 2The O composition also can access the opticglass with desired characteristic, but by containing the Na more than 0.1% 2The O composition can improve the liquidus temperature of glass, thereby can further improve the devitrification resistance of glass.Therefore, with respect to the glass total mass of oxide compound conversion composition, Na at this moment 2The lower value of O composition containing ratio is preferably 0.1%, more preferably 0.5%, more preferably 1.0%, most preferably is 2.0%.Can use for example Na 2CO 3, NaNO 3, NaF, Na 2SiF 6Deng as raw material, make glass contain Na 2The O composition.
K 2The O composition is to reduce the melting temperature (Tm) of glass and the composition of vitrifying point (Tg), is the composition of the devitrification resistance when improving glass formation simultaneously, is the optional member in the opticglass of the present invention.Especially, by making K 2The containing ratio of O composition is below 20.0%, can obtain the high refractive index expected easily, thereby the liquidus temperature that can reduce glass improves the stability of glass, thereby reduces glass generation devitrification etc.Therefore, with respect to the glass total mass that oxide compound converts and forms, K 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 15.0%, most preferably is less than 10.0%.Especially, in the opticglass of first and second embodiments, above-mentioned K 2The higher limit of O composition containing ratio be preferably less than 10.0%, more preferably 8.0%, more preferably 6.0%, most preferably be 5.0%.And, in the opticglass of third and fourth embodiment, above-mentioned K 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 15.0%, more preferably 12.0%, most preferably is 10.0%.In addition, in the opticglass of the 5th and the 6th embodiment, above-mentioned K 2The higher limit of O composition containing ratio is preferably 20.0%, more preferably 15.0%, most preferably is 10.0%.
In addition, even do not contain K 2The O composition also can access the opticglass with desired characteristic, but by containing the K more than 0.1% 2The O composition can improve the liquidus temperature of glass, thereby can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass of oxide compound conversion composition, K at this moment 2The lower value of O composition containing ratio is preferably 0.1%, more preferably 0.15%, more preferably 0.2%, more preferably 0.5%, most preferably is 1.0%.Can use K 2CO 3, KNO 3, KF, KHF 2, K 2SiF 6Deng as raw material, make glass contain K 2The O composition.
Wherein, the opticglass of the 6th embodiment preferably contains Li 2O composition, Na 2O composition and K 2At least a in the O composition as neccessary composition.Thus, because the vitrifying point (Tg) of opticglass reduces, thereby the forming temperature can reduce press molding the time, and can further reduce the press molding rear surface and occur concavo-convex or muddy.And, owing to can improve the devitrification resistance of opticglass, thereby can more stably make opticglass with desired optical.
In the opticglass of the present invention, Rn 2The O composition (in the formula, Rn be selected among Li, Na, the K more than a kind) quality of containing ratio and being preferably below 35.0%.Thus, owing to can suppress the reduction of the specific refractory power of glass, thereby can obtain the high refractive index expected easily.And,, can improve the stability of glass, thereby can improve the devitrification resistance of glass by reducing the liquidus temperature of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition containing ratio and higher limit be preferably 35.0%, more preferably 25.0%, most preferably be 15.0%.Especially, in the opticglass of first and second embodiments, above-mentioned quality and higher limit be preferably 15.0%, more preferably 13.0%, most preferably be 12.0%.Wherein, in the opticglass of the 3rd embodiment, this quality and higher limit be preferably 35.0%, more preferably 32.0%, most preferably be 30.0%.And, in the opticglass of the 4th embodiment, this quality and higher limit be preferably 35.0%, more preferably 25.0%, most preferably be 20.0%.In addition, in the opticglass of the 5th and the 6th embodiment, this quality and higher limit be preferably 35.0%, more preferably 30.0%, most preferably be 25.0%.
In addition, even all do not contain Rn 2The O composition also can access the opticglass with desired characteristic, but by containing the Rn more than 0.1% 2O composition at least a can be improved the liquidus temperature of glass, thereby be can further improve the devitrification resistance of glass.Therefore, with respect to the glass total mass of oxide compound conversion composition, Rn at this moment 2The quality of O composition containing ratio and lower value be preferably 0.1%, more preferably 1.0%, more preferably 2.0%, most preferably be 3.0%.
In addition, by making Rn 2The quality of O composition containing ratio and be more than 5.0%, can realize glass high chromatic dispersionization, reduce vitrifying point (Tg) and can improve the water tolerance and the resistance to detergents of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Rn 2The quality of O composition containing ratio and lower value be preferably 5.0%, more preferably 8.0%, most preferably be 10.0%.Wherein, in the opticglass of the 3rd embodiment, this quality and lower value be preferably more than 7.0%, more preferably 9.0%, most preferably be 10.0%.And, in the opticglass of above-mentioned the 4th embodiment, this quality and be preferably more than 8.0%, more preferably greater than 9.0%, most preferably be greater than 10.0%.And, in the opticglass of the 5th embodiment, this quality and lower value be preferably 5.0%, more preferably 6.0%, most preferably be 7.0%.In addition, in the opticglass of the 6th embodiment, this quality and lower value be preferably 5.0%, more preferably 8.0%, most preferably be 10.0%.
Especially, in the opticglass of four embodiment of the invention, particularly preferably be, the glass total mass with respect to oxide compound converts and forms in quality %, contains the BaO composition more than 15.0%, and in total amount, contains the Rn greater than 10.0% 2The O composition.Thus, can improve the resistance to detergents of glass especially, even thereby glass contact with lapping liquid or washings, also can reduce glass and take place muddy.
In the opticglass of the present invention, preferably contain Li 2O composition, Na 2O composition and K 2Composition more than 2 kinds in the O composition.Thus, can reduce the vitrifying point (Tg) of opticglass, the forming temperature in the time of can reducing press molding can further reduce in the generation of press molding rear surface concavo-convex and muddy.And, can improve the devitrification resistance of opticglass, thereby can more stably make opticglass with desired optical.
The MgO composition is the liquidus temperature that reduces glass, the composition that improves the devitrification resistance of glass, is the optional member in the opticglass of the present invention.Especially, be below 5.0% by making MgO composition containing ratio, can obtain high refractive index and the high chromatic dispersion expected easily.Therefore, with respect to the glass total mass that oxide compound converts and forms, the higher limit of MgO composition containing ratio is preferably 5.0%, more preferably 4.0%, most preferably is 3.0%.Can use for example MgCO 3, MgF 2Deng as raw material, make glass contain the MgO composition.
The CaO composition is the liquidus temperature that reduces glass, the composition that improves the devitrification resistance of glass, is the optional member in the opticglass of the present invention.Especially, be below 10.0% by the containing ratio that makes the CaO composition, high refractive index and the high chromatic dispersion expected can be obtained easily, and the reduction of devitrification resistance and chemical durability can be suppressed.Therefore, with respect to the glass total mass that oxide compound converts and forms, the higher limit of CaO composition containing ratio is preferably 10.0%, more preferably 8.0%, more preferably 6.0%, most preferably is 5.0%.Can use for example CaCO 3, CaF 2Deng as raw material, make glass contain the CaO composition.
The SrO composition is the liquidus temperature that reduces glass, the composition that improves the devitrification resistance of glass, is the optional member in the opticglass of the present invention.Especially, be below 10.0% by the containing ratio that makes the SrO composition, high refractive index and the high chromatic dispersion expected can be obtained easily, and the reduction of devitrification resistance and chemical durability can be suppressed.Therefore, with respect to the glass total mass that oxide compound converts and forms, the higher limit of SrO composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example Sr (NO 3) 2, SrF 2Deng as raw material, make glass contain the SrO composition.
In the opticglass of the present invention, the quality of RO composition (in the formula, R is more than one among Mg, Ca, Sr, the Ba) containing ratio and being preferably below 30.0%.Thus, the specific refractory power that the RO composition causes and the reduction of chromatic dispersion can be suppressed, thereby high refractive index and the high chromatic dispersion expected can be obtained easily.Therefore, with respect to the glass total mass that oxide compound convert to be formed, the quality of RO composition containing ratio and higher limit be preferably 30.0%, more preferably 20.0%, most preferably be 10.0%.Especially, in the opticglass of first and second embodiments, this quality and higher limit be preferably 20.0%, more preferably 17.0%, more preferably 15.0%, most preferably be 10.0%.In addition, in the opticglass of third and fourth embodiment, this quality and higher limit be preferably 30.0%, more preferably 28.0%, more preferably 27.0%, most preferably be 25.0%.And, in the opticglass of the 5th and the 6th embodiment, this quality and higher limit be preferably 30.0%, more preferably 25.0%, most preferably be 20.0%.
In addition, can not access opticglass yet, but pass through at least a of the RO composition of interpolation more than 0.1%, can improve the liquidus temperature of glass, thereby can further improve the devitrification resistance of glass with desired characteristic even all do not contain the RO composition.Therefore, with respect to the glass total mass that oxide compound convert to be formed, this moment RO composition containing ratio quality and lower value be preferably 0.1%, more preferably 0.5%, more preferably 1.0%, most preferably be 3.0%.
Y 2O 3Composition is to improve glass refraction, improve the composition of the chemical durability of glass simultaneously, is the optional member in the opticglass of the present invention.Especially, by making Y 2O 3The containing ratio of composition is below 10.0%, can obtain the high chromatic dispersion expected easily, and can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Y 2O 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example Y 2O 3, YF 3Deng as raw material, make glass contain Y 2O 3Composition.
La 2O 3Composition is to improve glass refraction, improve the composition of the chemical durability of glass simultaneously, is the optional member in the opticglass of the present invention.Especially, by making La 2O 3The containing ratio of composition is below 10.0%, can obtain the high chromatic dispersion expected easily, and can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, La 2O 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example La 2O 3, La (NO 3) 3XH 2O (X is an arbitrary integer) etc. make glass contain La as raw material 2O 3Composition.
Gd 2O 3Composition is to improve glass refraction, improve the composition of the chemical durability of glass simultaneously, is the optional member in the opticglass of the present invention.Especially, by making Gd 2O 3The containing ratio of composition is below 10.0%, can obtain the high chromatic dispersion expected easily, and can improve the devitrification resistance of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Gd 2O 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example Gd 2O 3, GdF 3Deng as raw material, make glass contain Gd 2O 3Composition.
In the opticglass of the present invention, Ln 2O 3Composition (in the formula, Ln be selected among Y, La, the Gd more than a kind) quality of containing ratio and being preferably below 20.0%.By making this quality and being below 20.0%, can suppress Ln 2O 3The rising of the Abbe number that composition causes, thereby obtain the high chromatic dispersion expected easily.Therefore, with respect to the glass total mass that oxide compound converts and forms, Ln 2O 3The quality of composition containing ratio and higher limit be preferably 20.0%, more preferably 18.0%, most preferably be 15.0%.
B 2O 3Composition is the composition that promotes to form stabilized glass, improves devitrification resistance, is the optional member in the opticglass of the present invention.Especially, by making B 2O 3The containing ratio of composition is below 10.0%, can suppress B 2O 3The reduction of the specific refractory power that composition causes, thereby obtain the high refractive index expected easily.And, can suppress the increase of glass average coefficient of linear expansion (α) thus.Therefore, with respect to the glass total mass that oxide compound converts and forms, B 2O 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, more preferably 6.0%, most preferably is 5.0%.In addition, even do not contain B 2O 3Composition also can obtain having the opticglass of desired characteristic, but by containing the B more than 0.1% 2O 3Composition can improve the liquidus temperature of glass, thereby can further improve the devitrification resistance of glass.Therefore, with respect to the glass total mass of oxide compound conversion composition, B at this moment 2O 3The lower value of composition containing ratio is preferably 0.1%, more preferably 0.2%, more preferably 0.3%, most preferably is 0.5%.Can use for example H 3BO 3, Na 2B 4O 7, Na 2B 4O 710H 2O, BPO 4Deng as raw material, make glass contain B 2O 3Composition.
GeO 2Composition is the composition that improves the specific refractory power of glass, promotes to form stabilized glass and improve the devitrification resistance of glass simultaneously, is the optional member in the opticglass of the present invention.Especially, by making GeO 2The containing ratio of composition is below 10.0%, can reduce the material cost of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, GeO 2The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example GeO 2Deng as raw material, make glass contain GeO 2Composition.
Bi 2O 3Composition is the specific refractory power that improves glass, the composition that improves the chromatic dispersion of glass, is the optional member in the opticglass of the present invention.Especially, by making Bi 2O 3The containing ratio of composition is below 20.0%, can improve the stability of glass and suppresses the reduction of devitrification resistance, can suppress the reduction of the transmissivity of glass.Therefore, with respect to the glass total mass that oxide compound converts and forms, Bi 2O 3The higher limit of composition containing ratio is preferably 20.0%, more preferably 15.0%, more preferably less than 10.0%, most preferably be less than 5.0%.
ZrO 2Composition is to reduce painted and improve the transmissivity of short-wavelength visible light, promote to form stabilized glass simultaneously and the composition that improves the devitrification resistance of glass, is the optional member in the opticglass of the present invention.Especially, by making ZrO 2The containing ratio of composition is below 10.0%, can suppress ZrO 2The reduction of the specific refractory power that composition causes can obtain the high refractive index of expecting easily.Therefore, with respect to the glass total mass that oxide compound converts and forms, ZrO 2The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example ZrO 2, ZrF 4Deng as raw material, make glass contain ZrO 2Composition.
The ZnO composition is the composition that reduces the liquidus temperature of glass and improve the devitrification resistance of glass, is the optional member in the opticglass of the present invention.Especially, be below 10.0% by the containing ratio that makes the ZnO composition, can obtain high refractive index and the high chromatic dispersion expected easily.Therefore, with respect to the glass total mass that oxide compound converts and forms, the higher limit of ZnO composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example ZnO, ZnF 2Deng as raw material, make glass contain the ZnO composition.
Al 2O 3Composition is the composition of the viscosity when improving the chemical durability of glass and improving glass melting, is the optional member in the opticglass of the present invention.Especially, by making Al 2O 3The containing ratio of composition is below 10.0%, can improve glass melting, and weakens the tendency towards devitrification of glass.And, can suppress the increase of average coefficient of linear expansion (α).Therefore, with respect to the glass total mass that oxide compound converts and forms, Al 2O 3The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 5.0%.Can use for example Al 2O 3, Al (OH) 3, AlF 3Deng as raw material, make glass contain Al 2O 3Composition.
Ta 2O 5Composition is the composition that improves the specific refractory power of glass, is the optional member in the opticglass of the present invention.Especially, by making Ta 2O 5The containing ratio of composition is below 10.0%, can make glass be difficult to devitrification.Therefore, with respect to the glass total mass that oxide compound converts and forms, Ta 2O 5The higher limit of composition containing ratio is preferably 10.0%, more preferably 8.0%, most preferably is 4.0%.Can use for example Ta 2O 5Deng as raw material, make glass contain Ta 2O 5Composition.
Sb 2O 3Composition is to improve the composition of glass to the transmissivity of short-wavelength visible light, is the composition that has the deaeration effect when melten glass simultaneously.Especially, by making Sb 2O 3The content of composition is below 1.0%, Sb 2O 3Composition is difficult to fusion equipment precious metals such as (particularly) Pt alloying take place, and reduce on the mould and adhere to impurity, thereby the surface that can reduce glass shaping body produces concavo-convex or muddy.Therefore, with respect to the total mass of oxide compound benchmark, Sb 2O 3The higher limit of component content is preferably 1.0%, more preferably 0.8%, most preferably is 0.5%.Can use for example Sb 2O 3, Sb 2O 5, Na 2H 2Sb 2O 75H 2O etc. make glass contain Sb as raw material 2O 3Composition.
Should illustrate, make the composition of glass clarifying, deaeration be not limited to above-mentioned Sb 2O 3Composition can use known finings in the glass manufacturing area, deaerating agent or their combination.
＜composition〉about not containing
Then, composition that should not contain in the opticglass of the present invention and the composition that does not preferably contain are described.
In the scope of not damaging glass performance of the present invention, can add other composition to opticglass of the present invention as required.
And, 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, no matter containing separately respectively or compound containing under a spot of situation, all can make glass coloring, the specific wavelength that has in visibility region produces the character that absorbs, therefore particularly in the opticglass that uses the visibility region wavelength, preferably do not contain above-mentioned metal ingredient in fact.
In addition, because lead compound such as PbO and Th, Cd, Tl, Os, each composition of Be, Se, tend to control its use as harmful chemical in recent years, not only in the manufacturing process of glass, even all need aspect environmental cure, take measures in the processing after manufacturing procedure and the commercialization.Therefore, under the situation of the influence aspect the attention environment, remove and inevitably sneak into, preferably do not contain these compositions in fact.Thus, can make the material that does not contain contaminate environment in the opticglass in fact.Therefore, even aspect environmental cure, do not take special measure, also can make, process and discard this opticglass.
Glass composition of the present invention, its composition uses the quality % of the glass total mass of forming with respect to the oxide compound conversion to represent, rather than directly represent with mole %, but satisfy each composition that exists in the glass composition of various characteristics of the presently claimed invention, the composition that it is represented with mole % is roughly following value in oxide compound conversion composition.
P 2O 5Composition 5.0～40.0mol% and
Nb 2O 5Composition 5.0～30.0mol%,
And
TiO 2Composition 0～40.0mol% and/or
BaO composition 0～30.0mol% and/or
Li 2O composition 0～50.0mol% and/or
Na 2O composition 0～50.0mol% and/or
K 2O composition 0～30.0mol% and/or
WO 3Composition 0～15.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
Wherein, in the opticglass of first and second embodiments, it is grouped into each one-tenth that mole % represents, converting to form in oxide compound is roughly following value.
P 2O 5Composition 5.0～40.0mol% and
Nb 2O 5Composition 5.0～30.0mol%,
And
TiO 2Composition 0～40.0mol% and/or
BaO composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
Li 2O composition 0～30.0mol% and/or
Na 2O composition 0～30.0mol% and/or
K 2O composition 0～15.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
WO 3Composition 0～15.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
In addition, in the opticglass of the 3rd embodiment, it is grouped into each one-tenth that mole % represents, converting to form in oxide compound is roughly following value.
P 2O 5Composition 5.0～40.0mol% and
Nb 2O 5Composition 5.0～30.0mol%,
And
TiO 2Composition 0～15.0mol% and/or
BaO composition 0～30.0mol% and/or
Li 2O composition 0～50.0mol% and/or
Na 2O composition 0～50.0mol% and/or
K 2O composition 0～30.0mol% and/or
WO 3Composition 0～15.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
In addition, in the opticglass of the 4th embodiment, it is grouped into each one-tenth that mole % represents, converting to form in oxide compound is roughly following value.
P 2O 5Composition 5.0～40.0mol%,
Nb 2O 5Composition 5.0～30.0mol% and
BaO composition 7.0～30.0mol%/or
And
Li 2O composition 0～50.0mol% and/or
Na 2O composition 0～50.0mol% and/or
K 2O composition 0～30.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
TiO 2Composition 0～40.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
WO 3Composition 0～15.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
In addition, in the opticglass of the 5th embodiment, it is grouped into each one-tenth that mole % represents, converting to form in oxide compound is roughly following value.
P 2O 5Composition 5.0～40.0mol%,
Nb 2O 5Composition 5.0～30.0mol% and
TiO 2Composition 13.0～40.0mol%
And
WO 3Composition 0～15.0mol% and/or
BaO composition 0～30.0mol% and/or
Li 2O composition 0～50.0mol% and/or
Na 2O composition 0～50.0mol% and/or
K 2O composition 0～30.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
In addition, in the opticglass of the 6th embodiment, it is grouped into each one-tenth that mole % represents, converting to form in oxide compound is roughly following value.
P 2O 5Composition 5.0～40.0mol% and
Nb 2O 5Composition 5.0～30.0mol%,
And
Li 2O composition 0～50.0mol% and/or
Na 2O composition 0～50.0mol% and/or
K 2O composition 0～30.0mol% and/or
BaO composition 0～20.0mol% and/or
WO 3Composition 0～15.0mol% and/or
MgO composition 0～20.0mol% and/or
CaO composition 0～25.0mol% and/or
SrO composition 0～15.0mol% and/or
Y 2O 3Composition 0～4.0mol% and/or
La 2O 3Composition 0～3.0mol% and/or
Gd 2O 3Composition 0～3.0mol% and/or
B 2O 3Composition 0～20.0mol% and/or
SiO 2Composition 0～20.0mol% and/or
GeO 2Composition 0～15.0mol% and/or
TiO 2Composition 0～40.0mol% and/or
Bi 2O 3Composition 0～4.0mol% and/or
ZrO 2Composition 0～13.0mol% and/or
ZnO composition 0～20.0mol% and/or
Al 2O 3Composition 0～15.0mol% and/or
Ta 2O 5Composition 0～3.0mol% and/or
Sb 2O 3Composition 0～0.3mol%.
[manufacture method]
Opticglass of the present invention for example can be made in the following ways.Promptly, above-mentioned raw materials is mixed the content that makes each composition to be reached in the specified range, after the mixture of making put into the thick fusion of quartz crucible or aluminium crucible, put into platinum crucible, platinum alloy crucible or iridium crucible again 1000～1300 ℃ temperature range fusion 2～10 hours, after stirring homogenizes and carries out de-bubble etc., be cooled to and carry out essence below 1250 ℃ again and stir (げ Stir mixes on the bodyguard) and remove vein, be cast into slowly cooling in the mould.
[rerum natura]
Opticglass of the present invention need both have high refractive index (n d) also have a high chromatic dispersion.Especially, the specific refractory power (n of opticglass of the present invention d) lower value be preferably 1.70, more preferably 1.75, more preferably 1.80, most preferably be 1.90, higher limit is preferably 2.20, more preferably 2.15, most preferably is 2.10.And, the Abbe number (ν of opticglass of the present invention d) higher limit be preferably 25, more preferably 22, more preferably 20, most preferably be 19.Thus, can increase the degree of freedom of optical design, even and the element attenuation also can be obtained very big refraction of light amount.Abbe number (the ν of opticglass of the present invention should be described d) lower value be not particularly limited, in most cases, according to the present invention and the Abbe number (ν of glass d) probably be more than 10, be specially more than 12, more specifically be more than 15.
And opticglass of the present invention is preferred painted few.Especially, if recently represent paintedly with the transmission of glass, spectral transmittance is shown as 70% o'clock wavelength (λ in the sample that opticglass thickness then of the present invention is 10mm 70) following for 500nm, more preferably 480nm following, more preferably 460nm following, most preferably be below the 450nm.Thus, the absorption limit of glass is positioned near the ultraviolet region, can improves the transparency of glass, thereby can use the material of this opticglass as optical elements such as lens in the visible region.
Especially, the preferred devitrification resistance height of the opticglass of first embodiment of the invention.Especially, opticglass of the present invention preferably has the low liquidus temperature below 1200 ℃.More specifically, the higher limit of the liquidus temperature of opticglass of the present invention is preferably 1200 ℃, more preferably 1150 ℃, most preferably is 1100 ℃.Thus,, also can reduce the glass generation crystallization of making, thereby can improve, can reduce influence the optical characteristics of the optical element that uses glass from the devitrification resistance of molten state when forming glass even more flowing out melten glass under the low temperature.On the other hand, the lower value of the liquidus temperature of opticglass of the present invention is not particularly limited, but according to the present invention and the liquidus temperature of glass, in most cases, probably be more than 500 ℃, be specially more than 550 ℃, more specifically be more than 600 ℃.Should illustrate, " liquidus temperature " in this specification sheets is meant, with being ground into diameter is that beaded glass sample about 2mm is placed on the platinum plate, this glass specimen is placed on to have 800 ℃ to 1220 ℃ inclination temperature (Wen Du Pour oblique) stove in 30 minutes, take out the cooling back by being to have or not crystallization in 80 times the microscopic examination glass with multiplying power, measure the minimum temperature that crystallization and devitrification do not take place in the glass.
In addition, the opticglass of first embodiment of the invention preferably has highly-acidproof.Especially, the chemical durability of measuring according to the glass powder method of JOGIS06-1999 (acid resistance) be preferably 1～5 grade, more preferably 1～4 grade, most preferably be 1～3 grade.Thus, when opticglass is carried out attrition process, can reduce the muddiness of the glass that acid lapping liquid and washings cause, thereby can carry out attrition process easilier.Wherein, " acid resistance " is meant the weather resistance of glass to acid attack, and this acid resistance can be measured by specification " measuring method of the chemical durability of opticglass " JOGIS06-1999 according to Japanese optics nitre industry.And " chemical durability (acid resistance) of powder method mensuration is 1～5 grade " is meant, in the rate of weight loss (reduction rate) of sample mass before and after measuring, the chemical durability of measuring according to JOGIS06-1999 (acid resistance) less than 2.20 quality %.Should illustrate, the rate of weight loss less than 0.20 quality % of sample mass before and after " 1 grade " of chemical durability (acid resistance) is meant and measures, the rate of weight loss of sample mass was the above and less than 0.35 quality % of 0.20 quality % before and after " 2 grade " was meant and measures, the rate of weight loss of sample mass was the above and less than 0.65 quality % of 0.35 quality % before and after " 3 grade " was meant and measures, the rate of weight loss of sample mass was the above and less than 1.20 quality % of 0.65 quality % before and after " 4 grade " was meant and measures, the rate of weight loss of sample mass was the above and less than 2.20 quality % of 1.20 quality % before and after " 5 grade " was meant and measures, and the rate of weight loss of sample mass was more than the 2.20 quality % before and after " 6 grade " was meant and measures.
On the other hand, the opticglass of second embodiment of the invention has specific wear intensity.Especially, the lower value of the wear intensity of measuring according to the measuring method of " measuring method of the wear intensity of JOGIS10-1994 opticglass " is preferably 100, more preferably 150, most preferably is 200, and higher limit is preferably 400, more preferably 350, most preferably is 300.By making wear intensity is more than 100, can grind glass easily when carrying out attrition process, thereby can improve the working (machining) efficiency of attrition process, easily carries out attrition process.On the other hand, be below 400 by making wear intensity, can reduce opticglass and produce unnecessary loss and damage, thereby can make the processing easeization of opticglass being carried out attrition process, thereby carry out attrition process easily.
In addition, the preferred average coefficient of linear expansion of the opticglass of second embodiment of the invention (α) is little.Especially, opticglass of the present invention preferably has low liquidus temperature, and this liquidus temperature is preferably 150 * 10 -7K -1Below, more preferably 120 * 10 -7K -1Below, most preferably be 100 * 10 -7K -1Below.Thus, when using mould that opticglass is carried out press molding, can reduce because of lens and the preformed articles of temperature variation after causing being shaped and expand or shrink.Therefore, when particularly after shaping, cooling off, can reduce to cause lens generation impression (depression) or crack to outside occurrence temperature gradient from lens are inner.
On the other hand, the opticglass of the present invention the 3rd, the 5th and the 6th embodiment has the vitrifying point (Tg) below 700 ℃.Thus, glass is more softening under the low temperature, thereby can carry out press molding to glass with lower temperature.And, also can reduce the mould generation acidifying that is used for precise pressurization shaping, thereby prolong the work-ing life of mould.Therefore, the higher limit of the vitrifying point of opticglass of the present invention (Tg) is preferably 700 ℃, more preferably 680 ℃, more preferably 670 ℃, most preferably is 650 ℃.Should illustrate, the lower limit of the vitrifying point of opticglass of the present invention (Tg) is as being not particularly limited, then according to the present invention and the vitrifying point (Tg) of glass, in most cases, probably be more than 100 ℃, be specially more than 150 ℃, more specifically be more than 200 ℃.
On the other hand, the opticglass of four embodiment of the invention preferably has high resistance to detergents.Especially, the resistance to detergents of measuring according to ISO test method(s) resistance to detergents (ISO9689:1990 (E)) (PR) is preferably 1～3 grade, more preferably 1～2 grade, most preferably is 1 grade.Thus, when after attrition process, opticglass being washed, can reduce the glass muddiness that causes because of water-washing liquid, therefore can easier opticglass be washed.Wherein " resistance to detergents " is meant, under the situation of before shaping, lens preliminary shaping material being washed, and perhaps under the situation that the lens that are shaped are washed, the quality of yellowing state when the drug class that is used to wash etc. contacts certain hour.This resistance to detergents can be measured by ISO test method(s) resistance to detergents (ISO9689:1990 (E)).And " resistance to detergents (PR) is 1～3 grade " is meant, the resistance to detergents of obtaining according to ISO test method(s) resistance to detergents (ISO9689:1990 (E)) (PR) is that the needed time of glass coating of corroding 0.1 μ m will be longer than 15 minutes.
[preformed articles and optical element]
Opticglass of the present invention can be used for various optical elements and optical design, and the wherein preferred especially method of being carried out press molding (precise pressurization shaping etc.) by opticglass of the present invention of using is made lens and optical elements such as prism, speculum.Thus, when being used for this opticinstrument that makes the visible transmission optical element such as photographic camera, projector, high meticulous and high-precision imaging characteristic can be realized, the miniaturization of optical system in these opticinstruments can be realized simultaneously.At this, during optical element that making is made of opticglass of the present invention, can omit machining and attrition process, thereby preferably the glass of molten state is dripped from the spout of outlet pipes such as platinum and make preformed articles for precise pressurization shaping such as spherical, again this preformed articles for precise pressurization shaping is carried out precise pressurization shaping.
[embodiment]
The table 1 expression embodiment of the invention (No.A1～No.A7) and the glass of comparative example (No.A1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70), liquidus temperature and the chemical durability (acid resistance) measured by powder method.And, the table 2 expression embodiment of the invention (No.B1～No.B5) and the glass of comparative example (No.B1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70), wear intensity and average coefficient of linear expansion.In addition, the table 3 expression embodiment of the invention (No.C1～No.C5) and the glass of comparative example (No.C1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70) and vitrifying point (Tg).In addition, the table 4 expression embodiment of the invention (No.D1～No.D5) and the glass of comparative example (No.D1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70) and the resistance to detergents (PR) that draws by the ISO test method(s).Table 5～table 7 expression the embodiment of the invention (No.E1～No.E14) and the glass of comparative example (No.E1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70) and vitrifying point (Tg).In addition, the table 8 expression embodiment of the invention (No.F1～No.F5) and the glass of comparative example (No.F1) composition, specific refractory power (n d), Abbe number (ν d), spectral transmittance is shown as 70% o'clock wavelength (λ 70) and vitrifying point (Tg).Should illustrate that following examples are to illustrate for example, the present invention is not limited only to these embodiment.
The embodiment of the invention (No.A1～No.A7, No.B1～No.B5, No.C1～No.C5, No.D1～No.D5, No.E1～No.E14, opticglass and the comparative example (No.A1 of No.F1～No.F5), No.B1, No.C1, No.D1, No.E1, No.F1) glass, all selected suitable with each composition raw material respectively oxide compound, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide and metaphosphoric acid compound etc. are usually used in the high-purity raw of opticglass, after carrying out weighing and mix according to the proportion of composing of each embodiment shown in table 1～table 8 and comparative example, put into platinum crucible, the fusion difficulty of forming according to glass is with electric furnace fusion 2～10 hours in 1000～1300 ℃ temperature range, after stirring homogenizes and carries out deaeration etc., be cooled to below 1250 ℃, restir homogenizes and is cast in the mould, slowly cools off and makes.
Wherein, the specific refractory power (n of the glass of the opticglass of embodiment and comparative example d) and Abbe number (ν d) can measure by specification JOGIS01-2003 according to Japanese optics nitre industry.Should illustrate, use the glass of handling in annealing furnace as annealing conditions with the slow speed of cooling of-25 ℃/hr, as the glass of this mensuration use.
And the transmissivity of the opticglass of embodiment and the glass of comparative example can be measured by specification JOGIS02 according to Japanese optics nitre industry.In addition, recently obtain glass by the transmission of measuring glass among the present invention non-coloring and painted degree are arranged.Particularly, measuring thickness according to JISZ8722 is the spectral transmittance of the parallel grinding object of opposite face under 200～800nm wavelength of 10 ± 0.1mm, obtains λ 70(transmittance is 70% o'clock a wavelength).
Wherein, (liquidus temperature of No.A1～opticglass No.A7) and the glass of comparative example (No.A1) is measured by the following method: the glass specimen the pulverized interval with 10mm is placed on the platinum plate for suitable with the opticglass of first embodiment, embodiment, place it in and have 800 ℃ and kept 30 minutes to the stove of 1220 ℃ of inclination temperature, take out the cooling back by being to have or not crystallization in 80 times the microscopic examination glass specimen with multiplying power.At this moment, opticglass is ground into the granular of diameter 2mm as sample.
In addition, embodiment (can measure by specification " measuring method of the chemical durability of opticglass " JOGIS06-1999 according to Japanese optics nitre industry by the acid resistance of No.A1～opticglass No.A7) and the glass of comparative example (No.A1).That is,, and put into the platinum cage with the glass specimen that is ground into granularity 425～600 μ m specific gravity flask of packing into.The platinum cage is put into flask at the bottom of the silica glass rounding that the 0.01N aqueous nitric acid is housed, in the ebullient water-bath, handled 60 minutes.Calculating the rate of weight loss (quality %) of the glass specimen after the processing, is that 1 grade, rate of weight loss less than 0.20～0.35 o'clock are that 2 grades, rate of weight loss less than 0.35～0.65 o'clock are that 3 grades, rate of weight loss less than 0.65～1.20 o'clock are that 4 grades, rate of weight loss less than 1.20～2.20 o'clock are that 5 grades, rate of weight loss are 2.20 to be 6 grades when above during this rate of weight loss (quality %) less than 0.20.At this moment, the acid resistance of the more little then glass of number of degrees is excellent more.
On the other hand, suitable with the opticglass of second embodiment, embodiment (measure according to " measuring method of the wear intensity of JOGIS10-1994 opticglass " by the wear intensity of No.B1～opticglass No.B5) and the glass of comparative example (No.B1).Promptly, sample with the glass gusset of 30 * 30 * 10mm size, be placed on per minute and horizontally rotate the last position of the 60 cast iron plates (250mm φ) that change apart from plate center 80mm, vertically apply the load of 9.8N (1kgf) on one side, supply with on one side the lapping liquid 5 minutes that in water 20ml, is added with 10g#800 (median size 20 μ m) abrasive substances (aluminum oxide A abrasive particle) equally, sample and plate are rubbed.Sample mass before and after grinding is measured, obtained the loss quality of sample.According to the loss quality of obtaining the specified standard test specimen of Japanese optics nitre industry meeting with quadrat method, calculate according to following formula:
Wear intensity={ (the wearing and tearing quality/proportion of sample)/(the wearing and tearing quality/proportion of standard test specimen) } * 100
In addition, the embodiment (average coefficient of linear expansion the when average coefficient of linear expansion (α) of No.B1～opticglass No.B5) and the glass of comparative example (No.B1) is obtained-30～+ 70 ℃ according to Japanese optics nitre industry meeting specification JOGIS08-2003 " measuring method of the thermal expansion of opticglass ".
On the other hand, suitable with the opticglass of the 3rd, the 5th and the 6th embodiment, embodiment (measure and obtain by using horizontal type exapnsion tester (horizontal type Peng Zhang Measuring decides device) by the vitrifying point (Tg) of No.C1～No.C5, No.E1～No.E14, No.F1～opticglass No.F5) and the glass of comparative example (No.C1, No.E1, No.F1).Wherein, survey the glass that periodic sample uses φ 4.5mm, length 5mm, heat-up rate is 4 ℃/min.
On the other hand, suitable with the opticglass of the 4th embodiment, embodiment (measure according to ISO test method(s) resistance to detergents (ISO9689:1990 (E)) by the resistance to detergents (PR) of No.D1～opticglass No.D5) and the glass of comparative example (No.D1).Promptly, 6 and be heated to 50 ℃ and be the refining tripolyphosphate sodium water solution of 0.01mol/L concentration will have been ground as test film, with its dip treating certain hour (15 minutes, 1 hour, 4 hours, 16 hours) for the glass specimen of 30mm * 30mm * 2mm plays to put into the platinum line.After the dip treating, the quality reduction of weighing sample, calculating corroding thickness according to following formula is the needed time of glass coating of 0.1 μ m.But it is the value that the minimum test duration of 1mg when above gets that quality reduction according to each sample is adopted in this calculating.And the needed time of glass coating of corroding 0.1 μ m is 1 grade when being longer than 240 minutes, and to be longer than 60 minutes and to be 2 grades below 240 minutes the time, be that 3 grades, less than are 4 grades below 60 minutes the time more than 15 minutes in the time of 15 minutes.At this moment, the resistance to detergents of the more little then glass of progression is excellent more.
t0.1＝te·d·S/((m1-m2)·100)
T0.1: the needed time of glass coating (branch) of corroding 0.1 μ m
Te: treatment time (branch)
D: proportion
S: the surface-area (cm of sample 2)
M1-m2: the quality reduction (mg) of sample
[table 1]
Figure BDA0000050241700000351
[table 2]
[table 3]
Figure BDA0000050241700000371
[table 4]
Figure BDA0000050241700000381
[table 5]
Figure BDA0000050241700000391
[table 6]
Figure BDA0000050241700000401
[table 7]
Figure BDA0000050241700000411
[table 8]
Figure BDA0000050241700000421
As shown in table 1, the liquidus temperature of the opticglass of the embodiment of the invention is below 1200 ℃, more specifically be 1120 ℃ of less thaies, and this liquidus temperature is more than 500 ℃.On the other hand, the liquidus temperature of the glass of comparative example (No.A1) is 1120 ℃.Hence one can see that, and (No.A1～opticglass No.A7) and the glassy phase ratio of comparative example (No.A1), liquidus temperature is low and be difficult for causing devitrification for the embodiment of the invention.
And as shown in table 2, (wear intensity of the opticglass of No.B1～No.B5) is below 400 the embodiment of the invention, more specifically is less than 300, and this wear intensity is more than 100, more specifically is more than 200.On the other hand, the wear intensity of the glass of comparative example (No.B1) is 300.Hence one can see that, and (No.B1～opticglass No.B5) and the glassy phase ratio of comparative example (No.B1), wear intensity is low for the embodiment of the invention.
In addition, shown in table 3 and table 5～table 8, (vitrifying point (Tg) of the opticglass of No.C1～No.C5, No.E1～No.E14, No.F1～No.F5) is below 700 ℃ the embodiment of the invention, more specifically is below 670 ℃.
Especially, (vitrifying point (Tg) of the opticglass of No.C1～No.C5, No.F1～No.F5) is below 650 ℃ the embodiment of the invention.On the other hand, the vitrifying point (Tg) of the glass of comparative example (No.C1, No.F1) is higher than 650 ℃.Hence one can see that, and (No.C1～No.C5, No.F1～opticglass No.F5) and the glassy phase ratio of comparative example (No.C1, No.F1) have reduced TG point (Tg), and soften under lower Heating temperature easily the embodiment of the invention.
In addition, as shown in table 4, (resistance to detergents (PR) that the opticglass of No.D1～No.D5) draws by the ISO test method(s) is 1～3 grade to the embodiment of the invention, more specifically is 1 grade.On the other hand, its resistance to detergents that draws by the ISO test method(s) (PR) of the glass of comparative example (No.D1) is 3 grades.Hence one can see that, the embodiment of the invention (No.D1～opticglass No.D5) and the glassy phase ratio of comparative example (No.D1), resistance to detergents excellence.
In addition, the λ of the opticglass of the embodiment of the invention 70(wavelength during transmissivity 70%) is below the 500nm, more specifically is below the 492nm, is in the scope of expectation.
Especially, the embodiment of the invention (λ of the opticglass of No.A1～No.A7) 70Be below the 450nm.On the other hand, the λ of the glass of comparative example (No.A1) 70Greater than 450nm.Hence one can see that, and (No.A1～opticglass No.A7) and the glassy phase ratio of comparative example (No.A1) are difficult to painted the embodiment of the invention.
And, the embodiment of the invention (λ of the opticglass of No.B1～No.B5) 70(wavelength during transmissivity 70%) is below the 480nm.On the other hand, the λ of the glass of comparative example (No.B1) 70Greater than 480nm.Hence one can see that, and (No.B1～opticglass No.B5) and the glassy phase ratio of comparative example (No.B1) are difficult to painted the embodiment of the invention.
In addition, the embodiment of the invention (λ of the opticglass of No.C1～No.C5, No.D1～No.D5) 70(wavelength during transmissivity 70%) is below the 450nm.On the other hand, the λ of the glass of comparative example (No.D1) 70Be 500nm.Hence one can see that, and (No.D1～opticglass No.D5) and the glassy phase ratio of comparative example (No.D1) are difficult to painted the embodiment of the invention.
In addition, the embodiment (λ of the opticglass of No.F1～No.F5) 70(wavelength during transmissivity 70%) is below the 470nm.On the other hand, the λ of the glass of comparative example (No.F1) 70Greater than 470nm.Hence one can see that, and (No.F1～opticglass No.F5) and the glassy phase ratio of comparative example (No.F1) are difficult to painted the embodiment of the invention.
In addition, the specific refractory power (n of the opticglass of the embodiment of the invention d) be more than 1.70, more specifically be more than 1.80, this specific refractory power (n simultaneously d) be below 2.20, more specifically be below 2.10, be in the scope of expectation.Especially, the embodiment (specific refractory power (n of the opticglass of No.C1～No.C5) d) be more than 1.86.And, the embodiment (specific refractory power (n of the opticglass of No.D1～No.D5) d) be more than 1.84.In addition, the embodiment (specific refractory power (n of the opticglass of No.E1～No.E14) d) be more than 1.90.In addition, the embodiment (specific refractory power (n of the opticglass of No.F1～No.F5) d) be more than 1.92.On the other hand, the embodiment of the invention (specific refractory power (n of the opticglass of No.B1～No.B5, No.C1～No.C5, No.D1～No.D5, No.E1～No.E14, No.F1～No.F5) d) be below 2.00.
In addition, the Abbe number (ν of the opticglass of the embodiment of the invention d) be more than 10, more specifically be more than 15, while its Abbe number (ν d) be below 25, be in the scope of expectation.Especially, the embodiment of the invention (Abbe number (ν of the opticglass of No.B1～No.B5) d) be more than 17.On the other hand, the embodiment of the invention (Abbe number (ν of the opticglass of No.B1～No.B5, No.D1～No.D5) d) be below 23.And, the embodiment (Abbe number (ν of the opticglass of No.C1～No.C5) d) be below 24.
Especially, the embodiment (Abbe number (ν of the opticglass of No.E1～No.E14, No.F1～No.F5) d) be below 20.On the other hand, the Abbe number (ν of the glass of comparative example (No.E1, No.F1) d) greater than 20.Hence one can see that, and (No.E1～No.E14, No.F1～opticglass No.F5) and the glassy phase ratio of comparative example (No.E1, No.F1) have high chromatic dispersion, low Abbe number (ν to the embodiment of the invention d).
And (its chemical durability (acid resistance) of measuring by powder method of the opticglass of No.A1～No.A7) is 1～5 grade to the embodiment of the invention, more specifically is 1～2 grade.On the other hand, the glass of comparative example (No.A1), its chemical durability (acid resistance) of measuring according to powder method is 4 grades.Hence one can see that, the embodiment of the invention (No.A1～opticglass No.A7) and the glassy phase ratio of comparative example (No.A1), acid resistance excellence.
In addition, (average coefficient of linear expansion (α) of the opticglass of No.B1～No.B5) is 150 * 10 to the embodiment of the invention -7K -1Below, more specifically be 100 * 10 -7K -1Below.On the other hand, the average coefficient of linear expansion (α) of the glass of comparative example (No.B1) is greater than 100 * 10 -7K -1Below.Hence one can see that, and (No.B1～opticglass No.B5) and the glassy phase ratio of comparative example (No.B1), (α) is little for average coefficient of linear expansion for the embodiment of the invention.
And, (opticglass of No.A1～No.A7) cuts and grinds and forms preformed articles to the embodiment of the invention, it is softening this preformed articles to be put into mold heated on one side, it is carried out press molding on one side, and the molding that obtains carried out attrition process, thereby can stably opticglass be processed into the shape of various lens.
In addition, (opticglass of No.B1～No.B5) is put into mould, makes it softening Yi Bian heat opticglass, Yi Bian it is carried out press molding with the embodiment of the invention, the molding that obtains is carried out attrition process, thus the shape that opticglass is processed into various lens that can be stable.
In addition, (opticglass of No.C1～No.C5, No.E1～No.E14, No.F1～No.F5) forms preformed articles for precise pressurization shaping to use the embodiment of the invention, preformed articles for precise pressurization shaping is carried out precise pressurization shaping processing, thereby can stably opticglass be processed into the shape of various lens.
In addition, (opticglass of No.D1～No.D5) cuts and grinds and forms preformed articles to the embodiment of the invention, this preformed articles being put into mold heated on one side makes it softening, it is carried out press molding on one side, and the molding that obtains carried out attrition process, the glass of washing after the attrition process, thus can stably opticglass be processed into the shape of various lens.
Hence one can see that, the specific refractory power (n of the opticglass of the embodiment of the invention d) be in the scope of expectation, have high chromatic dispersion (low Abbe number ν simultaneously d), and high to the transparency of the light of visible region wavelength.
Especially, the embodiment of the invention (the devitrification resistance height of opticglass when glass forms of No.A1～No.A7), and be difficult for taking place when making grinding rod muddy in the glass as can be known by glass.
In addition, as can be known the embodiment of the invention (opticglass of No.B1～No.B5) easily carries out attrition process, even and the glass occurrence temperature change and also be difficult to cause and expand or shrink.
In addition, as can be known the embodiment of the invention (opticglass of No.C1～No.C5, No.E1～No.E14, No.F1～No.F5) carries out low temperature softening easily.
In addition, as can be known the embodiment of the invention (opticglass of No.D1～No.D5) washs when making preliminary shaping material or optical element easily.
More than, to be exemplified as purpose the present invention being had been described in detail, present embodiment is only to be exemplified as purpose, can be understood as those skilled in the art and can not exceed thought of the present invention and scope and carry out many changes.

Claims (21)

1. opticglass, wherein, the glass total mass with respect to oxide compound converts and forms in quality %, contains the P below 40.0% more than 5.0% 2O 5Composition, the Nb more than 10.0% below 60.0% 2O 5Composition.
2. opticglass as claimed in claim 1, its spectral transmittance are shown as 70% o'clock wavelength (λ 70) be below the 500nm, and have the liquidus temperature below 1200 ℃ more than 500 ℃.
3. opticglass as claimed in claim 1, it has the wear intensity below 400 more than 100.
4. opticglass as claimed in claim 1, its resistance to detergents that draws by the ISO test method(s) (PR) is 1～3 grade.
5. opticglass as claimed in claim 1, it contains Li 2O composition, Na 2O composition, K 2At least a in the O composition as neccessary composition, and have vitrifying point (Tg) below 700 ℃.
6. as each described opticglass in the claim 1 to 5, wherein, the glass total mass that converts and form with respect to oxide compound is in quality %, TiO 2The content of composition is below 30.0%.
7. opticglass as claimed in claim 1, wherein, with respect to the glass total mass of oxide compound conversion composition, in quality %, its TiO 2Composition contain quantity not sufficient 10.0%, and have the vitrifying point (Tg) below 700 ℃.
8. opticglass as claimed in claim 1, wherein, with respect to the glass total mass that oxide compound converts and forms, in quality %, it contains the TiO below 30.0% more than 10.0% 2Composition has the vitrifying point (Tg) below 700 ℃.
9. as each described opticglass in the claim 1 to 8, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
WO 3Composition 0～20.0% and/or
BaO composition 0～30.0% and/or
SiO 2Composition 0～10.0%.
10. as each described opticglass in the claim 1 to 9, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
Li 2O composition 0～20.0% and/or
Na 2O composition 0～35.0% and/or
K 2O composition 0～20.0%.
11. opticglass as claimed in claim 10, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Li 2O+Na 2O+K 2O is below 35.0%.
12. as claim 10 or 11 described opticglass, it contains Li 2O composition, Na 2O composition and K 2Composition in the O composition more than 2 kinds.
13. as each described opticglass in the claim 1 to 12, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
MgO composition 0～5.0% and/or
CaO composition 0～10.0% and/or
SrO composition 0～10.0%.
14. opticglass as claimed in claim 13, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and MgO+CaO+SrO+BaO are below 30.0%.
15. as each described opticglass in the claim 1 to 14, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
Y 2O 3Composition 0～10.0% and/or
La 2O 3Composition 0～10.0% and/or
Gd 2O 3Composition 0～10.0%.
16. opticglass as claimed in claim 15, wherein, with respect to the glass total mass that oxide compound converts and forms, quality and Y 2O 3+ La 2O 3+ Gd 2O 3Be below 20.0%.
17. as each described opticglass in the claim 1 to 16, wherein, with respect to the glass total mass that oxide compound converts and forms, % counts with quality:
B 2O 3Composition 0～10.0% and/or
GeO 2Composition 0～10.0% and/or
Bi 2O 3Composition 0～20.0% and/or
ZrO 2Composition 0～10.0% and/or
ZnO composition 0～10.0% and/or
Al 2O 3Composition 0～10.0% and/or
Ta 2O 5Composition 0～10.0% and/or
Sb 2O 3Composition 0～1.0%.
18. as each described opticglass in the claim 1 to 17, it has the specific refractory power below 2.20 (nd) more than 1.70, has the Abbe number below 25 more than 10 (ν d).
19. as each described opticglass in the claim 1 to 18, its spectral transmittance is shown as 70% o'clock wavelength (λ 70) be below the 500nm.
20. an optical element, it is to be made by each described opticglass in the claim 1 to 19.
21. a preformed articles for precise pressurization shaping, it is to be made by each described opticglass in the claim 1 to 19.
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