CN102234180A - Optical glass, optical element and performing body for precision pressurizing forming - Google Patents

Optical glass, optical element and performing body for precision pressurizing forming Download PDF

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CN102234180A
CN102234180A CN2011100857410A CN201110085741A CN102234180A CN 102234180 A CN102234180 A CN 102234180A CN 2011100857410 A CN2011100857410 A CN 2011100857410A CN 201110085741 A CN201110085741 A CN 201110085741A CN 102234180 A CN102234180 A CN 102234180A
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composition
glass
content
opticglass
total amount
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津田哲也
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Ohara Inc
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Ohara Inc
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Abstract

The invention aims at obtaining an optical glass, an optical element using the optical glass, and a performing body for precision pressurizing forming, the refractive index (nd) of the optical glass is in an expected range, and the optical glass is provided with a low Abbe number (vd), the optical glass is also advantaged by good durability of reduction amount of transmissivity before and after irradiation of ultraviolet rays, high transparency of visible light, small part dispersion rate, easy softening at lower temperature, and easy grinding and processing. The optical glass, with respective to a glass total mass amount converted to an oxide composition, by mole%, comprises TeO2 with content of 30.0%-70.0%, P2O5 with content of 0%-25.0%, and Bi2O3 with content of 0%-20%, and the reduction amount of transmissivity before and after irradiation of ultraviolet rays is reduced to below 5.0%. The optical glass and the performing body for precision pressurizing forming are formed by the above optical glass.

Description

Opticglass, optical element and precision press formation preform
Technical field
The present invention relates to opticglass, optical element and precision press formation preform.
Background technology
In recent years, use the digitizing of machine of optical system and height to become more meticulous and develop rapidly, to being that the requirement of high precision int, lightweight and miniaturization of the optical elements such as lens that use in the various optical devices of representative is strong day by day with photographic equipments such as digital camera and pick up cameras.
Therefore, make in the opticglass of optical element, particularly the demand to following high refractive index high dispersive glass is very strong, described high refractive index high dispersive glass can realize optical element and optical system lighting and miniaturization, have the high refractive index (n below 2.20 more than 1.80 d) and have Abbe number (ν below 25 d).As above-mentioned high refractive index high dispersive glass, for example as specific refractory power (n d) be more than 1.8, have an Abbe number (ν about 20 d) opticglass, it is known that to have with patent documentation 1 and 2 be the tellurate glass of representative.
[patent documentation 1] TOHKEMY 2001-180971 communique
[patent documentation 2] TOHKEMY 2006-182577 communique
[patent documentation 3] TOHKEMY 2008-105869 communique
Summary of the invention
When using above-mentioned glass to make optical element, can adopt following method: glass heats is softening, moulding (second-heating extrusion forming), the glass ware forming product that obtain are carried out the grinding abrasive method; And with the thermoplastic of preform material, carry out the method (precision press formation) of extrusion forming with mould with high precision molding surface, described preform material cuts off glass gob or glass block, grind and obtain, or obtain by moulding such as known floating moulding.
But second-order transition temperature (Tg) height of disclosed glass also is difficult to soften even above-mentioned glass heats in patent documentation 1 and the patent documentation 2.Therefore, if when wanting by the glass making preform material of patent documentation 1, with thermoplastic of preform material and extrusion forming making optical element, must improve the temperature of thermoplastic preform material, therefore, mould that uses in the extrusion forming and preform material cause bonding, perhaps influence the optical characteristics of optical element.
On the other hand, owing to disclosed glass in the patent documentation 2 contains more TiO 2And WO 3So it has low Abbe number (ν d), but above-mentioned glass is all painted, and low to visible light transmittance.Therefore, disclosed glass is difficult to realize simultaneously the low Abbe number (ν of glass in the patent documentation 2 d) and to the high transparent of visible light.
On the other hand, the inventor has made disclosed glass in the patent documentation 3, and the result is the high glass of wear intensity (Aa).Therefore, disclosed glass all is easy to be difficult to carry out attrition process at surface formation cut in the patent documentation 3, so be difficult to improve attrition process.
The present invention finishes in view of the above problems, the optical element and the precision press formation preform that the objective of the invention is to obtain a kind of opticglass and use this opticglass, the specific refractory power (n of described opticglass d) in desired scope, have a low Abbe number (ν simultaneously d), good to the patience of the transmissivity decrease (solarization) before and after the uviolizing, high to the transparency of visible light, the part scatter coefficient is little, be easy to soften and be easy to carry out attrition process under low temperature.
In order to solve above-mentioned problem, the inventor etc. have carried out deep experimental study repeatedly, found that by containing TeO 2Composition is as must composition and contain P as required 2O 5Composition and Bi 2O 3Composition, with TeO 2Composition, P 2O 5Composition and Bi 2O 3The containing ratio of composition is controlled in the specialized range, can realize the high refractive indexization of glass, simultaneously improve to disperse, obtain low Abbe number, second-order transition temperature (Tg) reduce, to the patience of the transmissivity decrease before and after the uviolizing become well, glass to the visible light transmittance raising, the part scatter coefficient diminishes and the wear intensity step-down, thereby finished the present invention.Particularly, the invention provides following invention.
(1) a kind of opticglass, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %, TeO 2The content of composition is 30.0～70.0%, P 2O 5The content of composition is 0～25.0%, and Bi 2O 3The content of composition is 0～20.0%, and the transmissivity decrease before and after the uviolizing is below 5.0%.
(2) as (1) described opticglass, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %, Nb 2O 5The content of composition is 0～25.0%.
(3) as (2) described opticglass, above-mentioned opticglass has the wear intensity below 800 more than 300.
(4) as each described opticglass in (1) to (3), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
Li 2The content of O composition is 0～20.0%,
Na 2The content of O composition is 0～20.0%,
K 2The content of O composition is 0～15.0%,
Cs 2The content of O composition is 0～15.0%.
(5) as each described opticglass in (1) to (4), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, Rn 2The total amount of O material is below 20.0%, in the formula, Rn be selected among Li, Na, K, the Cs more than a kind.
(6) as each described opticglass in (1) to (5), wherein, spectral transmission is 70% wavelength (λ 70) be below the 500nm.
(7) as each described opticglass in (1) to (6), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
The content of ZnO composition is 0～30.0%,
The content of MgO composition is 0～15.0%,
The content of CaO composition is 0～20.0%,
The content of SrO composition is 0～20.0%,
The content of BaO composition is 0～20.0%.
(8) as each described opticglass in (1) to (7), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, the total amount of RO material is less than 25.0%, in the formula, R be selected among Zn, Mg, Ca, Sr, the Ba more than a kind.
(9) as each described opticglass in (1) to (8), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
WO 3The content of composition is 0～10.0%,
B 2O 3The content of composition is 0～30.0%,
La 2O 3The content of composition is 0～10.0%.
(10) as each described opticglass in (1) to (9), described opticglass is lead-containing compounds not in fact.
(11) as each described opticglass in (1) to (10), wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
SiO 2The content of composition is 0～30.0%,
GeO 2The content of composition is 0～10.0%,
Al 2O 3The content of composition is 0～30.0%,
ZrO 2The content of composition is 0～20.0%,
Ga 2O 3The content of composition is 0～20.0%,
In 2O 3The content of composition is 0～20.0%,
Ta 2O 5The content of composition is 0～20.0%,
TiO 2The content of composition is 0～30.0%,
Gd 2O 3The content of composition is 0～25.0%,
Y 2O 3The content of composition is 0～20.0%,
Yb 2O 3The content of composition is 0～20.0%,
Ag 2The content of O composition is 0～less than 20.0%,
Sb 2O 3The content of composition is 0～1.0%,
CeO 2The content of composition is 0～1.0%.
(12) as each described opticglass in (1) to (11), above-mentioned opticglass has the specific refractory power (n below 2.20 more than 1.80 d), have the Abbe number (ν below 30 more than 16 d).
(13) as each described opticglass in (1) to (12), wherein, (θ g is F) with Abbe number (ν for the part scatter coefficient d) between, at ν dSatisfy (0.0016 * ν in≤25 the scope d+ 0.63460)≤(θ g, F)≤(0.00563 * ν d+ 0.75873) relation is at ν dSatisfy (0.0025 * ν in＞25 the scope d+ 0.65710)≤(θ g, F)≤(0.0034 * ν d+ 0.70300) relation.
(14) as each described opticglass in (1) to (13), wherein, second-order transition temperature (Tg) for be higher than 250 ℃, below 550 ℃.
(15) a kind of optical element is formed by each described opticglass in (1) to (14).
(16) a kind of precision press formation preform is formed by each described opticglass in (1) to (14).
(17) a kind of optical element carries out precision press formation with (16) described precision press formation with preform and obtains.
According to the present invention, by containing TeO 2Composition is as must composition and contain P as required 2O 5Composition and Bi 2O 3Composition can be realized the high refractive indexization of glass, improve simultaneously disperse, obtain low Abbe number,, glass good to the patience of the transmissivity decrease before and after the uviolizing to visible light transmittance improve, the part scatter coefficient is little and the wear intensity step-down.Therefore, can obtain specific refractory power (n d) in desired scope, have a low Abbe number (ν simultaneously d), good to the patience of the transmissivity decrease before and after the uviolizing, high to the transparency of visible light, under low temperature, be easy to soften and be easy to carry out the opticglass of attrition process and use its optical element and precision press formation preform.
Description of drawings
[Fig. 1] (θ g F) is the longitudinal axis, Abbe number (ν in order to be illustrated in the part scatter coefficient d) be the figure of the normal (normal line) shown in the rectangular coordinates of transverse axis.
Embodiment
Opticglass of the present invention is with respect to being scaled the total amount of glass that oxide compound is formed, in mole % TeO 2The content of composition is 30.0～70.0%, P 2O 5Content be 0～25.0%, Bi 2O 3Content be 0～20.0%.By with TeO 2Composition, P 2O 5Composition and Bi 2O 3Composition Control can realize that thus the high refractive indexization of glass, raising simultaneously disperse, obtain the transmissivity decrease reduction of low Abbe number, uviolizing front and back, glass is to visible light transmittance raising, second-order transition temperature (Tg) step-down and obtain suitable wear intensity in specialized range.Therefore, can obtain specific refractory power (n d) in desired scope, have a low Abbe number (ν simultaneously d), the transmissivity decrease before and after the uviolizing is low, high to the transparency of visible light, the part scatter coefficient is little, be easy to soften under low temperature and be easy to carry out the opticglass of attrition process and use its optical element and precision press formation preform.
Below the embodiment of opticglass of the present invention is elaborated.The present invention is not limited to following embodiment, in the scope of the object of the invention, can carry out by appropriate change.Need to prove,, omit suitably explanation sometimes, but do not limit the purport of invention for the repeat specification part.
[glass ingredient]
The compositing range of each composition that constitutes opticglass of the present invention is as described below.In this manual, when the containing ratio of each composition does not specify, all represent with quality % with respect to the total amount of glass that is scaled the oxide compound composition." being scaled oxide compound forms " herein, being meant that oxide compound that hypothesis uses as the raw material of glass constituent of the present invention, composite salt, metal fluoride etc. all are decomposed when fusion when changing oxide compound into, is 100% to represent the composition of each composition of containing in the glass with total amount of this generation oxide compound.
＜about necessary composition, any composition 〉
TeO 2Composition is for forming the composition of glass, for the specific refractory power that improves glass and dispersion, improve the composition of transmissivity simultaneously.Particularly by making TeO 2The containing ratio of composition is more than 30.0%, can improve the dispersion and the specific refractory power of glass, so can obtain desired Abbe number (ν d) and specific refractory power.On the other hand, by making TeO 2The containing ratio of composition is below 70.0%, can reduce liquid temperature, the devitrification resistance when improving glass formation of glass.In addition, contain a large amount of TeO 2During composition, wearability is worsened.Therefore, TeO 2Composition is preferably 30.0% with respect to the lower limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 35.0% more preferably, most preferably is 40.0%.In addition, above-mentioned TeO 2The upper limit of the containing ratio of composition is preferably 70.0%, more preferably is 65.0%, and more preferably 60.0%, most preferably less than 55%.
TeO 2Composition can use for example TeO 2Deng being contained in the glass as raw material.
P 2O 5Composition forms, reduces the composition of glass devitrification for promoting stable glass.Particularly by making P 2O 5The containing ratio of composition is below 25.0%, and the specific refractory power that can suppress glass reduces, and improves transmissivity simultaneously, suppresses the rising of second-order transition temperature (Tg).In addition, contain a large amount of P 2O 5During composition, wearability is worsened.Therefore, P 2O 5Composition is preferably 25.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 23.0% more preferably, most preferably is 20.0%.In addition, because P 2O 5Composition is any composition, thus can not make glass of the present invention even do not contain this composition yet, but in order to be easy to bring into play above-mentioned effect, P 2O 5The lower limit of composition is preferably 2.0%, is 4.0% more preferably, most preferably is 6.0%.
P 2O 5Composition can use for example Al (PO 3) 3, Ca (PO 3) 2, Ba (PO 3) 2, BPO 4, H 3PO 4Deng being contained in the glass as raw material.
Bi 2O 3Composition is for improving the composition of glass refraction.Particularly by making Bi 2O 3The containing ratio of composition is below 20.0%, can improve the dispersion of glass, is easy to carry out TeO simultaneously 2The vitrifying of composition obtains desired Abbe number (ν d), can reduce the transmissivity decrease of uviolizing front and back, can improve wearability.Meanwhile, because the liquid temperature and second-order transition temperature (Tg) step-down of glass, so the devitrification resistance can improve glass and form the time is easy to carry out extrusion forming.In addition, contain a large amount of Bi 2O 3During composition, transmissivity is worsened.Therefore, Bi 2O 3Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 18.0% more preferably, most preferably is 16.0%.In addition, because Bi 2O 3Composition is any composition, thus can not make glass of the present invention even do not contain this composition yet, but in order to be easy to bring into play above-mentioned effect, Bi 2O 3The lower limit of composition preferably surpasses 0%, more preferably is 2.0%, and more preferably 4.0%, most preferably be 8.0%.
Bi 2O 3Composition can use for example Bi 2O 3Deng being contained in the glass as raw material.
Nb 2O 5Composition is for improving the specific refractory power and the dispersive composition of glass.Particularly by making Nb 2O 5The containing ratio of composition is below 25.0%, and the devitrification resistance that can suppress glass reduces, and improves transmissivity, improves wearability simultaneously, suppresses the rising of second-order transition temperature (Tg).In addition, contain a large amount of Nb 2O 5During composition, the patience that the transmissivity before and after the uviolizing is reduced is worsened.Therefore, Nb 2O 5Composition is preferably 25.0% with respect to the upper limit of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 20.0%, and more preferably 18.0%, most preferably be 15.0%.In addition, because Nb 2O 5Composition is any composition, thus can not make glass of the present invention even do not contain this composition yet, but in order to be easy to bring into play above-mentioned effect, Nb 2O 5The lower limit of composition is preferably greater than 0%, more preferably greater than 2.0%, more preferably greater than 3.0%, most preferably greater than 5.0%.
Nb 2O 5Composition can use for example Nb 2O 5Deng being contained in the glass as raw material.
Li 2The O composition is any composition in the opticglass of the present invention for the solvent temperature of reduction glass and the composition of second-order transition temperature (Tg).Particularly by making Li 2The containing ratio of O composition is below 20.0%, can reduce the coefficient of expansion of glass, the accurate transfer printing of lens face when being easy to carry out extrusion forming, and the specific refractory power that suppresses glass simultaneously reduces, and improves transmissivity, improves the chemical durability of glass.In addition, contain a large amount of Li 2During the O composition, wearability is worsened.Therefore, Li 2The O composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
In addition, because Li 2O is any composition, thus can not make glass of the present invention even do not contain this composition yet, but in order to be easy to bring into play above-mentioned effect, Li 2The lower limit of O composition is preferably 0.5%, more preferably is 1.0%, and more preferably 2.0%.
Li 2The O composition can use for example Li 2CO 3, LiNO 3, LiF etc. is contained in the glass as raw material.
Na 2The O composition is any composition in the opticglass of the present invention for the solvent temperature of reduction glass and the composition of second-order transition temperature (Tg).Particularly by making Na 2The containing ratio of O composition is below 20.0%, can suppress glass refraction and reduce, and improves transmissivity, improves the chemical durability of glass.In addition, contain a large amount of Na 2During the O composition, wearability is worsened.Therefore, Na 2The O composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
In addition, because Na 2O is any composition, thus can not make glass of the present invention even do not contain this composition yet, but in order to be easy to bring into play above-mentioned effect, Na 2The lower limit of O composition is preferably 0.5%, more preferably is 1.0%, and more preferably 2.0%.
Na 2The O composition can use for example Na 2CO 3, NaNO 3, NaF, Na 2SiF 6Deng being contained in the glass as raw material.
K 2The O composition is any composition in the opticglass of the present invention for the solvent temperature of reduction glass and the composition of second-order transition temperature (Tg).Particularly by making K 2The containing ratio of O composition is below 15.0%, can suppress glass refraction and reduce, and improves transmissivity, improves the chemical durability of glass.In addition, contain a large amount of K 2During the O composition, wearability is worsened.Therefore, K 2The O composition is preferably 15.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 13.0% more preferably, most preferably is 10.0%.
K 2The O composition can use for example K 2CO 3, KNO 3, KF, KHF 2, K 2SiF 6Deng being contained in the glass as raw material.
Cs 2The O composition is any composition in the opticglass of the present invention for the composition of the solvent temperature of reduction glass.Particularly by making Cs 2The containing ratio of O composition is below 15.0%, can suppress glass refraction and reduce, and improves transmissivity, improves the chemical durability of glass.In addition, contain a large amount of Cs 2During the O composition, wearability is worsened.Therefore, Cs 2The O composition is preferably 15.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 13.0% more preferably, most preferably is 10.0%.
Cs 2The O composition can use for example Cs 2CO 3, CsNO 3Deng being contained in the glass as raw material.
Devitrification resistance when the ZnO composition forms for improving glass, reduce glass painted, improve wearability, improve the deliquescent composition of glass, be any composition in the opticglass of the present invention.Be below 30.0% by the containing ratio that makes the ZnO composition particularly, the liquid temperature that can suppress the glass that causes because of the excessive ZnO of containing composition raises.Therefore, the ZnO composition is preferably 30.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 25.0% more preferably, most preferably is 20.0%.Need to prove, even do not contain the opticglass that the ZnO composition also can obtain having desired high dispersive and high pressurization processibility, but by containing the ZnO composition more than 1.0%, can improve the transparency of glass, so can reduce the painted of glass to visible light.Therefore, in these cases, the ZnO composition is preferably 1.0% with respect to the lower limit of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 3.0%, and more preferably 5.0%.
The ZnO composition can use for example ZnO, ZnF 2Deng being contained in the glass as raw material.
The MgO composition is any composition in the opticglass of the present invention for improving transmissivity, the solvability that improves glass and the stable composition of glass in visibility region.Be below 15.0% particularly, can suppress glass refraction and reduce that the liquid temperature that suppresses glass simultaneously raises by the containing ratio that makes the MgO composition.Therefore, the MgO composition is preferably 15.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 13.0% more preferably, most preferably is 10.0%.
The MgO composition can use for example MgCO 3, MgF 2Deng being contained in the glass as raw material.
The CaO composition is any composition in the opticglass of the present invention for improving transmissivity, the solvability that improves glass and the stable composition of glass in visibility region.Be below 20.0% particularly, can suppress glass refraction and reduce that the liquid temperature that suppresses glass simultaneously raises by the containing ratio that makes the CaO composition.Therefore, the CaO composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
The CaO composition can use for example CaCO 3, CaF 2Deng being contained in the glass as raw material.
The SrO composition is any composition in the opticglass of the present invention for improving transmissivity, the solvability that improves glass and the stable composition of glass in visibility region.Be below 20.0% particularly, can suppress glass refraction and reduce that the liquid temperature that suppresses glass simultaneously raises by the containing ratio that makes the SrO composition.Therefore, the SrO composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
The SrO composition can use for example Sr (NO 3) 2, SrF 2Deng being contained in the glass as raw material.
Solvability and the stable composition of BaO composition for improving glass is any composition in the opticglass of the present invention.Be below 20.0% particularly, can suppress glass refraction and reduce that the liquid temperature that suppresses glass simultaneously raises by the containing ratio that makes the BaO composition.Therefore, the BaO composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
The BaO composition can use for example BaCO 3, Ba (NO 3) 2Deng being contained in the glass as raw material.
WO 3Composition is any composition in the opticglass of the present invention for improving the specific refractory power and the dispersive composition of glass.Particularly by making WO 3The containing ratio of composition is below 10.0%, can suppress second-order transition temperature (Tg) and liquid temperature and raise, so can keep good devitrification resistance, obtains good pressurization characteristic simultaneously.In addition, contain a large amount of WO 3During composition, transmissivity is worsened.Therefore, WO 3Composition is preferably 10.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, more preferably is 8.0%, most preferably less than 5.0%.
WO 3Composition can use for example WO 3Deng being contained in the glass as raw material.
B 2O 3Composition is any composition in the opticglass of the present invention for grid, the devitrification resistance that improves glass that constitutes glass, the composition that homogenizes of realizing glass.Particularly by making B 2O 3The containing ratio of composition is below 30.0%, can be easy to obtain desired specific refractory power, improves the liquid temperature of glass, improves devitrification resistance, makes excelling in abrasion resistance.
Therefore, B 2O 3Composition is preferably 30.0% with respect to the upper limit of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 20.0%, and more preferably 9.0%, most preferably be 6.0%.
B 2O 3Composition can use for example H 3BO 3, Na 2B 4O 7, Na 2B 4O 710H 2O, BPO 4Deng being contained in the glass as raw material.
La 2O 3Composition is any composition in the opticglass of the present invention for the composition of the specific refractory power of raising glass.Particularly by making La 2O 3The containing ratio of composition is below 10.0%, can suppress second-order transition temperature (Tg) and raise, and is easy to keep good devitrification resistance, makes excelling in abrasion resistance.In addition, contain a large amount of La 2O 3During composition, devitrification resistance is worsened.Therefore, La 2O 3Composition is preferably 10.0% with respect to the upper limit of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 8.0%, and more preferably 5.0%, most preferably be 3.0%.
La 2O 3Composition can use for example La 2O 3, La (NO 3) 3XH 2O (X is an arbitrary integer) etc. is contained in the glass as raw material.
SiO 2Composition forms, reduces the composition of glass devitrification for promoting stable glass, is any composition in the opticglass of the present invention.Particularly by making SiO 2The containing ratio of composition is below 30.0%, and the specific refractory power that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.Therefore, SiO 2Composition is preferably 30.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 20.0% more preferably, most preferably is 10.0%.
SiO 2Composition can use for example SiO 2, K 2SiF 6, Na 2SiF 6Deng being contained in the glass as raw material.
GeO 2Composition forms, reduces the composition of glass devitrification for promoting stable glass, is any composition in the opticglass of the present invention.Particularly by making GeO 2The containing ratio of composition is below 10.0%, can suppress second-order transition temperature (Tg) and raise.Therefore, GeO 2Composition is preferably 10.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 8.0% more preferably, most preferably is 5.0%.
GeO 2Composition can use for example GeO 2Deng being contained in the glass as raw material.
Al 2O 3Composition is any composition in the opticglass of the present invention for the composition of the devitrification resistance of raising glass.Particularly by making Al 2O 3The containing ratio of composition is below 30.0%, and the specific refractory power that can suppress glass reduces.Therefore, Al 2O 3Composition is preferably 30.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 20.0% more preferably, most preferably is 10.0%.
Al 2O 3Composition can use for example Al 2O 3, Al (OH) 3, AlF 3Deng being contained in the glass as raw material.
ZrO 2Composition is any composition in the opticglass of the present invention for the specific refractory power of raising glass, to glass is carried out the composition that the devitrification the process of cooling suppresses from molten state.Particularly by making ZrO 2The containing ratio of composition is below 20.0%, and the devitrification resistance that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.Therefore, ZrO 2Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
ZrO 2Composition can use for example ZrO 2, ZrF 4Deng being contained in the glass as raw material.
Ga 2O 3Composition is any composition in the opticglass of the present invention for the composition of the specific refractory power of raising glass.Particularly by making Ga 2O 3The containing ratio of composition is below 20.0%, can improve the devitrification resistance of glass, increases the wear intensity of glass, is easy to carry out attrition process.Therefore, Ga 2O 3Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
Ga 2O 3Composition can use for example Ga 2O 3, GaF 3Deng being contained in the glass as raw material.
In 2O 3Composition is any composition in the opticglass of the present invention for improving the composition of glass refraction.Particularly by making In 2O 3The containing ratio of composition is below 20.0%, can improve the devitrification resistance of glass, increases the wear intensity of glass, is easy to carry out attrition process.Therefore, In 2O 3Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, is more preferably less than 10.0%, most preferably less than 5.0%.
In 2O 3Composition can use for example In 2O 3, InF 3Deng being contained in the glass as raw material.
Ta 2O 5Composition is any composition in the opticglass of the present invention for the composition of the specific refractory power of raising glass.Particularly by making Ta 2O 5The containing ratio of composition is below 20.0%, and the devitrification resistance that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.Therefore, Ta 2O 5Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
Ta 2O 5Composition can use for example Ta 2O 5Deng being contained in the glass as raw material.
TiO 2Composition is any composition in the opticglass of the present invention for the composition of the liquid temperature of the specific refractory power that improves glass and dispersion, reduction glass.Particularly by making TiO 2The containing ratio of composition is below 30.0%, and the devitrification resistance that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.In addition, contain a large amount of TiO 2During composition, transmissivity is worsened.Therefore, TiO 2Composition is preferably 30.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 20.0% more preferably, most preferably is 10.0%.
TiO 2Composition can use for example TiO 2Deng being contained in the glass as raw material.
Gd 2O 3Composition is any composition in the opticglass of the present invention for improving the composition of glass refraction.Particularly by making Gd 2O 3The containing ratio of composition is below 25.0%, and the devitrification resistance that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.Therefore, Gd 2O 3Composition is preferably 25.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 20.0% more preferably, most preferably is 10.0%.
Gd 2O 3Composition can use for example Gd 2O 3, GdF 3Deng being contained in the glass as raw material.
Y 2O 3Composition is any composition in the opticglass of the present invention for the specific refractory power that improves glass, the composition that improves the chemical durability of glass.Particularly by making Y 2O 3The containing ratio of composition is below 20.0%, and the devitrification resistance that can suppress glass reduces, and suppresses second-order transition temperature (Tg) simultaneously and raises.Therefore, Y 2O 3Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
Y 2O 3Composition can use for example Y 2O 3, YF 3Deng being contained in the glass as raw material.
Yb 2O 3Composition is any composition in the opticglass of the present invention for improving the composition of glass refraction.Particularly by making Yb 2O 3The containing ratio of composition is below 20.0%, can keep desired optical constant, is easy to keep good devitrification resistance simultaneously.Therefore, Yb 2O 3Composition is preferably 20.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
Yb 2O 3Composition can use for example Yb 2O 3Deng being contained in the glass as raw material.
Ag 2The O composition is any composition in the opticglass of the present invention for reducing the composition of second-order transition temperature (Tg).Particularly by making Ag 2The containing ratio of O composition is below 20.0%, can keep good devitrification resistance, and can suppress to generate the transmissivity deterioration that causes by the Ag colloid.Therefore, Ag 2The O composition is preferably 20.0% with respect to the upper limit of the containing ratio of the glass total mass that is scaled the oxide compound composition, is 15.0% more preferably, most preferably is 10.0%.
Ag 2The O composition can use for example AgNO 3, AgI etc. is contained in the glass as raw material.
Sb 2O 3Composition is any composition in the opticglass of the present invention for promoting the composition of glass deaeration.Particularly by making Sb 2O 3The containing ratio of composition is below 1.0%, can be difficult for producing excess foaming when glass melting, can make Sb 2O 3Composition is difficult for carrying out alloying with dissolution equipment precious metals such as (particularly) Pt.Therefore, Sb 2O 3Composition is preferably 1.0% with respect to the upper limit of the containing ratio of the glass total mass that is scaled the oxide compound composition, is 0.8% more preferably, most preferably is 0.5%.
Sb 2O 3Composition can use for example Sb 2O 3, Sb 2O 5, Na 2H 2Sb 2O 75H 2O etc. are contained in the glass as raw material.
CeO 2Composition is to the effective composition of glass clarifying, is any composition in the opticglass of the present invention.Particularly by making CeO 2The containing ratio of composition is below 1.0%, can obtain less painted and inside quality good optical glass.Therefore, CeO 2Composition is preferably 1.0% with respect to the upper limit of the containing ratio of the total amount of glass that is scaled the oxide compound composition, is 0.8% more preferably, most preferably is 0.5%.
CeO 2Composition can use for example CeO 2Deng being contained in the glass as raw material.
Need to prove, make the composition of glass clarifying and deaeration, be not limited to above-mentioned Sb 2O 3Composition or CeO 2Composition can use known finings and deaerating agent or their combination in glass manufacturing area.
＜composition〉about not containing
Then, to the composition that should not contain in the opticglass of the present invention, and the composition that does not preferably contain describe.
Can in the scope of the glass performance that does not hinder the present application, can add other compositions as required.Wherein, except that Ti, Nb, W, Zr, Ta, La, Gd, Y, each transiting metal component such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Mo, Eu, Nd, Sm, Tb, Dy and Er, even respectively independent or compound contain also have the glass coloring of making under a spot of situation, the certain wave strong point produce to absorb in visibility region character, so particularly at the wavelength of visibility region and in the opticglass that uses, preferably do not contain mentioned component in fact." do not contain in fact " herein and be meant not containing except the situation of sneaking into the form of impurity.
And then, lead compound and As such as PbO 2O 3Deng arsenic compound and Th, Cd, Tl, Os, each composition of Be, Se, exist in recent years as harmful chemical and tendency that Be Controlled is used, not only in glass manufacturing process, even also need measure aspect the environmental protection in the processing after manufacturing procedure and commercialization.Therefore, under the situation of the influence aspect the attention environment, except that inevitably sneaking into, preferably do not contain mentioned component in fact.Thus, the material that in opticglass, does not contain contaminate environment in fact.Therefore, even do not take the measure of special environmental protection aspect, also can make, process, reach discarded above-mentioned opticglass.
In the opticglass of the present invention, Rn 2The O composition (in the formula, Rn be selected among Li, Na, K, the Cs more than a kind) the total amount of material of containing ratio, be preferably below 20.0%.By the total amount that makes above-mentioned substance is below 20.0%, and the specific refractory power that can suppress glass reduces, and improves the chemical durability of glass simultaneously.Particularly in the wear intensity that can reduce opticglass, be easy to carry out attrition process aspect, Rn 20 composition is preferably 20.0% with respect to the upper limit of the total amount of the material of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 18.0%, and more preferably 15.0%, most preferably be 10.0%.
In the opticglass of the present invention, the RO composition (in the formula, R be selected among Mg, Ca, Sr, the Ba more than a kind) the total amount of material of containing ratio, be preferably below 25.0%.By the total amount that makes above-mentioned substance is below 25.0%, and the wear intensity step-down of glass is so can be easy to glass is carried out attrition process.Therefore, the RO composition is preferably 25.0% with respect to the upper limit of the total amount of the material of the containing ratio that is scaled the total amount of glass that oxide compound forms, and more preferably is 23.0%, and more preferably 20.0%, most preferably be 15.0%.
Because the composition of glass composition of the present invention is to represent with the mole % with respect to the total amount of glass that is scaled the oxide compound composition, so be not that direct representation is quality %, but the composition of representing with quality % of each composition that exists in satisfying the glass composition of desired each characteristic among the present invention is formed and is probably got following value to be scaled oxide compound.
TeO 2Composition 30.0～75.0 quality % reach
P 2O 5Composition 0～30.0 quality % reaches
Bi 2O 3Composition 0～55.0 quality %
And
Nb 2O 5Composition 0～35.0 quality % and/or
Li 2O composition 0～10.0 quality % and/or
Na 2O composition 0～12.0 quality % and/or
K 2O composition 0～18.0 quality % and/or
Cs 2O composition 0～40.0 quality % and/or
ZnO composition 0～30.0 quality % and/or
MgO composition 0～10.0 quality % and/or
CaO composition 0～10.0 quality % and/or
SrO composition 0～15.0 quality % and/or
BaO composition 0～20.0 quality % and/or
WO 3 Composition 0～35.0 quality % and/or
B 2O 3Composition 0～30.0 quality % and/or
La 2O 3Composition 0～40.0 quality % and/or
SiO 2Composition 0～13.0 quality % and/or
GeO 2Composition 0～20.0 quality % and/or
Al 2O 3Composition 0～20.0 quality % and/or
ZrO 2Composition 0～15.0 quality % and/or
Ga 2O 3Composition 0～25.0 quality % and/or
In 2O 3Composition 0～25.0 quality % and/or
Ta 2O 5Composition 0～40.0 quality % and/or
TiO 2Composition 0～15.0 quality % and/or
Gd 2O 3Composition 0～40.0 quality % and/or
Y 2O 3Composition 0～30.0 quality % and/or
Yb 2O 3Composition 0～35.0 quality % and/or
Ag 2O composition 0～30.0 quality % and/or
Sb 2O 3Composition 0～1.0 quality % and/or
CeO 2Composition 0～1.0 quality %
[manufacture method]
Opticglass of the present invention for example can be made as described below.Promptly, above-mentioned raw materials is mixed straight each composition that evenly makes in the scope of the containing ratio of regulation, the mixture of making is dropped in quartz crucible or the alumina crucible, after carrying out thick fusion, put into golden crucible, platinum crucible, platinum alloy crucible or iridium crucible, in 500～1200 ℃ temperature range, carry out fusion, stirring make its homogenize carry out froth breaking etc. after, be cast in the mould after being reduced to suitable temperature, slowly opticglass is made in cooling thus.
[rerum natura]
Opticglass of the present invention need have the high refractive index (n of regulation d), have high dispersive simultaneously.Particularly, the specific refractory power (n of opticglass of the present invention d) lower limit be preferably 1.80, more preferably be 1.85, most preferably be 1.90, its upper limit is preferably 2.20, more preferably be 2.18, most preferably be 2.15.
In addition, the Abbe number (ν of opticglass of the present invention d) lower limit be preferably 16.0, more preferably be 16.5, most preferably be 17.0, its upper limit is preferably 30, more preferably be 28, most preferably be 25.Thus, even increase the degree of freedom of optical design and then the slimming of realization element, also can obtain bigger refraction of light amount.
Transmissivity decrease before and after the preferred uviolizing of opticglass of the present invention is low.Particularly opticglass preferably has the transmissivity decrease of the uviolizing front and back below 5.0% based on the transmissivity decrease before and after the uviolizing in the measuring method of " measuring method of the transmissivity decrease before and after the uviolizing of JOGIS04-2005 opticglass ".Thus, even being installed, the equipment of opticglass also is difficult for variation through the long-time color balance that uses.The particularly remarkable more reduction of transmissivity decrease before and after the high more uviolizing of use temperature, therefore effective especially at the opticglass of the present invention under situation about using under the high temperature of vehicle mounted etc. and so on.Therefore, the lower limit of the wear intensity of opticglass of the present invention is preferably 5.0%, more preferably is 4.5%, and more preferably 4.0%, most preferably be 3.5%.
In addition, opticglass of the present invention preferably has the wear intensity of regulation.Particularly opticglass preferably has the wear intensity below 800 more than 300 based on the wear intensity (Aa) in the measuring method of " measuring method of the wear intensity of JOGIS 10-1994 opticglass ".By making wear intensity is more than 300, and glass is easy to be ground when carrying out attrition process, so can improve the working (machining) efficiency of attrition process, is easy to carry out attrition process.On the other hand, be below 800 by making wear intensity, owing to can reduce the required degree of opticglass above wearing and tearing and scuffing, so the operation can easily carry out attrition process to opticglass the time is easy to carry out attrition process.Therefore, the lower limit of the wear intensity of opticglass of the present invention is preferably 300, more preferably be 330, most preferably be 350, its upper limit is preferably 800, more preferably be 750, most preferably be 700.
In addition, opticglass of the present invention needs painted few.When opticglass particularly of the present invention was represented with the transmissivity of glass, spectral transmission was 70% wavelength (λ in the sample of thick 10mm 70) be below the 500nm, more preferably be below the 480nm, more preferably below the 450nm, most preferably be below the 440nm.In addition, spectral transmission is 5% wavelength (λ in the sample of the thick 10mm of opticglass of the present invention 5) be below the 420nm, more preferably be below the 410nm, more preferably below the 405nm, most preferably be below the 400nm.Thus, make the glass absorption limit be positioned near the position of ultraviolet region, improve the transparency of the glass in the visibility region, therefore can be with the material of this opticglass as optical elements such as lens.
In addition, opticglass of the present invention preferably has and is higher than 300 ℃ and be second-order transition temperature (Tg) below 550 ℃.By making second-order transition temperature (Tg) be higher than 300 ℃, can reduce the detrimentally affect that the heat of friction that produces because of attrition process causes when particularly glass being carried out attrition process.On the other hand, be below 550 ℃ by making second-order transition temperature (Tg), owing under lower temperature, soften,, reduce the oxidation of the mould that uses in the extrusion forming so can under low temperature, carry out extrusion forming, realize the long lifetime of mould.Therefore, the lower limit of the second-order transition temperature of opticglass of the present invention (Tg) preferably surpass 250 ℃, more preferably be 280 ℃, more preferably 300 ℃, most preferably be 310 ℃, its upper limit be preferably 550 ℃, more preferably be 530 ℃, most preferably be 500 ℃.
In the opticglass, (θ g is F) with Abbe number (ν at the part scatter coefficient of the part dispersiveness in expression short wavelength zone d) between have the collinear relation that is roughly.The straight line of expression above-mentioned relation is called normal, is that (θ g F) is the longitudinal axis, employing Abbe number (ν adopting the part scatter coefficient d) for will be on the rectangular coordinates of transverse axis to the part scatter coefficient of NSL7 and PBM2 and Abbe number formed 2 straight lines that are connected (referring to Fig. 1) of mapping.According to the difference of opticglass manufacturing firm and difference, but each company all defines with slope and the intercept that is equal to substantially as the normal glass of the benchmark of normal.(NSL7 and PBM2 are the opticglass of the hara of Co., Ltd. O corporate system, the Abbe number (ν of PBM2 d) be 36.3, (θ g is 0.5828 F) to the part scatter coefficient, the Abbe number (ν of NSL7 d) be 60.5, (θ g is 0.5436 F) to the part scatter coefficient.)
(θ g F) approaches normal to the preferred part scatter coefficient of opticglass of the present invention and the part scatter coefficient is little.
More specifically, (θ g is F) with Abbe number (ν for the part scatter coefficient of opticglass of the present invention d) between, at ν dSatisfy formula (1) in≤25 the scope: [(0.0016 * ν d+ 0.63460)≤(θ g, F)≤(0.00563 * ν d+ 0.75873) relation].Thus, have high dispersive, (θ g is F) with Abbe number (ν for the part scatter coefficient simultaneously d) drawing position approach the normal (Normal Line) of Fig. 1.Therefore, can infer that the aberration that is produced by the optical element that has used above-mentioned opticglass reduces.
At above-mentioned ν dIn≤25 the scope, preferred satisfied (0.0016 * ν d+ 0.63660)≤(θ g, relation F) more preferably satisfy (0.0016 * ν d+ 0.63860)≤(θ g, relation F).
In addition, at above-mentioned ν dIn≤25 the scope, preferably satisfy (θ g, F)≤(0.00563 * ν d+ 0.75673) relation, more preferably satisfy (θ g, F)≤(0.00563 * ν d+ 0.75473) relation, more preferably satisfy (θ g, F)≤(0.00563 * ν d+ 0.75273) relation.
In addition, (θ g is F) with Abbe number (ν for the part scatter coefficient of opticglass of the present invention d) between, at ν dSatisfy formula (2) in＞25 the scope: [(0.0025 * ν d+ 0.65710)≤(θ g, F)≤(0.0034 * ν d+ 0.70300) relation].
At above-mentioned ν dIn＞25 the scope, preferred satisfied (0.0025 * ν d+ 0.65910)≤(θ g, relation F) more preferably satisfy (0.0025 * ν d+ 0.66110)≤(θ g, relation F).
In addition, at above-mentioned ν dIn＞25 the scope, preferably satisfy (θ g, F)≤(0.00340 * ν d+ 0.70100) relation, more preferably satisfy (θ g, F)≤(0.00340 * ν d+ 0.69900) relation, more preferably satisfy (θ g, F)≤(0.00340 * ν d+ 0.69700) relation.Need to prove, particularly at Abbe number (ν d) in the little zone, and the part scatter coefficient of common glass (θ g, value F) is higher than normal, and (θ g is F) with Abbe number (ν for the part scatter coefficient of common glass d) relation curved.But,, use with ν among the present invention owing to be difficult to above-mentioned curve is similar to d=25 straight lines that have a Different Slope for the boundary represent that (θ g F) is lower than the situation of common glass to the part scatter coefficient.
Opticglass of the present invention satisfies above-mentioned relation.That is, for having high refractive index polymolecularity and the little opticglass of part scatter coefficient.
Need to prove, part scatter coefficient (θ g among the present invention, F) expression is by (θ g, F)=(ng-nF) value that formula/(nF-nC) is calculated, wherein, for the speed that slowly cools be-25 ℃/time opticglass that obtains, measure the specific refractory power (nC) that C line (wavelength 656.27nm) locates, the specific refractory power (nF) that F line (wavelength 486.13nm) is located, the specific refractory power (ng) that g line (wavelength 435.835nm) is located.
[preform and optical element]
Opticglass of the present invention is useful to each optical element and optical design, wherein, sees through in glass particularly preferably in lens, prism and mirror etc. in the purposes of optical element of visible light and uses.Thus, the aberration that is produced by the optical element that has used above-mentioned opticglass reduces, so when being used for optical device such as photographic camera and projector, can realize the miniaturization of optical element and optical system, realizes high meticulous and high-precision imaging characteristic simultaneously.Herein, when making the optical element that forms by opticglass of the present invention, can omit cutting and attrition process, make the precision press formation preform of spherical grade so preferably the glass of molten state is dripped from the spout of outlet pipes such as platinum, above-mentioned precision press formation is carried out precision press formation with preform.
[embodiment]
Embodiments of the invention (No.1～No.54), and comparative example (composition of No.1～No.2), and the specific refractory power (n of above-mentioned glass d), Abbe number (ν d), spectral transmission is 70% and 5% wavelength (λ 70, λ 5), the transmissivity decrease before and after the uviolizing, second-order transition temperature (Tg), wear intensity (Aa), part scatter coefficient (θ g, F) the results are shown in table 1～table 6.In the table, the composition of each composition is represented with quality %.Need to prove that following examples are not limited to these embodiment all the time for exemplary purposes.
Embodiments of the invention (the opticglass of No.1～No.54) and comparative example (all following making of glass of No.1～No.2): select corresponding oxide compound respectively, oxyhydroxide, carbonate, nitrate, fluorochemical, oxyhydroxide, the high-purity raw that uses in the common opticglass such as metaphosphoric acid compound is as the raw material of each composition, carry out weighing and be the ratio of the composition of each embodiment shown in table 1～table 6, after mixing, drop in quartz crucible or the platinum crucible, fusion complexity according to the glass composition, in electric furnace, in 500～1200 ℃ temperature range, carry out fusion, after stirring homogenizes it, be cast in the mould, slowly cooling.
Herein, the embodiment (opticglass of No.1～No.54) and the comparative example (specific refractory power (n of the glass of No.1～No.2) d) and Abbe number (ν d) be based on that the industry of Japanese optics nitre can regulations JOGIS01-2003 measures.Need to prove, the glass that uses in measuring as this, annealing conditions adopts following condition, and promptly slowly cooling underspeeds to-25 ℃/hr, is slowly handling in the cool furnace.
In addition, embodiment ((can measure by regulations JOGIS02-2003 according to Japanese optics nitre industry for the opticglass of No.1～No.54) and comparative example by the transmissivity of the glass of No.1～No.2).Need to prove, among the present invention, have or not glass coloring and its degree by measuring the transmissivity of glass, obtaining.Particularly, according to JISZ8722, the parallel grinding object in opposite of measuring thick 10 ± 0.1mm is the spectral transmission of the light of 200～800nm to wavelength, obtains λ 70(wavelength during transmissivity 70%) and λ 5(wavelength during transmissivity 5%).
In addition, ((the transmissivity decrease before and after the uviolizing of the glass of No.1～No.2) can regulations JOGIS04-2005 mensuration according to Japanese optics nitre industry for the opticglass of No.1～No.54) and comparative example for embodiment.Particularly, according to JISZ8722, measure that the parallel grinding object in opposite of thick 10 ± 0.1mm is the spectral transmission of the light of 200～800nm to wavelength before and after the uviolizing, with uviolizing before transmissivity 70% corresponding wavelength place obtain the reduction of postradiation transmissivity.
In addition, ((second-order transition temperature (Tg) of the glass of No.1～No.2) uses differential heat determination device (NETZSCH-Geratebau corporate system STA 409CD) to measure to embodiment for the opticglass of No.1～No.54) and comparative example.The sample granularity of setting this moment is that 425～600 μ m, heat-up rate are 10 ℃/min.
In addition, embodiment ((measure according to " measuring method of JOGIS 10-1994 opticglass wear intensity " for the opticglass of No.1～No.54) and comparative example by the wear intensity of the glass of No.1～No.2).Promptly, be that cast iron plane ware (250mm φ) that the sample level of the glass square plate of 30 * 30 * 10mm is placed on per minute rotation 60 times goes up and be positioned at apart from this ware center, plane with size be the fixed position of 80mm, apply the load of 9.8N (1kgf) in vertical direction, the lapping liquid that will be added with the abrasive substance (aluminum oxide A abrasive material) of 10g#800 (median size 20 μ m) simultaneously in 20mL water was similarly supplied with 5 minutes, make its friction, measure the sample mass before and after grinding, obtain the wearing and tearing quality.Similarly obtain the wearing and tearing quality of the specified standard test specimen of Japanese optics nitre industry meeting, calculate according to wear intensity={ (the wearing and tearing quality/proportion of sample)/(the wearing and tearing quality/proportion of standard test specimen) } * 100.
In addition, embodiment (the opticglass of No.1～No.54) and comparative example (part scatter coefficient (the θ g of the glass of No.1～No.2), F) by (θ g, F)=(ng-nF) formula/(nF-nC) is calculated, wherein, for the speed that slowly cools be-25 ℃/time opticglass that obtains, measure the specific refractory power (nC) that C line (wavelength 656.27nm) locates, the specific refractory power (nF) that F line (wavelength 486.13nm) is located, the specific refractory power (ng) that g line (wavelength 435.835nm) is located.
[table 1]
Figure BSA00000467703900231
[table 2]
Figure BSA00000467703900241
[table 3]
Figure BSA00000467703900251
[table 4]
Figure BSA00000467703900261
[table 5]
Figure BSA00000467703900271
[table 6]
Figure BSA00000467703900281
Shown in table 1～table 6, the specific refractory power (n of the opticglass of the embodiment of the invention d) be more than 1.80, more specifically be more than 1.90, and this specific refractory power (n d) be below 2.20, more specifically be below 2.10, in desired scope.
In addition, the Abbe number (ν of the opticglass of the embodiment of the invention d) be below 30, more specifically be below 25, Abbe number (ν d) be more than 16.Therefore, the opticglass that shows the embodiment of the invention has desired low Abbe number (ν d).
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 450nm.In addition, the λ of the opticglass of the embodiment of the invention 5(wavelength during transmissivity 5%) is below the 420nm, more specifically is below the 405nm.Therefore, the opticglass that shows the embodiment of the invention is difficult to painted, and is high to the transparency of visible light.
In addition, the transmissivity decrease before and after the uviolizing of the opticglass of the embodiment of the invention is below 5.0%.On the other hand, the transmissivity decrease before and after the uviolizing of comparative example 1 and 2 opticglass is more than 5.0%.Therefore, show the opticglass of the embodiment of the invention and the glassy phase ratio of comparative example 1 and 2, the transmissivity decrease before and after the uviolizing is good.
In addition, the second-order transition temperature of the opticglass of the embodiment of the invention (Tg) is below 550 ℃, more specifically is below 420 ℃.In addition, the second-order transition temperature of the opticglass of the embodiment of the invention (Tg) is higher than 250 ℃, more specifically is more than 370 ℃.Therefore, show that the opticglass of the embodiment of the invention has low Tg (Tg), under lower temperature, be easy to soften.
In addition, the wear intensity of the opticglass of the embodiment of the invention is below 800, more specifically is below 700, and its wear intensity is more than 300 simultaneously, more specifically is more than 400.Therefore, show the opticglass of the embodiment of the invention, so the processibility during glass grinding is good because wear intensity is low.On the other hand, the wear intensity of the opticglass of comparative example 2 is 702.That is, show the opticglass of the embodiment of the invention and the glassy phase ratio of comparative example 2, wear intensity is good.
In addition, (θ g is F) with Abbe number (ν at the part scatter coefficient of the opticglass of the embodiment of the invention d) relation in, ν d＞25 o'clock is (0.00250 * ν d+ 0.65710) more than, more specifically be (0.00250 * ν d+ 0.66110) more than, is (0.00340 * ν d+ 0.70300) below, more specifically be below (0.00340 * ν d+0.70100), and ν d≤25 o'clock are (0.00160 * ν d+ 0.63460) more than, more specifically be (0.00160 * ν d+ 0.63860) more than, is (0.00563 * ν d+ 0.75873) below.Therefore, (θ g F) approach normal, thereby aberration is little to show the part scatter coefficient of the opticglass of the embodiment of the invention.
Therefore, the specific refractory power (n that shows the opticglass of the embodiment of the invention d) and Abbe number (ν d) in desired scope, simultaneously the transmissivity decrease before and after the uviolizing is good, is easy to soften under lower temperature, the transparency in visibility region is high and be easy to carry out attrition process.
And then, use the opticglass of the embodiment of the invention to form attrition process and carry out grinding and grinding after with preform, be processed into lens and prismatical shape.In addition, use the opticglass of the embodiment of the invention to form the precision press formation preform, precision press formation is carried out precision press formation processing with preform, be processed into lens and prismatical shape.All can be processed into various lens and prismatical shape under above-mentioned any situation.
Below understand the present invention for exemplary purposes in detail, but present embodiment can be understood as to those skilled in the art and can carry out multiple change under the situation that does not break away from design of the present invention and scope all the time just for exemplary purposes.

Claims (17)

1. opticglass, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %, TeO 2The content of composition is 30.0～70.0%, P 2O 5The content of composition is 0～25.0%, and Bi 2O 3The content of composition is 0～20.0%, and the transmissivity decrease before and after the uviolizing is below 5.0%.
2. opticglass as claimed in claim 1, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %, Nb 2O 5The content of composition is 0～25.0%.
3. opticglass as claimed in claim 2, described opticglass have the wear intensity below 800 more than 300.
4. as each described opticglass in the claim 1 to 3, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
Li 2The content of O composition is 0～20.0%,
Na 2The content of O composition is 0～20.0%,
K 2The content of O composition is 0～15.0%,
Cs 2The content of O composition is 0～15.0%.
5. as each described opticglass in the claim 1 to 4, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, Rn 2The total amount of O material is below 20.0%, in the formula, Rn be selected among Li, Na, K, the Cs more than a kind.
6. as each described opticglass in the claim 1 to 5, wherein, spectral transmission is 70% wavelength (λ 70) be below the 500nm.
7. as each described opticglass in the claim 1 to 6, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
The content of ZnO composition is 0～30.0%,
The content of MgO composition is 0～15.0%,
The content of CaO composition is 0～20.0%,
The content of SrO composition is 0～20.0%,
The content of BaO composition is 0～20.0%.
8. as each described opticglass in the claim 1 to 7, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, the total amount of RO material is less than 25.0%, in the formula, R be selected among Zn, Mg, Ca, Sr, the Ba more than a kind.
9. as each described opticglass in the claim 1 to 8, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
WO 3The content of composition is 0～10.0%,
B 2O 3The content of composition is 0～30.0%,
La 2O 3The content of composition is 0～10.0%.
10. as each described opticglass in the claim 1 to 9, described opticglass is lead-containing compounds not in fact.
11. as each described opticglass in the claim 1 to 10, wherein, with respect to being scaled the total amount of glass that oxide compound is formed, in mole %,
SiO 2The content of composition is 0～30.0%,
GeO 2The content of composition is 0～10.0%,
Al 2O 3The content of composition is 0～30.0%,
ZrO 2The content of composition is 0～20.0%,
Ga 2O 3The content of composition is 0～20.0%,
In 2O 3The content of composition is 0～20.0%,
Ta 2O 5The content of composition is 0～20.0%,
TiO 2The content of composition is 0～30.0%,
Gd 2O 3The content of composition is 0～25.0%,
Y 2O 3The content of composition is 0～20.0%,
Yb 2O 3The content of composition is 0～20.0%,
Ag 2The content of O composition is 0～less than 20.0%,
Sb 2O 3The content of composition is 0～1.0%,
CeO 2The content of composition is 0～1.0%.
12. as each described opticglass in the claim 1 to 11, described opticglass has the specific refractory power (n below 2.20 more than 1.80 d), have the Abbe number (ν below 30 more than 16 d).
13. as each described opticglass in the claim 1 to 12, wherein, (θ g is F) with Abbe number (ν for the part scatter coefficient d) between, at ν dSatisfy (0.0016 * ν in≤25 the scope d+ 0.63460)≤(θ g, F)≤(0.00563 * ν d+ 0.75873) relation is at ν dSatisfy (0.0025 * ν in＞25 the scope d+ 0.65710)≤(θ g, F)≤(0.0034 * ν d+ 0.70300) relation.
14. as each described opticglass in the claim 1 to 13, wherein, second-order transition temperature (Tg) for be higher than 250 ℃, below 550 ℃.
15. an optical element is formed by each described opticglass in the claim 1 to 14.
16. a precision press formation preform is formed by each described opticglass in the claim 1 to 14.
17. an optical element carries out precision press formation with the described precision press formation of claim 16 with preform and obtains.
CN2011100857410A 2010-04-05 2011-04-02 Optical glass, optical element and performing body for precision pressurizing forming Pending CN102234180A (en)

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CN105005105A (en) * 2015-07-13 2015-10-28 安徽天堂唯高塑业科技有限公司 Glass bead for engineering-grade reflective film and preparation method thereof
CN110963705A (en) * 2014-08-11 2020-04-07 日本电气硝子株式会社 Infrared ray transmission glass
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Publication number Priority date Publication date Assignee Title
CN102515514A (en) * 2011-12-23 2012-06-27 沈阳大学 Transparent tellurate glass
CN102515514B (en) * 2011-12-23 2014-02-19 沈阳大学 Transparent tellurate glass
CN110963705A (en) * 2014-08-11 2020-04-07 日本电气硝子株式会社 Infrared ray transmission glass
CN105005105A (en) * 2015-07-13 2015-10-28 安徽天堂唯高塑业科技有限公司 Glass bead for engineering-grade reflective film and preparation method thereof
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