CN103145331A - Optical glass with high refractive index and manufacturing method thereof - Google Patents
Optical glass with high refractive index and manufacturing method thereof Download PDFInfo
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- CN103145331A CN103145331A CN2013101160200A CN201310116020A CN103145331A CN 103145331 A CN103145331 A CN 103145331A CN 2013101160200 A CN2013101160200 A CN 2013101160200A CN 201310116020 A CN201310116020 A CN 201310116020A CN 103145331 A CN103145331 A CN 103145331A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
Abstract
The invention relates to optical glass with high refractive index and a manufacturing method thereof. The invention discloses the optical glass, which has high refractive index, high dispersion, high transmission, low glass density and favorable devitrification resistance, and is suitable to be pressed repetitively in a secondary hot pressing process. The optical glass is characterized by comprising SiO2, B2O3, Gd2O3, Nb2O5, TiO2, BaO, CaO, Ta2O5, ZnO, Li2O, ZrO2 as required components, wherein the component of Bi2O3 with large proportion and expensive raw materials are not contained. The glass has the optical constants with the refractive index (nd) being more than 1.88 and the abbe number (Vd) being 23-26, the glass density being below 4.2, and the transformation temperature (Tg) being lower than 610 DEG C.
Description
Technical field
The present invention relates to the opticglass of a kind of high refraction, high dispersion, and the method for making this opticglass.More specifically, the present invention be more particularly directed to a kind of specified range that has, its specific refractory power (nd) more than 1.88, Abbe number (vd) are the optical constant of 23～26 scopes, and have high seeing through and low density, the opticglass of good stability.
Background technology
In recent years, universal and being widely used in people's life fast along with slr camera, the optical material that uses as the optical system in slr camera is used in a large number, especially as the glass of high refractive index, high dispersion, it not only satisfies the design requirements of the optical system of high digital performance camera, more need satisfy the slr camera optical system to the requirement of demand and the high definition of large size lens.
The opticglass that exploitation has a low Abbe number is very useful for the design of the optical system of slr camera.By two groups of Abbe number differences or two kinds of larger optical lenses of difference are combined, can reduce or eliminate the aberration of bi-coloured light, and then improve the image quality of lens.
As the opticglass in the high refraction of this class, high dispersion field, no matter from specific refractory power or Abbe number, have at present polytype, as series of phosphate glass or this class series Bi
2O
3The glass that component content is high.But this class glass will bring all that glass coloring is dark, transmitance is low, and after the irradiation along with UV-light, glass coloring also can be deepened, and the defective that this not only is difficult to overcome to lens manufacturing and following process increase also is difficult to satisfy the high transmission requirement of camera optics system.
In the manufacturing processed of opticglass, along with the increase of specific refractory power, the painted tendency aggravation of its glass, especially for the opticglass of height refraction, high dispersion, along with the increase of dispersion values, it is painted will be more serious.Particularly, when the glass that the painted tendency of use increases the weight of, the primary colours short wavelength side blue light susceptibility in the optical imaging system of camera descends, and this will badly influence the sharpness of image quality.
Moreover, for the opticglass of the high refraction of this class, high dispersion, in the secondary hot pressing process, the stability of its glass and good devitrification resistance be realize repeatedly, hot pressing repeatedly and do not occur the key of mist spot and devitrification phenomenon on die mould blank surface.
And as specific refractory power (nd) more than 1.88, Abbe number (vd) is 23～26 the high refraction of this class, the opticglass of high dispersion, and is at present known, belong to yet there are no of optical characteristics in this scope.The glass refraction that early stage patent documentation CN1204073C introduces is in this scope, but glass Abbe number (vd) is greater than 27, and glass density is large and devitrification resistance is poor; CN101012103A, its specific refractory power (nd) belongs to scope of the present invention, but dispersion values is low, Abbe number is greater than 26 or larger, CN1835895A, CN101318769A for another example, although Abbe number (vd) is 26 or lower, but specific refractory power (nd) less than 1.88 differs larger with optical constant of the present invention, can not satisfy the design requirements of present novel slr camera optical system; Satisfy repeatedly, the blank surface does not occur aspect defective in repeatedly hot pressing, CN1204073C, CN101012103A, CN1835895A be due to its high devitrification temperature, is difficult to overcome do not occur mist spot and the milkiness that type spare surface forms in secondary hot pressing.Moreover be also to consider from stability and the low cost operation that raising glass sees through and makes, so the defective of above existence is apparent.
Summary of the invention
The object of the invention is to, be not only the optical constant that the requirement with Optical System Design above-mentioned scope and that can satisfy camera is provided, on the basis of not introducing expensive composition, realize good devitrification resistance, reach stable, quantize to produce and realize good secondary hot pressing cheaply.Also realize simultaneously the lightweight of lens with low density, alleviate the weight of complete machine.With low transition temperature (Tg), be satisfied with the drawing of the preforming material of precise compression molding.And overcome above-mentioned deficiency and defective.
Moreover, another object of the present invention is to realize that optical lens has high seeing through, and maximum satisfies the design requirements of slr camera optical system.
Opticglass of the present invention contains: SiO
2, B
2O
3, Gd
2O
3, Nb
2O
5, TiO
2, BaO, CaO, Ta
2O
5, ZnO, Li
2O, ZrO
2As essential component, this opticglass have refractive index n d greater than 1.88, Abbe number vd is 23～26 optical constant.
Wherein, when representing with (wt%), described opticglass contains following composition:
10～25% SiO
2
1～11% B
2O
3Condition is: (SiO2/B2O3) weight ratio is greater than 2
5～15% Gd
2O
3
15～30% Nb
2O
5
5～22% TiO
2Condition is: (Nb2O5/TiO2) weight ratio is greater than 1
10～30% BaO
3～15% CaO
Greater than 0 but less than 5% Ta
2O
5
Greater than 0～but less than 5% ZnO
Greater than 0 but less than 6% Li
2The O condition is: (ZnO+Li2O) weight ratio is less than 1
ZrO less than 5%
2
0～5% WO
3
0～5% K
2O
0～5% SrO
0～2% SnO
2
0 or more but less than 1% Sb
2O
3
Preferably, when representing with (wt%), described opticglass contains following composition:
12～22% SiO
2
2～8% B
2O
3Condition is: (SiO2/B2O3) weight ratio is greater than 2
6～12% Gd
2O
3
16～28% Nb
2O
5
7～20% TiO
2Condition is: (Nb2O5/TiO2) weight ratio is greater than 1
12～28% BaO
4～11% CaO
Greater than 0 but less than 4% Ta
2O
5
Greater than 0～but less than 4% ZnO
Greater than 0 but less than 5% Li
2The O condition is: (ZnO/Li2O) weight ratio is less than 1
ZrO less than 4%
2
0～4% WO
3
0～3% K
2O
0～3% SrO
0～1% SnO
2
0 or more but less than 0.5% Sb
2O
3
Preferably, described opticglass contains following composition:
SiO
2 14.5～21.5%；
B
2O
3 2.7～6.9%；
Gd
2O
3 6.1～10.9%；
Nb
2O
5 19.2～26.7%；
TiO
2 11.3～18.3；
BaO 12.5～26.0%；
CaO 3.0～9.2%；
Ta
2O
5 0.6～3.8%；
ZnO 0.6～2.8%；
Li
2O 1.6～3.5%；
ZrO
2 0.7～3.2%；
WO3 0～3.1%；
K
2O 0～1.0%；
SrO 0～1.0%；
SnO
2 0～0.4%；
Sb
2O
3 0.1%。
Wherein, the inside of described glass sees through less than 412.
Wherein, the density of described glass is not higher than 4.2g/cm
3
Wherein, described glass transformation temperature Tg is not higher than 610 ℃, liquidus temperature L
TNot higher than 1080 ℃.
The manufacture method of opticglass of the present invention, it comprises following operation: comprise from uniform glass liquid state via leak materials device flow into cooling specific forming mould, be cured as constant thickness and width, make the blank material that is formed by aforesaid opticglass.
The present invention makes the method for second heat casting die, is with aforementioned blank material cutting, is processed into required specification and weight, then pass through thermoplastic, and under soft state, it is pressed, and obtains the not pressing spare of isomorph.
The present invention makes the preformed member method of precise compression molding, comprises following operation: to by aforesaid opticglass through thermoplastic, and be drawn into the prefabricated rods material under soft state.
The present invention is for reaching above-mentioned requirements, through constantly repeatedly finding in research, by to SiO
2, B
2O
3, Gd
2O
3, Nb
2O
5, TiO
2, BaO, CaO, Ta
2O
5, ZnO, Li
2O, etc. essential component the optimization proportioning and to WO
3, SrO, K
2The introducing adjustment of the optional components such as O and do not introducing Bi
2O
3When composition and expensive rare earth composition, not only reached the optical constant with above-mentioned specified range, and also have high see through, low glass density and low transition temperature, not only be satisfied with secondary hot pressing, also be applicable to the drawing of precise compression molding prefabricated rods.
Result of the present invention is also found, with the ratio of SiO2/B2O3 content adjust to greater than 2 or larger, ZnO/Li2O weight ratio less than 1, optimize and revise and proportioning, make except having specific optical constant, low glass density and low transition temperature, also make to see through and be further enhanced, devitrification resistance is further optimized, and has the opticglass of good stability, thereby completes the present invention.
Below will describe the glass ingredient and each component concentration that consist of the included glass 1～10 of opticglass of the present invention in detail represents with Wt% respectively with each per-cent (%) of organizing total content:
For realizing above-mentioned properties, opticglass of the present invention comprises SiO2 and the B2O3 as the essential component that forms glass network, comprise as Gd2O3, Nb2O5, the TiO2 of the essential component that improves specific refractory power and comprise ZnO and Li2O as the essential component that reduces transition temperature, wherein the introducing amount of alkaline earth metal oxide BaO, CaO, SrO at least two or more, limit simultaneously the introducing amount of SnO2, K2O.
In the glass of high refraction of the present invention, high dispersion, SiO2 forms the essential component of component as glass network, still the most effectively improves the component of glass metal viscosity, enhancing devitrification resistance.When the introducing amount of SiO2 was too low, glass viscosity reduced, the devitrification variation, and glass coloring is increased the weight of, and be difficult to form stable, high-quality glass.When if the introducing amount is excessive, the solubility variation of fusing, optical constant reduce, and are difficult to obtain desirable specific refractory power and dispersion values.Therefore preferred 10～25%, more preferably 11～24%, further preferred 12～22%.
B2O3 is most effective to form the glass network composition, and can be effective to the component that reduces solubility and reduce temperature of fusion.But in glass of the present invention, as too much in the introducing amount, glass coloring will increase the weight of, and therefore, the introducing amount is controlled at below 11%, and is preferred below 10, further preferred 8% or still less.
In the transmitance that an object of the present invention is to reach high, and when the ratio of content SiO2/B2O3 content, namely SiO2 content/B2O3 content was less than 2.0 o'clock, and the painted tendency of glass glass increases the weight of, simultaneously devitrification resistance descend, bad stability.Greater than 2.0 or when larger, glass coloring weakens gradually when the SiO2/B2O3 weight ratio, and transmitance improves, and stability, glass also improves thereupon.Therefore, the introducing proportion that improves in right amount SiO2 is necessary, and the SiO2/B2O3/ weight ratio is preferably greater than 2.0, alleviates glass coloring and improves transmitance.The ratio of above-mentioned SiO2/B2O3/ preferably at least 2.0, more preferably at least 2.5 or larger.
Gd2O3 is identical with La2O3, is all the component with the high refractive index of realizing.But, when the introducing amount is too much, being difficult to reach desired optical constant, stability, glass also will reduce, but the introducing amount is when too low, and the devitrification resistance of glass is also with variation.Therefore in the present invention, the introducing amount of Gd2O3 is controlled at 5～15%, and is preferred 5～13%, and more preferably 6～12%.
In the present invention, Nb2O5 realizes high refractive index, the important essential component of high dispersion, and can significantly improve the devitrification resistance performance of glass and improve stability, glass, but, lower than 15% the time, be difficult to obtain above-mentioned effect when its introducing amount, as greater than 30% the time, occur on the contrary, the devitrification resistance of glass and stability all will descend, and Abbe number also will exceed setting range.Therefore, its preferable range is 15～30%, and more preferably scope is 19～32%.Change 17～28% herein into
In the present invention, TiO2 is for the essential component that improves specific refractory power and dispersion values.But, lower than 5% the time, being difficult to reach the height refraction that sets, the optical constant of high dispersion as its introducing amount, glass density also will strengthen simultaneously.But the introducing amount surpasses 22%, will aggravate again the absorption to short wavelength side section and long-wave band, and glass coloring is increased the weight of, simultaneously glass devitrification resistance and solubility variation.Thereby the amount of being introduced into is controlled at 5～22%, and is preferred 6～21%, further preferred 8～19%, most preferably 10～19%.
For satisfying the above-mentioned optical characteristics that sets and realize high seeing through, the introducing amount of preferred Nb2O5 is greater than TiO2 introducing amount, and more preferably the weight ratio of Nb2O5/TiO2 is greater than 1.0, also more preferably the Nb2O5/TiO2 weight ratio greater than 1.2.
BaO not only has the glass of raising in the present invention to the effect that visible region short wavelength end sees through, and also has the effect that improves stability, glass and devitrification resistance, and especially when the introducing amount of TiO2 is too much, the effect of BaO will be more obvious.But when the introducing amount of BaO surpassed 30%, not only glass refraction can reduce, and stability, glass also will descend thereupon simultaneously.Therefore, the introducing amount of BaO-be controlled at 10～30%, preferred 12～28%, further preferred 14～26%.
When the introducing amount of CaO, can obviously improve the transmitance of short wavelength side section and alleviate glass density, and devitrification resistance state and the acceleration that can keep good makes the glass metal clarification when above 3%.But when the introducing amount surpasses 15%, its excessive introducing will reduce the obvious reduction of glass refraction, especially dispersion values, and make that glass viscosity diminishes, devitrification resistance and stability decreases.Therefore, its introducing amount is 3～15%, and is preferred 4～13%, more preferably 4～11%, further preferred 5～9%.
Ta2O5 increases specific refractory power, improves dispersion values and make optical constant reach setting range, and can significantly improve the important component of stability, glass simultaneously, as Ta2O5 less than 0.5% the time, its DeGrain, when surpassing 5%, not only do not reach the dispersion values that sets, also will increase glass density, the glass cost also will increase substantially simultaneously, be unfavorable for low cost movement.Therefore, controlling its introducing amount is 1～5%, preferred 1～4%, more preferably 1～3%.
In the present invention, ZnO is the component that reduces transition temperature, improves the stability, glass successful, particularly when Nb2O5 introducing amount is too much, more can play the effect of stability.But its content is difficult to reach specific refractory power and the dispersion values of expection too much, and glass coloring also will increase the weight of.Therefore, for the optical constant that glass reached set with alleviate glass coloring, its introducing amount controls 1～5%, and is preferred 1～4%, and more preferably 1～3%.
Compare with other alkali metal oxide compound, Li2O has the effect that improves specific refractory power, maximum amplitude reduction glass transformation temperature most, also has the effect of improving glass solubility, increase glass ware forming viscosity, alleviating glass coloring simultaneously, is essential component of the present invention.But, when introducing is excessive, the glass devitrification resistance is reduced, simultaneously optical constant will significantly be reduced.When preferred consideration improved glass solubility and transition temperature, its introducing amount was controlled at 1～6%, and preferred 1～5%, further preferred 1～4%.
By the adjustment to the ratio of ZnO/Li2O content, so that by reaching desired particular optical constant, and simultaneously can realize significantly reducing between transition temperature (Tg) and raising stability, glass and keep trim point, obtain low transition temperature (Tg) and realize the good solubility of glass.Preferred ZnO introducing amount is less than the introducing amount of Li2O, and more preferably the ZnO/Li2O weight ratio is less than 1, and further preferred ZnO/Li2O weight ratio is less than 0.5.
ZrO2 has the effect that improves specific refractory power and glass devitrification resistance in the situation that do not increase the weight of glass coloring.But greater than 5% the time, not only solubility is with variation when the introducing amount, and specific refractory power and dispersion values also will reduce simultaneously.Therefore, its introducing amount is preferred 0.5～5%, and more preferably 1～4%, further preferred 1～3%.
WO3 is to improving specific refractory power and dispersion values, improving increased devitrification resistance and have significant effect.But when the introducing amount surpasses 5%, the photoabsorption of visible region short wavelength side will strengthen, the aggravation of glass coloring tendency.Thereby as optional components, its introducing amount is 0～5%, and is preferred 0～4%, more preferably 0～3% or lower.
The same with Li2O, help to improve melting properties, reduce temperature of fusion as K2O of the same clan, alleviate the glass coloring that the introducing because of excessive TiO2 increases the weight of.But surpass 5% as the introducing amount, will make the control breakdown of glass devitrification resistance, specific refractory power and dispersion values also will significantly descend simultaneously.Therefore, its introducing amount is 0～5%, and is preferred 0～4%, more preferably 0～3% or lower.
SrO has the effect that improves the glass meltability and improves short wavelength side section transmitance as its optional components.But when the introducing amount is too high, glass refraction and stability will reduce, thereby to adjust its introducing amount be 0～5%, and will be preferred 0～4%, more preferably 0～3%.
SnO2 has the effect identical with ZrO2, and still, when the introducing amount was too much, the glass meltability was with variation, and specific refractory power and dispersion values also will reduce, and glass transformation temperature (Tg) will fast rise.Thereby its introducing amount is preferred 0～2%, more preferably 0～1.5% or lower.
Sb2O3 is any additive that uses as finings, as excessive interpolation and introducing, glass coloring is deepened, and transmitance descends, and the stability of fusing and glass inner quality will be degenerated.Thereby its introducing amount is 0～1%, and is preferred 0～0.6%, more preferably 0～0.5% or lower.
As mentioned above, improve in order to be not only the stability of manufacturing, and improve simultaneously the transmitance of visible region and alleviate glass density, realize simultaneously particular optical constant of the present invention and low transition temperature, preferred SiO2, B2O3, Gd2O3, Nb2O5, TiO2, Ta2O5, BaO, CaO, ZnO, Li2O,, ZrO2, component introducing amount be 95% or more, the introducing amount of the components such as WO3, K2O, SrO, SnO2 is 5% or still less, its total introducing amount is 100%.
Below with its physical and chemical performance explanation opticglass of the present invention
Optical glass refractive index of the present invention (nd) is greater than 1.88, and Abbe number (vd) is less than 26.When progressively improving specific refractory power, the glass devitrification resistance descends, yet the present invention's opticglass of the present invention can be realized excellent devitrification resistance and reach high transmitance, thereby can further improve specific refractory power (nd).Therefore, specific refractory power of the present invention (nd) preferably at least 1.88, more preferably 1.90 or 1.91.Stability for realizing making it is desirable to specific refractory power (nd) is limited in 1.92 or less, more preferably is limited in 1.91 or less.
Again and, for stability that realize to make with alleviate glass coloring, the Abbe number of opticglass of the present invention (vd) is preferably 24～26.
Opticglass of the present invention is mainly suppress or repeatedly make quadratic form spare for softening by second-heating, and through being processed into optical lens.Or soften, be drawn into through second-heating the prefabricated bar that is suitable for precise compression molding.Therefore its low transition temperature, good devitrification resistance are the keys of making both.
According to opticglass of the present invention, by constituent optimization and process corrections, interior see through (wavelength X 70) controlled to below 412nm preferred 410nm or less.Interior see through (wavelength X 5) is controlled at below 371nm preferred 370nm or less.Have 70% or higher see through and λ 5 more is offset the shortwave direction due to opticglass of the present invention in λ 70 wavelength regions, thereby be suitable for as various high pixels, high-resolution optical lens.
When excessive reduction glass density, the stability of its manufacturing reduces, the painted tendency of glass also will increase the weight of.Therefore, the glass density of opticglass of the present invention is controlled at greater than 4.0 but less than in 4.2 scope.
The prerequisite that realizes the stability of manufacturing is to have low liquidus temperature, and when the devitrification resistance of glass descended, its liquidus temperature sharply raise, the stability, glass variation.Thereby the liquidus temperature of opticglass of the present invention is controlled at lower than below 1080 ℃, more preferably 1070 ℃ or lower.
It is 1.88 or larger that opticglass of the present invention has high refractive index (nd), Abbe number (vd) is 26 or less, it is the optical glass having high refractive index with the low transition temperature that is suitable for precise compression molding, and when have satisfactory stability when the glass liquid state is directly formed to the blank material, in the secondary hot pressing process, devitrification does not appear in secondary hot pressing repeatedly, can be used for making the prefabricated bar of the use of precise compression molding.
Opticglass of the present invention, see through not higher than 412 in glass, density 4.17 or less, transition temperature (Tg) is 610 ℃ or lower, in addition, compare with existing high refraction, high-dispersive optical glass, also have good devitrification resistance and low cost, can realize low cost operation and volume production under stable state.
Obviously, according to foregoing of the present invention, according to ordinary skill knowledge and the customary means of this area, not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make modification, replacement or the change of other various ways.
The embodiment of form, be described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
The character of embodiment 1 opticglass of the present invention
Table 1,2 shown that the Bo Li Group of the embodiment № 1～№ 10 of opticglass of the present invention becomes and with the composition of the comparative example № a of glassy phase of the present invention glass of the same type～№ d.Below measure in each embodiment and comparative example be by-4.0/h annealing rate and the cooling opticglass that obtains, specific refractory power (nd), Abbe number (vd), the interior measurement result that sees through (λ 70) and (λ 5), density (ρ), transition temperature (Tg), liquidus temperature (LT), the result of measuring provides in table 1,2.
With the raw material of each component, mix with the proportion of composing weighing of comparative example by each embodiment, make admixtion, it is added in specific platinum container, and fusing at the temperature of 1150 ℃～1300 ℃, stirring, clarification are after again stirring, pour into or the die for molding of bleeding, get final product through annealing.
Measure by the following method the properties of above-mentioned glass:
(1) the annealing rate of temperature fall measured with-4.0/h of specific refractory power (nd) and Abbe number (vd) obtains glass specimen.
(2) measure respectively 5mm, the interior of 10mm sample with two parallel polished faces and see through, namely to be defined as the wavelength (nm) at λ 70,5% places be λ 5 to the wavelength at 70% place (nm).(the interior transmittance that sees through when not comprising the specimen surface reflection loss)
(3) determine that density (ρ) adopts Archimedes's method to measure.
(4) glass transformation temperature (Tg) under with 4.0 ℃/minute intensification speed, is used the thermal analyzer measurement device.
(5) liquidus temperature (L
T): add the 500g glass sample in little platinum container, be set as in the smelting furnace at 10 ℃ of intervals, be incubated respectively 2h under differing temps, and cooling samples, by the inner crystallization situation of every glass specimen of microscopic, determine liquidus temperature.
Table 1 fusing embodiment (% by weight)
Table 2 fusing embodiment (% by weight)
As shown in table 1,2, the opticglass № 1～№ 10 of the embodiment of the present invention has the optical constant of specified range, be that specific refractory power (nd) is 1.8812～1.9261, Abbe number (vd) 24.13～25.92, see through the upper limit in glass less than 412, lower limit is less than 371, and proportion is lower than 4.2, its transition temperature (Tg) is lower than 610 ℃, due to low liquidus temperature, not only can realize the well reproduced of secondary hot pressing, also can be suitable for the preforming material that precise compression molding is used.And can realize stable volume production.
Otherwise as shown in the comparative example in table 2, although a example specific refractory power (nd) reaches 1.90, Abbe number (vd) has exceeded 26, has not belonged to optical constant of the present invention.Glass density is also greater than the density of this scope simultaneously, and its liquidus temperature is high, and also contains expensive GeO
2Composition is unsuitable for carrying out stable, low-cost volume production.
Although b example Abbe number (vd) is less than 26, specific refractory power (nd) less than 1.88 does not belong to the optical constant of this category.Therefore, can not satisfy the design requirements of the optical system of slr camera.Moreover, the glass liquidus temperature is high, is difficult to reach stably produce.
The optical constant of c example be specific refractory power (nd) or Abbe number (vd) all lower than the specific optical constant of the present invention, and glass transformation temperature is high and devitrification resistance is poor, is unsuitable for for the making of the prefabricated bar of precise compression molding and the realization of secondary hot pressing.
Although d example specific refractory power (nd) also reaches 1.90, Abbe number (vd) does not possess particular optical constant of the present invention greater than 30 yet.Simultaneously owing to containing Bi
2O
3That composition, glass see through is poor, glass density is large.
To sum up, it is 1.88 or larger that opticglass of the present invention has high refractive index (nd), Abbe number (vd) is 26 or less, and the optical glass having high refractive index with the low transition temperature that is suitable for precise compression molding, and when have satisfactory stability when the glass liquid state is directly formed to the blank material, in the secondary hot pressing process, devitrification does not appear in secondary hot pressing repeatedly, can be made into the prefabricated bar of the use of precise compression molding.
Claims (10)
1. an opticglass, contain: SiO
2, B
2O
3, Gd
2O
3, Nb
2O
5, TiO
2, BaO, CaO, Ta
2O
5, ZnO, Li
2O, ZrO
2As essential component, this opticglass have refractive index n d greater than 1.88, Abbe number vd is 23～26 optical constant.
2. opticglass according to claim 1, it is characterized in that: when representing with (wt%), described opticglass contains following composition:
10～25% SiO
2
1～11% B
2O
3Condition is: (SiO2/B2O3) weight ratio is greater than 2
5～15% Gd
2O
3
15～30% Nb
2O
5
5～22% TiO
2Condition is: (Nb2O5/TiO2) weight ratio is greater than 1
10～30% BaO
3～15% CaO
Greater than 0 but less than 5% Ta
2O
5
Greater than 0 but less than 5% ZnO
Greater than 0 but less than 6% Li
2The O condition is: (ZnO+Li2O) weight ratio is less than 1
ZrO less than 5%
2
0～5% WO
3
0～5% K
2O
0～5% SrO
0～2% SnO
2
0 or more but less than 1% Sb
2O
3
3. according to claim 1 with 2 described opticglass, it is characterized in that: when representing with (wt%), described opticglass contains following composition:
12～22% SiO
2
2～8% B
2O
3Condition is: (SiO2/B2O3) weight ratio is greater than 2
6～12% Gd
2O
3
16～28% Nb
2O
5
7～20% TiO
2Condition is: (Nb2O5/TiO2) weight ratio is greater than 1
12～28% BaO
4～11% CaO
Greater than 0 but less than 4% Ta
2O
5
Greater than 0 but less than 4% ZnO
Greater than 0 but less than 5% Li
2The O condition is: (ZnO/Li2O) weight ratio is less than 1
ZrO less than 4%
2
0～4% WO
3
0～3% K
2O
0～3% SrO
0～1% SnO
2
0 or more but less than 0.5% Sb
2O
3
4. opticglass according to claim 2, it is characterized in that: described opticglass contains following composition:
SiO
2 14.5～21.5%；
B
2O
3 2.7～6.9%；
Gd
2O
3 6.1～10.9%；
Nb
2O
5 19.2～26.7%；
TiO
2 11.3～18.3；
BaO 12.5～26.0%；
CaO 3.0～9.2%；
Ta
2O
5 0.6～3.8%；
ZnO 0.6～2.8%；
Li
2O 1.6～3.5%；
ZrO
2 0.7～3.2%；
WO3 0～3.1%；
K
2O 0～1.0%；
SrO 0～1.0%；
SnO
2 0～0.4%；
Sb
2O
3 0.1%。
5. according to claim 1～4 described opticglass of any one is characterized in that: the inside of described glass sees through less than 412.
6. according to claim 1～5 described opticglass of any one, it is characterized in that: the density of described glass is not higher than 4.2g/cm
3
7. according to claim 1～6 described opticglass of any one, it is characterized in that: described glass transformation temperature Tg is not higher than 610 ℃, liquidus temperature L
TNot higher than 1080 ℃.
8. the manufacture method of the described opticglass of claim 1～7 any one, it is characterized in that, it comprises following operation: comprise from uniform glass liquid state via leak materials device flow into cooling specific forming mould, be cured as constant thickness and width, make the blank material that is formed by the described opticglass of any one in claim 1 or 3.
9. method of making the second heat casting die is with the blank material cutting of claim 8, is processed into required specification and weight, then pass through thermoplastic, and under soft state, it is pressed, and obtains the not pressing spare of isomorph.
10. preformed member method of making precise compression molding is characterized in that: comprise following operation: to by claim 1 or the described opticglass of 8 any one through thermoplastic, and be drawn into the prefabricated rods material under soft state.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310116020.0A CN103145331B (en) | 2013-04-03 | 2013-04-03 | High dioptrics glass and manufacture method thereof |
| PCT/CN2013/090302 WO2014161358A1 (en) | 2013-04-03 | 2013-12-24 | High-refraction optical glass and method of fabricating same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310116020.0A CN103145331B (en) | 2013-04-03 | 2013-04-03 | High dioptrics glass and manufacture method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145331A true CN103145331A (en) | 2013-06-12 |
| CN103145331B CN103145331B (en) | 2016-02-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310116020.0A Active CN103145331B (en) | 2013-04-03 | 2013-04-03 | High dioptrics glass and manufacture method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103145331B (en) |
| WO (1) | WO2014161358A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014161358A1 (en) * | 2013-04-03 | 2014-10-09 | 成都尤利特光电科技有限公司 | High-refraction optical glass and method of fabricating same |
| CN107663011A (en) * | 2017-10-25 | 2018-02-06 | 成都光明光电股份有限公司 | Optical glass |
| CN111406039A (en) * | 2017-12-27 | 2020-07-10 | 株式会社小原 | Optical glass, preform, and optical element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807305A (en) * | 2004-11-15 | 2006-07-26 | Hoya株式会社 | Optical glass, precision press-molding preform, process for producing the preform, optical element and process for producing the element |
| CN1970480A (en) * | 2005-11-25 | 2007-05-30 | 柯尼卡美能达精密光学株式会社 | Optical glass and optical element |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7320949B2 (en) * | 2002-04-02 | 2008-01-22 | Kabushiki Kaisha Ohara | Optical glass |
| JP5357429B2 (en) * | 2008-01-31 | 2013-12-04 | Ｈｏｙａ株式会社 | Optical glass, glass material for press molding, optical element and method for producing the same, and method for producing optical element blank |
| JP2010105902A (en) * | 2008-09-30 | 2010-05-13 | Ohara Inc | Optical glass and method for suppressing deterioration of spectral transmittance |
| JP2011037660A (en) * | 2009-08-07 | 2011-02-24 | Ohara Inc | Optical glass, lens preform and optical element |
| CN103145331B (en) * | 2013-04-03 | 2016-02-17 | 成都尤利特光电科技有限公司 | High dioptrics glass and manufacture method thereof |
-
2013
- 2013-04-03 CN CN201310116020.0A patent/CN103145331B/en active Active
- 2013-12-24 WO PCT/CN2013/090302 patent/WO2014161358A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807305A (en) * | 2004-11-15 | 2006-07-26 | Hoya株式会社 | Optical glass, precision press-molding preform, process for producing the preform, optical element and process for producing the element |
| CN1970480A (en) * | 2005-11-25 | 2007-05-30 | 柯尼卡美能达精密光学株式会社 | Optical glass and optical element |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014161358A1 (en) * | 2013-04-03 | 2014-10-09 | 成都尤利特光电科技有限公司 | High-refraction optical glass and method of fabricating same |
| CN107663011A (en) * | 2017-10-25 | 2018-02-06 | 成都光明光电股份有限公司 | Optical glass |
| CN107663011B (en) * | 2017-10-25 | 2021-03-23 | 成都光明光电股份有限公司 | Optical glass |
| CN111406039A (en) * | 2017-12-27 | 2020-07-10 | 株式会社小原 | Optical glass, preform, and optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014161358A1 (en) | 2014-10-09 |
| CN103145331B (en) | 2016-02-17 |
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Address after: West Port Avenue 610000 Sichuan city of Chengdu province Shuangliu County Southwest Airport Economic Development Zone No. 1499 two Patentee after: CHENGDU YOULITE PHOTOELECTRIC TECHNOLOGY CO., LTD. Address before: West Port Avenue 610225 Sichuan city of Chengdu province Shuangliu County Southwest Airport Economic Development Zone No. 1499 two Patentee before: Chengdu Unite Optoelectronics Technology Co., Ltd. |