CN102674685B

CN102674685B - Optical glass

Info

Publication number: CN102674685B
Application number: CN201210118370.6A
Authority: CN
Inventors: 赵仲勋
Original assignee: Hubei New Huaguang Information Materials Co Ltd
Current assignee: Hubei New Huaguang Information Materials Co Ltd
Priority date: 2012-04-23
Filing date: 2012-04-23
Publication date: 2014-08-27
Anticipated expiration: 2032-04-23
Also published as: CN102674685A

Abstract

The invention provides optical glass, of which the refractive index nd is 1.68-1.71, and the abbe number vd is 29-35. The optical glass contains the following components in percentage by weight: 30-39 percent of SiO2, 6-15 percent of B2O3, 20-30 percent of TiO2, 18-26 percent of Na2O+K2O+Li2O, 0-5 percent of CaO+SrO+BaO, 2-10 percent of ZnO, 0-7 percent of ZrO2 and 0-0.2 percent of Sb2O3, and the total content of the components is 100 percent, and at least one of niobium, lead, thorium, cadmium, arsenic and fluorine is not contained. The optical glass provided by the invention has the advantages of lower melting point, enough good chemical stability and lower cost, contains no PbO which is harmful to environment and no fluoride composition which is harmful to environment and is easy to volatilize.

Description

Opticglass

Technical field

The present invention relates to a kind of opticglass, specifically relate to a kind of specific refractory power (nd) between 1.68～1.71, the low melting point silicate opticglass of Abbe number (υ d) between 29～3 5.

Background technology

In recent years, along with the develop rapidly of photoelectricity industry, optical device has been proposed to small-sized, light, high performance requirement.In order to reduce the quantity that forms optical system lens in optical device, in optical design, use more and more non-spherical lens.The processing of non-spherical lens is divided into traditional method and precise compression molding method, and traditional method adopts first cutting, then secondary press, and the technique of last grinding and polishing is processed, and manufacturing cost is high; And precise compression molding refers to glass gob or softening gas preform impact briquetting in high-precision mould, this method has been saved the process of grinding, polishing, has low cost, the easy feature of volume production, has become the main stream approach of manufacturing non-spherical lens.

When adopting precise compression molding technological forming optical glass device, need under hot conditions, carry out, and under hot environment, die surface is easily oxidized, and affects the surface accuracy of extruded glass element, in order to extend the life-span of mould, reduce die mould cost, the second-order transition temperature of extruded glass (Tg), yield point temperature (Ts) need to be reduced, general requirement second-order transition temperature is less than 620 ℃, conventionally not higher than 560 ℃.

In Japanese patent laid-open 6-107425, disclosed opticglass belongs to borosilicate system optics glass together with the invention belongs to, but in its component, contains 0.5～25% Nb ₂o ₅and 1～4 5% BaO, Nb ₂o ₅a kind of active principle that improves glass refraction, dispersion, but Nb ₂o ₅expensive, this can cause the significantly raising of glass cost, and too much introducing can make the crystallization property variation of glass, transformation yield temperature raise; The alkalimetal oxides such as BaO are the effective constituent that improves glass refraction, but too much introduce transformation yield temperature and the proportion that can improve glass, are not all inconsistent with the requirement of the desired low yield temperature of this patent.

In patent application CN1126704A disclosed with the invention belongs to similar glass, but in its component, contain 48～64% SiO ₂, too much SiO ₂can make second-order transition temperature, the yield point temperature of glass raise, and its patent application requirement second-order transition temperature is up to 550 ℃, higher than the second-order transition temperature of this patent requirement.

In patent application CN101439930A disclosed with the invention belongs to similar glass, but its SiO ₂content be 40～60%, too much SiO ₂can make second-order transition temperature, the yield point temperature of glass raise.

The nd of disclosed glass in patent application CN1135207C, CN1099388C, υ d scope are consistent with this patent part, but do not belong to similar glass with the present invention, and it belongs to negative anomalous dispersion glass, and what this patent was protected is a kind of low melting glass.

In patent application CN1396132A, disclosed glass belongs to similar glass with the present invention, but contains as neccessary composition Nb in its component ₂o ₅, WO ₃, these compositions are expensive, and this can cause glass cost to rise, simultaneously WO ₃introducing can make glass coloring degree variation.

Disclosedly in patent application CN101070224A belong to similar glass with the present invention, but contain the Nb as neccessary composition in its component ₂o ₅, KHF ₂, these compositions are expensive, introduce the cost that can increase glass in glass, simultaneously KHF ₂introducing can cause glass in fusion process, to volatilize fluorochemical, contaminate environment.

In addition, although its nd of glass, the υ d in the disclosed inventions such as patent application CN1369448A, CN1446762A, CN101215086A approaches with present patent application, but its glass is phosphate system glass, completely different from this patent silicate glass system.

Summary of the invention

The object of the present invention is to provide that a kind of fusing point is low, the enough a kind of silicate opticglass of good, lower, the easy realization batch production of glass price simultaneously of chemical stability and crystallization property.

The invention provides a kind of opticglass, its refractive index n d is 1.68～1.71, and Abbe number υ d is 29～35, and described opticglass contains in % by weight: SiO ₂30～39%, B ₂o ₃6～15%, TiO ₂20～30%, Na ₂o+K ₂o+Li ₂o 18～26%, CaO+SrO+BaO 0～5%, ZnO 2～10%, ZrO ₂0～7%, Sb ₂o ₃0～0.2%, the total content of mentioned component is 100%, and not containing at least one in niobium, lead, thorium, cadmium, arsenic and fluorine.

According to opticglass provided by the invention, glass transition temperature Tg is less than 480 ℃, yield point temperature Ts and is less than 530 ℃, thereby a kind of opticglass of low melting point can be provided; According to the method test of GB/T17129, the water tolerance (D of opticglass of the present invention _w) be 2 grades, acid resistance (D _a) be 2 grades or better, chemical stability is enough good; Not containing Nb ₂o ₅, Ta ₂o ₅, WO ₃the composition high etc. price, thereby cost is lower; And opticglass of the present invention does not contain environmentally harmful Substance P bO and the harmful and volatile fluorochemical composition to environment.

Embodiment

Opticglass provided by the invention, its refractive index n d is 1.68～1.71, and Abbe number υ d is 29～35, and described opticglass contains in % by weight: SiO ₂30～39%, B ₂o ₃6～15%, TiO ₂20～30%, Na ₂o+K ₂o+Li ₂o 18～26%, CaO+SrO+BaO 0～5%, ZnO 2～10%, ZrO ₂0～7%, Sb ₂o ₃0～0.2%, the total content of mentioned component is 100%, and not containing at least one in niobium, lead, thorium, cadmium, arsenic and fluorine.

Japanese patent laid-open 6-107425, patent application CN1198414A and the disclosed opticglass of CN1225903A with the invention belongs to similar opticglass, but in the component of these opticglass, all contain Nb ₂o ₅composition, Nb ₂o ₅a kind of active principle that improves glass refraction and dispersion, but Nb ₂o ₅expensive, this can cause the significantly raising of glass cost, and too much introducing can make the crystallization property variation of glass.In the present invention, adopt cheap TiO ₂obtain the desired photosensitiveness of opticglass and dispersion.

According to opticglass provided by the invention, SiO wherein ₂being the neccessary composition of opticglass of the present invention, is the generation body of glass network, can also improve devitrification resistance and the chemical stability of the high temperature viscosity of glass, the tendency towards devitrification that suppresses glass, raising glass simultaneously.SiO ₂content be 30-39 % by weight, when its content is during higher than 39 % by weight, can make opticglass be difficult for melting, glass transformation temperature raises, thereby be unfavorable for opticglass compression molding, its content is during lower than 30 % by weight, and the one-tenth glass properties of glass is weak, crystallization property variation.SiO ₂content be preferably controlled at 32～39 % by weight, be more preferably controlled at 32%～36 % by weight.

B ₂o ₃be the neccessary composition of opticglass of the present invention, be the generation body of opticglass network simultaneously.B ₂o ₃introducing can improve opticglass melting properties, improve the chemical stability of opticglass, reduce second-order transition temperature and the yield point temperature of opticglass.B ₂o ₃content be 6-15 % by weight, work as B ₂o ₃when content is greater than 15 % by weight, at B ₂o ₃-TiO ₂in glass system, the degree of staining of opticglass meeting variation, is difficult to obtain the optical property of expecting, works as B ₂o ₃content while being less than 6%, the smelting temperature of glass will significantly improve, transition temperature, yield point temperature will significantly raise, and can not reach the low-yield temperature requirement of requirement of the present invention, so B ₂o ₃content be preferably controlled at 6～15 % by weight, be more preferably controlled at 8-12 % by weight.

ZrO ₂there is the effect that improves optical constant and improve devitrification resistance and chemical stability, can also play the effect that improves specific refractory power and dispersion.ZrO ₂be available composition, its content is 0-7 % by weight, and when its content is greater than 7 % by weight, the melting properties of glass, crystallization property can variation.ZrO ₂content be preferably controlled at 0～5 % by weight, be more preferably controlled at 1～3 % by weight.

ZnO can reduce the tendency towards devitrification of glass, in the present invention, when its amount is less than 2 % by weight, the DeGrain of the tendency towards devitrification of this reduction glass, and its content surpasses after 10 % by weight, the chemical stability of glass is variation gradually, so the content of ZnO should be controlled at 2～10 % by weight, is preferably controlled at 4～7 % by weight.

TiO ₂can effectively improve specific refractory power and the dispersion of glass, and cost is lower, specific refractory power and dispersion that a large amount of introducings can improve rapidly glass, if but introducing can make glass coloring deepen more at most, especially containing B ₂o ₃glass in can be more obvious.So TiO ₂content should be controlled at 20-30 % by weight, be preferably controlled at 22%～28 % by weight, be more preferably controlled at 24～27 % by weight.

Na ₂o, K ₂o and Li ₂o can reduce second-order transition temperature, density and the melting properties of glass effectively, can improve the chemical stability of glass by mixed alkali effect simultaneously.Therefore the total total amount of alkalimetal oxide should be even more for 18-26 % by weight, are preferably controlled at 18%～24 % by weight, are more preferably controlled at 20%～23 % by weight.Li wherein ₂o has good effect to reduction glass transformation temperature, yield point temperature, adds after 5% the amount of surpassing, and the chemical stability of glass and the remarkable variation of workability meeting, therefore Li ₂o content is preferably controlled at below 5%, is more preferably controlled at below 3.5%.

Sb ₂o ₃can be used as defrother and add arbitrarily, but its content in 0.2 % by weight with interior just enough, and if Sb ₂o ₃cross at most glass coloring degree by variation.So Sb ₂o ₃component concentration is preferably controlled at 0～0.1 % by weight.

In the present invention, can also add a small amount of alkaline earth metal oxide CaO, SrO and BaO except above composition, that can contribute to melting, can suitably add according to the requirement of specific refractory power, dispersion, its total amount should be controlled at below 5 % by weight, does not preferably contain.

For guaranteeing the spectral transmittance of the glass mould part that the present invention suppresses, opticglass provided by the invention is not artificially introduced the element that other except above component can be painted: V, Mo, Cr, Mn, Fe, Co, Ni, Cu and Ag.Meanwhile, artificially do not introduce the compound that contains following harmful element: Th, Cd, Tl, Os, Be, Se and F yet.

According to opticglass provided by the invention, can reduce glass transition temperature Tg and the yield point temperature Ts of opticglass, its glass transition temperature Tg is less than 480 ℃, yield point temperature Ts and is less than 530 ℃.

According to opticglass provided by the invention, the wavelength of described opticglass when externally transmitance is 80% is not more than 400nm.

According to opticglass provided by the invention, its chemical stability is fine, according to the testing method test of GB/T17129, the water tolerance D of described opticglass _wbe 2 grades, acid resistance D _ait is 2 grades or better.

Adopt the mode of specific embodiment to describe in further detail the present invention below.

Embodiment

Embodiment 1-10

Can be according to the method for preparing opticglass of routine, according to the formula ratio of each composition of frit providing in table 1, calculate, weigh, and mix these raw materials, and admixtion elder generation fritting in quartz crucible of making is prepared into grog, put into again in platinum crucible and at 1150～1300 ℃, carry out secondary smelting 2～5 hours, and suitably stir, clarify subsequently, temperature reduction technology, cast or leakage are noted in forming mould finally by annealing, the post-processed such as processing, or by the moulding of precise compression molding technology direct pressing, can make low melting point silicate opticglass or optical type part.

Comparative example 1-5

According to each composition of the frit providing in table 2, carry out the method for preparing opticglass identical with above-described embodiment 1-10, obtain opticglass.

Performance test

1, water tolerance D _wwith acid resistance D _atest

According to GB/T17129 standard, use powder method to test.

2, the test of second-order transition temperature T g and yield point temperature Ts

Method according to GB/T7692.16-87 standard regulation is tested.

3, the test of λ 80 and λ 5

Making thickness is 10 ± 0.1mm, has the flat glass sample being parallel to each other through optical grinding, and from the direction vertical with above-mentioned plane to this glass specimen, injecting intensity is I _inlight, adopt ultraviolet spectrophotometer to measure the intensity I of transmitted ray _out, by strength ratio I _out/ I _inthe outside transmitance that is called glass.

In the scope of wavelength 200～700nm, the wavelength that is 80% by outside transmitance is denoted as λ ₈₀, outside transmitance is 5% wavelength is denoted as λ ₅.

In the scope of wavelength 200～700nm, at λ ₈₀above wavelength region has obtained more than 80% outside transmitance, at λ ₅in above wavelength region, obtained more than 5% outside transmitance.

4, the test of refractive index n d and Abbe number υ d

Testing method according to GB/T7962.11-87 standard is measured.

Embodiment 1-10 and the preparation-obtained opticglass of comparative example 1-5 are tested according to above-mentioned testing method, and acquired results is shown in table 1 and table 2.

Table 2

In table 1 and table 2, ∑ R ₂o represents Na ₂o+K ₂o+Li ₂o, ∑ R ' O represents BaO+SrO+CaO.

From the test result of table 1 and table 2, can find out, embodiment of the present invention 1-10 compares with comparative example 1-5, possesses the advantage that second-order transition temperature and yield point temperature are low, chemical stability is good simultaneously.Embodiment 1-10 with contain Nb ₂o ₅comparative example 5 compare second-order transition temperature and yield point temperature is low.

Claims

1. an opticglass, its refractive index n d is 1.68～1.71, and Abbe number υ d is 29～35, and described opticglass contains in % by weight: SiO ₂30～39%, B ₂o ₃6～15%, TiO ₂20～30%, Na ₂o+K ₂o+Li ₂o18～26%, CaO+SrO+BaO0～5%, ZnO2～10%, ZrO ₂0～7%, Sb ₂o ₃0～0.2%, the total content of mentioned component is 100%, and not containing niobium, lead, thorium, cadmium, arsenic and fluorine, and the glass transition temperature Tg of described opticglass is less than 480 ℃, yield point temperature Ts and is less than 530 ℃.

2. opticglass according to claim 1, wherein said opticglass contains in % by weight: SiO ₂32～36%, B ₂o ₃8～12%, TiO ₂22～28%, Na ₂o+K ₂o+Li ₂o20～23%, CaO+SrO+BaO0～5%, ZnO4～7%, ZrO ₂1～3%, Sb ₂o ₃0～0.1%.

3. opticglass according to claim 1 and 2, the Li in wherein said opticglass ₂the content of O is counted below 3.5% with % by weight.

4. opticglass according to claim 1 and 2, the wavelength of described opticglass when externally transmitance is 80% is not more than 400nm.

5. opticglass according to claim 1 and 2, tests the water tolerance D of described opticglass according to the testing method of GB/T17129 _wbe 2 grades, acid resistance D _ait is 2 grades or better.