CN102674685A

CN102674685A - Optical glass

Info

Publication number: CN102674685A
Application number: CN2012101183706A
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: 2012-09-19
Anticipated expiration: 2032-04-23
Also published as: CN102674685B

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 lower melting point silicate of Abbe number (υ d) between 29～3 5 is opticglass.

Background technology

In recent years, along with the develop rapidly of photoelectricity industry, small-sized, light, high performance requirement has been proposed optical device.In order to reduce the quantity that constitutes optical system lens in the optical device, in optical design, use non-spherical lens more and more.The processing of non-spherical lens is divided into traditional method and precise compression molding method, and traditional method adopts cutting earlier, secondary press again, and the technology of last grinding and polishing is processed, and manufacturing cost is high; And precise compression molding is meant glass gob or the impact briquetting in high-precision mould of remollescent gas preform, and this method has been saved the process of grinding, polishing, has low cost, is prone to the characteristics of volume production, has become the main stream approach of making 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 prone to oxidation takes place, and influences the surface accuracy of extruded glass element, in order to prolong the life-span of mould; Reduce the die mould cost; Need second-order transition temperature (Tg), the yield point temperature (Ts) of extruded glass be reduced, the general requirement second-order transition temperature is not higher than 560 ℃ usually less than 620 ℃.

Disclosed opticglass belongs to borosilicate system optics glass together with the invention belongs among the japanese patent laid-open 6-107425, but contains 0.5～25% Nb in its component ₂O ₅And 1～4 5% BaO, Nb ₂O ₅Be a kind of active principle that improves glass refraction, dispersion, but Nb ₂O ₅Cost an arm and a leg, 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; Alkalimetal oxides such as BaO are the effective constituent that improves glass refraction, but too much introduce the transformation yield temperature and the proportion that can improve glass, and all the requirement with the desired low yield temperature of this patent is not inconsistent.

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

Among the patented claim CN101439930A disclosed with the invention belongs to similar glass, but its SiO ₂Content be 40～60%, too much SiO ₂Second-order transition temperature, the yield point temperature of glass are raise.

The nd of disclosed glass among patented claim CN1135207C, the 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.

Disclosed glass belongs to similar glass with the present invention among the patented claim CN1396132A, but contains as neccessary composition Nb in its component ₂O ₅, WO ₃, these compositions cost an arm and a leg, and this can cause the glass cost to rise, simultaneously WO ₃Introducing can make glass coloring degree variation.

Disclosedly among the patented claim CN101070224A belong to similar glass, but contain Nb in its component as neccessary composition with the present invention ₂O ₅, KHF ₂, these compositions cost an arm and a leg, and introducing in the glass to increase glass cost, KHF simultaneously ₂Introducing can cause glass in fusion process, to volatilize fluorochemical, contaminate environment.

In addition; Though its nd of glass, υ d in the disclosed inventions such as patented claim CN1369448A, CN1446762A, CN101215086A are approaching with present patent application; But its glass is phosphate system glass, and system is different fully with this patent silicate glass.

Summary of the invention

The object of the present invention is to provide that a kind of fusing point is low, chemicalstability and crystallization property is enough good, lower, the easy realization of glass price is simultaneously produced in batches a kind of silicate is opticglass.

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 said opticglass contains in 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 does not contain at least a in niobium, lead, thorium, cadmium, arsenic and the fluorine.

According to opticglass provided by the invention, glass transition temperature Tg less than 530 ℃, thereby can provide a kind of low-melting opticglass less than 480 ℃, yield point temperature Ts; 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, chemicalstability is enough good; Do not contain Nb ₂O ₅, Ta ₂O ₅, WO ₃Etc. the high composition of 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 said opticglass contains in 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 does not contain at least a in niobium, lead, thorium, cadmium, arsenic and the fluorine.

Japanese patent laid-open 6-107425, patented claim 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 ₅Be a kind of active principle that improves glass refraction and dispersion, but Nb ₂O ₅Cost an arm and a leg, 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 desired photosensitiveness of opticglass and chromatic 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 the anti-increased devitrification resistance and the chemicalstability of the high temperature viscosity of glass, the tendency towards devitrification that suppresses glass, raising glass simultaneously.SiO ₂Content be 30-39 weight %; When its content is higher than 39 weight %, can makes opticglass be difficult for melting, glass transformation temperature rising, thereby be unfavorable for the opticglass compression molding; When its content was lower than 30 weight %, the one-tenth glass properties of glass was weak, the crystallization property variation.SiO ₂Content preferably be controlled at 32～39 weight %, more preferably be controlled at 32%～36 weight %.

B ₂O ₃Being the neccessary composition of opticglass of the present invention, is the generation body of opticglass network simultaneously.B ₂O ₃Introducing can improve opticglass melting properties, improve the chemicalstability of opticglass, reduce the second-order transition temperature and the yield point temperature of opticglass.B ₂O ₃Content be 6-15 weight %, work as B ₂O ₃Content is during greater than 15 weight %, at B ₂O ₃-TiO ₂The degree of staining of opticglass can variation in the glass system, is difficult to the optical property that obtains to expect, works as B ₂O ₃Content less than 6% o'clock, the smelting temperature of glass will significantly improve, transition temperature, yield point temperature will raise significantly, can not reach the low-yield temperature requirement of requirement of the present invention, so B ₂O ₃Content preferably be controlled at 6～15 weight %, more preferably be controlled at 8-12 weight %.

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

ZnO can reduce the tendency towards devitrification of glass; In the present invention, when it measures less than 2 weight %, the DeGrain of the tendency towards devitrification of this reduction glass; And its content is above behind the 10 weight %; The chemicalstability of glass is variation gradually, so the content of ZnO should be controlled at 2～10 weight %, preferably is controlled at 4～7 weight %.

TiO ₂Can effectively improve the specific refractory power and the chromatic dispersion of glass, and cost is lower, specific refractory power and chromatic dispersion that a large amount of introducings can improve glass rapidly, but, especially containing B if introducing can make glass coloring deepen more at most ₂O ₃Glass in can be more obvious.So TiO ₂Content should be controlled at 20-30 weight %, preferably be controlled at 22%～28 weight %, more preferably be controlled at 24～27 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 chemicalstability of glass simultaneously through mixed alkali effect.Therefore the total total amount of alkalimetal oxide should be 18-26 weight % even more, preferably is controlled at 18%～24 weight %, more preferably is controlled at 20%～23 weight %.Li wherein ₂O has good effect to reduction glass transformation temperature, yield point temperature, adds above after 5% the amount, and so the chemicalstability of glass and the remarkable variation of workability meeting are Li ₂O content preferably is controlled at below 5%, more preferably is controlled at below 3.5%.

Sb ₂O ₃Can be used as defrother and add arbitrarily, but its content at 0.2 weight % with interior just enough, and if Sb ₂O ₃Cross at most the glass coloring degree with variation.So Sb ₂O ₃Component concentration preferably is controlled at 0～0.1 weight %.

Can also add small amount of alkali soil metal oxide CaO, SrO and BaO except that above composition, that can help melting among the present invention, can suitably add according to the requirement of specific refractory power, chromatic dispersion, its total amount should be controlled at below the 5 weight %, does not preferably contain.

Be to guarantee the spectral transmittance of the glass mould spare that the present invention suppressed, opticglass provided by the invention is not artificially introduced the element that except that above component other can be painted: V, Mo, Cr, Mn, Fe, Co, Ni, Cu and Ag.Simultaneously, 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 the glass transition temperature Tg and the yield point temperature Ts of opticglass, its glass transition temperature Tg less than 480 ℃, yield point temperature Ts less than 530 ℃.

According to opticglass provided by the invention, said opticglass externally transmitance is that 80% o'clock wavelength is not more than 400nm.

According to opticglass provided by the invention, its chemicalstability is fine, according to the testing method test of GB/T17129, the water tolerance D of said opticglass _WBe 2 grades, acid resistance D _AIt is 2 grades or better.

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

Embodiment

Embodiment 1-10

Can be according to the method for preparing opticglass of routine; Formula ratio according to each composition of frit that provides in the table 1 calculates, weighing, and mixes these raw materials, and admixtion elder generation fritting in quartz crucible of making is prepared into grog; Put into again in the platinum crucible and under 1150～1300 ℃, carried out secondary smelting 2～5 hours; And suitably stir, to clarify subsequently, temperature reduction technology, cast or leak is annotated in forming mould after post-processed such as annealing, processing; Perhaps, can make lower melting point silicate opticglass or optical type spare through the directly compression moulding of precise compression molding technology.

Comparative example 1-5

According to each composition of the frit that provides in the table 2, carry out the method that prepare opticglass identical with the foregoing description 1-10, obtain opticglass.

Performance test

1, water tolerance D _WWith acid resistance D _ATest

Use powder method to test according to the GB/T17129 standard.

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

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

3, the test of λ 80 and λ 5

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

In the scope of wavelength 200～700nm, be that 80% wavelength note is made λ with outside transmitance ₈₀, outside transmitance is that 5% wavelength note is made λ ₅

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

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

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

Embodiment 1-10 and the prepared opticglass that obtains of comparative example 1-5 are tested according to above-mentioned testing method, and gained is the result be shown in table 1 and the table 2.

Table 2

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

Can find out that from the test result of table 1 and table 2 embodiment of the invention 1-10 compares with comparative example 1-5, possesses the advantage that second-order transition temperature and yield point temperature are low, chemicalstability 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. opticglass, its refractive index n d is 1.68～1.71, and Abbe number υ d is 29～35, and said opticglass contains in 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 does not contain niobium, lead, thorium, cadmium, arsenic and fluorine.

2. opticglass according to claim 1, wherein said opticglass contains in weight %: SiO ₂32～36%, B ₂O ₃8～12%, TiO ₂22～28%, Na ₂O+K ₂O+Li ₂O 20～23%, CaO+SrO+BaO 0～5%, ZnO 4～7%, ZrO ₂1～3%, Sb ₂O ₃0～0.1%.

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

4. opticglass according to claim 1 and 2, the glass transition temperature Tg of wherein said opticglass less than 480 ℃, yield point temperature Ts less than 530 ℃.

5. opticglass according to claim 1 and 2, said opticglass externally transmitance are that 80% o'clock wavelength is not more than 400nm.

6. opticglass according to claim 1 and 2 is according to the testing method test of GB/T17129, the water tolerance D of said opticglass _WBe 2 grades, acid resistance D _AIt is 2 grades or better.