CN104341100B

CN104341100B - High-refractive and high-dispersive optical glass, optical element and optical instrument

Info

Publication number: CN104341100B
Application number: CN201310336770.9A
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2013-08-05
Filing date: 2013-08-05
Publication date: 2018-10-19
Anticipated expiration: 2033-08-05
Also published as: CN107686237B; CN107686237A; CN104341100A

Abstract

The present invention provides a kind of high-refractive and high-dispersive optical glass that light transmission rate is excellent.High-refractive and high-dispersive optical glass, component include by weight percentage：SiO₂：1~10%, B₂O₃：8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：7~20%, ZrO₂：0~10%, TiO₂：1~9%, Nb₂O₅：3~12%, ZnO：1~8%.The present invention does not contain the W of easy coloring by rational component proportion⁶⁺And Bi₂O₃, the degree of staining and light transmission rate of glass are excellent, and stability is preferable, have obtained the high-refractive and high-dispersive optical glass that refractive index is 1.93~2.0, Abbe number is 30~35.

Description

High-refractive and high-dispersive optical glass, optical element and optical instrument

Technical field

The present invention relates to a kind of high-refractive and high-dispersive optical glass, more particularly to a kind of refractive index (n_d) be 1.93~ 2.0, Abbe number (v_d) it is 30~35 high-refractive and high-dispersive optical glass, and prefabricated component, the light being made of the optical glass Learn element and optical instrument.

Background technology

Today of scientific and technological high speed development, the equipment such as digital camera, DV and camera mobile phone are more and more general And.By taking traditional slr camera as an example, several pieces spherical lenses are just needed inside a camera lens, and by using high-refraction high-dispersion Optical glass producing at non-spherical lens, can with it is a piece of replace several pieces spherical lenses, significantly reduce the weight of camera lens.Cause This, demand of the market to high-refractive and high-dispersive optical glass is just more and more big.

CN102161568 disclose a kind of refractive index be 1.945~1.97, the optical glass that Abbe number is 33~36, Contain a large amount of W in component⁶⁺, this makes glass be easy coloring, and Glass optical transmitance deteriorates.CN102459106 discloses one kind High-refractive and high-dispersive optical glass contains a considerable amount of Bi in component₂O₃, a large amount of Bi₂O₃Glass coloration can not only be made, And the stability of glass can be significantly reduced.

Invention content

Technical problem to be solved by the invention is to provide a kind of high-refractive and high-dispersive optical glass that light transmission rate is excellent.

The technical proposal for solving the technical problem of the invention is：High-refractive and high-dispersive optical glass, component is by weight Percentage includes：SiO₂：1~10%, B₂O₃：8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：7~20%, ZrO₂：0~10%, TiO₂：1~9%, Nb₂O₅：3~12%, ZnO：1~8%.

Further, also contain：Sb₂O₃：0~1%, R₂O：0~3%, wherein one or more of R Li, Na, K, It is measured by GB/T7962.12-2010 prescriptive procedures, interior transmitance is 80% or more at 10mm thickness samples 400nm.

Further, composition is by weight percentage：SiO₂：1~10%, B₂O₃：8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：7~20%, ZrO₂：0~10%, TiO₂：1~9%, Nb₂O₅：3~12%, ZnO：1~8%, Sb₂O₃：0~1%, R₂O：0~3%, wherein one or more of R Li, Na, K.

Further, wherein：TiO₂/(TiO₂+ ZnO) it is more than 0.5, Y₂O₃/(Y₂O₃+La₂O₃+Gd₂O₃) it is less than 0.1.

Further, wherein：SiO₂：3~6%.

Further, wherein：B₂O₃：10~15%.

Further, wherein：La₂O₃：38~46%.

Further, wherein：Y₂O₃：1~3%.

Further, wherein：Gd₂O₃：10~16%.

Further, wherein：ZrO₂：4~8%.

Further, wherein：TiO₂：5~9%.

Further, wherein：Nb₂O₅：5~9%.

Further, wherein：ZnO：1~5%.

Further, wherein：TiO₂/(TiO₂+ ZnO) it is more than 0.7, Y₂O₃/(Y₂O₃+La₂O₃+Gd₂O₃) it is less than 0.05.

Further, the optical glass refractive index is 1.93~2.0, and Abbe number is 30~35.

Further, the density of the optical glass is measured by GB/T7962.20-2010 prescriptive procedures, is 5.20g/cm³ Below；The coefficient of expansion is measured by GB/T7962.16-2010 prescriptive procedures, is≤72 × 10^-7/ DEG C,；Water-fast effect stability D_W It is 1 grade, acidproof effect stability D_AIt is 1 grade.

Using gas preform made of above-mentioned high-refractive and high-dispersive optical glass.

Using optical element made of above-mentioned high-refractive and high-dispersive optical glass.

Using optical instrument made of above-mentioned high-refractive and high-dispersive optical glass.

The beneficial effects of the invention are as follows：By rational component proportion, the W of easy coloring is not contained⁶⁺And Bi₂O₃, glass Degree of staining and light transmission rate are excellent, and stability is preferable, have obtained refractive index (n_d) it is 1.93~2.0, Abbe number (v_d) it is 30~35 High-refractive and high-dispersive optical glass.

Specific implementation mode

Each component of optical glass of the present invention is described below, unless otherwise indicated, the ratio of each constituent content is It is indicated with weight %.

B₂O₃It is that glass network generates oxide body, is the essential component for constituting glass network, especially reflects group of the lanthanides in height In glass, B₂O₃It is to obtain the main component of stabilized glass.Work as B₂O₃When content is less than 8%, the meltdown property of glass degenerates, resistance to Devitrification behavior is undesirable；Work as B₂O₃Content is higher than 20%, and design object, therefore, B is not achieved in the refractive index of glass₂O₃Content limit It is set to 8~20%, preferably 10~15%.

SiO₂And the network generation oxide body of glass is formed, a certain amount of SiO is added₂, the high temperature that can increase glass is viscous Degree, improves the devitrification resistance and chemical stability of glass.When its content is less than 1%, the production technology poor performance of glass；If its Content is more than 10%, then the refractive index of glass declines, and devitrification resistance property is deteriorated, therefore, SiO₂Content range be 1~10%, Preferably 3~6%.

La₂O₃It is the active ingredient for improving glass refraction, it is aobvious to the chemical stability and devitrification resistance effect that improve glass It writes, but when its content is less than 35%, required optical constant is not achieved；If content is higher than 50%, tendency towards devitrification increases instead, Therefore, La₂O₃Content be limited to 35~50%, preferably 38~46%.

Y₂O₃The refractive index and devitrification resistance that glass can be improved can also adjust the optical constant of glass and improve crystallization Performance, but when its content is more than 5%, devitrification resistance is obviously deteriorated, therefore, Y₂O₃Content be 0.1~5%, preferably 1~ 3%.

Gd₂O₃The refractive index and chemical stability that glass can be increased, with a certain amount of Gd₂O₃With La₂O₃Consolute, Ke Yiyou Improve the devitrification resistance property of glass in effect ground.But Gd₂O₃When content is less than 7%, effect unobvious；Work as Gd₂O₃Content is higher than 20% When, the devitrification resistance property of glass can instead deteriorated, therefore, Gd₂O₃Content be limited to 7~20%, preferably 10~16%.

The present inventor is the study found that by rationally adjusting Y₂O₃、La₂O₃And Gd₂O₃Content in glass and proportioning are carrying While high glass refraction, moreover it is possible to be obviously improved the chemical stability of glass, therefore, Y₂O₃/(Y₂O₃+La₂O₃+Gd₂O₃) excellent Choosing is less than 0.1, Y₂O₃/(Y₂O₃+La₂O₃+Gd₂O₃) more preferably less than 0.05.

ZrO₂Viscosity, hardness, elasticity, refractive index and the chemical stability of optical glass can be improved, and glass can be reduced Coefficient of thermal expansion.Work as ZrO₂Content when being more than 10%, crystallization will occur, and reduce the devitrification resistance of glass, because This, ZrO₂Content be 0~10%, preferably 4~8%.

TiO₂It can make glass that there is high refractive index, but too high levels can substantially reduce abbe number and increase crystallization and incline To, or even glass can be made obviously to colour, and therefore, TiO₂Content is limited to 1~9%, preferably 5~9%.

Nb₂O₅It is the high refraction for obtaining the present invention and the necessary component of high dispersion, is also a kind of raising glass The component of chemical durability.Work as Nb₂O₅Content be less than 3% when, design requirement is not achieved in optical constant；And when its content is more than When 12%, the devitrification resistance of glass reduces, therefore, Nb₂O₅Content be limited to 3~12%, preferably 5~9%.

ZnO can reduce the coefficient of thermal expansion of glass, improve chemical stability, thermal stability and the refractive index of glass, may be used also To reduce the tendency towards devitrification of glass.When the content of ZnO is more than 8%, the increased devitrification resistance of glass increases；When the content of ZnO is less than 1% When, the transition temperature of glass increases, and therefore, the content of ZnO is limited to 1~8%, preferably 1~5%.In this glass, TiO₂ With the content and proportioning of ZnO, the degree of staining and light transmission rate of glass will be directly influenced, to light transmission rate expected from acquisition and Degree of staining, preferably TiO₂/(TiO₂+ ZnO) it is more than 0.5, more preferable TiO₂/(TiO₂+ ZnO) it is more than 0.7.

R₂O (one or more of R Li, Na, K) can improve the stability and melting behaviour of glass, but introduce The split-phase trend of glass can mostly be aggravated, therefore, content is 0~3%, is preferably added without.

Sb₂O₃It is used in the present invention as fining agent, content is limited to 0~1%, is preferably added without.

The performance of the optical glass of the present invention is described below：

Density according to by《GB/T7962.20-2010 colouless optical glass test method density measurement methods》Test.

Refractive index and Abbe number according to《GB/T7962.1-2010 colouless optical glass test method refractive index and dispersion system Number》Test.The high-refractive and high-dispersive optical glass refractive index (nd) for measuring the present invention is 1.93~2.0, Abbe number (vd) is 30 ~35.

Thermalexpansioncoefficientα is by the average value that method measuring temperature is 20~120 DEG C as defined in GB/T7962.16-2010.

Transmitance (being indicated below with τ 400nm) is by GB/T7962.12-2010 prescriptive procedures at 10mm thickness samples 400nm It measures.

Water-fast effect stability D_W(powder method) presses the test method of GB/T17129, calculates according to the following formula：

D_W=(B-C)/(B-A) * 100

In formula：D_WGlass leaches percentage (%)

The quality (g) of B- filters and sample

The quality (g) of sample after C- filters and erosion

A- filter qualities (g)

By the leaching percentage being calculated, D is stablized into the water-fast effect of optical glass_WIt is divided into 6 classes see the table below.

Classification	1	2	3	4	5	6
							Leach percentage (D_W)	＜ 0.04	0.04-0.10	0.10-0.25	0.25-0.60	0.60-1.10	＞ 1.10

Acidproof effect stability D_A(powder method) presses the test method of GB/T17129, calculates according to the following formula：

D_A=(B-C)/(B-A) * 100

In formula：D_AGlass leaches percentage (%)

The quality (g) of B- filters and sample

The quality (g) of sample after C- filters and erosion

A- filter qualities (g)

By the leaching percentage being calculated, D is stablized into the acidproof effect of optical glass_AIt is divided into 6 classes see the table below：

Classification	1	2	3	4	5	6
							Leach percentage (D_A)	＜ 0.20	0.20-0.35	0.35-0.65	0.65-1.20	1.20-2.20	＞ 2.20

By test, optical glass of the invention has the following performance：Refractive index (nd) is 1.93~2.0, Abbe number (vd) it is 30~35, density (ρ) is 5.20g/cm³Hereinafter, the coefficient of expansion (α)≤72 × 10^-7/ DEG C, τ 400nm be 80% and with On, water-fast effect stability D_W(powder method) is 1 grade, acidproof effect stability D_A(powder method) is 1 grade.

The present invention also provides a kind of optical precast product and optical elements, by above-mentioned optical glass according to those skilled in the art Well known method is formed.Since there is the optical glass high refractive index and high dispersion, the optical element also to have High refractive index and high dispersion, can be applied to the equipment such as digital camera, digital camera, camera cell phone.

Embodiment

In order to further appreciate that technical scheme of the present invention, the embodiment of optical glass of the present invention will now be described.It should It is noted that there is no limit the scope of the present invention for these embodiments.

The optical glass (Examples 1 to 3 0) shown in 1~table of table 3 is by according to each embodiment shown in 1~table of table 3 Ratio weigh and hybrid optical glass common raw material (such as oxide, hydroxide, carbonate, nitrate), will mix Raw material is placed in platinum crucible, is melted in certain temperature, and after fusing, clarification, stirring and homogenizing, is not had Bubble and homogeneous melt glass without undissolved substance casting mold and anneal this melten glass in mold.

The composition of the embodiment of the present invention 1~30 and refractive index (nd), Abbe number (vd), density (ρ), the coefficient of expansion (α), τ The result of 400nm indicates in 1~table of table 3 together.In these tables, the composition of each component is indicated with weight %.

Table 1

Table 2

Table 3

As can be seen from the above embodiments, the refractive index (nd) of optical glass of the present invention is 1.93~2.0, Abbe number (vd) It is 30~35, density (ρ) is 5.20g/cm³Hereinafter, the coefficient of expansion (α)≤72 × 10^-7/ DEG C, τ 400nm are 80% or more, resistance to Water acts on stability D_W(powder method) is 1 grade, acidproof effect stability D_A(powder method) is 1 grade, suitable for being widely used in digital photograph In the equipment such as camera, DV and camera mobile phone.

Claims

1. high-refractive and high-dispersive optical glass, it is characterised in that：Its composition includes by weight percentage：SiO₂：1~6%, B₂O₃： 8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：10~20%, ZrO₂：0~10%, TiO₂：1~8.25%, Nb₂O₅：3~12%, ZnO：1.69~8%, TiO₂/(TiO₂+ ZnO) it is more than 0.7, by GB/T7962.12-2010 prescriptive procedures It measures, interior transmitance is 80% or more at 10mm thickness samples 400nm.

2. high-refractive and high-dispersive optical glass as described in claim 1, it is characterised in that：Also contain：Sb₂O₃：0~1%, R₂O：0~3%, wherein one or more of R Li, Na, K.

3. high-refractive and high-dispersive optical glass as described in claim 1, it is characterised in that：Its composition is by weight percentage： SiO₂：1~6%, B₂O₃：8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：10~20%, ZrO₂：0~ 10%, TiO₂：1~8.25%, Nb₂O₅：3~12%, ZnO：1.69~8%, Sb₂O₃：0~1%, R₂O：0~3%, wherein R For one or more of Li, Na, K, TiO₂/(TiO₂+ ZnO) it is more than 0.7.

4. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Y₂O₃/ (Y₂O₃+La₂O₃+Gd₂O₃) it is less than 0.1.

5. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： SiO₂：3~6%.

6. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： B₂O₃：10~15%.

7. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： La₂O₃：38~46%.

8. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： Y₂O₃：1~3%.

9. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： Gd₂O₃：10~16%.

10. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： ZrO₂：4~8%.

11. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： TiO₂：5~8.25%.

12. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： Nb₂O₅：5~9%.

13. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Wherein： ZnO：1.69~5%.

14. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：Y₂O₃/ (Y₂O₃+La₂O₃+Gd₂O₃) it is less than 0.05.

15. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：The light It is 1.93~2.0 to learn glass refraction, and Abbe number is 30~35.

16. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：The light The density for learning glass is measured by GB/T7962.20-2010 prescriptive procedures, is 5.20g/cm³Below；The coefficient of expansion presses GB/ T7962.16-2010 prescriptive procedures measure, and are≤72 × 10^-7/℃；Water-fast effect stability D_WIt is 1 grade, acidproof effect stability D_AIt is 1 grade.

17. pre- using glass made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16 Product.

18. using optics member made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16 Part.

19. using optics instrument made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~16 Device.