CN107686237A

CN107686237A - High-refractive and high-dispersive optical glass, optical element and optical instrument

Info

Publication number: CN107686237A
Application number: CN201710879580.XA
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: CDGM Glass Co Ltd; Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2013-08-05
Filing date: 2013-08-05
Publication date: 2018-02-13
Anticipated expiration: 2033-08-05
Also published as: CN107686237B; CN104341100B; CN104341100A

Abstract

The present invention provides a kind of light transmission rate excellent high-refractive and high-dispersive optical glass.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

The application is to be directed to Application No. 201310336770.9, and the applying date is August in 2013 5, entitled " height refraction The divisional application of the application for a patent for invention of 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) for 1.93~ 2.0th, Abbe number (ν_d) be 30~35 high-refractive and high-dispersive optical glass, and prefabricated component, the light being made up of the optical glass Learn element and optical instrument.

Background technology

Today of scientific and technological high speed development, digital camera, DV and camera mobile phone etc., equipment was 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 into non-spherical lens, several pieces spherical lenses can be replaced with a piece of, significantly reduce the weight of camera lens.Cause This, market is just more and more big to the demand of high-refractive and high-dispersive optical glass.

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

The content of the invention

The technical problems to be solved by the invention are to provide a kind of excellent high-refractive and high-dispersive optical glass of light transmission rate.

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, the one or more in R Li, Na, K, Measured by GB/T7962.12-2010 prescriptive procedures, at 10mm thickness samples 400nm in transmitance be 80% and more than.

Further, its 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, the one or more in 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 For 1 grade, acidproof effect stability D_AFor 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 (ν_d) it is 30~35 High-refractive and high-dispersive optical glass.

Embodiment

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

B₂O₃It is glass network generation oxide body, is the essential component for forming 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 the refractive index of glass does not reach design object, therefore, B₂O₃Content limit It is set to 8~20%, preferably 10~15%.

SiO₂And the network generation oxide body of glass is formed, add a certain amount of SiO₂, the high temperature that can increase glass glues Degree, improve 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, the chemical stability and devitrification resistance effect for improving glass is shown Write, but when its content is less than 35%, do not reach required optical constant；If content is higher than 50%, tendency towards devitrification increases on the contrary, Therefore, La₂O₃Content be defined to 35~50%, preferably 38~46%.

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

Gd₂O₃The refractive index and chemical stability of 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%, DeGrain；Work as Gd₂O₃Content is higher than 20% When, the devitrification resistance property of glass can on the contrary deteriorated, therefore, Gd₂O₃Content be defined to 7~20%, preferably 10~16%.

The present inventor, which studies, to be found, passes through Reasonable adjustment Y₂O₃、La₂O₃And Gd₂O₃Content and proportioning in glass, are being carried 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) it is 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 Thermal coefficient of expansion.Work as ZrO₂Content more than 10% when, will appear from crystallization, and reduce the devitrification resistance of glass, because This, ZrO₂Content be 0~10%, preferably 4~8%.

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

Nb₂O₅It is the high refraction for obtaining the present invention and the necessary component of high dispersion, it is also that one kind improves glass The component of chemical durability.Work as Nb₂O₅Content be less than 3% when, optical constant does not reach design requirement；And when its content exceedes When 12%, the devitrification resistance of glass reduces, therefore, Nb₂O₅Content be defined to 3~12%, preferably 5~9%.

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

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

Sb₂O₃Used in the present invention as fining agent, its content is defined 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/T 7962.20-2010 colouless optical glass method of testing density measurement methods》Test.

Refractive index and Abbe number according to《The colouless optical glass method of testing refractive indexes of GB/T 7962.1-2010 and dispersion Coefficient》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.

The average value that thermalexpansioncoefficientα method measurement temperature as defined in GB/T7962.16-2010 is 20~120 DEG C.

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

Water-fast effect stability D_W(powder method) presses GB/T17129 method of testing, is calculated according to following formula：

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

In formula：D_W- glass leaches percentage (%)

The quality (g) of B-filter and sample

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

A-filter quality (g)

By the leaching percentage being calculated, by the stable D of 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 GB/T17129 method of testing, is calculated according to following formula：

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

In formula：D_A- glass leaches percentage (%)

The quality (g) of B-filter and sample

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

A-filter quality (g)

By the leaching percentage being calculated, by the stable D of 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 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 element, by above-mentioned optical glass according to those skilled in the art Well known method is formed.Because described optical glass has high index of refraction and high dispersion, therefore the optical element also has High index of refraction and high dispersion, can apply to the equipment such as digital camera, digital camera, camera cell phone.

Embodiment

In order to further appreciate that technical scheme, the embodiment of optical glass of the present invention will now be described.Should It is noted that these embodiments do not limit the scope of the present invention.

The optical glass (embodiment 1~30) 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 melting, clarify, stirring and being homogenized, is not had Bubble and the homogeneous melt glass without undissolved material, by this melten glass in mould casting mold and anneal form.

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 400nm result represents in 1~table of table 3 together.In these tables, the composition of each component is represented 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) For 30~35, density (ρ) is 5.20g/cm³Hereinafter, the coefficient of expansion (α)≤72 × 10^-7/ DEG C, τ 400nm be 80% and more than, it is resistance to Water effect 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：SiO₂：1~10%, B₂O₃：8~20%, La₂O₃：35~50%, Y₂O₃：0.1~5%, Gd₂O₃：7~20%, TiO₂：1~9%, Nb₂O₅：3~ 12%th, ZnO：1~8%.

2. high-refractive and high-dispersive optical glass as claimed in claim 1, it is characterised in that also contain：ZrO₂：0~10%, Sb₂O₃：0~1%, R₂O：0~3%, wherein, the one or more in R Li, Na, K, by GB/T7962.12-2010 regulation sides Method measures, at 10mm thickness samples 400nm in transmitance be 80% and more than.

3. high-refractive and high-dispersive optical glass, it is characterised in that its 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, the one or more in R Li, Na, K.

4. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：TiO₂/ (TiO₂+ ZnO) it is more than 0.5；And/or 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%；And/or B₂O₃：10~15%；And/or La₂O₃：38~46%；And/or Y₂O₃：1~3%；And/or Gd₂O₃： 10~16%；And/or ZrO₂：4~8%；And/or TiO₂：5~9%；And/or Nb₂O₅：5~9%；And/or ZnO：1~5%.

6. the high-refractive and high-dispersive optical glass as described in claims 1 to 3 any claim, it is characterised in that：TiO₂/ (TiO₂+ ZnO) it is more than 0.7；And/or Y₂O₃/(Y₂O₃+La₂O₃+Gd₂O₃) it is less than 0.05.

7. the high-refractive and high-dispersive optical glass as described in claim 1~6 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.

8. the high-refractive and high-dispersive optical glass as described in claim 1~6 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_WFor 1 grade, acidproof effect stability D_AFor 1 grade；Measured by GB/T7962.12-2010 prescriptive procedures, at 10mm thickness samples 400nm in transmitance be 80% and more than.

9. using prefabricated glass made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~8 Part.

10. using optics member made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~8 Part.

11. using optics instrument made of the high-refractive and high-dispersive optical glass described in any claim in claim 1~8 Device.