CN103708727B

CN103708727B - Fluorophosphate optical glass

Info

Publication number: CN103708727B
Application number: CN201210371431.XA
Authority: CN
Inventors: 孙伟
Original assignee: Chengdu Guangming Optoelectronics Co Ltd
Current assignee: Chengdu Guangming Optoelectronics Co Ltd
Priority date: 2012-09-29
Filing date: 2012-09-29
Publication date: 2016-08-03
Anticipated expiration: 2032-09-29
Also published as: CN103708727A

Abstract

The present invention provides one not contain La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Etc. the fluorophosphate optical glass of valuable raw material, its percentage by weight consists of: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, Al (PO₃)₃: 0～5%.The refractive index of this optical glass is 1.40～1.50, Abbe number is 90～100, and density is 3.58g/cm³Hereinafter, transition temperature is less than 430 DEG C, and transmittance reaches wavelength X corresponding when 80%₈₀For below 345nm.

Description

Fluorophosphate optical glass

Technical field

The present invention relates to a kind of fluorophosphate optical glass, particularly relate to a kind of refractive index be 1.40～1.50, Abbe number be the fluorophosphate optical glass of 90～100.

Background technology

In recent years, along with the most universal of digital camera, video camera and camera mobile phone and use so that optical material also develops rapidly towards the direction of high precision int, miniaturization.For meeting requirements above, using non-spherical lens to carry out optical design becomes main flow.Increasingly come into one's own on Optical element manufacturing with the precise compression molding technology of low cost, high yield.

Fluorophosphate optical glass is as applying wide New Glasses Materials, there is the optical characteristics of low dispersion, low-refraction, second order spectrum especial dispersion can be eliminated in optical system, improve resolution, it is obviously improved optical system picture element, the most also there is relatively low softening point, directly can make senior non-spherical lens by precise compression molding.JP1270537 discloses the optical glass that a kind of refractive index is 1.42～1.47, wherein contains the La of high cost₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃In at least one composition, add the production cost of glass.

Summary of the invention

The technical problem to be solved is to provide one and does not contains La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Etc. the fluorophosphate optical glass of valuable raw material, the refractive index of this optical glass is 1.40～1.50, Abbe number is 90～100.

The present invention solves the technical scheme is that fluorophosphate optical glass of technical problem, does not contains La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Component, refractive index is 1.40～1.50, and Abbe number is 90～100, and density is 3.58g/cm³Hereinafter, transition temperature is less than 430 DEG C.

Further, its percentage by weight consists of: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, Al (PO₃)₃: 0～5%.

Further, wherein: P₂O₅: 4～8%.

Further, wherein: AlF₃: 25～35%, Al (PO₃)₃: 0～2%.

Further, wherein: NaF:0.5～2.5%.

Further, wherein: CaF₂: 10～20%, BaF₂: 10～20%.

Further, wherein: MgF₂: 5～12%, SrF₂: 15～25%.

Fluorophosphate optical glass, its percentage by weight consists of: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, Al (PO₃)₃: 0～5%.

Further, wherein: P₂O₅: 4～8%.

Further, wherein: AlF₃: 25～35%.

Further, wherein: Al (PO₃)₃: 0～2%.

Further, wherein: NaF:0.5～2.5%.

Further, wherein: CaF₂: 10～20%.

Further, wherein: BaF₂: 10～20%.

Further, wherein: MgF₂: 5～12%.

Further, wherein: SrF₂: 15～25%.

Further, P₂O₅: 4～8%, AlF₃: 25～35%, NaF:0.5～2.5%, MgF₂: 5～12%, CaF₂: 10～20%, BaF₂: 10～20%, SrF₂: 15～25%.

Use the gas preform that above-mentioned fluorophosphate optical glass is made.

Use the optical element that above-mentioned fluorophosphate optical glass is made.

Use the optical instrument that above-mentioned fluorophosphate optical glass is made.

The invention has the beneficial effects as follows: the fluorophosphate optical glass density (ρ) of the present invention is 3.58g/cm³Below；Refractive index (nd) 1.40～1.50；Abbe number (vd) is 90～100；Transition temperature (Tg) is less than 430 DEG C；Transmittance reaches wavelength X corresponding when 80%₈₀For below 345nm, and without La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Etc. valuable raw material, reduce production cost.

Detailed description of the invention

Each component of of the present invention optical glass is described below, and except as otherwise noted, the ratio of each constituent content is to represent by weight %.

P₂O₅It is that network generates body, its P introduced⁵⁺、O^2-It it is all the essential element constituting glass skeleton.P₂O₅The stability of glass can be kept, and the mechanical performance of glass can be effectively improved.When its content is less than 1%, the tendency towards devitrification of glass increases, bad stability；And when its content is more than 10%, it is difficult to obtain intended optical property, therefore P₂O₅Content be defined to 1～10%, preferred content is 4～8%.

AlF₃It is the necessary component of the present invention, introduces Al in glass³⁺、F^-With the formation of stabilized glass, refractive index and the dispersion of glass can be effectively reduced, if AlF₃Content is the lowest, it is impossible to obtain required optical constant；But content is the highest, the devitrification resistance property of glass deteriorates.Therefore AlF₃Content be defined to 20～35%, preferred content is 25～35%.

NaF can be effectively reduced the transition temperature of glass, but its too high levels, the thermal coefficient of expansion of glass can be caused to increase, resistance to water reduces, so the content of NaF is defined to 0.1～5%, preferred content is 0.5～2.5%.

MgF₂Dispersion and the refractive index of glass can be reduced, the chemical stability of glass can be improved simultaneously, but its too high levels, the devitrification resistance property of glass can be made to deteriorate, so MgF₂Content be defined to 5～15%, preferred content is 5～12%.

CaF₂It is possible not only to reduce Abbe number and the proportion of glass in glass, and can be with the formation of stabilized glass, if its content is too low, DeGrain；If its too high levels, glass devitrification resistance property deteriorates, therefore CaF₂Content be 10～30%, preferably 10～20%.

BaF₂Refractive index and the stabilized glass that can effectively regulate glass in glass are formed, if content is the lowest, do not reach above effect；Too high levels, not only makes the refractive index of glass increase, and the proportion of glass can increase, and chemical stability deteriorates, therefore BaF₂Content range be 10～30%, preferably 10～20.

SrF₂Effective to the devitrification resistance property improving glass, it is possible to effectively to adjust refractive index and the proportion of glass, if but its content is too much, and the refractive index of glass and dispersion can be made to become big, be extremely difficult to the optical property of anticipation, also can reduce the chemical stability of glass simultaneously.In order to preferably obtain optical property of the presently claimed invention, SrF₂Content be defined to 15～30%, preferably 15～25%.

Al(PO₃)₃With the formation of stabilized glass, but also can improve mechanical strength and the chemical stability of glass, but its too high levels, the refractive index of glass increases, it is impossible to reach required optical constant, therefore Al (PO₃)₃Content be defined to 0～5%, preferably 0～2%, be more preferably added without.

The performance of the accurate die pressing optical glass of the present invention is described below.

Wherein refractive index (nd) value is (-2 DEG C/h)～the annealing value of (-6 DEG C/h), and refractive index is tested according to " GB/T7962.1-1987 colouless optical glass method of testing refractive index and abbe number " with Abbe number.

Transition temperature (Tg) is tested according to " GB/T7962.16-1987 colouless optical glass method of testing linear expansion coefficient, transition temperature and sag temperature ", that is: sample is within the scope of certain temperature, temperature often raises 1 DEG C, on the expansion curve of sample, low-temperature region and high-temperature area straight line portion are extended and intersects, the temperature corresponding to its intersection point.

Density is tested according to " GB/T7962.20-1987 colouless optical glass method of testing density measurement method ".

Glass is fabricated to the sample of 10mm ± 0.1mm thickness, and tested glass reaches the wavelength X of 80% correspondence in transmittance₈₀。

Through test, the optical glass that the present invention provides has following performance: density (ρ) is 3.58g/cm³Below；Refractive index (nd) 1.40～1.50；Abbe number (vd) is 90～100；Transition temperature (Tg) is less than 430 DEG C；Transmittance reaches wavelength X corresponding when 80%₈₀For below 345nm.

The present invention also provides for a kind of optical element, above-mentioned optical glass formed according to method well known to those skilled in the art.Owing to described optical glass has low-refraction and relatively low glass transformation temperature, described optical element also has low-refraction and relatively low glass transformation temperature, can apply to the equipment such as digital camera, digital camera, camera cell phone.

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

In table 1～table 3, the optical glass (embodiment 1～30) of display is by weighing and hybrid optical glass common raw material (such as oxide, fluoride) according to the ratio of each embodiment shown in table 1～table 3, mixing raw material is placed in platinum crucible, melt in the temperature of 900～1000 DEG C, and through melting, clarify, stir and after homogenizing, obtain there is no bubble and the homogeneous melt glass without undissolved material, this melten glass casting mold annealing in mould are formed.

The composition of the embodiment of the present invention 1～30 reaches wavelength X corresponding when 80% with refractive index (nd), Abbe number (vd), density (ρ), glass transformation temperature (Tg), transmittance₈₀Result together in table 1～table 3 represent.In these tables, composition weight % of each component represents.

Table 1

Table 2

Table 3

From above-described embodiment it can be seen that the fluorophosphate optical glass density (ρ) of the present invention is 3.58g/cm³Below；Refractive index (nd) 1.40～1.50；Abbe number (vd) is 90～100；Transition temperature (Tg) is less than 430 DEG C；Transmittance reaches wavelength X corresponding when 80%₈₀For below 345nm, and without La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Etc. valuable raw material, reduce production cost.

Claims

1. fluorophosphate optical glass, it is characterised in that its percentage by weight composition contains: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, do not contain La₂O₃、Gd₂O₃、Y₂O₃And Yb₂O₃Component, refractive index is 1.40～1.50, and Abbe number is 90～100.

2. fluorophosphate optical glass as claimed in claim 1, it is characterised in that density is 3.58g/cm³Hereinafter, transition temperature is less than 430 DEG C.

3. fluorophosphate optical glass as claimed in claim 1, it is characterised in that its percentage by weight consists of: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, Al (PO₃)₃: 0～5%.

4. the fluorophosphate optical glass as described in claim 1-3, it is characterised in that wherein: P₂O₅: 4～8%.

5. the fluorophosphate optical glass as described in claim 1-3, it is characterised in that wherein: AlF₃: 25～35%, Al (PO₃)₃: 0～2%.

6. the fluorophosphate optical glass as described in claim 1-3, it is characterised in that wherein: NaF:0.5～2.5%.

7. the fluorophosphate optical glass as described in claim 1-3, it is characterised in that wherein: CaF₂: 10～20%, BaF₂: 10～20%.

8. the fluorophosphate optical glass as described in claim 1-3, it is characterised in that wherein: MgF₂: 5～12%, SrF₂: 15～25%.

9. fluorophosphate optical glass, it is characterised in that its percentage by weight consists of: P₂O₅: 1～10%, AlF₃: 20～35%, NaF:0.1～5%, MgF₂: 5～15%, CaF₂: 10～30%, BaF₂: 10～30%, SrF₂: 15～30%, Al (PO₃)₃: 0～5%.

10. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: P₂O₅: 4～8%.

11. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: AlF₃: 25～35%.

12. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: Al (PO₃)₃: 0～2%.

13. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: NaF:0.5～2.5%.

14. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: CaF₂: 10～20%.

15. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: BaF₂: 10～20%.

16. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: MgF₂: 5～12%.

17. fluorophosphate optical glass as claimed in claim 9, it is characterised in that wherein: SrF₂: 15～25%.

18. fluorophosphate optical glass as claimed in claim 9, it is characterised in that P₂O₅: 4～8%, AlF₃: 25～35%, NaF:0.5～2.5%, MgF₂: 5～12%, CaF₂: 10～20%, BaF₂: 10～20%, SrF₂: 15～25%.

19. use in claim 1～18 gas preform that the fluorophosphate optical glass described in any claim is made.

20. use in claim 1～18 optical element that the fluorophosphate optical glass described in any claim is made.

21. use in claim 1～18 optical instrument that the fluorophosphate optical glass described in any claim is made.