CN109626818A - Fluorophosphate optical glass, optical precast product, optical element and optical instrument - Google Patents

Abstract

The present invention provides a kind of medium refractive index and the low optical glass of thermal refractive index coefficient, and composition includes SiO₂、B₂O₃、La₂O₃, RO and Rn₂The optical glass of O, wherein R0 be one of MgO, CaO, SrO and BaO or more than one, Rn₂O is Li₂O、K₂O and Na₂One of O or more than one, the refractive index of the optical glass is 1.65~1.73, and Abbe number is 47~55, while having lower thermal refractive index coefficient, excellent devitrification resistance energy and chemical stability.

Description

Fluorophosphate optical glass, optical precast product, optical element and optical instrument

Technical field

The present invention relates to a kind of optical glass, more particularly, to a kind of fluorophosphate optical glass and by the optics glass Optical precast product, optical element made of glass and optical instrument.

Background technique

In optical system, in order to eliminate the color difference of lens, " colour killing " of the different glass of combination Abbe number is generallyd use Design, it is therefore desirable to the optical glass of different refractivity and Abbe number is combined, to form reasonable optical system.Fluorine phosphorus As widely used New Glasses Materials, the characteristic with low dispersion can disappear hydrochlorate optical glass in optical system Except second order spectrum especial dispersion, resolution ratio is improved, hence it is evident that improve optical system imaging quality, while also there is lower softening temperature Degree, can directly accurate die pressing advanced non-spherical lens is made.

In recent years, optical glass is widely applied in the fields such as vehicle-mounted, monitoring security protection, and is applied to the fields such as vehicle-mounted, security protection Optical glass is also higher to the chemical stability requirements such as acidproof, moisture resistance of optical glass due to being chronically exposed to outdoor.Separately On the one hand, optical glass in process, can also contact a large amount of corrosive medium, if its is acidproof, anti-moisture performance is poor, it will shadow The image quality of optical glass is rung, or even keeps the optical element of processing completely discarded.Therefore, field of photovoltaic materials is to excellent The demand of the fluorophosphate optical glass of chemical stability is more urgent.

Summary of the invention

In view of the foregoing, technical problem to be solved by the invention is to provide a kind of with the low of superior chemical stability Refractive low dispersive fluorophosphate optical glass.

The technical proposal for solving the technical problem of the invention is:

(1) fluorophosphate optical glass, component indicate by weight percentage, contain P⁵⁺: 3~18%, Al³⁺: 1~ 15%, Zn²⁺: greater than 0 but be less than or equal to 10%, R²⁺: 25~60%, F^-: 12~28%, O^2-: 12~28%, wherein Zn²⁺/ R²⁺Range be 0.01~0.4, R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

(2) fluorophosphate optical glass according to (1), component indicates by weight percentage, also contains: Ln³⁺: 0 ~8%, and/or Rn⁺: 0~5%, and/or Si⁴⁺: 0~5%, and/or B³⁺: 0~5%, and/or Zr⁴⁺: 0~5%, and/or Ti^{4 +}: 0~5%, and/or clarifying agent: 0~1%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of or a variety of, Rn⁺For Li⁺、 Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or it is a variety of.

(3) fluorophosphate optical glass, refractive index (nd) are 1.52~1.58, Abbe number (ν_d) it is 68~75, contain P^{5 +}、Al³⁺、Ba²⁺、F^-And O^2-As necessary component, component indicates by weight percentage, wherein (P⁵⁺+Al³⁺)/Ba²⁺Range be 0.2~1.0, F^-/O^2-Range be 0.7~1.5.

(4) fluorophosphate optical glass according to (3), component indicates by weight percentage, contains P⁵⁺: 3~ 18%, Al³⁺: 1~15%, Zn²⁺: greater than 0 but be less than or equal to 10%, Ba²⁺: 20~40%, Sr²⁺: 3~18%, Ca²⁺: 0~ 8%, Mg²⁺: 0~8%, Ln³⁺: 0~8%, Rn⁺: 0~5%, Si⁴⁺: 0~5%, B³⁺: 0~5%, Zr⁴⁺: 0~5%, Ti⁴⁺: 0 ~5%, clarifying agent: 0~1%, F^-: 12~28%, O^2-: 12~28%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺In one Kind or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of Or it is a variety of.

(5) fluorophosphate optical glass, component indicate by weight percentage, contain P⁵⁺: 3~18%, Al³⁺: 1~ 15%, Zn²⁺: greater than 0 but be less than or equal to 10%, Ba²⁺: 20~40%, Sr²⁺: 3~18%, F^-: 12~28%, O^2-: 12~ 28%.

(6) fluorophosphate optical glass according to (5), component indicates by weight percentage, also contains Ca²⁺: 0~ 8%, and/or Mg²⁺: 0~8%, and/or Ln³⁺: 0~8%, and/or Rn⁺: 0~5%, and/or Si⁴⁺: 0~5%, and/or B³⁺: 0~5%, and/or Zr⁴⁺: 0~5%, and/or Ti⁴⁺: 0~5%, and/or clarifying agent: 0~1%, wherein Ln³⁺For La³⁺、Gd³⁺、 Y³⁺And Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、 Br^-And I^-One of or it is a variety of.

(7) according to (1) or (2) any fluorophosphate optical glass, wherein (P⁵⁺+Al³⁺)/Ba²⁺Range be 0.2~1.0 and/or F^-/O^2-Range be 0.7~1.5.

(8) according to (3) or (4) any fluorophosphate optical glass, wherein Zn²⁺/R²⁺Range be 0.01~ 0.4, wherein R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

(9) according to (5) or (6) any fluorophosphate optical glass, wherein Zn²⁺/R²⁺Range be 0.01~ 0.4, and/or (P⁵⁺+Al³⁺)/Ba²⁺Range be 0.2~1.0 and/or F^-/O^2-Range be 0.7~1.5, wherein R²⁺For Mg^{2 +}、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

(10) according to any fluorophosphate optical glass in (1)~(9), component meets in following 5 kinds of situations It is one or more kinds of:

1)Rn⁺/Zn²⁺Range below 0.5；

2)Ln³⁺/Zn²⁺Range below 1.0；

3)Al³⁺/Sr²⁺Range be 0.05~1.0；

4)Mg²⁺/Sr²⁺Range be 2.5 or less；

5)Sr²⁺/Zn²⁺Range be 0.5~15.0.

(11) according to any fluorophosphate optical glass in (1)~(10), component indicates by weight percentage, contains There is P⁵⁺: 5~15%, and/or Al³⁺: 2~10%, and/or Zn²⁺: 1~8%, and/or Ba²⁺: 25~35%, and/or Sr²⁺: 5 ~15%, and/or Ca²⁺: 0.1~5%, and/or Mg²⁺: 0.1~5%, and/or Ln³⁺: 0~5%, and/or Rn⁺: 0~3%, And/or Si⁴⁺: 0~3%, and/or B³⁺: 0~3%, and/or Zr⁴⁺: 0~3%, and/or Ti⁴⁺: 0~3%, and/or clarifying agent: 0 ~0.5%, and/or F^-: 15~25%, and/or O^2-: 15~25%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of Or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or It is a variety of.

(12) according to any fluorophosphate optical glass in (1)~(11), component meets in following 8 kinds of situations It is one or more kinds of:

1)Rn⁺/Zn²⁺Range below 0.3；

2)Ln³⁺/Zn²⁺Range below 0.5；

3)Al³⁺/Sr²⁺Range be 0.1~0.8；

4)Mg²⁺/Sr²⁺Range be 0.01~1.0；

5)Sr²⁺/Zn²⁺Range be 1.0~10.0；

6)(P⁵⁺+Al³⁺)/Ba²⁺Range be 0.3~0.8；

7)F^-/O^2-Range be 0.8~1.3；

8)Zn²⁺/R²⁺Range be 0.02~0.25.

(13) according to any fluorophosphate optical glass in (1)~(12), component indicates by weight percentage, contains There is P⁵⁺: 7~12%, and/or Al³⁺: 3~8%, and/or Zn²⁺: 2~6%, and/or Ba²⁺: 25~32%, and/or Sr²⁺: 8~ 13%, and/or Ca²⁺: 1~5%, and/or Mg²⁺: 0.5~3%, and/or Ln³⁺: 0~3%, and/or Rn⁺: 0~1%, and/or Si⁴⁺: 0~1%, and/or Zr⁴⁺: 0~1%, and/or Ti⁴⁺: 0~1%, and/or clarifying agent: 0~0.1%, and/or F^-: 16~ 21%, and/or O^2-: 17~22%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺ One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or it is a variety of.

(14) according to any fluorophosphate optical glass in (1)~(13), component meets in following 8 kinds of situations It is one or more kinds of:

1)Rn⁺/Zn²⁺Range below 0.1；

2)Ln³⁺/Zn²⁺Range below 0.2；

3)Al³⁺/Sr²⁺Range be 0.2~0.6；

4)Mg²⁺/Sr²⁺Range be 0.05~0.35；

5)Sr²⁺/Zn²⁺Range be 2.0~6.0；

6)(P⁵⁺+Al³⁺)/Ba²⁺Range be 0.35~0.7；

7)F^-/O^2-Range be 0.9~1.2；

8)Zn²⁺/R²⁺Range be 0.05~0.15.

(15) according to any fluorophosphate optical glass in (1)~(14), wherein R²⁺: 30~60%, preferably R²⁺: 35~50%, R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

(16) according to any fluorophosphate optical glass in (1)~(15), Ln is not contained³⁺And/or Rn⁺。

(17) according to any fluorophosphate optical glass in (1)~(16), P in the fluorophosphate optical glass⁵⁺、 Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content in 95% or more, preferably P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content exist 97% or more, more preferable P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content 98% or more, further preferred P⁵⁺、Al³⁺、 Zn²⁺、R²⁺、F^-And O^2-Total content 99% or more.

(18) according to any fluorophosphate optical glass in (1)~(17), the folding of the fluorophosphate optical glass Penetrating rate (nd) is 1.52~1.58, preferably 1.53~1.57, more preferably 1.54~1.57；Abbe number (ν_d) it is 68~75, Preferably 69~74, more preferably 70~73.

(19) according to any fluorophosphate optical glass in (1)~(18), the fluorophosphate optical glass it is resistance to Absolute acid stability (RA) is 2 classes or more, preferably 1 class；Moisture resistance stability (RC) is 3 classes or more, more than preferably 2 classes.

(20) according to any fluorophosphate optical glass in (1)~(19), the gas of the fluorophosphate optical glass Bubble degree is B grades or more, preferably A grades or more, more preferably A₀Grade or more；And/or thermal expansion coefficient (α_{20~120 DEG C}) be 145 × 10^-7/ K is hereinafter, preferably 140 × 10^-7/ K is hereinafter, more preferably 135 × 10^-7/ K or less；And/or transition temperature (T_g) it is 500 DEG C hereinafter, preferably 490 DEG C hereinafter, more preferably 485 DEG C or less；And/or λ₈₀Less than or equal to 350nm, preferably λ₈₀Be less than or Equal to 345nm, more preferable λ₈₀Less than or equal to 340nm；And/or λ₅Less than or equal to 290nm, preferably λ₅It is less than or equal to 285nm, more preferable λ₅Less than or equal to 280nm, further preferred λ₅Less than or equal to 275nm.

The present invention also provides a kind of optical precast product,

(21) optical precast product is made of any optical glass in (1)~(20).

The present invention also provides a kind of optical element,

(22) optical element is made of any optical glass in (1)~(20), or using optics described in (21) Prefabricated component is made.

The present invention also provides a kind of optical instrument,

(23) optical instrument containing any optical glass in (1)~(20), or contains the member of optics described in (22) Part.

The beneficial effects of the present invention are: designing by reasonable component, there is fluorophosphate optical glass of the invention The optical property of low refractive low dispersive and excellent chemical stability, meet the needs of photoelectric information field.

Specific embodiment

In the following, the embodiment of fluorophosphate optical glass of the invention is described in detail, but the present invention is not limited to Embodiment disclosed below can carry out change appropriate in the range of the object of the invention to be implemented.In addition, about repeating to say Therefore bright part although there is the case where omitting the description appropriate, but not limits the purport invented, in the following contents, this Invention fluorophosphate optical glass is sometimes referred to as optical glass or glass.

[optical glass]

The each component content range of optical glass of the present invention is illustrated below.In the present specification, each component with from Sub- form indicates, content in case of no particular description, hundred that whole composition weights in glass are accounted for the composition weight Divide than indicating (i.e. constituent content indicates by weight percentage).Unless in particular situations it is further noted that number listed herein Value range includes upper limit value and lower limit value, " more than " and " following " include endpoint value, and it is all whole including in the range Several and score, and it is not limited to occurrence listed when limited range.Herein referred "and/or" is inclusive, such as " A and/ Or B ", refer to only A, perhaps only B or has A and B simultaneously.

It should be noted that the ioni valence of each ingredient described below be for convenience and the typical value that uses, with other Ioni valence be not different.A possibility that ioni valence of each component is there are other than typical value in optical glass.For example, P usually with Ioni valence is present in glass for the state of+5 valences, therefore in the present invention with " P⁵⁺" it is used as typical value, but exist with other Ioni valence state there are a possibility that, this is also within protection scope of the present invention.

<necessary component and optional components>

P⁵⁺It is the formation component of optical glass of the present invention, the work that there is the devitrification for inhibiting glass and Abbe number is inhibited to reduce With when its content is lower than 3%, the devitrification resistance of glass is reduced, and when its content is more than 18%, the stability of glass is reduced. Therefore, P in the present invention⁵⁺Content is 3~18%, preferably 5~15%, more preferably 7~12%.

Al³⁺The stability of fluorphosphate glass can be improved, and effectively improve the machinability and chemical stability of glass, The average linear expansion coefficient of glass can be reduced simultaneously.When its content is lower than 1%, stable glass skeleton can not be formed and obtained Above-mentioned effect；When its content is higher than 15%, the transition temperature and liquidus temperature of glass are increased, and are made to be melted and are become difficult, Simultaneously increase temperature when molding, causes the volatilization of glass to aggravate, so that glass cord degenerates；On the other hand, excessively high transformation Temperature can make compression molding difficult.Therefore, Al in the present invention³⁺Content be 1~15%, preferably 2~10%, more preferably 3~ 8%.

Zn²⁺The melting temperature of glass transition temperature and glass raw material, but Zn can be reduced in the present invention²⁺Content is higher than When 10%, the devitrification resistance of glass can deteriorate, and be easy to cause devitrification since viscosity is too low.Therefore, optical glass of the present invention In, Zn²⁺Content be 0~10%.On the other hand, by containing the Zn greater than 0% in the present invention²⁺, the chemistry of glass can be improved Stability, improve raw material meltability, promote glass blister discharge, reduce the high temperature viscosity of glass, it is therefore preferable that for greater than 0 but be less than or equal to 10%, more preferably 1~8%, further preferably 2~6%.

R in the present invention²⁺It indicates alkaline-earth metal ions, is Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of, the present invention In pass through 25~60% R that contains²⁺, can get chemical stability and the excellent optical glass of devitrification resistance, preferably R²⁺Contain Amount is 30~60%, more preferably 35~50%.

Ba²⁺The devitrification resistance of glass can be improved, adjust the thermal expansion coefficient of glass.Particularly, pass through introducing in the present invention 20% or more Ba²⁺, optical glass of the present invention can be made to obtain desired optical constant and chemical stability, therefore, Ba²⁺'s Content lower limit is 20%, preferred lower limit 25%.On the other hand, by making Ba²⁺Content is 40% hereinafter, the light of glass can be improved Transmittance, and keep the glass in melting more stable.Therefore, Ba²⁺Upper content limit be 40%, preferred upper limit 35%, more preferably The upper limit is 32%.

In some embodiments of the present invention, P⁵⁺、Al³⁺And Ba²⁺Synergistic effect to the thermal expansion coefficient of optical glass and Have an impact at glass stability.As (P⁵⁺+Al³⁺)/Ba²⁺When less than 0.2, optical glass is reduced at glass stability, while anti-crystallization Performance decline；As (P⁵⁺+Al³⁺)/Ba²⁺When greater than 1.0, the thermal expansion coefficient of optical glass increases, therefore (P⁵⁺+Al³⁺)/Ba²⁺ Range be 0.2~1.0, preferably 0.3~0.8, more preferably 0.35~0.7.

Sr²⁺The optical constant of glass can be effectively adjusted, passes through the Sr of 3% or more introducing in the present invention²⁺, can be improved The devitrification resistance energy of glass, but when its content is more than 18%, the devitrification resistance of glass reduces.Therefore, in the present invention, Sr²⁺'s Content is 3~18%, preferably 5~15%, more preferably 8~13%.

In some embodiments of the present invention, by controlling Sr²⁺/Zn²⁺Range be 0.5~15.0, optical glass can be made Obtain suitable high temperature viscosity and desired transition temperature；Especially Sr²⁺/Zn²⁺Range be 1.0~10.0 when, can also be into one Step improves the striped degree of glass, more preferable Sr²⁺/Zn²⁺Range be 2.0~6.0.

Ca²⁺It is the component for improving glass devitrification resistance, reducing glass abrasion degree.By making Ca in the present invention²⁺Content be 8% hereinafter, can inhibit the reduction of glass refraction while improving the devitrification resistance of glass.Therefore, Ca in the present invention²⁺ Content be 0~8%, preferably Ca²⁺Content be 0.1~5%, more preferably 1~5%.

Mg²⁺The optical constant of adjustable glass improves the chemical stability of glass.In the present invention by containing 8% with Under Mg²⁺, the meltbility of glass can be improved, the abrasion degree and density of glass are reduced.Therefore, Mg in the present invention²⁺Content be 0 ~8%, preferably Mg²⁺Content be 0.1~5%, more preferably 0.5~3%.

In some embodiments, by controlling Mg²⁺/Sr²⁺For 2.5 hereinafter, the devitrification resistance of glass can be improved, into one Step, work as Mg²⁺/Sr²⁺When being 0.01~1.0, the devitrification resistance of glass can be improved while the density for inhibiting glass rises Can, more preferable Mg²⁺/Sr²⁺Content is 0.05~0.35.

In certain embodiments of the present invention, Al is controlled³⁺/Sr²⁺1.0 hereinafter, melten glass liquid can be reduced to crucible Corrosion, but Al³⁺/Sr²⁺When less than 0.05, the thermal expansion coefficient of glass increases, therefore, Al³⁺/Sr²⁺Range preferably from 0.05 ~1.0.Further, work as Al³⁺/Sr²⁺When below 0.8, it can also inhibit the volatilization of F, more preferable Al to a certain extent³⁺/ Sr²⁺Range is 0.1~0.8, further preferred Al³⁺/Sr²⁺Range is 0.2~0.6.

It is found by inventor's lot of experiments, works as Zn²⁺/R²⁺Value when being more than 0.4, the chemical stability drop of glass It is low, work as Zn²⁺/R²⁺Value when being lower than 0.01, the transition temperature of glass rises, therefore, Zn in optical glass of the present invention²⁺/R²⁺Model Enclose is 0.01~0.4.It is found by further investigation, works as Zn²⁺/R²⁺When in 0.02~0.25 range, glass also can further improve The bubble degree of glass reaches A grades or more, more preferable Zn²⁺/R²⁺It is 0.05~0.15.

Rn is used in the present invention⁺It indicates alkali metal ion, is Li⁺、Na⁺、K⁺One of or a variety of, Rn⁺Have in the present invention Having reduction transition temperature, the effect of adjusting process performance, but its content is more than 5%, and the thermal expansion coefficient of glass can be made to increase, drop Low chemical stability and processing performance, and the volatilization of glass metal is increased, it is unfavorable for the elimination of striped, preferably Rn⁺Content be 3% with Under, more preferably 1% or less.In some embodiments, even if a small amount of contains Rn⁺, can also make the chemical stability of glass Sharply decline, therefore does not preferably introduce Rn⁺。

In some embodiments of the present invention, by making Rn⁺/Zn²⁺0.5 hereinafter, the devitrification resistance energy of glass can be improved, Especially control Rn⁺/Zn²⁺0.3 hereinafter, also can further improve the acid-resistant stability of glass, prevent the viscosity of glass too low, Improve bubble degree, more preferable Rn⁺/Zn²⁺Below 0.1.

Ln³⁺It is the component for improving glass refraction and improving chemical durability of glass, is appointing in optical glass of the present invention Component is selected, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of or it is a variety of.By by Ln³⁺Content control be 8% or less The devitrification resistance property that can be improved glass prevents optical property that design requirement is not achieved, and reduces the cost of glass.Therefore, exist In optical glass of the invention, Ln³⁺The upper limit value of content range is 8%, preferred upper limit 5%, and the more preferable upper limit is 3%.? In some embodiments, even if a small amount of contains Ln³⁺, the devitrification resistance for also resulting in glass can sharply deteriorate, therefore preferably not Contain Ln³⁺。

In some embodiments of the present invention, by making Ln³⁺/Zn²⁺1.0 hereinafter, the moisture resistance stabilization of glass can be improved Property, especially make Ln³⁺/Zn²⁺0.5 hereinafter, can also improve the degree of staining of glass, more preferable Ln³⁺/Zn²⁺Below 0.2.

Si⁴⁺The devitrification resistance that glass can be improved reduces the abrasion degree of glass and improves processability, when its content is more than When 5%, the meltdown property of glass declines, therefore Si in optical glass of the present invention⁴⁺Content is 0~5%, preferably 0~3%, more Preferably 0~1%.

B³⁺The devitrification resistance of glass can be improved, reduce the density of glass, but be added in the optical glass containing F, glass is molten Change will appear stronger volatilization, cause the optical constant of glass unstable and striped, therefore B³⁺Content be limited to 5% hereinafter, Preferably 3% hereinafter, more preferably 1% hereinafter, do not introduce further preferably.

Zr⁴⁺It is appropriate addition can inhibit the striped formed in glass by volatilization, if its content is more than 5%, optics glass Glass becomes infusibility, and optical constant becomes difficult to control, thus its content be limited to 5% hereinafter, preferably 3% hereinafter, further Preferably 1% or less.

Ti⁴⁺The devitrification resistance of glass can be improved, if its content is higher than 5%, the refractive index of glass can be improved and reduce transmission Rate.Therefore, Ti⁴⁺Content be limited to 0~5%, preferably 0~3%, more preferably 0~1%.

Contain F in optical glass of the present invention^-As necessary component, pass through the F containing 12% or more^-, glass can be improved Abbe number and devitrification resistance, therefore F in the present invention^-Lower limit be 12%, preferred lower limit 15%, more preferable lower limit be 16%； Work as F^-When content is more than 28%, the volatilization of glass increases, and striped is deteriorated, and abrasion degree reduces, therefore upper content limit is in the present invention 28%, preferred upper limit 25%, the more preferable upper limit is 21%.

Pass through the O containing 12% or more in the present invention^2-, the devitrification resistance of glass can be improved and at glass stability, preferably O^2- Content lower limit is 15%, more preferable O^2-Content lower limit is 17%；But work as O^2-Content is more than 28%, the chemical stability of glass and Devitrification resistance has a declining tendency, therefore O^2-Upper content limit is 28%, preferred upper limit 25%, and the more preferable upper limit is 22%.

In the present invention, work as F^-/O^2-When greater than 1.5, F volatilization increases, and F is worked as in the striped degree decline of glass^-/O^2-Less than 0.7 When, the chemical stability of glass reduces, by making F^-/O^2-In 0.7~1.5 range, can get excellent chemical stability and Striped degree；Further, by making F^-/O^2-In 0.8~1.3 range, it can also improve the devitrification resistance and degree of staining of glass, more It is preferred that F^-/O^2-It is 0.9~1.2.

It is optional in the present invention, 0~1% clarifying agent can also be added, it is described clear to promote the discharge of Bubbles in Glass Clear agent is Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or it is a variety of, preferably clarification agent content be 0~0.5%, more preferably 0~0.1%.

In the range of not damaging glass performance of the invention, its above-mentioned not referred to can be added on a small quantity as needed His component, such as Ge⁴⁺、W⁶⁺、Nb⁵⁺、Te⁴⁺、Bi³⁺、Ta⁵⁺And Ga³⁺Etc. components.

In certain embodiments of the present invention, preferably make P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content 95% More than, it can make fluorophosphate optical glass that there is excellent devitrification resistance, chemical stability and bubble degree, preferably P⁵⁺、Al³⁺、Zn^{2 +}、R²⁺、F^-And O^2-Total content 97% or more, devitrification resistance and striped degree, more preferable P can also be advanced optimized⁵⁺、Al^{3 +}、Zn²⁺、R²⁺、F^-And O^2-Total content 98% or more, further preferred P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total contain Amount is 99% or more.

<ingredient that should not contain>

In glass of the present invention, the ion of the transition metal such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo, even if individually or In the case that compound ground contains on a small quantity, glass is also subject to coloration, and the specific wavelength in visible light region generates absorption, to subtract The property of weak visible light transmittance effect of the invention, therefore it is desirable, especially for the transmitance of visible light region wavelength requires Optical glass, preferably do not contain actually.

The cation of Th, Cd, Tl, Os, Be and Se have what control used to incline as harmful chemical substance in recent years To being to the measure of environmental protection in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization not only must It needs.Therefore, it in the case where paying attention to the influence to environment, other than being inevitably mixed into, does not preferably contain actually They.Optical glass becomes the substance actually without containing pollution environment as a result,.Therefore, even if not taking special environment pair Measure in plan, optical glass of the invention are also able to carry out manufacture, processing and discard.

" not introducing " " not containing " " 0% " described herein, which refers to, is not deliberately added to this for the component as raw material In invention optical glass；But as production optical glass raw material and/or equipment, can exist it is certain be not deliberately add it is miscellaneous Matter or component a small amount of or trace can contain in final optical glass, and such situation is also in the scope of protection of the patent of the present invention It is interior.

In the following, being illustrated to the performance of optical glass of the invention.

<refractive index and Abbe number>

Optical glass refractive index (nd) and Abbe number (ν_d) tested according to method as defined in GB/T 7962.1-2010.

The refractive index (nd) of optical glass of the present invention is 1.52~1.58, preferably 1.53~1.57, more preferably 1.54 ~1.57；Abbe number (ν_d) it is 68~75, preferably 69~74, more preferably 70~73.

<acid-resistant stability>

Optical glass acid-resistant stability (RA) (surface method) is tested according to method as defined in GB/T 7962.14-2010.

The acid-resistant stability (RA) of optical glass of the present invention is 2 classes or more, preferably 1 class.

<moisture resistance stability>

Stability that optical glass is moisture resistance (RC) (surface method) is tested according to method as defined in GB/T 7962.15-2010.

The moisture resistance stability (RC) of optical glass of the present invention is 3 classes or more, more than preferably 2 classes.

<bubble degree>

The bubble degree of optical glass is by the test of method as defined in GB/T7962.8-2010.

Optical glass bubble degree of the present invention is B grades or more, preferably A grades or more, more preferably A₀Grade or more.

<devitrification resistance energy>

The devitrification resistance energy test method of glass in the present invention are as follows: mother glass is cut into 20 × 20 × 10mm specification, It is put into heat preservation in the Muffle furnace that temperature is Tg+230 DEG C of temperature to preset 30 minutes, Xu Leng in heat-preservation cotton is put into after taking-up, after cooling Surface Crystallization situation is visually observed, no obvious crystallization is denoted as " A ", has obvious crystallization to be denoted as " B ".

For the optical glass that the present invention obtains without obvious crystallization, devitrification resistance can be excellent.

<thermal expansion coefficient>

Thermal expansion coefficient (α_20~120DEG C) tested according to method as defined in GB/T7962.16-2010.

Thermal expansion coefficient (the α of optical glass of the invention_{20~120 DEG C}) it is 145 × 10^-7/ K is hereinafter, preferably 140 × 10^-7/ K is hereinafter, more preferably 135 × 10^-7/ K or less.

<transition temperature>

Transition temperature (the T of glass_g) tested by method as defined in GB/T7962.16-2010.

Transition temperature (the T of optical glass of the invention_g) be 500 DEG C hereinafter, preferably 490 DEG C hereinafter, more preferably 485 DEG C or less.

<degree of staining of optical glass>

The degree of staining λ of optical glass of the present invention₈₀/λ₅It indicates.λ₈₀Refer to that glass transmittance reaches corresponding wave when 80% It is long, λ₅Refer to that glass transmittance reaches corresponding wavelength when 5%.Wherein, λ₈₀Measurement be using with parallel to each other and optics The glass with a thickness of 10 ± 0.1mm of the opposite plane of two of polishing, measures the light splitting in the wavelength domain from 280nm to 700nm Transmissivity and the wavelength for showing transmissivity 80%.So-called spectral transmission or transmissivity are vertical to the above-mentioned surface of glass Ground incident intensity I_inLight, project intensity I through glass and from plane_outLight in the case where pass through I_out/I_inIt indicates Amount, and also contain the transmissivity of the surface reflection loss on the above-mentioned surface of glass.

Optical glass λ of the invention₈₀Less than or equal to 350nm, preferably λ₈₀Range be less than or equal to 345nm, it is more excellent Select λ₈₀Range be less than or equal to 340nm；λ₅Less than or equal to 290nm, preferably λ₅Range be less than or equal to 285nm, More preferable λ₅Range be less than or equal to 280nm, further preferred λ₅Range be less than or equal to 275nm.

<striped degree>

The striped degree of optical glass is measured by method as defined in MLL-G-174B.Method is with point light source and lens group At schlieren instrument, from the direction for being easiest to see striped, and standard sample audit by comparison is divided into 4 grades, respectively A, B, C, D grades, the A grades of stripeds to be visible by naked eyes under regulation testing conditions, B grades are to have striped that is thin and dispersing, C under regulation testing conditions Grade is to have slight parallel stripes under regulation testing conditions, and D grades are to have rough striped under regulation testing conditions.

The striped degree of optical glass of the invention is C grades or more, preferably B grades or more.

[manufacturing method]

The manufacturing method of optical glass of the present invention is as follows: glass of the invention is produced using conventional raw material and common process, The use of carbonate, nitrate, sulfate, oxide, fluoride, metaphosphate etc. is raw material, according to a conventional method after ingredient, will match Good furnace charge is put into 1000~1100 DEG C of smelting furnace and is melted, after clarified and abundant homogenizing, in 900 DEG C of temperature below Casting or leakage injection forming, can be obtained optical glass of the invention.Those skilled in the art can according to actual needs, suitably Select raw material, process and technological parameter.

[optical precast product and optical element]

Molded such as the means of attrition process or reheating, compression molding precise punch forming means can be used, Optical precast product is made by made optical glass.I.e., it is possible to mechanical by being ground and being ground to optical glass etc. Processing makes optical precast product, or by the preform for making compression molding by optical glass, to the preform Carry out carrying out attrition process again after reheating is molded to make optical precast product, or and to attrition process is carried out it is manufactured pre- Precise punch forming is carried out at parison to make optical precast product.

It should be noted that the means for preparing optical precast product are not limited to above-mentioned means.As described above, optics of the invention Glass is useful for various optical elements and optical design, wherein particularly preferably by optical glass of the invention formed it is pre- at Parison carries out molded, precise punch forming of reheating etc., the optical elements such as production lens, prism using the preform.

Optical precast product and optical element of the invention is formed by the optical glass of aforementioned present invention.Optics of the invention Prefabricated component has excellent characteristics possessed by optical glass；Optical element of the invention has excellent spy possessed by optical glass Property, it is capable of providing the optical elements such as the costly various lens of optics, prism.

As the example of lens, can enumerate lens face be spherical surface or aspherical recessed meniscus shaped lens, male bend moon-shaped lens, The various lens such as biconvex lens, biconcave lens, plano-convex lens, plano-concave lens.

[optical instrument]

Optical glass of the present invention is formed by optical element and can make such as camera installation, picture pick-up device, display equipment and prison Control the optical instruments such as equipment.

Embodiment

<optical glass embodiment>

In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided.

The present embodiment obtains the optics glass with component shown in 1~table of table 2 using the manufacturing method of above-mentioned optical glass Glass.In addition, the test method measures the characteristic of each glass through the invention, and measurement result is indicated in 1~table of table 2 In.

Table 1

Table 2

Ln in upper 1~table of table 2, in embodiment 5³⁺It is by La that content, which is 1.1%,³⁺: 0.5% and Gd³⁺: 0.6% is constituted； Rn in embodiment 7⁺It is by Li that content, which is 1.2%,⁺: 0.5%, Na⁺: 0.5% and K⁺: 0.2% is constituted；Rn in embodiment 11⁺ It is by Li that content, which is 2.2%,⁺: 0.7%, Na⁺: 0.5% and K⁺: 1.0% is constituted；Ln in embodiment 12³⁺Content is By La³⁺: 1%, Gd³⁺: 0.75% and Y³⁺: 0.5%；Rn in embodiment 14⁺It is by Li that content, which is 1.5%,⁺: 0.5% and Na⁺: 1% is constituted；Rn in embodiment 16⁺It is by Li that content, which is 1.25%,⁺: 1% and Na⁺: 0.25% is constituted；Ln in embodiment 16³⁺Contain Amount is by Gd for 1.4%³⁺: 1.0% and Y³⁺: 0.4% is constituted.

<optical precast product embodiment>

The means of the obtained glass of optical glass Examples 1 to 20 use such as attrition process or reheating are molded, The means of the compression moldings such as precise punch forming, it is saturating to make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, concave-concave The prefabricated component of the various lens such as mirror, plano-convex lens, plano-concave lens, prism etc..

<optical element embodiment>

By obtained these prefabricated components annealing of above-mentioned optical precast product embodiment, the same of the deformation of inside glass is being reduced When be finely adjusted so that the optical characteristics such as refractive index reach desirable value.

Then, each prefabricated component is ground, ground, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens, The various lens such as biconcave lens, plano-convex lens, plano-concave lens, prism.It can also Tu Bufang on the surface of obtained optical element Reflectance coating.

<optical instrument embodiment>

By optical element made from above-mentioned optical element embodiment by optical design, by using one or more optics Element forms optical component or optical module, can be used for such as imaging device, sensor, microscope, medical science, number and throws Shadow, communication, optical communication technique/information transmission, optics/illumination in automotive field, photoetching technique, excimer laser, crystalline substance Piece, computer chip and integrated circuit and electronic device including such circuit and chip, or taking the photograph for automotive field As equipment and device.

Claims (23)

1. fluorophosphate optical glass, which is characterized in that its component indicates by weight percentage, contains P⁵⁺: 3~18%, Al³⁺: 1 ~15%, Zn²⁺: greater than 0 but be less than or equal to 10%, R²⁺: 25~60%, F^-: 12~28%, O^2-: 12~28%, wherein Zn^{2 +}/R²⁺Range be 0.01~0.4, R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

2. fluorophosphate optical glass according to claim 1, which is characterized in that its component indicates by weight percentage, Also contain: Ln³⁺: 0~8%, and/or Rn⁺: 0~5%, and/or Si⁴⁺: 0~5%, and/or B³⁺: 0~5%, and/or Zr⁴⁺: 0 ~5%, and/or Ti⁴⁺: 0~5%, and/or clarifying agent: 0~1%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of or It is a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or it is more Kind.

3. fluorophosphate optical glass, which is characterized in that its refractive index nd is 1.52~1.58, Abbe number ν_dIt is 68~75, contains P⁵⁺、Al³⁺、Ba²⁺、F^-And O^2-As necessary component, component indicates by weight percentage, wherein (P⁵⁺+Al³⁺)/Ba²⁺Range For 0.2~1.0, F^-/O^2-Range be 0.7~1.5.

4. fluorophosphate optical glass according to claim 3, which is characterized in that its component indicates by weight percentage, Contain P⁵⁺: 3~18%, Al³⁺: 1~15%, Zn²⁺: greater than 0 but be less than or equal to 10%, Ba²⁺: 20~40%, Sr²⁺: 3~ 18%, Ca²⁺: 0~8%, Mg²⁺: 0~8%, Ln³⁺: 0~8%, Rn⁺: 0~5%, Si⁴⁺: 0~5%, B³⁺: 0~5%, Zr⁴⁺: 0 ~5%, Ti⁴⁺: 0~5%, clarifying agent: 0~1%, F^-: 12~28%, O^2-: 12~28%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺ And Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^- And I^-One of or it is a variety of.

5. fluorophosphate optical glass, which is characterized in that its component indicates by weight percentage, contains P⁵⁺: 3~18%, Al³⁺: 1 ~15%, Zn²⁺: greater than 0 but be less than or equal to 10%, Ba²⁺: 20~40%, Sr²⁺: 3~18%, F^-: 12~28%, O^2-: 12 ~28%.

6. fluorophosphate optical glass according to claim 5, which is characterized in that its component indicates by weight percentage, Also contain Ca²⁺: 0~8%, and/or Mg²⁺: 0~8%, and/or Ln³⁺: 0~8%, and/or Rn⁺: 0~5%, and/or Si⁴⁺: 0 ~5%, and/or B³⁺: 0~5%, and/or Zr⁴⁺: 0~5%, and/or Ti⁴⁺: 0~5%, and/or clarifying agent: 0~1%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺And Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb^{3 +}、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-And I^-One of or it is a variety of.

7. according to claim 1 or fluorophosphate optical glass described in 2 any claims, which is characterized in that wherein (P⁵⁺+ Al³⁺)/Ba²⁺Range be 0.2~1.0 and/or F^-/O^2-Range be 0.7~1.5.

8. according to fluorophosphate optical glass described in claim 3 or 4 any claims, which is characterized in that wherein Zn²⁺/ R²⁺Range be 0.01~0.4, wherein R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

9. according to fluorophosphate optical glass described in claim 5 or 6 any claims, which is characterized in that wherein Zn²⁺/ R²⁺Range be 0.01~0.4, and/or (P⁵⁺+Al³⁺)/Ba²⁺Range be 0.2~1.0 and/or F^-/O^2-Range be 0.7 ~1.5, wherein R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

10. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that its component is full Be enough one of lower 5 kinds of situations or more than one:

1)Rn⁺/Zn²⁺Range below 0.5；

2)Ln³⁺/Zn²⁺Range below 1.0；

3)Al³⁺/Sr²⁺Range be 0.05~1.0；

4)Mg²⁺/Sr²⁺Range be 2.5 or less；

5)Sr²⁺/Zn²⁺Range be 0.5~15.0.

11. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that its component is pressed Weight percent indicates, contains P⁵⁺: 5~15%, and/or Al³⁺: 2~10%, and/or Zn²⁺: 1~8%, and/or Ba²⁺: 25~ 35%, and/or Sr²⁺: 5~15%, and/or Ca²⁺: 0.1~5%, and/or Mg²⁺: 0.1~5%, and/or Ln³⁺: 0~5%, And/or Rn⁺: 0~3%, and/or Si⁴⁺: 0~3%, and/or B³⁺: 0~3%, and/or Zr⁴⁺: 0~3%, and/or Ti⁴⁺: 0~ 3%, and/or clarifying agent: 0~0.5%, and/or F^-: 15~25%, and/or O^2-: 15~25%, wherein Ln³⁺For La³⁺、Gd³⁺、 Y³⁺And Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、 Br^-And I^-One of or it is a variety of.

12. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that its component is full Be enough one of lower 8 kinds of situations or more than one:

1)Rn⁺/Zn²⁺Range below 0.3；

2)Ln³⁺/Zn²⁺Range below 0.5；

3)Al³⁺/Sr²⁺Range be 0.1~0.8；

4)Mg²⁺/Sr²⁺Range be 0.01~1.0；

5)Sr²⁺/Zn²⁺Range be 1.0~10.0；

6)(P⁵⁺+Al³⁺)/Ba²⁺Range be 0.3~0.8；

7)F^-/O^2-Range be 0.8~1.3；

8)Zn²⁺/R²⁺Range be 0.02~0.25.

13. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that its component is pressed Weight percent indicates, contains P⁵⁺: 7~12%, and/or Al³⁺: 3~8%, and/or Zn²⁺: 2~6%, and/or Ba²⁺: 25~ 32%, and/or Sr²⁺: 8~13%, and/or Ca²⁺: 1~5%, and/or Mg²⁺: 0.5~3%, and/or Ln³⁺: 0~3% and/ Or Rn⁺: 0~1%, and/or Si⁴⁺: 0~1%, and/or B³⁺: 0~1%, and/or Zr⁴⁺: 0~1%, and/or Ti⁴⁺: 0~1%, And/or clarifying agent: 0~0.1%, and/or F^-: 16~21%, and/or O^2-: 17~22%, wherein Ln³⁺For La³⁺、Gd³⁺、Y³⁺With Yb³⁺One of or a variety of, Rn⁺For Li⁺、Na⁺、K⁺One of or a variety of, clarifying agent Sb³⁺、Sn⁴⁺、Ce⁴⁺、Cl^-、Br^-With I^-One of or it is a variety of.

14. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that its component is full Be enough one of lower 8 kinds of situations or more than one:

1)Rn⁺/Zn²⁺Range below 0.1；

2)Ln³⁺/Zn²⁺Range below 0.2；

3)Al³⁺/Sr²⁺Range be 0.2~0.6；

4)Mg²⁺/Sr²⁺Range be 0.05~0.35；

5)Sr²⁺/Zn²⁺Range be 2.0~6.0；

6)(P⁵⁺+Al³⁺)/Ba²⁺Range be 0.35~0.7；

7)F^-/O^2-Range be 0.9~1.2；

8)Zn²⁺/R²⁺Range be 0.05~0.15.

15. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that wherein R²⁺: 30~60%, preferably R²⁺: 35~50%, R²⁺For Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺One of or it is a variety of.

16. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that do not contain Ln^{3 +}And/or Rn⁺。

17. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that the fluorine phosphorus P in hydrochlorate optical glass⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content in 95% or more, preferably P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^- And O^2-Total content 97% or more, more preferable P⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content 98% or more, into The preferred P of one step⁵⁺、Al³⁺、Zn²⁺、R²⁺、F^-And O^2-Total content 99% or more.

18. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that the fluorine phosphorus The refractive index nd of hydrochlorate optical glass is 1.52~1.58, preferably 1.53~1.57, more preferably 1.54~1.57；Abbe number ν_dIt is 68~75, preferably 69~74, more preferably 70~73.

19. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that the fluorine phosphorus The acid-resistant stability RA of hydrochlorate optical glass is 2 classes or more, preferably 1 class；Moisture resistance stability RC is 3 classes or more, preferably 2 classes More than.

20. fluorophosphate optical glass described in any claim according to claim 1~6, which is characterized in that the fluorine phosphorus The bubble degree of hydrochlorate optical glass is B grades or more, preferably A grades or more, more preferably A₀Grade or more；And/or thermal expansion coefficient α_{20~120 DEG C}It is 145 × 10^-7/ K is hereinafter, preferably 140 × 10^-7/ K is hereinafter, more preferably 135 × 10^-7/ K or less；And/or transformation Temperature T_gFor 500 DEG C hereinafter, preferably 490 DEG C hereinafter, more preferably 485 DEG C or less；And/or λ₈₀It is excellent less than or equal to 350nm Select λ₈₀Less than or equal to 345nm, more preferable λ₈₀Less than or equal to 340nm；And/or λ₅Less than or equal to 290nm, preferably λ₅It is less than Or it is equal to 285nm, more preferable λ₅Less than or equal to 280nm, further preferred λ₅Less than or equal to 275nm.

21. optical precast product is made of optical glass described in claim 1~20 any claim.

22. optical element is made of optical glass described in claim 1~20 any claim, or is wanted using right Optical precast product described in asking 21 is made.

23. optical instrument containing optical glass described in claim 1~20 any claim, or contains claim 22 The optical element.