CN106830671A - Optical glass and optical element - Google Patents

Optical glass and optical element Download PDF

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Publication number
CN106830671A
CN106830671A CN201710156101.1A CN201710156101A CN106830671A CN 106830671 A CN106830671 A CN 106830671A CN 201710156101 A CN201710156101 A CN 201710156101A CN 106830671 A CN106830671 A CN 106830671A
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glass
optical
less
optical glass
equal
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CN106830671B (en
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袁伟
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Priority to CN201710156101.1A priority patent/CN106830671B/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

It is the optical glass that 1.78~1.83, Abbe number is 48~53 that the present invention provides a kind of refractive index.Optical glass, the percentage by weight composition of its cation contains：Si4+：More than 0 but less than or equal to 15%；B3+：More than 0 but less than or equal to 20%, wherein, Si4+/B3+It is 0.5~1；La3+：42~58%；Gd3+：18~33%；Y3+：1~15%；Ta5+：More than 0 but less than or equal to 10%；Zr4+：0~10%；Its anion contains O2‑And F‑, wherein, F‑/O2‑It is more than 0 but less than or equal to 0.3.The present invention is designed by rational component, introduces appropriate rare earth ion La3+、Gd3+、Y3+, and a small amount of F‑, the dispersion of glass is reduced, the optical glass with refractive low dispersive characteristic high is obtained, the optical glass is applied to the optical element of high-quality.

Description

Optical glass and optical element
Technical field
The present invention relates to a kind of optical glass, the optical glass of more particularly to a kind of refractive low dispersive high and by the glass Prefabricated component and optical element that glass is formed.
Background technology
The lens that high-refraction low-dispersion optical glass for mold is formed can eliminate optics with the lens combination of high-refraction high-dispersion The aberration of system so that optical system it is compacter, with better performance.Therefore, folding particularly of the present invention The rate of penetrating is that the market demand of the glass of the refractive low dispersive high that 1.78~1.83, Abbe number is 48~53 will increase.
For the glass of refractive low dispersive high, in the case where keeping refractive index higher so that dispersion becomes smaller, above-mentioned Glass is market needs, but such " limit " glass is rare.Containing a large amount of in optical glass disclosed in CN1377847 Nb2O5, and its dispersion is still higher, it is impossible to meet the requirement now for high refractive low dispersive glass.
The content of the invention
It is that 1.78~1.83, Abbe number is 48~53 that technical scheme to be solved by this invention is to provide a kind of refractive index Optical glass.
The present invention also provides the prefabricated component and optical element that a kind of above-mentioned glass is formed.
The technical proposal for solving the technical problem of the invention is：Optical glass, the percentage by weight group of its cation Into containing：Si4+：More than 0 but less than or equal to 15%；B3+：More than 0 but less than or equal to 20%, wherein, Si4+/B3+For 0.5~ 1；La3+：42~58%；Gd3+：18~33%；Y3+：1~15%；Ta5+：More than 0 but less than or equal to 10%；Zr4+：0~ 10%；Its anion contains O2-And F-, wherein, F-/O2-It is more than 0 but less than or equal to 0.3.
Further, also contain：Nb5+：0~5%；Zn2++Sr2++Ba2+：0~10%；Sb3+：0~0.2%.
Optical glass, the percentage by weight of its cation constitutes and is：Si4+：More than 0 but less than or equal to 15%；B3+：Greatly In 0 but less than or equal to 20%, wherein, Si4+/B3+It is 0.5~1；La3+：42~58%；Gd3+：18~33%；Y3+：1~ 15%；Ta5+：More than 0 but less than or equal to 10%；Zr4+：0~10%；Nb5+：0~5%；Zn2++Sr2++Ba2+：0~10%； Sb3+：0~0.2%；Its anion contains O2-And F-, wherein, F-/O2-It is more than 0 but less than or equal to 0.3；Si4+/F-It is 0.3 ~1.5.
Further, wherein：Si4+/F-It is 0.3~0.9；And/or (Ta5++Zr4+)/(La3++Gd3++Y3+) be more than 0 but Less than or equal to 0.3.
Further, wherein, Si4+：1~10%；And/or B3+：1~15%；And/or La3+：42~55%；And/or Gd3 +：20~31%；And/or Y3+：2~13%；And/or Ta5+：1~8%；And/or Zr4+：0.5~8%.
Further, the content of the ion meets one or more in following 4 kinds of conditions：
1)Si4+/F-It is 0.3~0.7；
2)(Ta5++Zr4+)/(La3++Gd3++Y3+) it is 0.05~0.2；
3)Si4+/B3+It is 0.62~1；
4)F-/O2-It is 0.05~0.2.
Further, wherein, Si4+：2~9%；And/or B3+：1~13%；And/or Zn2++Sr2++Ba2+：0~7%； And/or Sb3+：0~0.1%；Nb is not contained5+、W6+、Ti4+。
Further, the percentage by weight composition of its anion contains：F-：5~20%；O2-：80~95%.
Further, the percentage by weight composition of its anion contains：F-：7~19%；O2-：81~93%.
Further, the glass refraction is 1.78~1.83, and Abbe number is 48~53.
Gas preform, is made of above-mentioned optical glass.
Optical element, is made of above-mentioned optical glass.
The beneficial effects of the invention are as follows：Designed by rational component, appropriate rare earth ion La is introduced in optical glass3 +、Gd3+、Y3+, and a small amount of F-, the dispersion of glass is reduced, the optical glass with refractive low dispersive characteristic high is obtained, and should The prefabricated component that optical glass is formed, the optical glass is applied to the optical element of high-quality.
Specific embodiment
Component contained by optical glass of the present invention will be described in detail belows, the content of each component is being not particularly illustrated In the case of, cationic componentses content refers to the percentage that the cation accounts for whole cation gross weights, anionic group content Refer to percentage that the anion accounts for whole anion gross weights.Si4+/F-Ratio refer to Si4+Account for whole cation weights hundred Divide ratio and F-Account for the ratio of whole anion percentage by weights.In addition, in the following description (except special instruction), mentioning rule Also the setting is included when below definite value or more than setting.
Si4+It is glass generation body cation constituent, a certain amount of Si4+The viscosity of glass can be increased, prevent glass from analysing Crystalline substance, improves chemical durability of glass, prevents glass devitrification.If Si4+Content very little, the easy crystallization of glass, refractive index can not Reach required scope；But if Si4+Content be higher than 15%, the reduction of the meltability of optical glass, glass will devitrification.Cause This, Si4+Content be more than 0 but less than or equal to 15% preferably 1~10%.More preferably 2~9%.
B3+It is also a kind of optical glass network generation body component, there is preferable fluxing action, appropriate B3+To suppressing glass Crystallization it is very good.If B3+Content very little, glass melting is very poor, the easy devitrification of glass, it is more difficult to form glass；But such as Fruit B3+Content be higher than 20%, the chemical stability of glass can be poor.Therefore, B3+Content be more than 0 but be less than or equal to 20%, preferably 1~15%, more preferably 1~13%.
Because the lanthanide glass of refractive low dispersive high is narrower into glass scope, need to be by Si4+Content and B3+The ratio Si of content4+/ B3+In rational scope, glass has suitable high temperature viscosity within this range, is prevented from the crystallization of glass for control.Through hair The discovery of person of good sense's numerous studies, controls Si4+/B3+For 0.5~1 when, when preferably 0.62~1, glass of the invention has preferable High temperature viscosity and it is difficult crystallization.
La3+It is the core component to form high-refractivity and low-dispersion glass.If La3+Content be less than 42%, refractive index is not Required scope can be reached；But if La3+Content be higher than 58%, thermal stability be deteriorated, glass easily crystallization, devitrification Tendency is very big.Therefore, La3+Content be 42~58%, preferably 42~55%.
Gd3+Glass refraction and dispersion can be adjusted, the stability of glass is improved.If Gd3+Content be less than 18%, The optical constant of glass can not reach required scope；But if Gd3+Content be higher than 33%, thermal stability be deteriorated, Glass easily crystallization, tendency towards devitrification is very big.Therefore, Gd3+Content be 18~33%, preferably 20~31%.
The present invention is by introducing appropriate Y3+With La3+Consolute, can form the glass of better heat stability.If Y3+Contain Amount is less than 1%, and the optical constant of glass can not reach required scope；But if Y3+Content be higher than 15%, glass is easily Crystallization, it is easy to devitrification.Therefore, Y3+Content be 1~15%, preferably 2~13%.
Ta5+Optical glass refractive index can be significantly improved, suppresses the crystallization of glass.If Ta5+Content very little, glass Easy crystallization；But if Ta5+Content be higher than 10%, the dispersion of glass can be significantly increased, and not reach the purpose of low dispersion, and meeting The meltdown property of glass is deteriorated, can also greatly improve glass production cost.Therefore, Ta5+Content be more than 0 but less than or wait In 10%, preferably 1~8%.
Zr4+The refractive index of optical glass can be improved, the chemical stability of glass is improved, glass devitrification is also prevented from, Reduce recrystallization temperature.In the present invention, if its content is higher than 10%, glass is difficult to melt, and smelting temperature rises, and is easily caused glass Occurs field trash inside glass.Therefore, Zr4+Content be 0~10%, preferably 0.5~8%.
The present inventor's research finds, by Ta5+、Zr4+Content sum and La3+、Gd3+、Y3+Content sum ratio (Ta5 ++Zr4+)/(La3++Gd3++Y3+) in the range of more than 0 but less than or equal to 0.3, glass inherent quality preferably, is difficult out for control The now situation such as material calculus, field trash, and, preferably (Ta very good to the crystallization of suppression glass5++Zr4+)/(La3++Gd3++Y3+) It is 0.05~0.2.
Nb5+To realizing that glass high index of refraction has larger effect, but if Nb5+Content more than 5%, the dispersion of glass will Can be very big, cannot get the glass of low dispersion.Therefore, Nb5+Content be 0~5%, preferably do not contain Nb5+.In addition, of the invention W is not contained in glass yet6+、Ti4+Both drastically raise the ion of dispersion.
Ba2+、Zn2+、Sr2+Refractive index and the dispersion of glass can be adjusted.When its total amount is more than 10%, glass is easy Devitrification.Therefore, Ba2+、Zn2+、Sr2+Total content (Zn2++Sr2++Ba2+) it is 0~10%, preferably 0~7%.
Sb3+Used as fining agent in the present invention, its content is 0~0.2%, preferably 0~0.1%.
In the present invention, anion contains O2-And F-。
F-It is neccessary composition of the invention, can effectively reduces the dispersion of glass, realizes the requirement of the low dispersion of glass, separately The transition temperature of glass can also be reduced outward.If F-Content be less than 5%, it is impossible to reach reduce glass dispersion purpose；But such as Fruit F-Content be higher than 20%, glass volatilization is very big, causes the constant data of glass very unstable, and production difficulty is big, while easily The refractive index of glass is caused not reach claimed range.Therefore, F-Content be 5~20%, preferably 7~19%.
O2-It is also necessary anion of the invention, the glass of stabilization can be formed, prevents glass devitrification.Therefore, O2-Contain It is 80~95% to measure, preferably 81~93%.
The present inventor's research finds, by F-Content and O2The ratio F of content-/O2-Control when within the scope of rational, glass The volatilization of glass is small, is capable of the constant data of stabilized glass, reduces striped, increases the meltbility of glass.Therefore, F-/O2-It is more than 0 But less than or equal to 0.3, preferably 0.05~0.2.
In addition, working as Si4+Content and F-The ratio Si of content4+/F-Control can effectively suppress when within the scope of rational This devitrification into the extremely narrow glass of glass scope, additionally it is possible to increase the transmitance of glass.Therefore, Si4+/F-It is 0.3~1.5, preferably It is 0.3~0.9, more preferably 0.3~0.7.
The optical glass that the present invention is provided is made according to preparation method well known to those skilled in the art, i.e.,：Raw material is entered Row fusing, clarification, stirring homogenizing, be cooled to suitable temperature shaping, you can obtain refractive index provided by the present invention for 1.78~ 1.83rd, Abbe number is 48~53 optical glass with refractive low dispersive performance high.
The method of testing of each performance parameter of the optical glass that the present invention is provided is as follows：
Refractive index (nd), Abbe number (vd) according to《The colouless optical glass method of testing refractive indexes of GB/T 7962.1-2010 And abbe number》Test.
By above-mentioned test, the refractive index (nd) of the optical glass of the invention for obtaining is 1.78~1.83, Abbe number (vd) it is 48~53.
Degree of staining (the λ of glass80/λ5)：Using with two thickness of optical polish plane parallel to each other be 10 ± The glass sample of 0.1mm, determines spectral transmission, is calculated according to its result.
After measured, the transmittance of glass of the present invention reaches corresponding wavelength X when 80%80In below 395nm, preferably Below 390nm.
The present invention also provides a kind of optical precast product and optical element, and the optical precast product and element are by optics of the present invention What glass was formed, therefore the optical precast product and optical element have all characteristics of the invention described above optical glass.This hair Bright optical glass has the performance of refractive low dispersive high, and refractive index (nd) is 1.78~1.83, and Abbe number is 48~53.This hair The optical precast product and optical element of bright offer can preferably eliminate the aberration of optical system, so that optical system is more stepped up Gather, with better performance, be capable of achieving device miniaturization, light-weighted demand.
Embodiment
In order to further appreciate that technical scheme, the present invention will be described preferably with reference to following specific embodiment Embodiment.It should be noted that and understand, these embodiments are intended merely to be better described the features of the present invention and excellent Point, not restricted claim of the invention.
The optical glass component (being represented with anions and canons percentage by weight respectively) that embodiments of the invention 1~30 are provided And its corresponding performance is as shown in Table 1 to Table 3.By by the various cations of optical glass in 1~table of table 3 each embodiment and The corresponding oxide of anion, fluoride, carbonate etc. are weighed according to its ratio, are sufficiently mixed uniform rear addition optical glass and are melted In stove, under appropriate technological temperature after fusing, clarification, stirring are homogenized, are cooled to suitable temperature, the glass that this is melted It is poured into preheated metal die in advance and is molded and anneals, just can obtain required optical glass.
The composition and respective performances of a kind of optical glass with refractive low dispersive high that the present invention is provided are such as：Refractive index (nd), dispersion (nF-nC), Abbe number (vd), degree of staining (λ80/λ5) result all in the embodiment 1~30 of 1~table of table 3 table Show.
Table 1
Table 2
Table 3
From above-described embodiment as can be seen that optical glass its refractive index (nd) that the present invention is provided is 1.78~1.83, Ah Shellfish number be 48~53, with refractive low dispersive high, transmitance is high the characteristics of, can preferably eliminate the aberration of optical system so that So that optical system is compacter, with better performance, device miniaturization, light-weighted demand are capable of achieving.

Claims (12)

1. optical glass, it is characterised in that the percentage by weight composition of its cation contains：Si4+：More than 0 but it is less than or equal to 15%；B3+：More than 0 but less than or equal to 20%, wherein, Si4+/B3+It is 0.5~1；La3+：42~58%；Gd3+：18~ 33%；Y3+：1~15%；Ta5+：More than 0 but less than or equal to 10%；Zr4+：0~10%；
Its anion contains O2-And F-, wherein, F-/O2-It is more than 0 but less than or equal to 0.3.
2. optical glass as claimed in claim 1, it is characterised in that also contain：Nb5+：0~5%；Zn2++Sr2++Ba2+：0~ 10%；Sb3+：0~0.2%.
3. optical glass, it is characterised in that the percentage by weight composition of its cation is：Si4+：More than 0 but it is less than or equal to 15%；B3+：More than 0 but less than or equal to 20%, wherein, Si4+/B3+It is 0.5~1；La3+：42~58%；Gd3+：18~ 33%；Y3+：1~15%；Ta5+：More than 0 but less than or equal to 10%；Zr4+：0~10%；Nb5+：0~5%；Zn2++Sr2++ Ba2+：0~10%；Sb3+：0~0.2%；
Its anion contains O2-And F-, wherein, F-/O2-It is more than 0 but less than or equal to 0.3；
Si4+/F-It is 0.3~1.5.
4. the optical glass as described in claim 1-3 any claims, it is characterised in that wherein：Si4+/F-For 0.3~ 0.9；And/or (Ta5++Zr4+)/(La3++Gd3++Y3+) it is more than 0 but less than or equal to 0.3.
5. the optical glass as described in claim 1-3 any claims, it is characterised in that wherein, Si4+：1~10%；With/ Or B3+：1~15%；And/or La3+：42~55%；And/or Gd3+：20~31%；And/or Y3+：2~13%；And/or Ta5+：1 ~8%；And/or Zr4+：0.5~8%.
6. the optical glass as described in claim 1-3 any claims, it is characterised in that the content of the ion meet with One or more in lower 4 kinds of conditions：
1)Si4+/F-It is 0.3~0.7；
2)(Ta5++Zr4+)/(La3++Gd3++Y3+) it is 0.05~0.2；
3)Si4+/B3+It is 0.62~1；
4)F-/O2-It is 0.05~0.2.
7. the optical glass as described in claim 1-3 any claims, it is characterised in that wherein, Si4+：2~9%；With/ Or B3+：1~13%；And/or Zn2++Sr2++Ba2+：0~7%；And/or Sb3+：0~0.1%；Nb is not contained5+、W6+、Ti4+。
8. the optical glass as described in claim 1-3 any claims, it is characterised in that the percentage by weight of its anion Composition contains：F-：5~20%；O2-：80~95%.
9. the optical glass as described in claim 1-3 any claims, it is characterised in that the percentage by weight of its anion Composition contains：F-：7~19%；O2-：81~93%.
10. the optical glass as described in claim 1-3 any claims, it is characterised in that the glass refraction is 1.78~1.83, Abbe number is 48~53.
11. gas preforms, are made of the optical glass described in claim 1-10 any claims.
12. optical elements, are made of the optical glass described in claim 1-10 any claims.
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CN114956548A (en) * 2018-09-27 2022-08-30 成都光明光电股份有限公司 Optical glass, and glass preform, optical element and optical instrument made of the same

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