CN108623152A - Optical glass, optical precast product and optical element - Google Patents
Optical glass, optical precast product and optical element Download PDFInfo
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- CN108623152A CN108623152A CN201810614692.7A CN201810614692A CN108623152A CN 108623152 A CN108623152 A CN 108623152A CN 201810614692 A CN201810614692 A CN 201810614692A CN 108623152 A CN108623152 A CN 108623152A
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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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
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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
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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
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- 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
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
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Abstract
The present invention provides a kind of optical glass with excellent devitrification resistance energy and chemical stability, optical glass, including P5+、Al3+And R2+, wherein R2+For Ba2+、Sr2+、Ca2+And Mg2+In one or more;In terms of cation mole %, contain:P5+:20 36%;Al3+:5 25%;Ba2+:25 40%;Wherein Ba2+/R2+It is 0.5 or more;Anion contains F‑And O2‑, wherein F‑Content and F‑And O2‑Total content molar ratio F‑/(F‑+O2‑) it is 0.35 0.55.The present invention passes through the proportioning between rationally adjusting each component, make fluorophosphate optical glass of the present invention while the Abbe number with 1.53 1.60 refractive index, 68 75, with excellent devitrification resistance energy and chemical stability, meet modern photoelectric field growth requirement.
Description
Technical field
The present invention relates to a kind of optical glass, are 1.53-1.60 more particularly, to a kind of refractive index, Abbe number 68-75
Optical glass, and the optical precast product and optical element that are formed by the optical glass.
Background technology
In the optical systems such as camera, in order to eliminate the aberration of lens, generally use combines the different glass of Abbe number
" colour killing " design, it is therefore desirable to the optical glass of different refractivity and Abbe number is combined, to form reasonable optical system
System.Fluorophosphate optical glass is as widely used New Glasses Materials, the characteristic with low dispersion, in optical system
In can eliminate second order spectrum especial dispersion, improve resolution ratio, hence it is evident that improve optical system imaging quality, while also having lower
Softening temperature, can directly accurate die pressing advanced non-spherical lens is made.But current refractive index is 1.53-1.60, Abbe number is
The usual devitrification resistance of fluorophosphate optical glass of 68-75 can be poor, is easier to crystallization during production and accurate die pressing, reduces
The yields of glass.
In recent years, optical glass is widely applied in the fields such as vehicle-mounted, monitoring security protection, and applied to fields such as vehicle-mounted, security protections
Optical glass is chronically exposed to outdoor, therefore also higher to the chemical stability requirements of optical glass.Therefore, field of photovoltaic materials
Demand to the fluorophosphate optical glass with superior chemical stability and devitrification resistance energy is more and more urgent.
Invention content
Technical problem to be solved by the invention is to provide a kind of with excellent devitrification resistance energy and chemical stability
Optical glass, and the optical precast product and optical element that are formed by the optical glass.
The technical proposal for solving the technical problem of the invention is:Optical glass, as necessary cationic components, packet
Include P5+、Al3+And R2+, wherein R2+For Ba2+、Sr2+、Ca2+And Mg2+In one or more;In terms of cation mole %,
Contain:P5+:20-36%;Al3+:5-25%;Ba2+:25-40%;Wherein Ba2+/R2+It is 0.5 or more;
Anion contains F-And O2-, wherein F-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.35-
0.55。
Further, also contain:Sr2+:0-20%;And/or Ca2+:0-10%;And/or Mg2+:0-10%;And/or Gd3+:
0-10%;And/or Y3+:0-10%;And/or La3+:0-10%;And/or Si4+:0-10%;And/or B3+:0-10%;And/or Na+:0-10%;And/or Li+:0-10%;And/or K+:0-10%;And/or Zn2+:0-10%;And/or Nb5+:0-10%;And/or
Ti4+:0-10%;And/or Zr4+:0-10%;And/or W6+:0-10%.
Optical glass, in terms of cation mole %, consisting of P5+:20-36%;Al3+:5-25%;Ba2+:25-40%;
Sr2+:0-20%;Ca2+:0-10%;Mg2+:0-10%;Gd3+:0-10%;Y3+:0-10%;La3+:0-10%;Si4+:0-
10%;B3+:0-10%;Na+:0-10%;Li+:0-10%;K+:0-10%;Zn2+:0-10%;Nb5+:0-10%;Ti4+:0-
10%;Zr4+:0-10%W6+:0-10%;Sb3+:0-1%;
Anion is F-、Cl-And O2-, wherein F-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.35-
0.55。
Further, each component meets the one or more in following 5 kinds of conditions:
1)Sr2+Content is more than Mg2+Content;
2)(Gd3++La3+)/Ln3+For 0.2-0.8, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 1 or less;
4)Sr2+/Ba2+For 0.1-0.5;
5)Li+/(R++Ln3+) it is 0.5 or less, wherein R+For Na+、Li+、K+Total content.
Further, each component meets the one or more in following 5 kinds of conditions:
1)Ba2+/R2+It is 0.6 or more;
2)(Gd3++La3+)/Ln3+For 0.3-0.7, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 0.8 or less;
4)Sr2+/Ba2+For 0.15-0.5;
5)Li+/(R++Ln3+) it is 0.3 or less, wherein R+For Na+、Li+、K+Total content.
Further, each component meets the one or more in following 5 kinds of conditions:
1)Ba2+/R2+For 0.65-0.9;
2)(Gd3++La3+)/Ln3+For 0.4-0.65, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 0.5 or less;
4)Sr2+/Ba2+For 0.2-0.4;
5)Li+/(R++Ln3+) it is 0.25 or less, wherein R+For Na+、Li+、K+Total content.
Further, wherein:P5+:25-35%;And/or Al3+:10-22%;And/or Ba2+:25-36%;And/or Sr2+:
5-20%;And/or Ca2+:0-8%;And/or Mg2+:0-8%;And/or Gd3+:0-8%;And/or Y3+:0.5-8%;And/or La3 +:0-8%;And/or Si4+:0-5%;And/or B3+:0-5%;And/or Na+:0-5%;And/or Li+:0-5%;And/or K+:0-
5%;And/or Zn2+:0-5%;And/or Nb5+:0-5%;And/or Ti4+:0-5%;And/or Zr4+:0-5%;And/or W6+:0-
5%.
Further, wherein:P5+:28-35%;And/or Al3+:13-20%;And/or Ba2+:28-36%;And/or Sr2+:
5-15%;And/or Ca2+:0.5-5%;And/or Mg2+:0-5%;And/or Gd3+:0.5-5%;And/or Y3+:0.5-6%;With/
Or La3+:0.5-5%;And/or Si4+:0-3%;And/or B3+:0-3%;And/or Na+:0-3%;And/or Li+:0-3%;With/
Or K+:0-3%;And/or Zn2+:0-3%;And/or Nb5+:0-3%;And/or Ti4+:0-3%;And/or Zr4+:0-3%;And/or
W6+:0-3%.
Further, also contain Sb3+:0-1%;And/or Sn4+:0-1%;And/or Ce4+:0-1%;And/or Cl-:0-
1%;And/or Br-:0-1%;And/or I-:0-1%.
Further, F-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.38-0.52, preferably
0.4-0.48。
Further, the refractive index nd of glass is 1.53-1.60, Abbe number νdFor 68-75.
Further, the transition temperature Tg of glass is 530 DEG C or less;The density of glass is 4.50g/cm3Below.
Further, the optical glass powder method water-resistant stability DWFor 1 class;Powder method acid-resistant stability DAFor 1 class.
Optical precast product 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:By rationally adjusting the proportioning between each component, make fluorophosphate optics of the present invention
Glass with 1.53-1.60 refractive index, 68-75 Abbe number while, have excellent devitrification resistance can and chemistry it is steady
It is qualitative, meet modern photoelectric field growth requirement.
Specific implementation mode
I, optical glass
It is illustrated below for each ingredient for the optical glass for constituting the present invention.
In the present specification, in case of no particular description, cationic components content is with the sun for the content of each ingredient
The degree that ion accounts for all cationic total moles indicates, it is total that anionic group content with the anion accounts for whole anion
Mole degree indicate.In addition, in the following description, when mentioning specified value or less or specified value or more, also including
The specified value.
It should be noted that the ioni valence of each ingredient described in the invention be for convenience and the typical value that uses, with
Other ioni valences are not different.There are the possibility other than the typical value for the ioni valence of each ingredient present in optical glass
Property.For example, P usually exists with the state that ioni valence is 5 valences in glass, therefore in the present specification with " P5+" it is used as representative,
But there is also with possibility existing for the state of other ioni valences, this is also within protection scope of the present invention.
[about cation constituent]
P5+It is a kind of important cationic components of glass network former, when its content is less than 20%, the stabilization of glass
Property reduce.On the other hand, by controlling P5+Content hereinafter, can inhibit the devitrification of glass, and can inhibit glass Abbe 36%
Several reductions, therefore the glass of the readily available stabilization with low dispersion.Therefore, P5+Content is limited to 20-36%, preferably
25-35%, further preferably 28-35%.In the present invention, H can be used3PO4、Al(PO3)3、Ca(PO3)3、Ba(PO3)3、B
(PO3)3P is introduced Deng as raw material5+。
Al3+The thermal stability of glass can be improved, and effectively improves the machinability and chemical durability of glass, is dropped simultaneously
The average linear expansion coefficient of low glass.When its content is less than 5%, stable glass skeleton can not be formed and obtain above-mentioned effect
Fruit;When its content be higher than 25% when, the transition temperature and liquidus temperature of glass increase significantly, make be melted become difficult, simultaneously
So that temperature when molding is increased, causes the volatilization of glass to aggravate so that glass cord degenerates;On the other hand, excessively high transition temperature
Compression molding can be made difficult.Therefore, Al3+Content is 5-25%, preferably 10-22%, more preferably 13-20%.In the present invention,
Al (PO can be used3)3、AlF3、Al2O3Etc. modes introduce Al3+。
Mg2+The abrasion degree of glass can be improved to a certain extent, if but its content is more than 10%, the devitrification of glass can be made
Performance and hardness reduce, therefore Mg2+Content range be limited to 0-10%, preferably 0-8%, more preferably 0-5%, more into one
Step is preferably 0-3%.In the present invention, MgCO can be used3、Mg(PO3)3、MgO、MgF2Etc. modes introduce Mg2+。
Ca2+Have in optical glass of the present invention and improves the devitrification resistance of glass, refractive index is inhibited to reduce, reduce glass
The property of abrasion degree.When its content is more than 10%, the devitrification resistance of glass deteriorates, therefore Ca in optical glass of the present invention2+'s
Content range is limited to 0-10%, preferably 0-8%, further preferably 0.5-5%.In the present invention, CaCO can be used3、Ca
(PO3)3、CaF2Etc. modes introduce Ca2+。
By inventor the study found that working as Mg2+Content and Ca2+The ratio Mg of content2+/Ca2+When being 1 or less, glass can be improved
The water-resistant stability and weatherability of glass optimize the devitrification resistance energy of glass, preferably Mg2+/Ca2+For 0.8 hereinafter, more preferable Mg2+/
Ca2+It is 0.5 or less.
Sr2+The linear expansion coefficient of glass can be reduced, and can effectively adjust the refractive index and proportion of glass, if but its contain
It measures excessively high, so that the refractive index of glass and dispersion is become larger, it is difficult to reach preset optical property, while can also reduce glass
Chemical stability.Therefore, in the present invention, Sr2+Content range be limited to 0-20%, preferably 5-20%, further preferably
It is still more preferably 6-12% for 5-15%.In the present invention, Sr (NO can be used3)2、SrF2Etc. modes introduce Sr2+.To obtain
Excellent devitrification resistance energy, optical transmittance and linear expansion coefficient, the present invention in preferred Sr2+Content is more than Mg2+Content.
Optical glass of the present invention introduces 25% or more Ba2+As necessary component, the devitrification resistance energy of glass can be improved
And chemical stability, while the linear expansion coefficient of glass can be reduced, maintain low dispersibility and hardness;When its content is more than 40%
When, the density of glass increases, it is difficult to meet light-weighted requirement, and the thermal stability of glass reduces, therefore optics glass of the present invention
Ba in glass2+Content range be limited to 25-40%, preferably 25-36%, further preferably 28-36%.It, can in the present invention
Use Ba (PO3)3、BaCO3、Ba(NO3)2、BaF2Etc. modes introduce Ba2+。
The present invention passes through preferred Sr2+Content and Ba2+The ratio Sr of content2+/Ba2+For 0.1-0.5, glass of the present invention can be made
With excellent thermal refractive index coefficient and devitrification resistance energy, while the linear expansion coefficient of glass, transition temperature and close can be reduced
Degree, preferably Sr2+/Ba2+For 0.15-0.5, more preferable Sr2+/Ba2+For 0.2-0.4.
In glass of the present invention, by controlling Ba2+With Ba2+、Sr2+、Ca2+And Mg2+Total content R2+Ratio Ba2+/R2+
It is 0.5 or more, the thermal refractive index coefficient of glass can be improved, improves the devitrification resistance energy of glass, increase the chemical stabilization of glass
Property and hardness, preferably Ba2+/R2+It is 0.6 or more, more preferable Ba2+/R2+For 0.65-0.9.
La3+The refractive index and hardness of glass can be improved, and the anomalous dispersion of glass is made to be not easy to reduce, is led in the present invention
It crosses and introduces 10% La below3+, the devitrification resistance of glass, preferably La can be improved3+For 0-8%, more preferably 0.5-5%.This
In invention, La can be used2O3、LaF3Etc. modes introduce La3+。
Gd3+The stability and durability of glass can be improved, and keep low dispersivity while properly increasing refractive index,
If its content is more than 10%, the proportion of glass can rise, therefore Gd3+Content range is 0-10%, preferably 0-8%, more excellent
It is selected as 0.5-5%.In the present invention, Gd can be used2O3、GdF3Etc. modes introduce Gd3+。
Y3+The refractive index that glass can be improved improves the devitrification resistance property of glass, on the appropriate transition temperature Tg for inhibiting glass
It rises.If its content is higher than 10%, the refractive index of glass exceeds design requirement, therefore Y3+Content is 0-10%, preferably 0.5-
8%, more preferably 0.5-6%.In the present invention, Y can be used2O3、YF3Etc. modes introduce Y3+。
It is found through inventor's numerous studies, works as Gd3+And La3+Total amount and Ln3+Ratio (Gd3++La3+)/Ln3+For
When between 0.2-0.8, hardness, devitrification resistance energy and the chemical stability of glass can be improved, wherein Ln3+For Y3+、Gd3+、La3+'s
Total amount, especially as (Gd3++La3+)/Ln3+When between 0.3-0.7, the viscosity of glass is also can further improve, glass is made
It is more easily molded, further preferred (Gd3++La3+)/Ln3+For 0.4-0.65.
Li+It is added in glass ingredient, can effectively reduce the Tg temperature of glass.But optical glass is usually using platinum or platinum
Alloy vessel melting, during high melt, the Li in glass ingredient+Platinum or platinum alloy vessel are easily corroded, finished product is caused
More platiniferous foreign matter is generated in glass, leads to the quality decline of glass.On the other hand, such glass is used for precise compression molding process
When middle, the risk of glass elements surface blur is easy tod produce, reason is to be typically coated with the releasing agent of carbon elements, glass in mold
Li in glass component+It is easy to react with the carbon in releasing agent, coarse opaque coating is generated on glass original paper surface
Layer.Therefore, Li in the present invention+Content be limited to 0-10%, preferably 0-5%, more preferably 0-3%, further preferably
It does not contain.In the present invention, Li can be used2CO3、LiNO3, the modes such as LiF introduce Li+。
Na+The melting characteristic that glass can be improved reduces the yield point and liquidus temperature of glass, still, when its content is more than
When 10%, the deterioration of glass devitrification resistance energy can be accelerated, while can extend glass when being cooled and shaped to become solid from liquid
Time creates conditions to crystallization, therefore its content controls as 10% hereinafter, preferably 0-5%, further preferably 0-3%.This
In invention, Na can be used2CO3、NaNO3、NaF、Na2SiF6Etc. modes introduce Na+。
K+As optional component in the present invention, its devitrification resistance can be maintained when glass is molded and reduces Tg temperature, but is worked as
When its content is more than 10%, its water resistance can be caused to be deteriorated, therefore K+Content be limited to 10% hereinafter, preferably 5% hereinafter, into
One step is preferably 3% or less.In the present invention, K can be used2CO3、KNO3、KF、K2SiF6、KHF2Etc. modes introduce K+。
The present invention is by controlling Li+With R+、Ln3+The sum of ratio Li+/(R++Ln3+) it is 0.5 hereinafter, glass can be improved
Devitrification resistance energy and chemical stability maintain the hardness of glass, preferably Li+/(R++Ln3+) it is 0.3 hereinafter, more preferable Li+/(R++
Ln3+) it is 0.25 or less.
Si4+The devitrification resistance and refractive index of glass can be improved, glass abrasion degree is reduced and improves processability, when its content
When more than 10%, the meltdown property of glass declines, therefore Si in optical glass of the present invention4+Content is 0-10%, preferably 0-
5%, more preferably 0-3%.In the present invention, SiO can be used2、K2SiF6、Na2SiF6Etc. modes introduce Si4+。
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 10% hereinafter,
Preferably 5% hereinafter, more preferably 3% hereinafter, be further preferably added without.In the present invention, H can be used3BO3、Na2B4O7、
BPO4Etc. modes introduce B3+。
Nb5+Belong to high-refraction high-dispersion component, glass refraction can be improved by being added in glass ingredient, adjust glass Ah
Shellfish number.In system glass of the present invention, if its content is higher than 10%, the refractive index and Abbe number of glass are not achieved design and want
It asks, and the devitrification resistance of glass will can drastically decline.Therefore, Nb5+Content be 0-10%, preferably 0-5%, further it is excellent
It is selected as 0-3%.In the present invention, Nb can be used2O5Introduce Nb5+。
Zn2+Have the function of improving thermal stability while reducing the Tg temperature of glass, when its content is more than 10%,
The dispersion of glass increases, it is difficult to obtain required optical constant, and glass devitrification resistance reduces, therefore Zn2+Content is limited to
10% hereinafter, preferably 5% hereinafter, further preferably 3% hereinafter, more preferably do not introduce.In the present invention, Zn can be used
(PO3)2、ZnF2, the modes such as ZnO introduce Zn2+。
Zr4+It is appropriate addition can inhibit the striped formed by volatilization in glass, if its content is more than 10%, optical system
Number is difficult to control, therefore its content is limited to 10% hereinafter, preferably 5% hereinafter, further preferably 3% or less.The present invention
In, ZrO can be used2、ZrF4Etc. modes introduce Zr4+。
Ti4+The devitrification stability of glass can be improved, if its content is higher than 10%, the refractive index of glass can be improved, and drop
Low transmission.Therefore, Ti4+Content be limited to 0-10%, preferably 0-5%, further preferably 0-3%.It, can in the present invention
Pass through TiO2Introduce Ti4+。
W6+It is the ingredient for improving glass refraction, is the optional member in glass of the present invention, especially makes glass W6+Contain
When amount is 10% or less, the reduction of glass Abbe number is can inhibit, and reduce the coloring of glass, preferred content 0-5%, into one
Step is preferably 0-3%.In the present invention, WO can be passed through3Introduce W6+。
Sb3+、Sn4+、Ce4+As fining agent, can be introduced respectively with 1% content below, preferred content is respectively
0.5% or less.Sb can be passed through in the present invention2O3、SnO、SnO2、CeO2Etc. modes introduce Sb3+、Sn4+、Ce4+。
[about anion component]
Anion in optical glass of the present invention mainly has F-And O2-, to obtain performance needed for optical glass of the present invention, this
F in invention optical glass-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.35-0.55, preferably 0.38-
0.52, preferably 0.4-0.48.
F-There is larger effect for reducing thermal refractive index coefficient and Tg, is to improve Abbe number and abnormal dispersed important
Component.If its too high levels, the stability of glass can be weakened, increased in coefficient of thermal expansion, especially fusion process, the volatilization of F
The defects of not only polluting the environment, but also it is uneven that the inside of glass can be made to form, causing data exception and striped.When its content
When less than 35%, Abbe number and the exception for being unable to get design are dispersed;If its content is higher than 55%, the Abbe number of glass can become
It is too much, and volatilization can sharply increase when melting and for accurate die pressing, therefore F-Content is limited to 35-55%, preferably
38-52%, further preferably 40-48%.F-AlF can be passed through3、YF3、GdF3、MgF2、CaF2、BaF2Etc. heretofore described
The mode of fluoride of cation introduce.
Contain O in optical glass of the present invention2-, especially, by containing 45% or more O2-, the mistake of glass can be inhibited
Thoroughly, abrasion degree rises.Therefore O2-Content design 45% be lower limit, preferably 48% be lower limit, more preferable 52% be lower limit.It is another
Aspect, by by O2-Content be designed as 65% hereinafter, can in the case where ensureing stability, glass, make other anion at
Divide and preferably reach effect, therefore O is designed as by 65%2-Upper content limit, preferably 62% is the upper limit, and further preferred 60% is upper
Limit.O2-Al (PO can be passed through3)3、Ca(PO3)3、Ba(PO3)3、Y2O3、Gd2O3Draw etc. forms such as the oxide of above-mentioned cation and salt
Enter.
To improve the clarifying effect of glass, the Cl of 0-1% can be separately added into-、Br-And I-Be used as fining agent, preferred content
Respectively 0.5% hereinafter, more preferably content is respectively 0.2% or less.
[about the ingredient that should not contain]
In the range of not damaging the characteristic of glass of the present invention, can add as needed it is above-mentioned do not referred to it is other at
Point.But even if the transiting metal components such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo have respectively individually or compound
In the case that ground contains on a small quantity, glass is also coloured, and the specific wavelength in visible light region, which generates, to be absorbed to weaken this hair
The property of bright raising visible light transmittance effect, therefore especially make in the optical glass that the wavelength of visible light region penetrates,
It is preferred that not including actually.
The cation of Pb, Th, Cd, Tl, Os, Be and Se, in recent years exist as harmful chemical substance and controlling makes
Tendency, not only in the manufacturing process of glass, the disposition after manufacturing procedure and commercialization, arranging in environmental cure
It is required to apply.Therefore, in the case where paying attention to influence environmentally, other than being inevitably mixed into, preferably actually
Without containing them.Become the substance for not including pollution environment actually in optical glass as a result,.Therefore, though do not take it is special
Environmental cure on measure, also can optical glass of the present invention be manufactured, processed and be discarded.
In the following, being illustrated to the characteristic of the optical glass of the present invention.
[optical constant of optical glass]
Optical glass refractive index (nd) of the present invention and Abbe number (νd) carried out according to method as defined in GB/T7962.1-2010
Test.
The ranging from 1.53-1.60 of optical glass refractive index (nd) of the present invention, preferably ranging from 1.54-1.59;This hair
Abbe number (the ν of bright glassd) ranging from 68-75, preferred scope 69-74.
[transition temperature (Tg) of optical glass]
The transition temperature (Tg) of optical glass is measured by method as defined in GB/T7962.16-2010.
The transition temperature (Tg) of glass of the present invention at 540 DEG C hereinafter, it is preferred that 530 DEG C hereinafter, more preferably 520 DEG C or less.
[density of optical glass]
The density of optical glass is measured by method as defined in GB/T7962.20-2010.
The density (ρ) of glass of the present invention is in 4.50g/cm3Hereinafter, preferably 4.40g/cm3Hereinafter, more preferably 4.30g/
cm3Below.
[water-resistant stability (the D of optical glassW)]
Glass powder method water-resistant stability (DW) measured using GB/T17129 testing standards.
Optical glass (D of the present inventionW) it is 2 classes and 2 classes or more, preferably 1 class.
[water-resistant stability (the D of optical glassA)]
Glass powder method acid-resistant stability (DA) measured using GB/T17129 testing standards.
Optical glass (D of the present inventionA) it is 2 classes and 2 classes or more, preferably 1 class.
[devitrification resistance energy]
The crystallization property of glass of the present invention detects in the following way:
Laboratory sample is processed as 20*20*10mm specifications, sample is put into the analysis that temperature is Tg+200 DEG C by polishing both surfaces
Brilliant stove inside holding 30 minutes, take out it is cooling after, then to two big mirror polish, judge the crystallization property of glass according to the following table 1, A grades
To be best, E grades are worst.
Table 1:The classification of crystallization and criterion
Number | Rank | Standard |
1 | A | The crystallization particle being visible by naked eyes |
2 | B | Visually visible crystallization particle, quantity is few and disperses |
3 | C | Visually visible larger dispersion or comparatively dense and small crystallization particle |
4 | D | Crystallization particle is larger and intensive |
5 | E | The complete crystallization devitrification of glass |
The devitrification resistance of optical glass of the present invention can be B grades or more, preferably A grades.
II, optical precast product and optical element
In the following, the optical precast product and optical element of the description present invention.
The optical precast product of the present invention is formed with optical element by the optical glass of aforementioned present invention.The optics of the present invention
Prefabricated component has low dispersion characteristics;The optical element of the present invention has low dispersion characteristics, and optics value can be provided with low cost
The optical elements such as high various lens, prism.
By the optical glass made, the hand of the compression moldings such as type, precision press molding is made using such as hot repressing
Section, can make optical precast product.That is, the optical glass molded blank of compression molding can be made by optical glass,
And polishing is carried out after carrying out reheating compression moulding to the optical glass molded blank to make optical precast product.It needs
Illustrate, the means for making optical precast product are not limited to the above.
The optical precast product so made is useful on various optical elements and optical design.It is particularly preferred to by
The optical glass of the present invention sets out, and the optical elements such as camera lens, prism, speculum are made using means such as precision press moldings.
When the optical instrument for making visible light-transmissive being used for as a result, in the optical elements such as camera, projector, high definition and height can be realized
The imaging characteristic etc. of precision, can realize the lightweight of the optical system in these optical instruments.
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, planoconvex spotlight, plano-concave lens.This lens by with the high dispersion glass of high refractive index
Lens combination made of glass, recoverable aberration are suitable as the lens of chromatic aberration correction.In addition, for the compact of optics system
It is also effective lens to change.
The melting of optical glass of the present invention and forming method may be used that well known to a person skilled in the art technologies.I.e.:It will
Glass raw material (fluoride, carbonate, nitrate, sulfate, metaphosphate, oxide, boric acid etc.) matching according to glass ion
Merge after mixing than weighing to match, puts into smelting apparatus (such as platinum crucible), then taken at 900~1200 DEG C appropriate
After stirring, clarification, homogenizing, be cooled to 900 DEG C hereinafter, cast or leakage note in molding die, the later stages such as last annealed, processing
Processing, or be molded by precise compression molding technology direct pressing.
Embodiment
The present invention is explained using following examples, but the present invention should not be limited to these embodiments.
[optical glass embodiment]
Measure the performance of optical glass of the present invention by above-mentioned shown method, and by optical glass component of the present invention and its property
It can be listed in detail in the embodiment 1-40 of table 2- tables 5.
Table 2
Table 3
Table 4
Table 5
[gas preform embodiment]
[gas preform embodiment]
The obtained optical glass of embodiment 1-10 in table 2 is cut into predefined size, then is equably coated on the surface
Then releasing agent is heated, softens, is press-formed, make recessed meniscus shaped lens, male bend moon-shaped lens, biconvex lens,
The prefabricated component of the various lens such as biconcave lens, planoconvex spotlight, plano-concave lens, prism.
[optical element embodiment]
By obtained these prefabricated components annealing of above-mentioned gas preform 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, planoconvex spotlight, plano-concave lens, prism.Antireflection can be also coated on the surface of gained optical element
Film.
Claims (15)
1. optical glass, which is characterized in that as necessary cationic components, including P5+、Al3+And R2+, wherein R2+For Ba2+、
Sr2+、Ca2+And Mg2+In one or more;In terms of cation mole %, contain:P5+:20-36%;Al3+:5-25%;
Ba2+:25-40%;Wherein Ba2+/R2+It is 0.5 or more;
Anion contains F-And O2-, wherein F-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.35-0.55.
2. optical glass as described in claim 1, which is characterized in that also contain:Sr2+:0-20%;And/or Ca2+:0-10%;
And/or Mg2+:0-10%;And/or Gd3+:0-10%;And/or Y3+:0-10%;And/or La3+:0-10%;And/or Si4+:0-
10%;And/or B3+:0-10%;And/or Na+:0-10%;And/or Li+:0-10%;And/or K+:0-10%;And/or Zn2+:
0-10%;And/or Nb5+:0-10%;And/or Ti4+:0-10%;And/or Zr4+:0-10%;And/or W6+:0-10%.
3. optical glass, which is characterized in that in terms of cation mole %, consisting of P5+:20-36%;Al3+:5-25%;Ba2 +:25-40%;Sr2+:0-20%;Ca2+:0-10%;Mg2+:0-10%;Gd3+:0-10%;Y3+:0-10%;La3+:0-10%;
Si4+:0-10%;B3+:0-10%;Na+:0-10%;Li+:0-10%;K+:0-10%;Zn2+:0-10%;Nb5+:0-10%;
Ti4+:0-10%;Zr4+:0-10%W6+:0-10%;Sb3+:0-1%;
Anion is F-、Cl-And O2-, wherein F-Content and F-And O2-Total content molar ratio F-/(F-+O2-) it is 0.35-
0.55。
4. the optical glass as described in claim 1-3 any claims, which is characterized in that each component meets following 5 kinds of items
One or more in part:
1)Sr2+Content is more than Mg2+Content;
2)(Gd3++La3+)/Ln3+For 0.2-0.8, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 1 or less;
4)Sr2+/Ba2+For 0.1-0.5;
5)Li+/(R++Ln3+) it is 0.5 or less, wherein R+For Na+、Li+、K+Total content.
5. the optical glass as described in claim 1-3 any claims, which is characterized in that each component meets following 5 kinds of items
One or more in part:
1)Ba2+/R2+It is 0.6 or more;
2)(Gd3++La3+)/Ln3+For 0.3-0.7, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 0.8 or less;
4)Sr2+/Ba2+For 0.15-0.5;
5)Li+/(R++Ln3+) it is 0.3 or less, wherein R+For Na+、Li+、K+Total content.
6. the optical glass as described in claim 1-3 any claims, which is characterized in that each component meets following 5 kinds of items
One or more in part:
1)Ba2+/R2+For 0.65-0.9;
2)(Gd3++La3+)/Ln3+For 0.4-0.65, wherein Ln3+For La3+、Gd3+And Y3+Total content;
3)Mg2+/Ca2+It is 0.5 or less;
4)Sr2+/Ba2+For 0.2-0.4;
5)Li+/(R++Ln3+) it is 0.25 or less, wherein R+For Na+、Li+、K+Total content.
7. the optical glass as described in claim 1-3 any claims, which is characterized in that wherein:P5+:25-35%;With/
Or Al3+:10-22%;And/or Ba2+:25-36%;And/or Sr2+:5-20%;And/or Ca2+:0-8%;And/or Mg2+:0-
8%;And/or Gd3+:0-8%;And/or Y3+:0.5-8%;And/or La3+:0-8%;And/or Si4+:0-5%;And/or B3+:0-
5%;And/or Na+:0-5%;And/or Li+:0-5%;And/or K+:0-5%;And/or Zn2+:0-5%;And/or Nb5+:0-
5%;And/or Ti4+:0-5%;And/or Zr4+:0-5%;And/or W6+:0-5%.
8. the optical glass as described in claim 1-3 any claims, which is characterized in that wherein:P5+:28-35%;With/
Or Al3+:13-20%;And/or Ba2+:28-36%;And/or Sr2+:5-15%;And/or Ca2+:0.5-5%;And/or Mg2+:0-
5%;And/or Gd3+:0.5-5%;And/or Y3+:0.5-6%;And/or La3+:0.5-5%;And/or Si4+:0-3%;And/or B3 +:0-3%;And/or Na+:0-3%;And/or Li+:0-3%;And/or K+:0-3%;And/or Zn2+:0-3%;And/or Nb5+:0-
3%;And/or Ti4+:0-3%;And/or Zr4+:0-3%;And/or W6+:0-3%.
9. optical glass as claimed in claim 1 or 2, which is characterized in that also contain Sb3+:0-1%;And/or Sn4+:0-1%;
And/or Ce4+:0-1%;And/or Cl-:0-1%;And/or Br-:0-1%;And/or I-:0-1%.
10. the optical glass as described in claim 1-3 any claims, which is characterized in that F-Content and F-And O2-Always contain
The molar ratio F of amount-/(F-+O2-) it is 0.38-0.52, preferably 0.4-0.48.
11. the optical glass as described in claim 1-3 any claims, which is characterized in that the refractive index nd of glass is
1.53-1.60, Abbe number νdFor 68-75.
12. the optical glass as described in claim 1-3 any claims, which is characterized in that the transition temperature Tg of glass is
530 DEG C or less;The density of glass is 4.50g/cm3Below.
13. the optical glass as described in claim 1-3 any claims, which is characterized in that the optical glass powder method
Water-resistant stability DWFor 1 class;Powder method acid-resistant stability DAFor 1 class.
14. optical precast product is made of the optical glass described in claim 1-13 any claims.
15. optical element is made of the optical glass described in claim 1-13 any claims.
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