CN1854100A - Optical glass, press-molding preform, process for the production thereof, optical element and process for the production thereof - Google Patents
Optical glass, press-molding preform, process for the production thereof, optical element and process for the production thereof Download PDFInfo
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- CN1854100A CN1854100A CNA200610079429XA CN200610079429A CN1854100A CN 1854100 A CN1854100 A CN 1854100A CN A200610079429X A CNA200610079429X A CN A200610079429XA CN 200610079429 A CN200610079429 A CN 200610079429A CN 1854100 A CN1854100 A CN 1854100A
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Abstract
A low-dispersion optical glass suitable for producing a quality preform from a molten glass and suitable for precision press-molding, which is a fluorophosphate glass containing, as essential cationic components, P 5+ , Al 3+ , at least two members selected from Mg 2+ , Ca 2+ , Sr 2+ and Ba z+ as divalent cationic components (R 2+ ) and Li + and containing, by cationic %, 10 to 45 % of P 5+ , 5 to 30 % of Al 3+ , 0 to 20% of Mg 2+ , 0 to 25 % of Ca 2+ , 0 to 30 % of Sr 2+ , 0 to 33 % of Ba 2+ , 1 to 30 % of Li + , 0 to 10 % of Na + , 0 to 10 % of K + , 0 to 5 % of Y 3+ , and 0 to 15 % of B 3+ , the molar ratio of the content of F - to the total content of F - and O 2- , F - / (F - + O 2- ), being 0.25 to 0.85, the optical glass having a refractive index (N d ) of 1.40 to 1.58 and an Abbe's number (v d ) of 67 to 90.
Description
Technical field
The present invention relates to a kind of fluorine phosphorescence and learn the method for glass, press-molding preform (precast body that is used for mold pressing), the method for making this press-molding preform, optical element and this optical element of manufacturing.
Background technology
Fluorine phosphorous glass is very useful as a kind of low dispersion.As this fluorine phosphorous glass, be known that the glass of describing in the flat 3-500162 communique of special table.
Summary of the invention
When fusion fluorine phosphorous glass raw material under heating, and when the melten glass that obtains is shaped to glassy product, fluorine in the melten glass evaporates from having the pyritous glass surface, thereby glassy product has the inhomogeneous part of optics in the layer that is formed at its near surface, that be called " striped ".
Melten glass is being shaped in the glassy product, is making melten glass flow out pipe and be poured in the model etc. to obtain glassy product.In this case, the temperature of effusive glass is high more, and fluorine evaporates just manyly more, thereby is occurring striped to a greater extent.In order to reduce the appearance of striped, need to reduce the temperature that flows out glass.Yet when reducing this temperature, effusive glass has high viscosity, thereby just involves a problem, and promptly when with gob (gob) when separating with molten glass flow, excellent fractional melting glass gob is difficult.
In order to overcome the problems referred to above, need provide a kind of demonstration to be suitable for the glass of the viscosity of moulding at low temperatures.This glass not only has the low temperature that is used for the melten glass moulding, and have a glass transformation temperature of reduction, so it is suitable for efficiently providing optical element with relative complex structure such as non-spherical lens and does not rely on and grind and the accurate die pressing method of polishing.
Created the present invention in these cases, an object of the present invention is to provide a kind of being suitable for to form high-quality glass, and further be suitable for the low-dispersion optical glass for mold of accurate die pressing by its melten glass.
Another object of the present invention provides a kind of press-molding preform and manufacture method thereof that is formed by above-mentioned glass, and a further object of the present invention provides a kind of optical element and manufacture method thereof that is formed by above-mentioned glass.
The present invention according to being used to realize above-mentioned purpose provides;
(1) a kind of opticglass, it is a kind of fluorine phosphorous glass, as necessary cationic components, comprises P
5+, Al
3+, be selected from Mg
2+, Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+), and Li
+, in positively charged ion %, it comprises:
The P of 10-45%
5+,
The Al of 5-30%
3+,
The Mg of 0-20%
2+,
The Ca of 0-25%
2+,
The Sr of 0-30%
2+,
The Ba of 0-33%
2+,
The Li of 1-30%
+,
The Na of 0-10%
+,
The K of 0-10%
+,
The Y of 0-5%
3+With
The B of 0-15%
3+,
F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.25-0.85, the specific refractory power (N of this opticglass
d) be 1.40-1.58, Abbe number (v
d) be 67-90,
(2) opticglass as enumerating in top (1), it contains Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+),
(3) opticglass as enumerating in top (1) is wherein as divalent cation component (R
2+) Mg
2+, Ca
2+, Sr
2+And Ba
2+Total content be at least 1 positively charged ion %,
(4) opticglass as enumerating in top (1) is wherein as divalent cation component (R
2+) Mg
2+, Ca
2+, Sr
2+And Ba
2+In each content all be at least 1 positively charged ion %,
(5) a kind of opticglass, it is a kind of fluorine phosphorous glass, and shows the viscosity of 30dPas under 700 ℃ or lower temperature,
(6) opticglass as enumerating in top (5), it contains the Li of 1-30 positively charged ion %
+,
(7) opticglass as enumerating in top (1) or (5), it supplies the usefulness of accurate die pressing,
(8) a kind of press-molding preform is to be formed by the opticglass of enumerating in top (1) or (5),
(9) a kind of press-molding preform, it is to be that 450 ℃ or lower fluorine phosphorescence are learned glass and formed by glass transformation temperature, and the usefulness of confession accurate die pressing,
(10) press-molding preform as enumerating in top (8) or (9), its whole surface are to form by the vitrification that makes molten state,
(11) a kind of method of making press-molding preform, this method comprise makes melten glass flow out pipe, separate have the molten glass gobs of predetermined weight and in glass cooling process, described glass gob is shaped to above the precast body enumerated in (8) or (9),
(12) a kind of as top (11) in the method for the manufacturing press-molding preform enumerated, wherein after moulding prefabricated body, remove described precast body surface by etching,
(13) a kind of as top (11) in the method for the manufacturing press-molding preform enumerated, wherein moulding prefabricated body after, remove described precast body surface by grinding and polishing,
(14) a kind of method of making press-molding preform, this method comprise melten glass are shaped to glass ware forming material and the described glass ware forming material of mechanical workout, thus the precast body of enumerating in (8) or (9) above making,
(15) a kind of optical element is to be formed by the opticglass of enumerating in top (1) or (5),
(16) a kind of method of making optical element, this method comprise precast body that heating is also enumerated in (8) or (9) above the accurate die pressing or the precast body of making by the method for enumerating in top (11) or (14),
(17) a kind of as top (16) in the method for the manufacturing optical element enumerated, wherein described precast body is introduced in the pressing mold, heat together described pressing mold and this precast body with carry out accurate die pressing and
(18) a kind of as top (16) in the method for the manufacturing optical element enumerated, be that hot described precast body is incorporated in the pre-warmed pressing mold to carry out accurate die pressing after wherein will heat.
The invention effect
According to the present invention, can provide a kind of and be suitable for, and further be suitable for the low-dispersion optical glass for mold of accurate die pressing with melten glass moulding high-quality glass.
According to the present invention, the precision press-molding preform and the manufacture method thereof that are formed by above-mentioned glass can also be provided, the optical element and the manufacture method thereof that are formed by above-mentioned glass also are provided.
Description of drawings
Fig. 1 is the accurate die pressing schematic representation of apparatus of using in the embodiment of the invention.
Embodiment
[opticglass]
First embodiment of opticglass of the present invention (hereinafter, being called " opticglass I ") is a kind of fluorine phosphorous glass, as necessary cationic components, comprises P
5+, Al
3+, be selected from Mg
2+, Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+), and Li
+, in positively charged ion %, it comprises:
The P of 10-45%
5+,
The Al of 5-30%
3+,
The Mg of 0-20%
2+,
The Ca of 0-25%
2+,
The Sr of 0-30%
2+,
The Ba of 0-33%
2+,
The Li of 1-30%
+,
The Na of 0-10%
+,
The K of 0-10%
+,
The Y of 0-5%
3+With
The B of 0-15%
3+,
F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.25-0.85,
Specific refractory power (the N of this opticglass
d) be 1.40-1.58, Abbe number (v
d) be 67-90.
Opticglass I of the present invention preferably contains Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+).
And, in opticglass I of the present invention, preferably, as divalent cation component (R
2+) Mg
2+, Ca
2+, Sr
2+And Ba
2+Total content be at least 1 positively charged ion %.More preferably, as divalent cation component (R
2+) Mg
2+, Ca
2+, Sr
2+And Ba
2+In each content all be at least 1 positively charged ion %.
Hereinafter, will it be elaborated with regard to the composition of above-mentioned opticglass I.For the cationic components content that will be described below, % represents the positively charged ion % based on mol ratio, and for the anionic group content that will be described below, % represents the negatively charged ion % based on mol ratio.
Basically opticglass I is divided into opticglass Ia and opticglass Ib, in opticglass Ia, F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.50-0.85, its Abbe number (v
d) be 75-90, in opticglass Ib, F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.25-0.50 (not comprising 0.50), its Abbe number (v
d) be 67-75 (not comprising 75).In order to obtain this opticglass Ia and Ib, there are differences between the preferable range of cationic components content among the preferable range of cationic components content and the opticglass Ib among the opticglass Ia.
P
5+It is a kind of important cationic components as glass network former.When its content was lower than 10%, stability, glass reduced.When its more than 45% the time, because need introduce P as new raw material with form from phosphatic oxide compound
5+So the content of oxygen is huge, thereby can't satisfy predetermined optical property.Therefore, with P
5+Content be restricted to 10-45%.In order to obtain opticglass Ia, P
5+Content be preferably 10-40%, more preferably 10-35% is more preferably 12-35%, still more preferably 20-35%, most preferably 20-30%.In order to obtain opticglass Ib, P
5+Content be preferably 25-45%, more preferably 25-40% is more preferably 30-40%.Use PCl
5Introduce P
5+Be inappropriate, because PCl
5Corrosion is made thereby overslaugh is stable as the platinum and the strong volatilization of fusion tank material.Preferably introduce P with phosphatic form
5+
Al
3+It is a kind of component that improves fluorine phosphorous glass stability.When its content was lower than 5%, stability, glass reduced.When its more than 30% the time, glass transformation temperature (Tg) and liquidus temperature (LT) raise greatly, so mold temperature raises.In this case, because the surface volatilization causes producing strongly striped in formative stage, therefore can not make uniform glass ware forming product, particularly press-molding preform again.With Al
3+Content be limited in 5-30%.In order to obtain opticglass Ia, Al
3+Content be preferably 7-30%, more preferably 8-30% is more preferably 10-30%, still more preferably 15-25%.In order to obtain opticglass Ib, Al
3+Content be preferably 5-20%, more preferably 5-12%.
As divalent cation component (R
2+) Mg
2+, Ca
2+, Sr
2+And Ba
2+When introducing, be used to improve stability, glass.In these components, introduce two or more, more preferably, introduce Ca
2+, Sr
2+And Ba
2+In at least two kinds.In order further to improve divalent cation component (R
2+) effect, preferably, with Mg
2+, Ca
2+, Sr
2+And Ba
2+Total content be adjusted into 1 positively charged ion % or more.In addition, the content of each all surpasses on it in limited time in these components, and stability is variation sharply.Though can introduce Ca relatively in large quantities
2+And Sr
2+, but when a large amount of the introducing, Mg
2+And Ba
2+Make bad stability especially.Yet, because Ba
2+Be a kind ofly can realize high refractive index, keep the component of low chromatic dispersion simultaneously, so preferably introduce a large amount of Ba
2+, only otherwise the stability of infringement glass gets final product.Therefore, with Mg
2+Content be restricted to 0-20%, and in order to obtain opticglass Ia, Mg
2+Content be preferably 1-20%, more preferably 3-17% is more preferably 3-15%, more preferably 5-15% still, preferred especially 5-10%.In order to obtain opticglass Ib, Mg
2+Content be preferably 0-15%, more preferably 0-12% is more preferably 1-10%.
And, Ca
2+Content be 0-25%.In order to obtain opticglass Ia, Ca
2+Content be preferably 1-25%, more preferably 3-24% is more preferably 3-20%, more preferably 5-20% still, preferred especially 5-16%.In order to obtain opticglass Ib, Ca
2+Content be preferably 0-15%, more preferably 1-10%.
And, Sr
2+Content be 0-30%, and in order to obtain opticglass Ia, Sr
2+Content be preferably 1-30%, more preferably 5-25% is more preferably 7-25%, more preferably 8-23% still, further more preferably 9-22%, preferred especially 10-20%.In order to obtain opticglass Ib, Sr
2+Content be preferably 0-15%, more preferably 1-15% is more preferably 1-10%.
Ba
2+Content be 0-33%, and in order to obtain opticglass Ia, Ba
2+Content be preferably 0-30%, more preferably 0-25% is more preferably 1-25%, more preferably 1-20% still, further more preferably 3-18%, further more preferably 5-15%, preferred especially 8-15%.In order to obtain opticglass Ib, Ba
2+Content be preferably 0-30%, more preferably 10-30% is more preferably 15-30%, still more preferably 15-25%.
Li
+It is a kind of important component that is used to reduce glass transformation temperature (Tg) and does not damage stability, glass.Yet when its content was lower than 1%, above-mentioned effect was insufficient.When its more than 30% the time, the weather resistance of infringement glass, and, make the poor processability of glass simultaneously.Therefore, with Li
+Content be restricted to 1-30%, this content is preferably 2-30%, more preferably 3-30% is more preferably 4-30%.In order to obtain opticglass Ia, Li
+Content be preferably 4-25%, more preferably 5-25%, and in order to obtain opticglass Ib, this content is preferably 5-30%, more preferably 10-25%.
Na
+And K
+With Li
+Work to reducing glass transformation temperature (Tg) equally respectively, though they compare Li
+Be easy to make the thermal expansivity of glass to become big.And, comparing with LiF, NaF and KF have very large water solubility, thereby make the water tolerance variation of glass, therefore with Na
+And K
+In each content all be restricted to 0-10%.In opticglass Ia and Ib any, Na
+And K
+In each content all be preferably 0-5%, more preferably, do not introduce them.
Y
3+Stability and the weather resistance that improves glass worked.Work as Y
3+Content more than 5% o'clock, will make bad stability on the contrary, and glass transformation temperature (Tg) raises to a great extent also, therefore with Y
3+Content be restricted to 0-5%.In order to obtain opticglass Ia, Y
3+Content be preferably 0-3%, more preferably 0.5-3%, and in order to obtain opticglass Ib, Y
3+Content be 0-4%, more preferably 0-3% is more preferably 0.5-3%.
B
3+Be that a kind of glass forms component, therefore glass had stable effect.Yet when introducing was excessive, it made the weather resistance variation of glass, and along with B
3+The increase of content, O in the glass
2-Content increase, therefore be difficult to the optical property that obtains to be scheduled to.Therefore, with B
3+Content be restricted to 0-15%.Yet, because melt stage its easily with BF
3Form volatilization, and therefore cause striped, so preferred with the B among opticglass Ia and the Ib
3+Content all be restricted to 0-10%, more preferably be restricted to 0-5%.When tending to reduce the volatilization of glass, preferably with B
3+Content be limited in 0-0.5%, more preferably do not introduce B
3+
In order stably to make high quality optical glass, preferably with opticglass Ia and the Ib P in each
5+, Al
3+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, Li
+And Y
3+Total content, in positively charged ion %, all be adjusted into greater than 95%, more preferably greater than 98%, be more preferably, still more preferably greater than 100% greater than 99%.
Opticglass I of the present invention can contain lanthanon except that above-mentioned cationic components, that do not damage the object of the invention amount such as Ti, Zr, Zn, La, Gd etc. as cationic components.
And, for the stability of glass can be introduced Si
4+Yet, because use low temperature to come fusion opticglass, so when excessive introducing, Si
4+Not fusion of meeting, or volatilization largely appears in melt stage, stable thereby infringement is made.Therefore, in each in opticglass Ia and Ib, preferably all with Si
4+Content be restricted to 0-10%, more preferably 0-8% is more preferably 0-5%.
For the content ratio of anionic group,, realize the opticglass of required optical property simultaneously, with F in order to obtain to have excellent stability
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be adjusted into 0.25-0.85.In opticglass Ia, preferably above-mentioned mol ratio is adjusted into 0.50-0.85, and in opticglass Ib, preferably above-mentioned mol ratio is adjusted into 0.25-0.50 (not comprising 0.50), be preferably 0.27-0.45, more preferably 0.30-0.45.And, in each of opticglass Ia and Ib, preferably, all with F in the whole anion-content
-And O
2-Total content be adjusted into 100%.
In opticglass I of the present invention, specific refractory power (N
d) be 1.40-1.58, Abbe number (v
d) be 67-90, preferred 70-90.And, in opticglass Ia, above-mentioned Abbe number (v
d) be 75-90, preferred 79-89, and in opticglass Ib, above-mentioned Abbe number (v
d) be 67-75 (not comprising 75).
Unless the adding tinting material, otherwise opticglass I shows high transmissivity at visible region.When having flat surfaces parallel to each other with opticglass I of the present invention preparation and thickness is the sample of 10mm, and make light when the direction with above-mentioned Surface Vertical enters sample, the transmissivity of opticglass I of the present invention (getting rid of the reflection loss on sample surfaces) is at 400-2,000nm wavelength place is at least 80%, preferably at least 95%.
Opticglass I of the present invention has specific Li
+Content, it has 470 ℃ or lower, preferred 430 ℃ or lower glass transformation temperature (Tg).
And, because from alkalimetal ion, mainly introduce Li
+So opticglass I of the present invention has relatively little thermal expansivity, and show outstanding relatively water tolerance.Therefore, can this glass be formed press-molding preform by polishing, perhaps can be by being processed to form high-quality optical element with smooth glass surface.
Opticglass I of the present invention shows excellent in water resistance and chemical stability.Therefore, when making press-molding preform, and before mold pressing during long storage, precast body can not stand any surface modification.And, because the optical element that is formed by opticglass I of the present invention also is not easy to change from the teeth outwards, so can be there not to be this optical element of health state life-time service of blushing from the teeth outwards.
And, according to opticglass I of the present invention, with have the optical constant that equates with the optical constant of opticglass I of the present invention but do not contain the glassy phase ratio of Li, the glass melting temperature can descend about 50 ℃, therefore can reduce or overcome in melt stage by the platinum from groove dissolve caused defective such as glass coloring, bubble is mingled with and striped.
When flowing out, fluorine phosphorous glass has high viscosity usually, and has following defective.When the molten glass gobs that will have predetermined weight was separated with the melten glass of effusive fluorine phosphorous glass and is shaped to certain shape, this glass began to form filament from separate part, and thread part remains on this glass gob surface, thereby formed ridge.When attempting to overcome above-mentioned defective by the viscosity that reduces outflow glass, need to improve the temperature that flows out glass, therefore just involve the problems referred to above, promptly because of having quickened fluorine, so cause striped strongly from glass surface volatilization.
In opticglass I of the present invention, reduce be suitable for the melten glass moulding temperature to overcome the problems referred to above, for this reason, determine that like this its glass forms, promptly the glass temperature during the glass display predetermined viscosity is lower than this temperature of conventional fluorine phosphorous glass.Glass transformation temperature is far below the temperature of moulding melten glass, and when glass has low glass transformation temperature, also can reduce the temperature of above-mentioned moulding melten glass.Therefore, in formative stage, form silk, striped etc., adjust glass and form so that glass has the glass transformation temperature of above-mentioned scope in order to overcome.
And, when reducing glass transformation temperature, can reduce the temperature of heating precast body in the mold pressing, particularly accurate die pressing, therefore, can produce to alleviate and react the effect that maybe can increase the pressing mold life-span between glass and the pressing mold.
Therefore, opticglass I of the present invention is suitable for as the mold pressing glass material, particularly as the accurate die pressing glass material.
In addition, can be by preparing phosphate material, fluoride materials etc., these materials of weighing, mix them, mixture is supplied in the fusion tank of being made by platinum alloy, heat, fusion, clarification and homogenization, make the glass of generation flow out pipe and moulding (molded) glass obtains opticglass of the present invention.
Second embodiment (being called hereinafter, " opticglass II ") of opticglass of the present invention then, is described.
Opticglass II of the present invention is a kind of fluorine phosphorous glass, and has following characteristic, and promptly the temperature the during viscosity of this glass display 30dPas is 700 ℃ or lower.
I is the same with opticglass, in opticglass II, contains 1-30 positively charged ion %Li
+Glass be preferred, contain 2-30 positively charged ion %Li
+Glass be preferred, contain 3-30 positively charged ion %Li
+Glass be more preferably, contain 4-30 positively charged ion %Li
+Glass be still preferred.
The preferred glass composition of opticglass II is formed the same with optical constant with optical constant with the glass of opticglass I.Therefore, also the corresponding section with above-mentioned opticglass I is the same for the preferred glass component of opticglass II, their content, optical constant and other performance.Needn't require opticglass II to satisfy all to the kind of opticglass I glass ingredient and the requirement of content.Opticglass II preferably satisfies some to the kind of the glass ingredient of formation opticglass I and the requirement of content, and more preferably it satisfies all requirements.
Opticglass II of the present invention has overcome problems such as formation melten glass silk, striped.
Can overcome the formation of above-mentioned silk in formative stage by raising precast body mold temperature (temperature after melten glass has just flowed out) with the viscosity that reduces glass.On the other hand, preferably reduce the precast body mold temperature to reduce or to prevent striped in the formative stage.Any conventional fluorine phosphorous glass all is difficult to satisfy this two requirements.Yet, the inventor has been found that: the temperature the when lower limit that can prevent the precast body mold temperature (temperature after glass has just flowed out) when silk forms is equivalent to the viscosity of glass display 30dPas, and can reduce or prevent striped by the opticglass that is provided at 700 ℃ or the above-mentioned viscosity of lower demonstration, prevent the formation of silk simultaneously.
In addition, opticglass I also preferably shows the viscosity of 30dPas under 700 ℃ or lower temperature, and opticglass I and II more preferably show the viscosity of 30dPas under 680 ℃ or lower temperature.
[press-molding preform and manufacture method thereof]
The characteristic that first embodiment of press-molding preform of the present invention has is that it is to be formed by opticglass of the present invention.
When using in this article, precast body refers to by weight being equaled glass as the molded product weight of finished product and is pre-formed as the product that the shape that is suitable for mold pressing obtains.
For example, have a rotation axes of symmetry and for around all symmetric molded product of any rotation angle such as the lens of this rotation axes of symmetry in order to make, preferably moulding also has a rotation axes of symmetry and also for around all symmetric precast body of any rotation angle of this rotation axes of symmetry or the precast body that moulding has spherical form.And, when carrying out mold pressing, carry out mold pressing because be to contain between the surface of the molding surface of pressing mold and precast body under the state of ambiance gas, so can reduce the form accuracy of pressing.In order to prevent this phenomenon, ideally, determine the curvature on precast body surface by the curvature of considering to be compression molded into profile.Press-molding preform of the present invention is particularly suitable as the accurate die pressing precast body.When using press-molding preform of the present invention, can on the whole surface of precast body, be formed on accurate die pressing and have known membrane that makes glass function of abundant expansion in pressing mold or the known membrane that is used to improve the model release property in the stage as precision press-molding preform.
Second embodiment of press-molding preform of the present invention (hereinafter, being called " precast body II ") has such characteristic, and promptly it is to be that 450 ℃ or lower fluorine phosphorous glass form by glass transformation temperature, and uses in accurate die pressing.In precast body II of the present invention, glass transformation temperature is preferably 440 ℃ or lower, and more preferably 430 ℃ or lower, be more preferably 420 ℃ or lower, still more preferably 410 ℃ or lower, further preferred 400 ℃ or lower.
Though fluorine phosphorous glass has low glass transformation temperature usually, the fluorine phosphorous glass that constitutes precast body II is a kind of glass with low especially glass transformation temperature.Because fluorine phosphorous glass has low glass transformation temperature usually, so think that fluorine phosphorous glass is used for accurate die pressing and does not have special problem.Yet, be difficult to make optical element with high productive rate by it by accurate die pressing.Its reason is as follows.General fluorine phosphorous glass has and is higher than 460 ℃ to 600 ℃ glass transformation temperature, and this fluorine phosphorous glass has the narrow temperature that is suitable for accurate die pressing.Therefore, even when when accurate die pressing reduces glass temperature in the stage a little, glass also can be broken.Even when raising glass temperature a little, glass bubbles, thereby can not reentry the high-quality optical element.
By contrast, according to precast body II of the present invention, therefore the feed glass transition temperature can widen accurate die pressing temperature design scope being 450 ℃ or lower, and can stably make fragmentation and blistered optical element can not take place.
And, because reduced glass transformation temperature, so can reduce accurate die pressing annealed temperature afterwards.Annealing is to carry out being lower than under glass transformation temperature 10-50 ℃ the temperature range, so the annealed optimum temps changes with glass transformation temperature.When annealing temperature was very high, the fluorine that exists on the accurate die pressing product surface was partly substituted by the oxygen in the ambient atmosphere, thereby the specific refractory power on optical element top layer has increase slightly.This phenomenon is subjected to the influence of annealing temperature level.In order on optical element, to form optical multilayer such as anti-reflection film, according to the optical multilayer of the optical property designing optimal of glass.Even designed this best optical multilayer, but because the above-mentioned variation of top layer specific refractory power also causes the optical multilayer of actual formation to depart from best film.
Yet, because used precast body II of the present invention,, therefore can suppress above-mentioned oxygen replacement fluorine so can reduce annealing temperature, can guarantee that like this specific refractory power of optical element surface does not change.Therefore, can optimize the design of optical multilayer based on the optical property of glass.And, owing to use precast body II, can reduce the temperature of accurate die pressing, therefore can reduce before accurate die pressing temperature and raise required time and behind accurate die pressing, reducing the glass molding required time of product temperature, and this can make productivity improve.For the glass transformation temperature of controlling precast body II of the present invention to be 450 ℃ or lower, preferably introduce the Li positively charged ion as glass ingredient, more preferably the cationic content of Li is adjusted into 1-30 positively charged ion %.And, ideally, determine the content of anionic group like this, i.e. F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.25-0.85.The fluorophosphate optical glass that constitutes precast body II of the present invention preferably satisfies above-mentioned during opticglass I component is required one or some, more preferably satisfies all above-mentioned requirements.
Precast body II preferably has the precast body of the structure of precast body I, i.e. the precast body that is formed by opticglass of the present invention.
And, the surface that the whole surface of each among precast body I and the II all preferably forms by the vitrification that makes molten state.
When constitute with fluorine phosphorous glass among precast body I and the II with following transmissivity feature each the time, can be suitable as water white transparency optical element by the accurate die pressing manufacturing such as optical elements such as lens, prism, diffraction grating, described transmissivity feature is in the whole wavelength region may of 370-700nm, and the outside transmissivity that converts the 10mm heavy sheet glass to is 80% or higher.
The method of manufacturing press-molding preform provided by the invention will be described below.
First embodiment of the method for manufacturing press-molding preform provided by the invention (hereinafter, be called " precast body manufacture method I ") comprise and make melten glass flow out pipe, separate and to have the molten glass gobs of predetermined weight and in glass cooling process, this glass gob to be shaped to the precast body that the opticglass by the invention described above forms.
With the above-mentioned melten glass of having described of the same preparation.Make melten glass flow out the pipe of being made by platinum alloy or platinum continuously and with constant speed, this pipe is heated to preset temperature by electrical heating method, frequency dielectric heating means or the heating means that make up these two kinds of methods.Weight is equaled the molten glass gobs of a precast body weight or weight separates from effusive melten glass for the molten glass gobs that adds the weight that the weight for the treatment of a part of removing by aftermentioned obtains on the weight of a precast body.When the fractional melting glass gob, it is desirable to not use cutting blade, therefore not residual cutting vestige.For example, the method that melten glass is fallen from the outlet of pipe, or a kind of like this method, wherein use the front end of the effusive melten glass of supporter supports, in the time can separating molten glass gobs, move down this upholder rapidly, thereby molten glass gobs is separated with the front end of molten glass gobs by the surface tension of utilizing melten glass with predetermined weight.
In addition, when the temperature that melten glass will be flowed out is set in 700 ℃ or lower following time of temperature, the glass that shows 30dPas viscosity under 700 ℃ or lower temperature does not manifest and anyly separates caused silk by above-mentioned melten glass and form phenomenon.
In glass cooling process, on the recessed portion of precast body forming model, isolating molten glass gobs is shaped to predetermined shape.In this case, in the process of glass cools, on the precast body surface, to form gauffer or prevent that the glass that is called crackle from damaging, and preferably, carries out moulding under the state that air pressure upwards is applied on the glass gob that is positioned on the recessed portion in order to prevent.
After glass temperature is reduced to the temperature range that glass is not out of shape because of external force, from the precast body forming model, take out precast body, and cooling gradually.
Volatilize from glass surface in order to reduce fluorine, glass is flowed out and moulding prefabricated body.
Though the opticglass of the invention described above is not easy to have striped, if but precast body has slight striped in its surface, then remove the top layer,, therefore can obtain highly uniform precast body on one without stripes, the optics because striped is present in the top layer partly by etching or polishing.
When carrying out above-mentioned etching, precast body can be immersed in the etching solution of acid or alkali, or this etching solution be injected on the whole surface of precast body to remove the top layer like this, promptly remove the whole surface of precast body.After etching, cleaning and dry precast body.
When removing the top layer by polishing, it is desirable to remove like this top layer, promptly remove the whole surface of precast body.Polishing is suitable for spherical precast body or has the precast body of flat surfaces, and etching and shape are irrelevant, can tackle different shape.
In etching and polishing under any situation, it is desirable to separate weight and be added to the molten glass gobs of the weight that obtains on the weight of a precast body after removing the top layer, to have predetermined weight with the top layer by will be to be removed.
Second embodiment of the method for manufacturing press-molding preform provided by the invention (hereinafter, be called " precast body manufacture method II ") comprise melten glass is shaped to glass ware forming material and this glass ware forming material of mechanical workout, thus make the precast body that forms by opticglass of the present invention.
With the above-mentioned melten glass of having described of the same preparation.The method of removing the whole surface of precast body among the precast body manufacture method I also is equivalent to the precast body manufacture method II of mechanical workout glass ware forming material.The method of mentioning among the precast body manufacture method I in addition will be described below.
At first, make melten glass flow out pipe continuously, thereby it is poured in the mold.Mold to be used has flat and each three side that formed by sidewall, a lateral opening.Be provided with like this and stationary die, make that two sidewalls adjacent with the bottom with open side are parallel to each other relative, the bottom surface be centered close to that pipe exports under, and placed horizontally bottom surface.The melten glass that flows in the mold is expanded in by the sidewall region surrounded to have homogeneous thickness, from the opening of open side, taken out refrigerative glass with constant speed along continuous straight runs.Transfer in the annealing furnace formed material that takes out and annealing.Obtain the foliated glass formed material that forms by opticglass of the present invention in this way, and have constant width and constant thickness.
Then, cutting or this foliated glass formed material separately, thus be divided into the sheet glass of many being called " section ", grind and polish this sheet glass, thereby finish the press-molding preform that respectively has predetermined weight.
As another kind of method, the mold that will have cylindrical hole like this arrange and be fixed on the pipe outlet under, the central axis that makes through hole is on vertical direction.In this case, preferably, arrange mold like this, the central shaft that is about to through hole place the pipe outlet under.Then, melten glass is flow into the through hole of mold from pipe, thereby fill this through hole, take out solidified glass vertically downward from the lower ending opening part of through hole with constant speed with glass, and cooling gradually, thereby the glass ware forming material of acquisition cylindrical bar shape.The glass ware forming material that annealing obtains so then from the vertical direction cutting of the central shaft of this cylindrical bar shape glass ware forming material or separate, thereby obtains many sheet glass.Then, grind and the polished glass sheet, thereby finish the press-molding preform that respectively has predetermined weight.
Precast body manufacture method I and II are suitable as the method for making precision press-molding preform, because they can make the high high-quality precast body of weight precision.
[making the method for optical element]
The characteristic that optical element of the present invention has is that it is to be formed by opticglass of the present invention.Optical element of the present invention is that the opticglass by the invention described above forms, and therefore the optical element of the low chromatic dispersion of effective utilization can be provided.And this optical element is that the glass by water tolerance and chemical stability excellence forms, and therefore can provide does not have defective as the optical element by the caused surperficial blushing of life-time service.
Optical element is not particularly limited for its kind, shape etc.This optical element is suitable as non-spherical lens, spherical lens, microlens, lens arra, prism, diffraction grating, has the prism of lens, has the lens of diffraction grating etc.The object lesson of non-spherical lens and spherical lens comprises male bend moon-shaped lens, recessed meniscus shaped lens, biconvex lens, biconcave lens, plano-convex lens, plano-concave lens etc.
From the viewpoint of using, this optical element is suitable as the optical element that is used for the composing images senser element, as the photographic camera of lens for digital camera, camera cell phone with lens, optics pick-up lens, collimator tube etc.
The surface of optical element can have optical thin film such as anti-reflection film as required.
The method of manufacturing optical element provided by the invention will be described below.
The method of manufacturing optical element provided by the invention comprises heating press-molding preform of the present invention or press-molding preform and this precast body of accurate die pressing of being made by press-molding preform manufacture method provided by the invention.
Above-mentioned accurate die pressing is also referred to as " moulded optical moulding (mold optics molding) ", is well-known in the field of the invention.In optical element, transmission, refraction, diffraction or catoptrical surface are called optical function surface (for example, the sphere of the non-spherical surface of lens surface such as non-spherical lens or spherical lens is equivalent to this optical function surface).In accurate die pressing, give glass with the shape accurate transfer that is compression molded into profile, can form optical function surface by mold pressing thus, do not need to use mechanical processing techniques such as grinding, polishing to finish this optical function surface.
Therefore, the method for manufacturing optical element provided by the invention is suitable for making optical element such as lens, lens arra, diffraction grating, prism etc., and it is particularly suitable for the utmost point and makes non-spherical lens efficiently.
Method according to manufacturing optical element provided by the invention, can make optical element with above-mentioned optical property, in addition, because (Tg) is low for the glass transformation temperature of glass, so can reduce molding temperature, therefore reduced being compression molded into the destruction of profile, and therefore can increase the life-span of pressing mold.And, have high stability because constitute the glass of precast body, so even in reheat and pressing step, also can prevent the glass devitrification effectively.And, can the utmost point carry out efficiently beginning to finish the series of steps that product finish from fusion.
Can use known pressing mold as by on the molding surface of refractory cast material such as silicon carbide, zirconium white, aluminum oxide etc., providing pressing mold that mold release film obtains as the accurate die pressing pressing mold.Particularly, be preferred by the pressing mold of silicon carbide manufacturing, can use to contain carbon film etc. as mold release film.Consider weather resistance and cost, carbon film is particularly preferred.
In accurate die pressing, ideally, in molded process, use non-oxidizing gas as atmosphere so that the molding surface of pressing mold remain under the good state.Non-oxidizing gas is preferably selected from nitrogen, the mixture of nitrogen and hydrogen etc.
The accurate die pressing that is used to make optical element provided by the invention comprises following two embodiment-accurate die pressings 1 and accurate die pressing 2.
(accurate die pressing 1)
Accurate die pressing 1 is a kind of like this method, wherein above-mentioned precast body is incorporated in the pressing mold, adds hot-die and precast body together to carry out accurate die pressing.
In above-mentioned accurate die pressing 1, pressing mold and precast body are heated to the glass display 10 that constitutes precast body
6-10
12Temperature during the viscosity of dPas is carried out accurate die pressing.
And, ideally, before from pressing mold, taking out the accurate die pressing product, preferably this accurate die pressing product is cooled to above-mentioned glass display at least 10
12DPas, more preferably at least 10
14DPas, be more preferably at least 10
16Temperature during the viscosity of dPas.
Under these conditions, can give glass, and can take out this accurate die pressing product and do not make its distortion the shape accurate transfer that is compression molded into profile.
(accurate die pressing 2)
Accurate die pressing 2 is a kind of like this methods, wherein the precast body of preheating is incorporated in the pressing mold of preheating to carry out accurate die pressing.
According to accurate die pressing 2, in being incorporated into pressing mold before the above-mentioned precast body of preheating, therefore can make the optical element that does not have surface imperfection and have excellent surface accuracy, reduced cycle time simultaneously.
Preferably the temperature with pre-hot-die is arranged on than under the low temperature of the temperature of preheating precast body.Because the temperature of pre-hot-die is set under the lower temperature, therefore can reduce the wearing and tearing of pressing mold.
In accurate die pressing 2, the glass heats that preferably will constitute precast body is to this glass display 10
9DPas or lower, more preferably 10
9Temperature during the viscosity of dPas.
And, preferably, when above-mentioned precast body is floated preheating it, more preferably this precast body is preheated to the glass display 10 that constitutes this precast body
5.5-10
9Temperature during the viscosity of dPas is more preferably and is preheated to above-mentioned glass display at least 10
5.5DPas but be lower than 10
9Temperature during the viscosity of dPas.
And, preferably with begin to suppress simultaneously or in the process of suppressing, begin to cool down glass.
The temperature of pressing mold is adjusted to the temperature lower than the temperature of above-mentioned preheating precast body, but can uses above-mentioned glass display 10
9-10
12Temperature during the viscosity of dPas is as target.
In this method, preferably, in that being cooled to above-mentioned glass, this accurate die pressing product has at least 10
12After the temperature during viscosity of dPas, take out this accurate die pressing product from model.
Take out the optical element that obtains by accurate die pressing from pressing mold, and cool off it as required gradually.When moulded product is during such as the such optical element of lens, the moulded product surface can be coated with optical thin film as required.
The method of manufacturing optical element provided by the invention as mentioned above.Except aforesaid method, for example, can flow out by making melten glass, thereby form the glass ware forming material, anneal it, then mechanical workout it make optical element of the present invention.For example, along with the vertical direction of the axle above-mentioned cylindrical bar shape glass ware forming material of cutting into slices of post, and grind and column glass that polishing obtains.Can make optical element such as various lens in such a way.
Embodiment
Hereinafter, reference example is illustrated in greater detail the present invention, though the present invention is not subjected to the restriction of these embodiment.
Use corresponding to the phosphoric acid salt of glass ingredient, fluorochemical etc. as the glass starting material.These starting material of weighing are to obtain the having glass of forming shown in the table 1, and these starting material of thorough mixing place platinum crucible with mixture.In electric furnace, at this mixture of fusion 1-3 hour under 850-950 ℃ the temperature, in atmosphere, under heating is stirred simultaneously.Homogenizing and clarifying glass melt are poured in the model of 40 * 70 * 15mm that is made by carbon.The glass of cast is cooled to glass transformation temperature gradually, after this is introduced at once in the annealing furnace, annealing is 1 hour under near the temperature this transition temperature.In annealing furnace, glass is cooled to room temperature gradually.In such a way, obtain the opticglass shown in table 1-1 and the 1-2.
Observe them by the glass that amplifies such acquisition with microscope, find not have crystal to separate out or do not have a residual not melting material.
Measure the specific refractory power (N of the opticglass of above-mentioned acquisition by the following method
d), Abbe number (v
d), glass transformation temperature (Tg) and the temperature when showing the viscosity of 30dPas.Table 1 has shown the result.
(1) specific refractory power (N
d) and Abbe number (v
d)
Measurement is by cooling off the opticglass of acquisition gradually with-30 ℃/hour speed.
(2) glass transformation temperature (Tg)
Thermomechanical analysis device (the trade(brand)name: Thermoplas TMA8310), under 4 ℃/minute temperature rise rate, measure opticglass that provides with Rigaku Corporation.
(3) temperature the during viscosity of glass display 30dPas
According to the viscosity measurement method of JIS Z8803, (the high temperature viscosity measuring apparatus RHEOTRONIC II (modified version) that TokyoKogyo K.K. provides) measures with coaxial dual rotary round shape rotational viscosimeter.Temperature when determine showing the viscosity of 30dPas, it is easy and simple using a kind of like this method, wherein measure the viscosity of glass under each differing temps, the graphic representation that concerns between preparation explanation viscosity and the temperature, the temperature when reading the viscosity that shows 30dPas by this graphic representation.
Table 1-1
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | |
| P 5+ | 26.0 | 27.0 | 27.0 | 27.0 | 27.0 | 27.0 | 27.0 | 33.0 | 29.0 | 27.0 | 27.0 | 26.0 | 13.0 | 17.0 |
| Al 3+ | 20.0 | 21.0 | 21.0 | 21.0 | 21.0 | 21.0 | 21.0 | 21.0 | 19.1 | 15.0 | 11.0 | 21.0 | 21.0 | 27.0 |
| Mg 2+ | 10.0 | 4.0 | 8.0 | 8.0 | 12.0 | 7.3 | 4.9 | 6.3 | 6.6 | 8.3 | 9.0 | 7.5 | 9.7 | 8.0 |
| Ca 2+ | 17.0 | 14.0 | 18.0 | 19.5 | 14.0 | 9.1 | 6.2 | 7.9 | 8.3 | 10.5 | 11.3 | 9.3 | 12.1 | 10.0 |
| Sr 2+ | 17.0 | 17.0 | 17.0 | 17.0 | 17.0 | 15.6 | 10.5 | 13.4 | 14.1 | 17.7 | 19.2 | 15.9 | 20.7 | 17.0 |
| Ba 2+ | 5.0 | 12.0 | 6.0 | 4.5 | 6.0 | 11.0 | 7.4 | 9.4 | 9.9 | 12.5 | 13.5 | 11.3 | 14.5 | 12.0 |
| Li + | 4.0 | 4.0 | 2.0 | 2.0 | 2.0 | 8.0 | 22.0 | 8.0 | 12.0 | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 |
| Na + | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| Y 3+ | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Total content | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| F -/(F -+O 2-) | 0.641 | 0.628 | 0.632 | 0.632 | 0.632 | 0.621 | 0.595 | 0.538 | 0.582 | 0.611 | 0.603 | 0.635 | 0.818 | 0.768 |
| T g[℃] | 428 | 430 | 446 | 445 | 449 | 417 | 359 | 420 | 396 | 393 | 383 | 406 | 383 | 400 |
| N d | 1.490 | 1.503 | 1.495 | 1.494 | 1.493 | 1.500 | 1.488 | 1.511 | 1.505 | 1.505 | 1.507 | 1.495 | 1.464 | 1.468 |
| v d | 82 | 81 | 82 | 81 | 82 | 81 | 81 | 79 | 79 | 80 | 79 | 82 | 88 | 88 |
| Temperature when showing the viscosity of 30dPas [℃] | - | - | - | - | - | 665 | - | - | - | 642 | - | 648 | - | - |
Table 1-2
| 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25 | |
| P 5+ | 38.0 | 38 | 34 | 38 | 38 | 29 | 29 | 31 | 38 | 35 | 35 |
| Al 3+ | 17.0 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 12 | 9 |
| Mg 2+ | 0 | 6 | 6 | 4 | 6 | 6 | 6 | 10 | 6 | 6 | 9 |
| Ca 2+ | 4.0 | 4 | 8 | 6 | 4 | 2 | 4 | 4 | 4 | 4 | 4 |
| Sr 2+ | 5.0 | 5 | 13 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Ba 2+ | 22.0 | 16 | 16 | 16 | 16 | 27 | 23 | 19 | 16 | 16 | 16 |
| Li + | 13.0 | 21 | 13 | 21 | 21 | 21 | 21 | 21 | 18 | 21 | 21 |
| Na + | 0.0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 3 | 0 | 0 |
| Y 3+ | 1.0 | 1 | 1 | 1 | 1 | 1 | 3 | 1 | 1 | 1 | 1 |
| Total content | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| F -/(F -+O 2-) | 0.389 | 0.335 | 0.375 | 0.335 | 0.274 | 0.423 | 0.429 | 0.416 | 0.335 | 0.390 | 0.380 |
| T g[℃] | 427 | 374 | 420 | 372 | 392 | 367 | 367 | 364 | 357 | 366 | 355 |
| N d | 1.553 | 1.5499 | 1.55049 | 1.55224 | 1.55772 | 1.54692 | 1.54567 | 1.5357 | 1.54194 | 1.5353 | 1.53816 |
| v d | 73 | 71.5 | 72.2 | 71.0 | 70.8 | 72.3 | 72.6 | 73.4 | 71.5 | 72.9 | 72.3 |
| Temperature when showing the viscosity of 30dPas [℃] | - | 625 | 660 | - | 650 | 630 | 625 | 625 | 650 | 640 | - |
As show shown in 1-1 and the 1-2, all glass all has predetermined specific refractory power, Abbe number and glass transformation temperature, and shows excellent low temperature softening ability and meltability, so they are suitable as accurate die pressing optical glass.
Then, make have melten glass that form shown in table 1-1 and the 1-2, clarification and homogenizing flow out by the platinum alloy manufacturing, temperature is adjusted to and this stabilization flowed out and the pipe in the temperature range of devitrification not, by the molten glass gobs of dripping or separation has predetermined precast body weight by the following method, in described method, support the front end of melten glass and upholder is moved downward rapidly with the separation of glasses gob.Then, be used in the molten glass gobs that the bottom has the reception model reception acquisition of venting port, this glass gob is shaped to press-molding preform, discharge gas from venting port simultaneously.Make precast body in the above described manner, and about the shape of precast body, the spherical or compressed globular shape that provides by the interval of adjusting and be provided with fractional melting glass is provided precast body.The weight of the precast body that each obtains like this is all consistent with set(ting)value exactly, and all precast bodies all have slick surface.
In order to take all possible measure to guarantee that precast body does not have residual striped, with each moulding and annealed precast body be dipped in fully as in the hydrochloric acid soln of etching solution removing the whole surface of each precast body, cleaning and dry these precast bodies are to form on the optics precast body uniformly.
In another approach, the whole surface of spherical precast body of grinding and polishing each moulding according to known method to be to remove whole surface, obtains on the optics precast body uniformly thus.
Individually, independently every kind of melten glass is poured in the mold they are shaped to the shape of foliated glass or column rod, the glass of this moulding of annealing.Then, the glass that cuts each moulding is to obtain sheet glass, and grinding and polish this sheet glass all is slick precast body to form whole separately surface.
Obtain precast body like this to produce non-spherical lens with pressing unit accurate die pressing shown in Figure 1.Specifically, precast body 4 is placed between the drag parts 2 and last model assembly 1 of pressing mold with last model assembly 1, drag parts 2 and sleeve 3.Then, with the atmosphere in the nitrogen atmosphere displacement silica tube 11, electricity drives well heater 12 and comes the inside of heated quarty tube 11.The pressing mold temperature inside is set to glass display 10 to be molded
8-10
10Temperature during the viscosity of dPas, when keeping this temperature, pressure bar 13 moves downward suppressing model assembly 1, thereby suppresses the precast body of putting into pressing mold.Be compressed under the pressure of 8MPa and carried out 30 seconds.After the compacting, remove this pressing pressure, and under the glass molding product that obtains by mold pressing and drag parts 2 and last model assembly 1 state of contact, this glass molding product is cooled to this glass display 10 gradually
12DPas or more full-bodied temperature.Then, this glass molding product is cooled to room temperature rapidly, and from pressing mold, takes out, thereby produce non-spherical lens.The non-spherical lens of Huo Deing has very high surface accuracy in the above described manner.
In Fig. 1, reference number 9 expression supporting bars, reference number 10 expression drag parts and sleeve bearings, reference number 14 expression thermopairs.
The non-spherical lens that is obtained by accurate die pressing has anti-reflection film as required.
By the following method accurate die pressing different precast body identical with above-mentioned precast body with aforesaid method.In this method, at first, precast body is preheated to the glass that constitutes this precast body has 10
8Temperature during the viscosity of dPas makes this precast body floating simultaneously.By oneself, will have last model assembly, drag parts and telescopic pressing mold is heated to the glass that constitutes above-mentioned precast body and has 10
9-10
12Temperature during the viscosity of dPas.Above-mentioned preheating precast body is incorporated in the chamber of pressing mold, and under 10MPa accurate die pressing.When beginning to suppress, begin to cool down glass and pressing mold, and continue to have 10 until molded glass
12DPas or higher viscosity are taken out molded product then, thereby are produced non-spherical lens from pressing mold.The non-spherical lens of Huo Deing has significantly high surface accuracy in this manner.
The non-spherical lens that is obtained by accurate die pressing has anti-reflection film as required.In the manner described above, make the high optical element of internal soundness efficiently with the high precision utmost point.
Industrial applicability
According to the present invention, can obtain the optical glass that has low dispersion and have low glass transformation temperature and have the low temperature softening performance, can carry out the optical glass of accurate die pressing, can be with above-mentioned optical glass for the manufacture of the mold pressing precast body, and further for the manufacture of optical element such as various lens.
Claims (18)
1. opticglass, it is a kind of fluorine phosphorous glass, as necessary cationic components, comprises P
5+, Al
3+, be selected from Mg
2+, Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+), and L
I+, in positively charged ion %, it comprises:
The P of 10-45%
5+,
The Al of 5-30%
3+,
The Mg of 0-20%
2+,
The Ca of 0-25%
2+,
The Sr of 0-30%
2+,
The Ba of 0-33%
2+,
The Li of 1-30%
+,
The Na of 0-10%
+,
The K of 0-10%
+,
The Y of 0-5%
3+With
The B of 0-15%
3+,
F
-Content and F
-And O
2-The mol ratio F of total content
-/ (F
-+ O
2-) be 0.25-0.85,
Specific refractory power (the N of this opticglass
d) be 1.40-1.58, Abbe number (v
d) be 67-90.
2. the opticglass of claim 1, it contains Ca
2+, Sr
2+And Ba
2+In at least two kinds as divalent cation component (R
2+).
3. the opticglass of claim 1, wherein, as divalent cation component (R
2+), Mg
2+, Ca
2+, Sr
2+And Ba
2+Total content be at least 1 positively charged ion %,
4. the opticglass of claim 1, wherein, as divalent cation component (R
2+), Mg
2+, Ca
2+, Sr
2+And Ba
2+In each content all be at least 1 positively charged ion %,
5. opticglass, it is a kind of fluorine phosphorous glass, shows the viscosity of 30dPas under 700 ℃ or lower temperature.
6. the opticglass of claim 5, it contains the Li of 1-30 positively charged ion %
+
7. claim 1 or 5 opticglass, it is for the usefulness of accurate die pressing.
8. press-molding preform is that the opticglass by claim 1 or 5 forms.
9. press-molding preform, it is to be that 450 ℃ or lower fluorine phosphorescence are learned glass and formed by glass transformation temperature, and the usefulness of confession accurate die pressing.
10. claim 8 or 9 press-molding preform, its whole surface is to form by the vitrification that makes molten state.
Make melten glass flow out pipe 11. a method of making press-molding preform, this method comprise, separate and have the molten glass gobs of predetermined weight and in glass cooling process, described glass gob is shaped to precast body in claim 8 or 9.
12. the method as the manufacturing press-molding preform of claim 11, the surface of wherein after moulding prefabricated body, removing described precast body by etching.
13. the method as the manufacturing press-molding preform of claim 11, the wherein surface of after moulding prefabricated body, removing described precast body by grinding and polishing.
14. a method of making press-molding preform, this method comprise melten glass is shaped to glass ware forming material and the described glass ware forming material of mechanical workout, thereby makes the precast body of claim 8 or 9.
15. an optical element is that the opticglass by claim 1 or 5 forms.
16. a method of making optical element, this method comprise the precast body of heating and accurate die pressing claim 8 or 9 or the precast body of making by the method for claim 11 or 14.
17. the method as the manufacturing optical element of claim 16 is wherein introduced described precast body in the pressing mold, heats described pressing mold and this precast body together to carry out accurate die pressing.
18. the method as the manufacturing optical element of claim 16 will be that the described precast body of heat is incorporated in the pressing mold of preheating to carry out accurate die pressing after wherein will heating.
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| JP2005099014 | 2005-03-30 | ||
| JP2005099014 | 2005-03-30 | ||
| JP2005-099014 | 2005-03-30 | ||
| JP2006-045502 | 2006-02-22 | ||
| JP2006045502A JP4570576B2 (en) | 2005-03-30 | 2006-02-22 | Optical glass, press-molding preform and manufacturing method thereof, and optical element and manufacturing method thereof |
| JP2006045502 | 2006-02-22 |
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| Publication Number | Publication Date |
|---|---|
| CN1854100A true CN1854100A (en) | 2006-11-01 |
| CN1854100B CN1854100B (en) | 2012-05-09 |
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ID=37194603
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591143A (en) * | 2008-05-30 | 2009-12-02 | Hoya株式会社 | Opticglass, glass material for press molding, optical element blank, optical element and manufacture method thereof |
| CN101622207A (en) * | 2007-03-06 | 2010-01-06 | Hoya株式会社 | Opticglass, preform for press forming, optical element and their manufacture method |
| WO2010108435A1 (en) | 2009-03-27 | 2010-09-30 | 成都光明光电股份有限公司 | Fluorophosphate optical glass |
| CN102260043A (en) * | 2010-05-18 | 2011-11-30 | 株式会社小原 | Optical glass, optical element and preform |
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2009
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Also Published As
| Publication number | Publication date |
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| JP2010042998A (en) | 2010-02-25 |
| JP5072942B2 (en) | 2012-11-14 |
| CN1854100B (en) | 2012-05-09 |
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