CN101857362A - Optical glass, glass material for pressing molding, optical glass blank, manufacturing method of optical component and coloring inhibiting method of optical glass - Google Patents
Optical glass, glass material for pressing molding, optical glass blank, manufacturing method of optical component and coloring inhibiting method of optical glass Download PDFInfo
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- CN101857362A CN101857362A CN201010144492A CN201010144492A CN101857362A CN 101857362 A CN101857362 A CN 101857362A CN 201010144492 A CN201010144492 A CN 201010144492A CN 201010144492 A CN201010144492 A CN 201010144492A CN 101857362 A CN101857362 A CN 101857362A
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Abstract
The present invention relates to an optical glass, a glass material for pressing molding, an optical glass blank, a manufacturing method of the optical component and a coloring inhibiting method of optical glass. The manufacturing method of the optical glass comprises the following steps: preparing molten glass and molding the prepared molten glass, wherein the molten glass comprises Fe. Furthermore the glass composition converted according to oxide additionally comprises 0.01-3wt% of SnO2 and 0-0.1wt% of Sb2O3. Additionally, relatively to the glass mass except for Fe2O3, SnO2 and Sb2O3, the content of TiO2 is 0-1wt%, and the content of WO3 is 0-4wt%.
Description
Technical field
The present invention relates to be suitable as the manufacture method of opticglass of various used for optical elements materials and the compression moulding that constitutes by above-mentioned opticglass manufacture method with frit, optical element blank and optical element.
In addition, the invention still further relates to the coloring inhibiting method of opticglass.
Background technology
Lens, prism etc. require to have the high transparency as the opticglass of the material of used for optical elements, and be promptly painted few.
About reducing the painted of glass, for example document 1 (TOHKEMY 2007-112697 communique) has proposed interpolation Sb
2O
3And/or As
2O
3Contain TiO with reduction
2The painted scheme of borate-based opticglass.
In addition, document 2 (TOHKEMY 2005-75665 communique) has been put down in writing by being to add Sb in the opticglass at the phosphoric acid that contains the high refractive index composition
2O
3Can reduce painted content.
Summary of the invention
Disclose in the above-mentioned document 1 to relate to reducing and contained TiO
2The painted technology of glass.Relative therewith, according to the inventor's research as can be known, for boric acid group of the lanthanides glass, even reduce TiO
2The glass of content or do not contain TiO
2Glass, also can take place paintedly, and document 1 disclosed technology can not fully suppress this painted.In addition, according to the inventor's research also as can be known, even, can not rely on Sb as document 2 disclosed phosphate-based glass
2O
3Interpolation fully suppress painted.
Therefore, the object of the present invention is to provide the method for making the painted opticglass that is minimized.
To achieve these goals, the inventor furthers investigate repeatedly, and the result has obtained following cognition.
In the document 1, to the painted mechanism of glass, it has put down in writing following content: it is few and contain TiO in a large number to form composition for network
2Borate-based glass, it is the reason of glass coloring that the coloring function that the Ti ion causes increases.In addition, document 2 has been put down in writing following content: for the phosphate-based glass of high refractive index, the reduction of high refractive index composition is painted reason.
But, according to the inventor's research as can be known,, except coloring mechanisms, also have near the coloring mechanism of the photoabsorption wavelength 360nm～370nm that causes by Fe due to strengthening as document 1 and 2 records for the opticglass that contains Fe.
Therefore, the inventor has further carried out research repeatedly based on above-mentioned cognition, and new discovery as a result is by adding the SnO of predetermined amount
2, can reduce the painted of above-mentioned wavelength region, thereby finish the present invention.
That is, above-mentioned purpose is achieved through the following technical solutions.
[1] a kind of manufacture method of opticglass, it comprises preparation melten glass and step that prepared melten glass is carried out moulding, described melten glass contains Fe, and, during forming, the glass that converts by oxide compound additionally contains the SnO of 0.01～3 quality %
2Sb with 0～0.1 quality %
2O
3, and, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.
[2] as the manufacture method of [1] described opticglass, wherein, to be added with the Sn compound as must additive, be added with the Sb compound and carry out heating and melting as the frit of selective additives, prepare described melten glass thus.
[3] as the manufacture method of [1] described opticglass, wherein, to be added with the Sn compound as must additive, be added with the Sb compound and heat fusion as the frit of selective additives, next cullet material is made in cooling, cullet material to made carries out heating and melting, prepares described melten glass thus.
[4] as the manufacture method of each described opticglass of [1]～[3], wherein, press Fe
2O
3Convert, described melten glass contains greater than 0ppm and is the Fe below the 20ppm.
[5] as the manufacture method of [4] described opticglass, wherein, press Fe
2O
3Convert, described melten glass contains the Fe of 0.05ppm～20ppm.
[6] as the manufacture method of [1]～[3] and [5] each described opticglass, wherein, in the scope of wavelength 200～700nm, thickness is that the outside transmitance of the described opticglass of 10nm is 70% wavelength X
70Below 400nm.
[7] a kind of compression moulding wherein, is made opticglass by each described method of above-mentioned [1]～[6] with the manufacture method of frit, and the opticglass of made is shaped to the compression moulding frit.
[8] a kind of manufacture method of optical element blank, wherein, make the compression moulding frit, use under the frit remollescent state in the compression moulding that makes made by heating by above-mentioned [7] described method, the use press-moulding die is pressed, and makes optical element blank thus.
[9] a kind of manufacture method of optical element wherein, is made optical element blank by above-mentioned [8] described method, the optical element blank of made is ground cut and/or grind, and makes optical element thus.
[10] a kind of manufacture method of optical element, wherein, make the compression moulding frit, use under the frit remollescent state in the compression moulding that makes made by heating by above-mentioned [7] described method, use press-moulding die to carry out precision press molding, make optical element thus.
[11] a kind of method of colouring that suppresses opticglass, it is by additionally containing the SnO of 0.01～3 quality % in the glass that converts by oxide compound is formed
2Sb with 0～0.1 quality %
2O
3Suppress, described opticglass contains Fe, and, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.
[12] as [11] described method, wherein, described painted inhibition comprises the steps: the scope at wavelength 200～700nm, and the outside transmitance that to thickness is the described opticglass of 10nm is 70% wavelength X
70And/or described outside transmitance is 80% wavelength X
80Carry out the short wavelengthization.
[13] as [11] or [12] described method, wherein, press Fe
2O
3Convert, described opticglass contains greater than 0ppm and is the Fe below the 20ppm.
[14] as [13] described method, wherein, press Fe
2O
3Convert, described opticglass contains the Fe of 0.05ppm～20ppm.
According to the present invention, the compression moulding that can provide the painted opticglass that is minimized that Fe causes, is made of above-mentioned opticglass is with the manufacture method of frit, optical element blank and optical element.
Embodiment
[manufacture method of opticglass]
The manufacture method of opticglass of the present invention comprises preparation melten glass and step that prepared melten glass is carried out moulding, and described melten glass contains Fe, and, during forming, the glass that converts by oxide compound additionally contains the SnO of 0.01～3 quality %
2Sb with 0～0.1 quality %
2O
3, and, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.
Among the present invention, " forming by the glass that oxide compound converts " is meant according to frit and all is decomposed when the fusion and the material that exists with oxide form in melten glass or in the opticglass resulting glass that converts is formed.In addition, among the present invention, " additionally " is meant to remove Fe in the glass composition that converts by oxide compound
2O
3, SnO
2And Sb
2O
3Outside glass quality be 100% o'clock relative mass %.In addition, the Fe that is converted into described later
2O
3The content aspect of Fe, with the ppm unit representation its with respect to comprising Fe
2O
3, SnO
2And Sb
2O
3The content of glass total mass.
According to the inventor's research, for the opticglass that contains Fe, near the photoabsorption enhancing wavelength 360nm～370nm that Fe causes can cause taking place painted.On the other hand, document 1 and 2 described technology are to suppress the painted and caused painted technology of the reduction high refractive index composition that Ti causes, so be difficult to reduce painted that above-mentioned Fe causes by document 1 and 2 described technology.
Relative therewith, in the manufacture method of opticglass of the present invention, contain the Sn compound in the melten glass as neccessary composition, can suppress above-mentioned painted thus.With SnO
2Convert, its extra content is in the scope of 0.01～3 quality %.Above-mentioned when containing quantity not sufficient 0.01 quality %, be difficult to obtain enough painted inhibition effects, and during greater than 3 quality %, produce not melts, can not obtain the glass of homogeneous.From having homogenizing and reducing painted aspect and consider of glass concurrently, above-mentioned content is preferably 0.01～2 quality %, more preferably in the scope of 0.01～1 quality %.
In addition, in the manufacture method of opticglass of the present invention, contain the Sb compound in the melten glass as the selectivity composition.With Sb
2O
3Convert, the scope of its extra content is 0～0.1 quality %.Above-mentioned content is during greater than 0.1 quality %, can not fully obtain adding the effect of the painted inhibition that the Sn compound brought.In addition, also can cause following problem: the thermotolerance metal such as platinum or the thermotolerance alloy that constitute melt container or constitute the pipe of circulation melten glass are etched, form with metal ion is fused into glass, thereby glass coloring is strengthened, perhaps eater is blended in the glass with the form of impurity and becomes the scattering of light source, or the like.Above-mentioned content be preferably 0～0.05 quality %, more preferably less than 0.02 quality %, more preferably 0～0.01 quality %, be more preferably 0～0.005 quality %, further be more preferably 0～0.001 quality %, further preferably do not add the Sb compound.
In the manufacture method of opticglass of the present invention, use the melten glass that contains Fe to make opticglass as melten glass.The Sb compound that Sn compound by making above-mentioned amount and selectivity are added coexists as in the melten glass that contains Fe, can access the painted opticglass that is suppressed that is caused by Fe thus.
Press Fe
2O
3Convert, the content of the Fe in the above-mentioned melten glass is preferably more than 0ppm and is below the 20ppm.Need to prove that it is identical to form the glass composition that is considered as with melten glass by the glass that melten glass is carried out the resulting opticglass of moulding.Above-mentioned Fe amount is 20ppm when following, then can obtain adding the painted inhibition effect that the Sn compound is brought well.Above-mentioned Fe amount be preferably 15ppm following, more preferably 10ppm following, more preferably below the 7ppm.In addition, as above-mentioned Fe amount, even the amount that is incorporated into the amount of the Fe in the glass and the Fe that the use high-purity raw is also sneaked into inevitably when the mass production opticglass with the form of the impurity of frit is generally more than the 0.05ppm.Allow to improve raw materials cost and use ultra-high purity raw material or high-purity raw to suppress when glass is sneaked into Fe, above-mentioned Fe amount is generally more than the 0.05ppm and less than 2ppm.In addition, when using general opticglass raw material in order to control raw materials cost, above-mentioned Fe amount is generally 2ppm～20ppm, and when this scope further suppressed the mixed volume of Fe, above-mentioned Fe amount was generally 2ppm～7ppm.Among the present invention, by adding the Sn compound of predetermined amount, even service rating high raw material unlike essence does not contain the high purity glass raw material of Fe impurity also can obtain the painted glass that is suppressed.So, because the present invention is not subject to the restriction of raw material, so suppress raw materials cost when high-quality opticglass can stably be provided.
In addition, using the device mediation frit that so ferruginous material is made with stainless steel or supplying raw material under the situation of melting plant, the abrasion owing to above-mentioned materials causes Fe to be blended in the raw material sometimes.According to the present invention, even in this case, also can suppress the painted of glass, the opticglass of homogeneous is provided.In addition,, also needn't worry the quality of glass is caused detrimentally affect, so can also realize the raising of productivity by the raising of weather resistance of device even glass manufacturing apparatus has used the so high material of ferruginous weather resistance of stainless steel.
In addition,, utilize the clarification of the Sb compound of Sn compound and selectivity interpolation, can access the opticglass of the homogeneous of noresidue bubble according to the present invention.Particularly owing to compare with the Sb compound, the Sn compound is little to the aggressiveness of crucible, so when being neccessary composition with the Sn compound, can suppress the painted amount that can obtain sufficient clarifying effect again even add, also can not promote the erosion to crucible.
But for containing TiO in a large number
2, WO
3Glass, even find to add the Sb compound that Sn compound and selectivity are added, also be difficult to suppress painted.By inference this be because, for containing TiO in a large number
2Glass because the painted influence that causes of Ti, though suppressed that Fe causes painted, still the painted of glass can take place also; For containing WO in a large number
3Glass, W has eliminated the effect that Sn, Sb bring in the absorption in short wavelength zone.
Therefore, for the glass that is added with the Sb compound that Sn compound and selectivity add among the present invention, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.The painted effect of improving that interpolation Sn compound brings is at TiO
2Content, WO
3The fewer glass of content in performance obviously.Based on such reason, TiO
2The preferable range of content be 0～0.5%, further preferred range is 0～0.1%, is more preferably and does not contain TiO
2Glass.For WO
3, WO
3Content be preferably set to 0～3%, more preferably be set at 0～2%, further be preferably set to 0～1%, further be more preferably and be set at 0～0.5%, further be more preferably and be set at 0～0.1%, also more preferably do not contain WO
3Glass.
As the optimal way of the manufacture method of opticglass of the present invention, can enumerate the mode for preparing melten glass by any means of following method 1,2.
(method 1)
To be added with the Sn compound as must additive, be added with the Sb compound and carry out heating and melting as the frit of selective additives, prepare melten glass thus.
(method 2)
To be added with the Sn compound as must additive, be added with the Sb compound and heat fusion as the frit of selective additives, next cullet material is made in cooling, cullet material to made carries out heating and melting, prepares melten glass thus.
In the method 1 and 2,, can suitably use oxide compound, oxyhydroxide, carbonate, nitrate etc. as frit, Sn compound and Sb compound.In the method 1, take by weighing these raw materials and additive, mix with predetermined ratio, make the mediation raw material, in the fusion of melt container internal heating, next clarify, stir, homogenize and carry out glass culletization, can not contained bubble, the melten glass of the homogeneous of liquefactent not thus.
Method 1 is a what is called direct scorification in batches, wherein is in harmonious proportion raw material in batches, carries out fusion, produces opticglass.And method 2 is following method: earlier by raw material is carried out fusion, cooling comes vitrifying, makes cullet material, to cullet material be in harmonious proportion, fusion, obtain melten glass thus.In more detail, in the method 2, to slightly fuse with frit and Sn compound (and Sb compound of selectivity interpolation) and in melt container, heat together, slightly fuse, the liquefactent that obtains is carried out chilling, make cullet material, use this cullet material, glass is carried out fusion, clarifies and homogenizes, the melten glass that obtains is carried out moulding, make opticglass.In method 1, the method 2, the amount that the addition of Sn compound and Sb compound is adjusted to Sn is scaled SnO
2Extra addition be that the amount of 0.01～3 quality %, Sb is scaled Sb
2O
3Extra addition be 0～0.1 quality %, thus, these two kinds of methods all can be reduced in the painted of the opticglass that is mixed with Fe.
In the manufacture method of opticglass of the present invention, use the melten glass that contains Fe as melten glass.As the mode of in melten glass, sneaking into Fe, can enumerate following mode.According to the present invention, even, also can suppress painted to sneak into the glass of Fe by following any-mode.
(1) is intended to mix in the frit Fe compound.
(2) use the frit of sneaking into Fe.
(3) sneak into Fe by the device in the opticglass manufacturing process.
Below, above-mentioned (3) are described in detail.
For example, the two or more compound of the powder shaped of the corresponding glass ingredient of weighing and as the Sn compound of additive (SnO for example
2), put into the stainless steel container made, use the mixing tool of stainless steel to carry out thorough mixing, can obtain being in harmonious proportion raw material thus.Use this mediation feedstock production melten glass, effusive melten glass is injected mold, carry out moulding, the glass ware forming product that obtain are annealed, can obtain opticglass thus.The preparation of melten glass can followingly be carried out.
At first, the raw material that will be in harmonious proportion is placed in raw material feed device, next, raw material is put in the glass melting container with an amount of piecemeal, heats, fusion, clarifies, homogenizes, flows out.The input of raw material can roughly remain on constant basis by the glass in the glass melting container and come continuously or carry out off and on.
In the above-mentioned operation, the stainless steel container made that uses when for example raw material is in harmonious proportion, the face that contacts with raw material of mixing tool are owing to the friction with raw material is ground, though should measure seldom, stainless sometimes micropowder can be blended in the raw material.Contain iron in the stainless steel, therefore can in raw material, sneak into Fe.In addition, the part of being made by ferruginous alloys such as iron or stainless steels in the raw material feed device also is ground sometimes, and sneaks into iron in raw material.Calculate iron contamination amount in the glass according to the amount of the iron that contains as impurity in frit or the additive in advance, compare with this value, sometimes the iron contamination amount in Shi Ce the glass is more, can think that this species diversity is that the iron that is blended in the raw material owing to above-mentioned reason in the glass manufacturing causes.Even use the ultra-high purity raw material, as mentioned above, also have iron sometimes and be blended in the raw material, in this case,, add in the raw material by Sn compound and can reduce, suppress the painted of glass predetermined amount according to the present invention.
In the above-mentioned example, use the powder shaped compound to be in harmonious proportion raw material, replace using the powder shaped compound and glass is carried out under the fused situation, also can obtain identical effect by adding the Sn compound but in method 2, be in harmonious proportion glass cullet.
Method 1, method 2 all can by melten glass is carried out moulding, slowly cooling obtains opticglass of the present invention.As forming method, can use technique known such as cast molding, bar moulding, compression moulding.The glass of forming is transferred to usually and is heated near the annealing furnace of second-order transition temperature, slowly cool to room temperature in advance.The glass that obtains is suitably implemented to cut off, grind and cut, grind.As required, can cut off glass, hot pressing, can also make accurate grumeleuse (go Block), heat, precision press molding is a non-spherical lens etc.The purposes of the opticglass that obtains by manufacture method of the present invention is seen below literary composition.
Below, the glass of the opticglass that obtains by manufacture method of the present invention is formed and rerum natura describes.
According to the manufacture method of opticglass of the present invention, as mentioned above, can access by the painted opticglass that is suppressed due near the photoabsorption of Fe wavelength 360nm～370nm.For whether being the glass that has so suppressed painted, can scope with wavelength 200～700nm in, for thickness 10nm, outside transmitance reaches 70% wavelength X
70Or reach 80% wavelength X
80For index is estimated.The opticglass that obtains by manufacture method of the present invention can show for example λ below the 400nm
70, even can show the λ that 395nm is following, 380nm is following
70To λ
70Lower limit be not particularly limited, for example be about 300nm.In addition, preferred λ
80Below 460nm.To λ
80Lower limit be not particularly limited, for example be about 330nm.
λ among the present invention
70And λ
80It is the value of measuring by the method shown in the embodiment described later.Need to prove, by the λ of the mensuration of the method shown in the embodiment described later
5Be that the said external transmitance reaches 5% wavelength, it is the numerical value at the few wavelength place of the transit dose of light, thus few to painted influence, but consider preferred λ from the painted aspect of further inhibition
5Below 360nm.To λ
5Lower limit be not particularly limited, for example about 230nm.
As long as above-mentioned opticglass contains Fe, and with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %, and then its glass composition is not subjected to special qualification.But, based on the glassy phase that contains a large amount of Sb with reason, preferably do not contain oxidation capacity be better than Sb, promptly to the glass of the high As of the aggressiveness of thermotolerance metals such as platinum.In addition, the strong toxicity of As, big to the burden of environment, therefore,, preferably do not add As above-mentioned opticglass, promptly there is not As glass.
In addition, consider from the problem of environmental pressure, preferably do not contain Pb glass (no Pb glass), do not contain Cd glass (no Cd glass), do not contain Th glass (no Th glass), do not contain U glass (no U glass), do not contain the glass (no Cr glass) of Cr.
Then, the preferred glass that illustrates above-mentioned opticglass is formed.
The 1st example is a borate glass.Wherein, it is low dispersed the time that the borate glass that contains lanthanum has high refractive index, except impurity such as Fe cause painted, glass itself painted considerably less, so to use the present invention be effective.Because it is low dispersed to bring into play less colored, high refractive index, above-mentioned opticglass is suitable as the optical element material that constitutes high function, small-sized optical system.Consider that from obtaining the low aspect of glass that disperses of excellent high refractive index such as stability, devitrification resistance the content of the lanthanum in the above-mentioned glass is preferably pressed La
2O
3Be scaled 10～60 quality %.More preferably 15 quality % above, more preferably 20 quality % above, further be preferably more than the 25 quality %.In addition, be preferably 55 quality % following, more preferably 50% quality following, more preferably below 45% quality.For the same reason, above-mentioned glass is fit to contain and is preferably 2～50 quality %, the B of 10～45 quality % more preferably
2O
3
The 2nd example is a phosphate glass.The fusion excellence of phosphate glass can be set melting temperature (Tm) than the lowland.Therefore, can suppress to constitute the erosion of the thermotolerance metals such as platinum of melt container, can reduce the amount of metal that fuses into the platinum etc. of glass with the ionic form, also can reduce painted.Phosphate glass no matter be as high refractive index high dispersive glass, or to disperse glass all be useful glass as low.For high refractive index high dispersive glass, import more Nb
2O
5, TiO
2, WO
3, Bi
2O
3Deng the composition of giving high refractive index, high dispersive to improve specific refractory power, dispersion.The importing of these compositions uses oxide raw material to carry out usually, but refining and carbonate raw material, nitrate raw material, the vitriol raw material etc. of oxide raw material refining compared trouble and cost also can increase.Therefore, reduce grades of raw materials and when seeking cost and reducing, have to use the oxide raw material that contains Fe impurity, it is painted that resulting opticglass can take place significantly that Fe causes.In order to reduce painted that this Fe causes, have to use the high-purity raw of extremely having got rid of Fe impurity, cause cost to improve.Relative therewith, according to the present invention, can access painted few phosphate glass, and not need from the oxide raw material that contains Fe impurity, to get rid of fully Fe.Particularly contain Nb more than the 30 quality % in total
2O
5, TiO
2, WO
3And Bi
2O
3Phosphate glass in, therefore preferably the effect of painted inhibition is bigger, adds up to the Nb that contains (particularly 40～70 quality %) more than the 30 quality % in the glass that converts by oxide compound is formed
2O
5, TiO
2, WO
3And Bi
2O
3Phosphate glass in use the present invention.
In addition, the present invention also can be suitable for fluorphosphate glass, fluor borate glass, silicate glass.
[the compression moulding manufacture method of frit]
Compression moulding of the present invention is with in the manufacture method of frit, and the manufacture method of the opticglass by the invention described above is made opticglass, and the opticglass of made is shaped to the compression moulding frit.Above-mentioned frit is made of the glass that paintedly is suppressed, uniformity is high, and is therefore very useful when making high-quality optical element by compression moulding.
As first mode of compression moulding of the present invention, can enumerate the following manner that opticglass is processed with the manufacture method of frit.
For example, the melten glass through clarifying, homogenizing is poured in the mold, carries out chilling, moulding, the glass forming body that obtains is annealed, this formed body is cut off or cuts off, be divided into sheet glass, sheet glass ground cut, grind, make the compression moulding frit.By grinding, the precision press molding preform can be made through level and smooth accurately machined frit in the surface.By sheet glass is carried out barreling, also can make and be used to make the frit of grinding with the compression moulding product, described grinding is used for cutting by after compression moulding the surface of moulding product being ground, grinds and form optical element with the compression moulding product.
As second mode, can enumerate following mode: preparing the fused glass block of 1 part above-mentioned frit, above-mentioned fused glass block is applied blast, is the compression moulding frit at emersion state compacted under.According to second mode,, can make the frit on the surface that constitutes by free surface with level and smooth and aptychus owing to be under the emersion state, fused glass block to be carried out moulding.The compression moulding that so obtains is suitable as the precision press molding preform with frit.
For the precision press molding preform, make the coating of glass in the time that precision press moldings such as containing carbon film can being formed on the surface along the abundant curtain coating of forming mould molding surface.
[manufacture method of optical element blank]
In the manufacture method of optical element blank of the present invention, make the compression moulding frit by compression moulding of the present invention with the manufacture method of frit, use under the frit remollescent state in the compression moulding that makes made by heating, the use press-moulding die is pressed, and makes optical element blank thus.
Optical element blank is meant that the shape of shape and purpose optical element is close, has been undertaken grinding the glass article of cutting, grinding by the shape of above-mentioned optical element, is to cut, grind the optical element mother metal that is finish-machined to optical element by the surface is ground.In addition, in the manufacture method of opticglass of the present invention, also can be pressed to melten glass, thereby obtain opticglass with the form of optical element blank by using press-moulding die.In this case, on the molding surface of press-moulding die, evenly be coated with Powdered releasing agents such as boron nitride, hitherward supply with when being pressed behind the melten glass, can positively prevent the fusion of glass and forming mould, in addition, can also make the molding surface smooth flow of glass along press-moulding die, preferred thus.
In the manufacture method of optical element blank of the present invention, can in atmosphere, carry out heating, the compression moulding of frit simultaneously.The even Powdered releasing agent such as coating boron nitride on the surface of frit, and heat, during compression moulding, can positively prevent the fusion of glass and forming mould, in addition, can also make glass along the level and smooth curtain coating of the molding surface of press-moulding die.The optical element blank that compression moulding is obtained from forming mould take out, annealing, when reducing inner distortion, preferably finely tune, make optical characteristics such as specific refractory power reach desired value.Among the present invention, by the Sn compound (with the Sb compound of selectivity interpolation) that adds aequum, the variation of devitrification resistance can not take place, so the opticglass that obtains by the present invention is fit to make above-mentioned optical element blank during glass heats.
Manufacture method according to optical element blank of the present invention, a kind of optical element blank can be provided, it is painted to be minimized, do not contain residual bubble, has the uniform inside quality of optical property, can access high-quality optical element by this optical element blank is ground to cut, grind.
[manufacture method of optical element]
The manufacture method of optical element of the present invention comprises following 2 kinds of modes:
(1) a kind of manufacture method of optical element, wherein, the manufacture method by optical element blank of the present invention is made optical element blank, the optical element blank of made is ground cut and/or grind, and makes optical element thus;
(2) a kind of manufacture method of optical element, wherein, make the compression moulding frit by compression moulding of the present invention with the manufacture method of frit, use under the frit remollescent state in the compression moulding that makes made by heating, use press-moulding die to carry out precision press molding, make optical element thus.
The optical element that pass-through mode (1) and (2) obtain is made of the painted glass that is minimized, does not contain the homogeneous of residual bubble, thus be suitable as optical imaging element, projection with optical element, optical communication with optical element, be used for writing data or from optical pickup lens, other optical elements of optical recording medium reading of data to optical recording medium.
As optical imaging element, projection optical element, can enumerate sphere positive meniscus lens, sphere crescent moon concavees lens, sphere biconcave lens, sphere crescent moon biconvex lens, spherical plano-convex lens, sphere plano-concave lens, aspheric surface positive meniscus lens, aspheric surface crescent moon concavees lens, aspheric surface biconcave lens, aspheric surface crescent moon biconvex lens, aspheric surface plano-convex lens, aspheric surface plano-concave lens, prism etc.These optical elements are suitable for imaging lens system, the imaging lens system of onboard camera, the incidental projecting lens of liquid crystal projector, prism of the incidental imaging lens system of exchange lens, digital still camera, digital camera, mobile telephone, the incidental imaging lens system of PC, the monitor camera of single-lens reflex camera etc.
As the optical communication optical element, can enumerate between the optical fiber or the coupling lens of optical fiber and light portion product etc.
As other optical elements, can enumerate diffraction grid, Fresnel lens, spectral filter etc.
Can also be as required at surface coated antireflection film, partial reflection film, the highly reflecting films of these optical elements, have the reflectance coating of wavelength interdependence etc.
In the mode (1), grind cut, grind can application of known method, the processing back by optical element surface is fully cleaned, drying etc., can access the high optical element of inside quality and surface quality.Mode (1) is suitable as the method for making optical elements such as various spherical lenses, prism.
As everyone knows, the precision press molding in the mode (2) also is known as molding optical moulding (モ one Le De オ プ テ イ Network ス moulding), and it is the method that forms the optical function face of optical element by the molding surface of transfer printing press-moulding die.In addition, the optical function face is meant refraction of light, reflection, the diffraction that makes controlled member in the optical element, the face of going into outgoing, and the lens face in the lens etc. is equivalent to this optical function face.In the precision press molding, can adopt known method, prepare preform in advance,, carry out precision press molding this preform heating as the compression moulding frit.In the mode (2), owing to will heat once more glass, the glass that therefore requires to constitute frit has excellent devitrification resistance.According to the present invention, by adding the Sn compound and the Sb compound of aequum, can not damage the devitrification resistance of glass, so, can not have the optical element of devitrification with the high productivity volume production by the manner.The coupling lens that the various non-spherical lenses of the suitable manufacturing of mode (2), optical pickup lens, optical communication are used.
[coloring inhibiting method of opticglass]
The invention still further relates to the method for colouring of the opticglass that suppresses to contain Fe.
Coloring inhibiting method of the present invention additionally contains the SnO of 0.01～3 quality % in the glass that converts by oxide compound is formed
2Sb with 0～0.1 quality %
2O
3Thereby, can suppress to contain opticglass painted of Fe.Herein, as mentioned above, in the glass as painted inhibition object, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.In addition, above-mentioned " painted inhibition " be meant, with respect to except not containing the SnO of above-mentioned amount
2And Sb
2O
3Outside have the opticglass that same glass is formed, painted being minimized.Near wavelength 360nm～370nm that the repressed painted Fe of being preferably causes painted.Fe causes painted be suppressed this point can by with except not containing the SnO of above-mentioned amount
2And Sb
2O
3Outside have the opticglass that same glass forms and compare aforementioned wavelength X
70And/or λ
80The short wavelengthization has taken place to be confirmed.
SnO in the coloring inhibiting method of the present invention
2Consumption, Sb
2O
3Consumption, the suitable details such as opticglass that use are as mentioned above.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
1. make embodiment, the comparative example of opticglass formed body
Use compounds such as boric acid, oxide compound, carbonate, with the opticglass of the composition that obtains the embodiment 1～21 shown in the table 1 with have ratio weighing above-claimed cpd, the mixing of opticglass of the composition of comparative example 1～22, be in harmonious proportion frit.
In addition, except embodiment 11 and comparative example 6, the frit that is used to obtain the opticglass of embodiment, comparative example uses common opticglass raw material to be in harmonious proportion with compound.In embodiment 5～7,9,10 and the comparative example 2～4, add the Fe of the amount of Table 1 in the frit
2O
3The opticglass raw material of embodiment 11 and comparative example 6 uses highly purified compound to be in harmonious proportion.That is, the opticglass raw material of embodiment 11 and comparative example 6 is high-purity raws.
Next, these frits are imported to the glass melting groove on one side, heat on one side, fusion, the melten glass that obtains is injected the clarifying tank that is connected with fusion tank by pipe connecting, after clarifying, be injected into the operation slot that is connected with clarifying tank by pipe connecting, after stirring homogenizes it, it is flowed out from the outlet pipe that is installed in the operation slot bottom, be poured in the mold, carry out moulding.Above-mentioned fusion tank, clarifying tank, operation slot, each pipe connecting, outlet pipe are platinum alloy system.
In addition, the mixing device of frit, frit be to the stainless steel device of the throwing device useful life longevity excellence of fusion tank, because suppressed the abrasion that frit causes, so can think not sneaking into from the Fe of device.Therefore,, measure the Fe amount in the frit, the Fe amount (Fe in the melten glass that will calculate according to measured value for embodiment and the comparative example beyond embodiment 5～7 and the comparative example 2～4
2O
3Conversion) is shown in table 1.For embodiment 5～7,9,10 and comparative example 2～4, with the Fe that adds
2O
3Amount and with the above-mentioned Fe amount (Fe that similarly calculates by the Fe in frit amount
2O
3Conversion) is shown in table 1.In addition, the Fe in resulting opticglass amount can be considered as identical with Fe amount in the melten glass shown in the table 1.
In addition, in the making of above-mentioned glass, the glass melting temperature in the fusion tank is set at temperature (clarifying temp) that 1100～1400 ℃, fusion time are set at the glass in 1～5 hour, clarifying tank is set at temperature that 1200～1500 ℃, settling time are set at the glass in 1～6 hour, operation slot and is set at 1000～1300 ℃, the outflow temperature of glass and is set at 900～1300 ℃.In addition, above-mentioned glass manufacturing apparatus according to melten glass from fusion tank to clarifying tank, constitute from the mode of clarifying tank to operation slot continuous flow.Therefore, above-mentioned fusion time, settling time are respectively the mean times that glass is trapped in fusion tank, clarifying tank.
After the opticglass that moulding is obtained remains near the second-order transition temperature, with-30 ℃/hour speed of cooling slowly after the cooling, gather and be used to measure degree of staining λ
80, λ
70, λ
5, refractive index n d, Abbe number ν d, glass transition temperature Tg, yield-point Ts sample, measure above-mentioned each characteristic.Measurement result sees Table 1.
In addition, the opticglass that obtains is not seen crystallization or residual bubble.
Enumerate the measuring method of above-mentioned each characteristic below.
(1) degree of staining λ
80, λ
70, λ
5
Making thickness is 10 ± 0.1mm, has the planar glass specimen that is parallel to each other through optical grinding, from injecting intensity I with the vertical direction in above-mentioned plane to this glass specimen
InLight, measure the intensity I of transmitted ray
Out, with strength ratio I
Out/ I
InThe outside transmitance that is called glass.In the scope of wavelength 200～700nm, be that 80% wavelength note is made λ with outside transmitance
80, outside transmitance is that 70% wavelength note is made λ
70, outside transmitance is that 5% wavelength note is made λ
5In the scope of wavelength 200～700nm, at λ
80Above wavelength region has obtained the outside transmitance more than 80%, at λ
70Above wavelength region obtained the outside transmitance more than 70%, at λ
5Above wavelength region has obtained the outside transmitance more than 5%.In addition, in the high opticglass of specific refractory power, the reflectivity height of the light on glass specimen surface, outside sometimes transmitance can not reach 80%.In this case, can not λ
80, perhaps can not accurately measure, so not provide corresponding value in the table 1.
(2) refractive index n d, Abbe number ν d
Can measure by standard JOGIS " measuring method of the specific refractory power of opticglass " according to Japanese optics nitre industry.
(3) glass transition temperature Tg, yield-point Ts
Use the thermo-mechanical analysis device, under the condition of 4 ℃/minute of heat-up rates, measure.
Except Sn addition, Sb addition, Fe mixed volume, the composition of the opticglass of embodiment 1～11, comparative example 1～6 is identical.As shown in Table 1, will be converted into Fe
2O
3The identical embodiment of the amount of Fe and the opticglass of comparative example compare the λ of the opticglass that is added with Sn of embodiment
80And λ
70Value less than the value of the opticglass that does not add Sn of comparative example.In addition, relatively form identical embodiment 2 and embodiment 4 Sb as can be known,, cause adding the trend that painted inhibition effect that Sn brings has reduction by adding Sb except having or not to add.The Sb addition is many more, and this trend is big more, presses Sb
2O
3The Sb addition that converts is difficult to obtain adding the painted inhibition effect that Sn brings during greater than 0.1 quality %, therefore, among the present invention, adds under the situation of Sb, presses Sb
2O
3Convert, its addition is set at below the 0.1 quality %.
Similarly, embodiment and the comparative example of forming identical other in the table 1 except Sn addition, Fe mixed volume compared as can be known, compare the λ of the opticglass that is added with Sn of embodiment with the opticglass that does not add Sn of comparative example
80And/or λ
70Be worth forr a short time, suppressed painted.
On the other hand, in the opticglass of comparative example 14～16, TiO
2Content is greater than 1 quality % and WO
3Content is greater than 4 quality %, and except Sn addition, Sb addition, the composition of opticglass is identical; In the opticglass of comparative example 17～19, TiO
2Content is greater than 1 quality %, and except Sn addition, Sb addition, the composition of opticglass is identical; In the opticglass of comparative example 20～22, WO
3Content is greater than 4 quality %, and except Sn addition, Sb addition, opticglass is formed identical.In these comparative examples, do not observe and add the λ that the Sn compound is brought
80And even λ
70Reduction.
By The above results as can be known, at TiO
2Content is the following and WO of 1 quality %
3Content is in the following compositional system of 4 quality %, by adding Sn, the painted effect that can be inhibited and be caused by Fe.
Be that the frit that the mediation compound obtains is carried out fusion, moulding above, directly make the example of opticglass, but also can followingly obtain having the opticglass of composition, characteristic shown in the table 1: the harmonization compound, prepare thick fusion and uses frit, suitably add SnO
2, Sb
2O
3After, in melt container, heat, slightly fuse, with resulting melts chilling, make cullet material, make two or more cullet materials, be in harmonious proportion these cullet materials, import in the platinum alloy system crucible being in harmonious proportion good cullet material by the mode of the opticglass that obtains having the purpose optical characteristics, through heating, fusion, clarify and homogenize, moulding, obtain opticglass.
2. make the embodiment of compression moulding with frit
Make compression moulding that the opticglass by the various embodiments described above constitutes with frit, optical element blank and optical element by following method 1-1 or method 1-2.
(method 1-1)
To have the opticglass fusion of forming shown in the table 1, be poured in the mold, obtain glass forming body through chilling, moulding, the glass forming body that obtains is annealed, this formed body is cut off or cuts off, be divided into sheet glass, sheet glass ground cut, grind, make the compression moulding frit.
(method 1-2)
Preparation applies blast by having 1 part compression moulding that the opticglass formed shown in the table 1 the constitutes fused glass block with frit to fused glass block, is the compression moulding frit at emersion state compacted under.
3. make the embodiment of optical element blank
Make the optical element blank that the opticglass by the various embodiments described above constitutes by following method 2-1 or method 2-2.
(method 2-1)
Each compression moulding that is obtained by aforesaid method 1-1 or 1-2 is heated with frit, use press-moulding die to be pressed, make optical element blank.The heating of frit, compression moulding are all carried out in atmosphere.The even Powdered releasing agent of coating boron nitride etc. on the surface of frit heats, compression moulding.The optical element blank that repressed moulding is obtained takes out from forming mould, anneals, and when lowering inner distortion, finely tunes and makes optical characteristics such as specific refractory power reach desired value.
(method 2-2)
Use press-moulding die to being pressed the making optical element blank by having the melten glass that homogenizes that the opticglass formed shown in the table 1 constitutes.Molding surface at press-moulding die evenly is coated with Powdered releasing agents such as boron nitride, hitherward supplies melten glass, is pressed.
4. the embodiment of optical element
Make the optical element that the opticglass by the various embodiments described above constitutes by following method 3-1～method 3-3.
(method 3-1)
Each optical element blank that obtains by aforesaid method 2-1 or 2-2 ground cut, grind, make various spherical lenses, prism.
(method 3-2)
To have the opticglass fusion of forming shown in the table 1, be poured in the mold, obtain glass forming body, this glass forming body is cut off, grinds and cut, grind, make the precision press molding preform of surface smoothing through chilling, moulding; Perhaps prepare by having the fused glass block that the opticglass formed shown in the table 1 constitutes, precision press molding after making its emersion to moulding heats with preform, use press-moulding die, carry out precision press molding, make various optical elements such as non-spherical lens, microlens.
(method 3-3)
To have the opticglass fusion of forming shown in the table 1, be poured in the mold, obtain glass forming body, glass forming body is cut off, grinds and cut, grind, make various spherical lenses, prism through chilling, moulding.
No matter whether contain Fe impurity, above-mentioned optical element arbitrarily all is high-quality opticglass system optical elements, its painted being minimized, and do not find residual bubble or devitrification.
In addition, can be as required on the surface of each optical element, form optical multilayers such as antireflection film.
Industrial applicibility
The optical glass that obtains by the present invention is fit to make various optical elements.
Claims (14)
1. the manufacture method of an opticglass, it comprises preparation melten glass and the step that prepared melten glass is carried out moulding, described melten glass contains Fe, and, during forming, the glass that converts by oxide compound additionally contains the SnO of 0.01～3 quality %
2Sb with 0～0.1 quality %
2O
3, and, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.
2. the manufacture method of opticglass as claimed in claim 1, wherein, to be added with the Sn compound as must additive, be added with the Sb compound and carry out heating and melting as the frit of selective additives, prepare described melten glass thus.
3. the manufacture method of opticglass as claimed in claim 1, wherein, to be added with the Sn compound as must additive, be added with the Sb compound and heat fusion as the frit of selective additives, next cullet material is made in cooling, cullet material to made carries out heating and melting, prepares described melten glass thus.
4. as the manufacture method of each described opticglass of claim 1～3, wherein, press Fe
2O
3Convert, described melten glass contains greater than 0ppm and is the Fe below the 20ppm.
5. the manufacture method of opticglass as claimed in claim 4 wherein, is pressed Fe
2O
3Convert, described melten glass contains the Fe of 0.05ppm～20ppm.
6. as the manufacture method of each described opticglass of claim 1～3, wherein, in the scope of wavelength 200～700nm, thickness is that the outside transmitance of the described opticglass of 10nm is 70% wavelength X
70Below 400nm.
7. a compression moulding wherein, is made opticglass by each described method of claim 1～6 with the manufacture method of frit, and the opticglass of made is shaped to the compression moulding frit.
8. the manufacture method of an optical element blank, wherein, make the compression moulding frit, use under the frit remollescent state in the compression moulding that makes made by heating by the described method of claim 7, the use press-moulding die is pressed, and makes optical element blank thus.
9. the manufacture method of an optical element wherein, is made optical element blank by the described method of claim 8, the optical element blank of made is ground cut and/or grind, and makes optical element thus.
10. the manufacture method of an optical element, wherein, make the compression moulding frit, use under the frit remollescent state in the compression moulding that makes made by heating by the described method of claim 7, use press-moulding die to carry out precision press molding, make optical element thus.
11. a method of colouring that suppresses opticglass, it is by additionally containing the SnO of 0.01～3 quality % in the glass that converts by oxide compound is formed
2Sb with 0～0.1 quality %
2O
3Suppress, described opticglass contains Fe, and, with respect to except Fe
2O
3, SnO
2And Sb
2O
3Outside glass quality, TiO
2Content is 0～1 quality %, WO
3Content is 0～4 quality %.
12. method as claimed in claim 11, wherein, described painted inhibition comprises the steps: the scope at wavelength 200～700nm, and the outside transmitance that to thickness is the described opticglass of 10nm is 70% wavelength X
70And/or described outside transmitance is 80% wavelength X
80Carry out the short wavelengthization.
13., wherein, press Fe as claim 11 or 12 described methods
2O
3Convert, described opticglass contains greater than 0ppm and is the Fe below the 20ppm.
14. method as claimed in claim 13 wherein, is pressed Fe
2O
3Convert, described opticglass contains the Fe of 0.05ppm～20ppm.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009096630 | 2009-04-13 | ||
| JP2009-096630 | 2009-04-13 | ||
| JP2010-048515 | 2010-03-05 | ||
| JP2010048515A JP5727149B2 (en) | 2009-04-13 | 2010-03-05 | Optical glass, glass material for press molding, optical element blank, optical element manufacturing method, and optical glass coloring suppression method |
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| Publication Number | Publication Date |
|---|---|
| CN101857362A true CN101857362A (en) | 2010-10-13 |
Family
ID=42943558
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010144492A Pending CN101857362A (en) | 2009-04-13 | 2010-04-12 | Optical glass, glass material for pressing molding, optical glass blank, manufacturing method of optical component and coloring inhibiting method of optical glass |
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| Country | Link |
|---|---|
| CN (1) | CN101857362A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485252A (en) * | 2018-06-19 | 2019-03-19 | 原思平 | Color additive, application and the functional glass of the functional glass of a kind of high visible light and absorption near infrared ray |
| CN113307472A (en) * | 2021-05-26 | 2021-08-27 | 苏州融睿电子科技有限公司 | Glass-containing packaging device and packaging method and application thereof |
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| CN1524815A (en) * | 2002-12-27 | 2004-09-01 | Hoya株式会社 | Optical glass, press-molding glass gob and optical element |
| CN101289276A (en) * | 2008-06-19 | 2008-10-22 | 成都光明光电股份有限公司 | High-refraction and high- dispersion optical glass and method of manufacture |
| CN101389574A (en) * | 2006-02-20 | 2009-03-18 | 旭硝子株式会社 | Optical glass |
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2010
- 2010-04-12 CN CN201010144492A patent/CN101857362A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524815A (en) * | 2002-12-27 | 2004-09-01 | Hoya株式会社 | Optical glass, press-molding glass gob and optical element |
| CN101389574A (en) * | 2006-02-20 | 2009-03-18 | 旭硝子株式会社 | Optical glass |
| CN101289276A (en) * | 2008-06-19 | 2008-10-22 | 成都光明光电股份有限公司 | High-refraction and high- dispersion optical glass and method of manufacture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485252A (en) * | 2018-06-19 | 2019-03-19 | 原思平 | Color additive, application and the functional glass of the functional glass of a kind of high visible light and absorption near infrared ray |
| CN109485252B (en) * | 2018-06-19 | 2021-09-28 | 原思平 | Coloring additive for functional glass with high visible light transmittance and near infrared ray absorption, application and functional glass |
| CN113307472A (en) * | 2021-05-26 | 2021-08-27 | 苏州融睿电子科技有限公司 | Glass-containing packaging device and packaging method and application thereof |
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Application publication date: 20101013 |