CN102557431A

CN102557431A - Optical glass, glass gob for press molding, glass molding, optical element and method for producing them

Info

Publication number: CN102557431A
Application number: CN201210005847XA
Authority: CN
Inventors: 下西司; 田岛英身
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2005-09-21
Filing date: 2006-09-21
Publication date: 2012-07-11
Also published as: CN1935716A; JP4446982B2; CN1935716B; JP2007112697A

Abstract

To provide an optical glass having a high refractive index capable of responding to the miniaturization and improved performance of an optical instrument and allowing the correction of color balance. An optical glass has TiO2 borate system as the glass component. The transmissivity property of the optical glass satisfies the following formula (1) when the length of wave with a thickness of 10.0mm and a transmissivity of 70% is set as lambda 70nm by controlling the type and quantity of the additives or conducting thermal treatment.

Description

Opticglass, glass cup for die pressing, glass shaping body, optical element and method of manufacture thereof

The application is female case dividing an application for following application:

The applying date: on September 21st, 2006

Application number: 200610139840.1

Denomination of invention: opticglass, glass cup for die pressing, glass shaping body, optical element and method of manufacture thereof.

Technical field

The glass cup for die pressing (glass gob), glass shaping body, optical element and the method for manufacture thereof that the present invention relates to have the high refractive index of miniaturized and high performance that can adaptive optics equipment and can carry out the gauged opticglass of colour balance, form by this glass.

Background technology

Be accompanied by the miniaturized and the high performance of opticinstrument, require the higher glass material of specific refractory power.In the past,, use the glass that contains the lead of high density in the glass ingredient as patent documentation 1 record in order to realize the glass of high refractive index.

But the glass of lead that contains high density so need the influence of consideration to environment, should be controlled its use because plumbous poisonous.As the composition that improves specific refractory power, can substitute the TiO that has of PbO ₂In order to realize specific refractory power more than or equal to 2.0 superelevation refractive index glass, usually, with B ₂O ₃Or with B ₂O ₃And SiO ₂Import a lot of TiO in the composition system as main glass network formation composition ₂

But in the time of near refractive index n d brings up to 2, the spectral transmission of short wavelength's end moves to long wavelength side significantly, if such glass is used in image pickup optical system, then exists and is difficult to carry out the colour balance calibration problem.

[patent documentation 1] spy opens clear 63-274638 communique.

Summary of the invention

In view of the foregoing, the object of the present invention is to provide a kind of have can adaptive optics high refractive index and glass cup for die pressing, glass shaping body, optical element and the method for manufacture thereof that can carry out the gauged opticglass of colour balance, form by this glass of miniaturized and high performance of instrument.

In order to achieve the above object, the present inventor is through exploratory development repeatedly, and the result finds: a kind of TiO that comprises as glass ingredient ₂With Sb as additive ₂O ₃Or As ₂O ₃Borate opticglass or comprise TiO as glass ingredient ₂Borate opticglass, wherein have the opticglass that transsmissivity and specific refractory power satisfy the transmission characteristics of particular kind of relationship and have high refractive index, can carry out colour balance and proofread and correct, and this opticglass can utilize specific method manufacturing.

Find in addition, through using above-mentioned opticglass, thereby can obtain glass cup for die pressing, glass shaping body and optical element.

In borate opticglass, play the B that has that glass network forms the composition effect ₂O ₃Comprising SiO ₂, GeO ₂Situation under, make these compositions play network and be formed into branch.In this composition system, to form the content of composition few and improve the TiO of specific refractory power when above-mentioned network ₂Content for a long time, the Ti of 4 valencys can be used for remedying the deficiency of B, Si, Ge, plays and network forms the equal effect of composition.

The substruction of such glass with include B ₂O _3,SiO ₂And GeO ₂The a lot of TiO of total content ₂Glass different.That is, at B ₂O _3,SiO ₂And GeO ₂The few and TiO of total content ₂The more composition of content in, for a certain reason, Ti ionic lighting function, be that the photoabsorption function of the short wavelength side of visible region improves greatly, glass coloring clearly.In contrast, even at TiO ₂The many but B of content ₂O ₃, SiO ₂And GeO ₂The also more composition of total content in, above-mentioned this type glass is difficult to produce significantly painted.

And then, form less, the TiO of composition at network ₂In the more glass of content, if add the Sb of minute quantity ₂O ₃Or As ₂O ₃Additive is then for reducing painted having a significant effect.This is because the structure of above-mentioned glass causes, is the phenomenon that other glass can't see.Have again, though have Sb ₂O ₃Or As ₂O ₃Situation as finings uses still, compares with the content that can obtain clarifying effect, and the addition that can obtain above-mentioned effect is few.

The present inventor is forming few, the TiO of composition to network ₂The glass that content is many carries out after the detailed analysis, know after on the index of the λ 70 that states, above-mentioned glass painted has certain limit.And, through Sb in the interpolation minute quantity ₂O ₃Or As ₂O ₃The time control addition according to These parameters, realized painted few glass thereby break above-mentioned boundary first.

The present invention accomplishes of the present invention according to this opinion.

That is, the present invention provides:

(1) a kind of opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, it is characterized in that:, have and satisfy following relational expression (1) when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm

Transmission characteristics.

(2) opticglass (to call opticglass I in the following text) of above-mentioned (1) record is if represent B with the percentage ratio of quality ₂O ₃And SiO ₂Total content smaller or equal to 20%, GeO ₂Content be 0～10%, TiO ₂Content more than or equal to 20%, simultaneously, comprise Sb as additive ₂O ₃And/or As ₂O ₃, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, the amount of above-mentioned additive is controlled in the scope that can show the transmission characteristics that satisfies relational expression (1).

(3) opticglass of above-mentioned (2) record does not contain As ₂O ₃, with Sb ₂O ₃Addition be controlled in the scope of 0.004～0.09 quality %.

(4) above-mentioned (2) or the opticglass of (3) record, comprise the above BaO of 5 quality % or 5 quality %.

(5) opticglass of any one record in above-mentioned (2)～(4) if represent with the percentage ratio of quality, comprises 1～20% B ₂O ₃, 0～18% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂

(6) opticglass (to call opticglass II in the following text) of above-mentioned (1) record comprises the Sb as additive ₂O ₃, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have the transmission characteristics that satisfies following relational expression (1).

(7) opticglass of above-mentioned (6) record, Sb ₂O ₃Addition be 0.004～0.09 quality %.

(8) above-mentioned (6) or the opticglass of (7) record, comprise the above TiO of 20 quality % or 20 quality % ₂

(9) opticglass of any one record in above-mentioned (6)～(8) comprises the above BaO of 5 quality % or 5 quality %.

(10) opticglass of any one record in above-mentioned (6)～(9) if represent with the percentage ratio of quality, comprises 1～45% B ₂O ₃, 0～30% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂

(11) opticglass of any one record in above-mentioned (5)～(10) as any composition, if represent with the percentage ratio of quality, comprises 0～20% Gd ₂O ₃, 0～15% Y ₂O ₃, 0～15% Yb ₂O ₃, 0～18% Ta ₂O ₅, 0～20% Bi ₂O ₃, 0～10% Ga ₂O ₃, 0～10% GeO ₂, total content is 0～10% MgO, CaO and SrO, 0～15% ZnO, 0～10% Al ₂O ₃, total content is 0～5% Li ₂O, Na ₂O and K ₂O.

(12) opticglass of any one record in above-mentioned (1)～(11), refractive index n d is more than or equal to 2.00.

(13) opticglass of any one record in above-mentioned (1)～(12) comprises the above TiO of 22 quality % or 22 quality % ₂

(14) opticglass of any one record in above-mentioned (1)～(13), the concentration of Pt is smaller or equal to 30ppm.

(15) opticglass of any one record in above-mentioned (1)～(14) illustrates the viscosity smaller or equal to 4dPas under liquidus temperature.

(16) opticglass of any one record in above-mentioned (1)～(15) is used for reheat and is shaped.

(17) opticglass (to call opticglass III in the following text) of above-mentioned (1) record; Refractive index n d is more than or equal to 2.01; And, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have the transmission characteristics that satisfies following relational expression (1).

(18) opticglass of above-mentioned (17) record does not contain Sb in fact ₂O ₃And As ₂O ₃

(19) above-mentioned (17) or the opticglass of (18) record, if represent B with the percentage ratio of quality ₂O ₃And SiO ₂Total content smaller or equal to 20%, TiO ₂More than or equal to 20%.

(20) a kind of glass shaping body is characterized in that: the opticglass by any one record in above-mentioned (1)～(19) forms, and is made up of the glass shaping body that has the solid bar of certain external diameter along axle.

(21) a kind of glass cup for die pressing is characterized in that: the opticglass by any one record in above-mentioned (1)～(19) forms.

(22) a kind of optical element is characterized in that: the opticglass by any one record in above-mentioned (1)～(19) forms.

(23) a kind of method of manufacture of opticglass (to call method of manufacture I in the following text), this opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, it is characterized in that, comprise following operation:

If represent, can obtain B with the percentage ratio of quality ₂O ₃And SiO ₂Total content smaller or equal to 20%, GeO ₂Content be 0～10%, TiO ₂Content more than or equal to 20% glass, in the blending raw material, add Sb as additive ₂O ₃And/or As ₂O ₃,

Control the amount of above-mentioned additive,, can be met following relational expression (1) when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm

Transmission characteristics, and above-mentioned raw materials heated make its fusion.

(24) method of manufacture of the opticglass of above-mentioned (23) record is not added As ₂O ₃, with Sb ₂O ₃Addition be controlled in the scope of 0.004～0.09 quality %.

(25) above-mentioned (23) or the method for manufacture of opticglass of (24) record, wherein concoct raw material, the content that makes BaO is more than or equal to 5 quality %.

(26) method of manufacture of the opticglass of any one record in above-mentioned (23)～(25) if represent with the percentage ratio of quality, through concocting raw material, can obtain comprising 1～20% B ₂O ₃, 0～18% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂Glass.

(27) a kind of method of manufacture of opticglass (to call method of manufacture II in the following text), this opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have and satisfy following relational expression (1)

Transmission characteristics,

In the process that makes the melten glass cooling forming, it is kept near the oxidizing gas of the temperature the tansition temperatures that is equivalent to above-mentioned glass, then this glass is cooled off.

(28) a kind of method of manufacture of opticglass (to call method of manufacture II in the following text), this opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have and satisfy following relational expression (1)

Transmission characteristics,

To comprise TiO ₂Borate glass be kept near the oxidizing gas of temperature the tansition temperatures that is equivalent to above-mentioned glass, after thermal treatment, cool off.

(29) method of manufacture of the solid bar-shaped glass shaping body of above-mentioned (20) record; It is characterized in that: use mold with communicating pores; Melten glass is continuously flowed into from the inlet of above-mentioned communicating pores, make to be full of glass in the communicating pores, and take out from the outlet of above-mentioned communicating pores continuously.

(30) a kind of method of manufacture of glass shaping body; It is characterized in that: use mold with communicating pores; Will be in above-mentioned (23)～(26) the resulting melten glass of fusion operation of the method for any one record continuously flow into from the inlet of above-mentioned communicating pores; Make to be full of glass in the communicating pores, and take out from the outlet of above-mentioned communicating pores continuously, obtain having the solid bar-shaped glass shaping body of certain external diameter along axle.

(31) a kind of method of manufacture of glass cup for die pressing; It is characterized in that: have following operation: cut off utilize above-mentioned (29) or glass shaping body of making of the method for manufacture of (30) record so that the axle of the above-mentioned glass shaping body of crosscut, and making sheet glass.

(32) a kind of method of manufacture of optical element; It is characterized in that: have following operation: the glass cup for die pressing of above-mentioned (21) record or the glass cup for die pressing that utilizes above-mentioned (31) the method for manufacture of putting down in writing to make are heated, make its die forming.

(33) a kind of method of manufacture of optical element is characterized in that: have the glass shaping body that the opticglass by any one record in above-mentioned (1)～(19) is formed or utilize above-mentioned (29) or the glass shaping body made of the method for manufacture of (30) record operation of processing.

(34) a kind of method of manufacture of optical element; It is characterized in that: supply in the model forming module after having the melten glass of making outflow; And in above-mentioned shaping dies with the operation of glass die forming, and produce the optical element that the opticglass by any one record in above-mentioned (1)～(19) forms.

If according to the present invention, comprising TiO ₂Borate opticglass in, kind and the amount through the control additive or heat-treat, thus although can provide the very high painted few opticglass of specific refractory power to reach the optical element that forms by this opticglass.

Specifically, can provide Sb ₂O ₃And/or As ₂O ₃As the opticglass I of necessary additive, specific refractory power more than or equal to 1.95 and with Sb ₂O ₃As the opticglass II of necessary additive and the optical element that forms by this opticglass I and II respectively.Above-mentioned opticglass I and II contain an amount of Sb as necessary additive ₂O ₃And/or As ₂O ₃So, even glass is heated, make it softening, or in non-oxidized gas, heat, make it softening glass through burning combustible gas, can prevent the painted of chilled glass.Like this; When glass is carried out pyroprocessing; According to environmental gas is oxidizing gas or reducing gas; Glass painted has very big difference, so, can carry out stable batch process to perspectives such as the certain glass shaping body of transmission characteristics, glass cup for die pressing and optical elements.

In addition, although can provide a kind of specific refractory power high, be specific refractory power more than or equal to the painted less opticglass III of the glass of 2.01 superelevation specific refractory power, and the optical element that forms by this opticglass III.And then, if according to not containing Sb in fact ₂O ₃Form, can realize that painted ratio contains Sb ₂O ₃Glass glass still less.

Molding of the present invention is the solid bar that has certain external diameter along axle, so through carrying out the slice processing of the above-mentioned axle of crosscut, can produce the sheet glass of definite shape, certain volume expeditiously.And then; The surface-area of glass shaping body is increased with respect to its volume; And glass is Homogeneouslly-radiating from the side, so be lower than the inner at least high-quality glass shaping body that does not have the devitrification position of the simple glass that is not high refractive index although can produce stability.

If according to glass cup for die pressing of the present invention, a kind of mold pressing starting material can be provided, these mold pressing starting material are used for making the die-formed product that forms by at the painted less glass of high this index region.

If according to optical element of the present invention, can provide to be used for making the optical element that forms by high index ellipsoid and painted less glass.

If method of manufacture I, II, III according to opticglass of the present invention can produce high refractive index and painted less opticglass.

If method of manufacture according to glass shaping body of the present invention; Although the viscosity pole in the time of can producing stability and be lower than the simple glass that is not high refractive index and melten glass and be shaped is low, the inner at least high-quality glass shaping body that does not have devitrification position or brush line.

And, cut off the glass shaping body of making by aforesaid method with the mode of crosscut axle and make sheet glass, through the manufacturing procedure of any increase, can produce high-quality glass cup for die pressing effectively to above-mentioned sheet glass.

If according to the method for manufacture of optical element of the present invention, the method for the optical element that a kind of manufacturing is high by specific refractory power, painted less opticglass forms can be provided.

If according to above-mentioned each optical element, d is high because of refractive index n, more than or equal to 1.95 or more than or equal to 2.01, so can reduce the component counts such as lens that constitute optical system, perhaps makes the lens miniaturized, so can make the optical system miniaturized.In addition, although be that the glass of superelevation specific refractory power is painted less, can correcting color equilibrated optical system so can provide.

Description of drawings

Fig. 1 is the explanatory view of a form of the manufacturing installation that uses in the method for manufacture of glass shaping body of the present invention.

Fig. 2 is the explanatory view of another form of the manufacturing installation that uses of the method for manufacture of glass shaping body of the present invention.

Fig. 3 is the explanatory view of form of the cut-off method of glass shaping body in the method for manufacture of expression glass shaping body of the present invention.

Fig. 4 is the explanatory view of form of the cut-off method of glass shaping body in the method for manufacture of expression glass shaping body of the present invention.

Fig. 5 is the explanatory view of form of the cut-off method of glass shaping body in the method for manufacture of expression glass shaping body of the present invention.

Fig. 6 is the explanatory view of the side pressure process of chopping.

Fig. 7 is the explanatory view of the side pressure process of chopping.

Fig. 8 is the graphic representation of relation of specific refractory power (nd) and λ 70 of the opticglass of expression embodiment 1 and comparative example 1.

Embodiment

Opticglass of the present invention is to have the TiO that comprises as glass ingredient ₂The opticglass of borate-based composition, it is characterized in that:, have and satisfy following relational expression (1) when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm

Transmission characteristics.

As previously mentioned, realize the for example superelevation specific refractory power more than 1.95 or 1.95, do not use the glass of high density lead content, and import TiO in order to make refractive index n d ₂But, when in phosphate-based composition, importing a large amount of TiO ₂Make specific refractory power (nd) reach 1.95 or 1.95 when above, short wavelength's end of spectral transmission moves to long wavelength side significantly, and glass coloring is obvious.Therefore, in opticglass of the present invention, as basal component do not use phosphate glass and with borate-based composition as its basal component.Here, borate-based composition is the B that comprises as glass ingredient ₂O ₃Composition.Specific refractory power (nd) for example more than or equal to 1.95 high-index regions in, the content of high refractive index composition increases, so, B sometimes ₂O ₃The content of quality want little to several percentage points.Under these circumstances, in borate-based composition, if represent with the percentage ratio of quality, B then ₂O ₃Content compare P ₂O ₅Content (comprise and do not contain P ₂O ₅Situation) height.In addition, in preferred form, if represent quality with percentage ratio, B then ₂O ₃Content compare SiO ₂Content also high.

The quantitative Treatment of glass coloring is following.Used thickness is the sheet glass test portion behind the optical grinding of 10.0mm two sides; If establishing the light intensity of a face vertical incidence in the face behind above-mentioned optical grinding is Iin; The light intensity that face behind another optical grinding penetrates is Iout, and then defining Iout/Iin is the outside transsmissivity that is equivalent to thickness 10.0mm.That is, from Iin to Iout, except the internal losses of glass test portion, also comprise the caused loss of reflection on test portion surface.In wavelength was the wavelength zone of 280nm～700nm, the outside transsmissivity that will be equivalent to thickness 10.0mm was that 70% wavelength (nm unit) is made as λ 70.The wavelength of λ 70 is long more, and glass coloring increases more, and the wavelength of λ 70 is short more, and glass coloring reduces more.

Borate glass is painted less as above-mentioned, still, if increase TiO ₂Content, specific refractory power (nd) is for example reached more than 1.95 or 1.95, then λ 70 moves to long wavelength's direction, painted increase.And, contain TiO ₂Borate glass have certain inherent character, that is, use for the value Billy of the λ 70 of specific refractory power (nd) when representing of regulation with nm

The value of obtaining is big, and this value also is the boundary of λ 70.

In the present invention, utilize the kind of additive or amount is controlled or thermal treatment, break above-mentioned boundary, although provide a kind of specific refractory power high painted few opticglass.

Below, the 3 kinds of forms of opticglass I, II, III in the opticglass of the invention described above are shown.

[opticglass I and II]

Opticglass I has the TiO that comprises as glass ingredient ₂The opticglass of borate-based composition, if represent B with the percentage ratio of quality ₂O ₃And SiO ₂Total content below 20% or 20%, GeO ₂Content be 0～10%, TiO ₂Content more than 20% or 20%, comprise Sb as additive ₂O ₃(or) As ₂O ₃, control above-mentioned content of additive, making this opticglass is 70% wavelength during as λ 70nm in the outside transsmissivity that is 10.0mm with thickness, has the transmission characteristics that satisfies above-mentioned relation formula (1).

On the other hand, opticglass II has the TiO that comprises as glass ingredient ₂The opticglass of borate-based composition, comprise Sb as additive ₂O ₃, specific refractory power is more than or equal to 1.95, more preferably greater than equaling 2.00, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have the transmission characteristics that satisfies above-mentioned relation formula (1).

The essentially consist of above-mentioned opticglass I is a borate, B ₂O ₃And SiO ₂Total content smaller or equal to 20 quality %, GeO ₂Content be 0～10 quality %, TiO ₂Content be 20 quality %, as must additive adding Sb ₂O ₃(or) As ₂O ₃This addition is the amount of the transmission characteristics that can obtain being represented by above-mentioned (1) formula.Have, the specific refractory power of opticglass I (nd) is more preferably greater than equaling 1.95, if better more than or equal to 2.00 again.

Consider that from the environmental health aspect opticglass I of the present invention does not preferably add As ₂O ₃, and add Sb ₂O ₃

Opticglass II is the same with opticglass I, and its essentially consist is a borate, in above-mentioned composition, makes Sb ₂O ₃The content optimizing.In opticglass II, Sb ₂O ₃Be must additive, its addition be the amount of the transmission characteristics that can obtain being represented by above-mentioned (1) formula.

Opticglass I and opticglass II are as aforementioned, in order to realize satisfying the necessary Sb of glass of (1) formula ₂O ₃Addition be atomic little amount, so, through being that purpose is managed, thereby can make Sb to obtain above-mentioned transmission characteristics ₂O ₃The addition optimizing.

As the transmission characteristics index λ 5 arranged together with λ 70.λ 5 is that the outside transsmissivity of thickness 10.0mm is 5% wavelength (nm unit).In being equivalent to the glass that thickness is 10.0mm, the light of λ 5 or λ 5 following wavelength almost is blocked, so, come the regulation transmission characteristics very important by λ 5.The optimal morphology of opticglass I, II is the glass with transmission characteristics of (1-a) formula below satisfying, that is, be to have added Sb ₂O ₃Be met the glass of the transmission characteristics of (1-a) formula.

If according to above-mentioned optimal morphology; Send semiconductor camera elements such as CCD or MOS type transmitter to with can the graphicinformation from the visibility region of the body that is taken being had no shortcoming; In case of necessity; The output data of above-mentioned imaging apparatus is carried out look proofread and correct, thus, can verily have been reproduced the view data of color etc.

Have, the optimal morphology of opticglass I, II is the glass with transmission characteristics of (1-b) formula below satisfying again, and then is the glass with transmission characteristics of (1-c) formula below satisfying.

In opticglass I and II, Sb ₂O ₃Addition can determine as above-mentioned that still, its upper limit generally is 0.09 quality %.As the Sb that adds ₂O ₃Surpass above-mentioned going up in limited time, λ 70 moves to long wavelength side, and the tendency of glass coloring is strengthened.On the other hand, expectation Sb ₂O ₃The lower limit of addition generally be 0.004 quality %.As the Sb that adds ₂O ₃Do not satisfy above-mentioned following prescribing a time limit, be difficult to realize desirable transmission characteristics, in addition, be difficult to make the Sb of trace ₂O ₃Be evenly distributed in the whole glass.In addition, suitably add Sb ₂O ₃As after state, have the effect of minimizing from the platinum mixed volume of platinum melt container.

When pressing borate and form the glass of the high-quality high refractive index of dissolving, when using quartz crucible to carry out the thick fusion of frit, crucible is by etch, SiO ₂Dissolve in the glass, specific refractory power drops under the desirable value, and simultaneously, glass coloring is obvious.Because such reason should avoid the use of quartz crucible, do not use quartz crucible when fusing high-quality glass, and use platinum crucible.

The present inventor attempts using platinum crucible to fuse, and reduces specific refractory power (nd) more than 1.95 or 1.95 and contain TiO ₂Borate glass painted, obtain following knowledge from experimental chemistry.

Specific refractory power (nd) contains a large amount of TiO more than or equal to 1.95 glass of high refractive index, particularly specific refractory power (nd) more than or equal to 2.0 superelevation refractive index glass ₂Deng composition with high refractive index, so, as the B of network formation composition ₂O ₃Content reduce relatively.Can become the SiO that network forms composition with comprising ₂Situation the same.When network forms the amount minimizing of composition, the stability decreases of glass, the devitrification temperature zone high temperatureization of high-temperature zone, the result, in order to prevent devitrification, the whipping temp of melten glass or outflow temperature all uprise, and the viscosity of melten glass becomes extremely low value.And, be difficult to become the high-quality glass of no devitrification or brush line from melten glass, be difficult to produce painted few glass, still, even because of melten glass in the clarification operation also shows lower viscosity, so also can be with the elimination bubble even do not add finings.

Sb as everybody knows ₂O ₃Be to have the finings that goes the bubble effect very by force, still,, the addition of 0.1 quality % must be arranged at least in order to obtain defoaming effect.But, if as finings to containing TiO ₂The superelevation refractive index glass add Sb more than or equal to 0.1 quality % ₂O ₃, then different with existing glass, λ 70 long wavelengthizations, glass coloring grow.

Even opticglass I, II there is no need to add the Sb that glass coloring is strengthened because be not add finings also can fully remove the glass that steeps so the present inventor thinks fully ₂O ₃In addition, because of Sb ₂O ₃Show very strong oxidisability, so have the danger that occurs the platinum foreign matter in etch platinum crucible, the glass or make glass coloring because of fusing into of platinum.

But the present inventor finds as if the addition ratio Sb ₂O ₃Amount as finings uses also will be lacked, and following new phenomenon then can occur and obtains and above-mentioned expection reverse effect.

As the Sb that adds minute quantity ₂O ₃The time, glass coloring is than not adding Sb ₂O ₃The time a little less than, that is, the short wavelength of spectral transmission end moves to short wavelength side.But, if increase Sb ₂O ₃, then above-mentioned short wavelength's end moves painted enhancing to long wavelength side.That is, reducing aspect glass painted Sb ₂O ₃Addition have optimum value.

When the Pt concentration in the analysis glass, the unexpected interpolation Sb that finds ₂O ₃Than not adding Sb ₂O ₃The time Pt concentration low, painted dying down.

Know by above, in the scope that is less than the amount of using as finings far away, add Sb ₂O ₃The time, the painted mechanism of certain in the glass dies down, and simultaneously, can suppress Pt stripping from platinum crucible, and glass coloring is reduced, still, if Sb ₂O ₃When surpassing painted few amount, then painted increase.

Opticglass I, II obtain according to such principle.

As previously mentioned, Sb ₂O ₃Optimum addition few.Therefore, be difficult in uniform distribution in the whole frit.And, if with Sb ₂O ₃Addition be set within the limit tolerable limit, probably the transsmissivity of the glass that comes out of fusion can be at Sb ₂O ₃The significant variation taken place between raw material part that distributes more and the raw material part that distributes less.For fear of such thing takes place, as regulation Sb ₂O ₃Addition following in limited time, its optimum range is 0.004 quality % or more than the 0.004 quality %.Therefore, Sb ₂O ₃The optimum range of addition be 0.004～0.09 quality %, optimal scope is 0.01～0.05 quality %.

As previously mentioned, the concentration of the Pt in the glass and Sb ₂O ₃Addition relevant, so, in opticglass I, II, can utilize the Pt concentration in the glass to come to Sb ₂O ₃Minimum addition carry out indirect control.With Sb ₂O ₃The concentration of the suitable Pt of minimum addition be 30ppm going under the dissolution conditions that steeps, if begin to increase Sb from minimum addition ₂O ₃Though, the Pt density loss,, preferably note not making Sb ₂O ₃Addition surpass 0.09 quality %.

In opticglass I, II, best Pt concentration is at 30ppm or below the 30ppm, and is better in 20ppm or the scope below the 20ppm.Though for the not restriction of the lower limit of ppm concentration,, as previously mentioned, if reduce concentration and the superfluous Sb of interpolation of Pt ₂O ₃, then glass coloring worsens, so should be noted that.

In opticglass I, II, almost can not expect the Sb that adds ₂O ₃Play finings.But, have under the liquidus temperature viscosity (to call liquid phase viscosity in the following text) smaller or equal to the opticglass I of the characteristic of 4dPas, II because of viscosity low and go to steep effective, so can realize not containing the high-quality less colored glass of bubble.From removing the foam method face, the scope of best liquid phase viscosity is smaller or equal to 4dPas, generally is 3dPas or 3dPas, and then, then better smaller or equal to the scope of 1.5dPas.

Among opticglass I, the II because of adding Sb ₂O ₃And the painted reduction effect that produces is at TiO ₂Content during more than or equal to 20 quality % clearly.Therefore, opticglass I is the TiO that comprises more than or equal to 20 quality % ₂Glass, comprise TiO more than or equal to 22 quality % ₂Glass better, comprise TiO more than or equal to 25 quality % ₂Glass the most desirable.Opticglass II generally is the TiO that comprises more than or equal to 20 quality % ₂Glass, comprise TiO more than or equal to 22 quality % ₂Glass better, comprise TiO more than or equal to 25 quality % ₂Glass the most desirable.TiO ₂The upper limit of content after the stability of considering glass etc., determine again.Its upper limit can be a target with 40 quality %.

Glass go to steep as previously mentioned such clarification the time the influence of viscosity, still, also how much receive the influence of the gaseous constituent content such as carbonic acid gas or nitrogen oxide in the glass.When the content of these gaseous constituents after a little while, go to steep the tendency that deterioration is arranged.When the content of gaseous constituent for a long time, go to steep the tendency that improvement is arranged.And the above-mentioned gas composition is to import glass as the raw material of carbonate or nitrate salt.

In the high glass of the specific refractory power as opticglass I, II, nearly all glass ingredient all imports as oxide compound.As the composition that imports with the compound outside the oxide compound, the B that forms composition as network is arranged ₂O ₃(can import), alkali metal component and earth alkali metal composition by the boric acid raw material, but a little less than the effect of alkali metal component to the raising specific refractory power, in addition, damage the stability of glass easily, so, should not use in a large number.In the earth alkali metal composition, that do not reduce that specific refractory power can import gaseous constituent again is BaO.Therefore, in opticglass I, II, preferably comprise BaO as glass ingredient.The content of BaO is generally more than or equal to 5 quality %, and is better more than or equal to 7 quality %, and then more than or equal to 8 quality %, it would be desirable more than or equal to 10 quality %.Through importing BaO like this, even Sb ₂O ₃The few glass of content, also can fully go the bubble, can obtain high-quality opticglass.As the raw material that is used for importing BaO, generally be barium carbonate, nitrate of baryta and barium metaphosphate.

Secondly, the composition of opticglass I is described.

[opticglass I]

Opticglass I is B if represent with the percentage ratio of quality ₂O ₃And SiO ₂Total content smaller or equal to 20%, GeO ₂Content 0～10%, TiO ₂Content more than or equal to 20% glass, as optimal morphology, have to comprise 1～20% B ₂O ₃, 0～18% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂Glass.

Have again, below, single represent the content of glass ingredient, only otherwise specify that it representes ' quality % ' with ' % '.

In opticglass I, B ₂O ₃And SiO ₂Play network and be formed into branch.

B ₂O ₃Be the very resultful composition of temperature reduction, preferably import more than 1% or 1% meltbility and mobile viscosity.But, if surpass 20% tendency that specific refractory power descends again.Therefore, B ₂O ₃Content generally in 1～20% scope, 1～15% scope is better, and then 2～10% scope is better, optimal scope is 3～8%.

SiO ₂Produce effect to keeping anti-increased devitrification resistance,, the tendency that the meltbility of making worsens, specific refractory power reduces is arranged if surpass 18%.Therefore, SiO ₂The ideal range of content is that 0～18%, 0～10% scope is better, and further comparatively ideal scope is 1～8%, and optimal scope is 2～6%.

B ₂O ₃And SiO ₂Total content be below 20% or 20% from the viewpoint of the glass that obtains high refractive index, generally be 1～20%, 1～15% better, 3～10% is the most desirable.

Have again,, preferably make B from keeping the viewpoint of meltbility and anti-increased devitrification resistance ₂O ₃Content compare SiO ₂High.

La ₂O ₃Obtaining high refractive index, hanging down dispersive on glass is very important composition.If its content is less than 10% and is difficult to realize desirable specific refractory power, may worsen if surpass 50% anti-increased devitrification resistance.Therefore, La ₂O ₃The scope of content generally is 10～15%, 18～47% better, and further comparatively ideal scope is 20～47%, and 26～38% is better, and 27～36% is the most desirable.

TiO ₂Be that the glass of low concentration lead content or lead-free glass are improved the composition that its specific refractory power plays an important role, and play the effect that improves chemical durability, anti-increased devitrification resistance.As previously mentioned, from realizing the viewpoint of refractive index n d, though TiO more than or equal to 1.95 glass ₂Content more than or equal to 20%, but if import volume surpasses 40%, then anti-increased devitrification resistance has the tendency of decline.Therefore, TiO ₂The scope of content generally is 20～40%, 20～38% better, and better scope is 20～36%, and 22～35% is the most desirable.

Nb ₂O ₅Be the composition of glass being given high refractive index, an amount of importing can improve anti-increased devitrification resistance.But, the enhanced tendency is arranged if surpass 30% glass coloring.Therefore, Nb ₂O ₅The scope of content generally is 0～30%, and better scope is 1～30%, and 1～20% is better, and further better scope is 1～15%, and in addition, comparatively ideal scope is 5～15%, and 6～13% is better, and 6～12% is desirable especially.

BaO imports gaseous constituent to play in the glass to improve to remove the composition of bubble effect, is in such composition, to work the composition that improves the specific refractory power effect.In addition, suitable importing can reduce the painted of glass.But if surpass 35%, then anti-increased devitrification resistance has the tendency of deterioration.Therefore, the ideal range of BaO content generally is 5～35%, 5～30% better, and further comparatively ideal scope is 5～25%, and 7～17% is better, and 8～15% is further better, and 10～15% is desirable especially.

WO ₃Play the anti-increased devitrification resistance of improvement through a small amount of importing, still, too much importing meeting reinforced glass is painted.WO ₃The scope of content generally is that 0～7%, 0～3% scope is better.When in above-mentioned scope, paying the utmost attention to the bubble that reduces in the glass, preferably do not import WO ₃, when in above-mentioned scope, paying the utmost attention to the keeping of anti-increased devitrification resistance, WO ₃Import volume preferably surpass 0%, more than or equal to 0.1% better, further better more than or equal to 0.5%.

ZrO ₂Be the composition that makes glass have high refractive index, also play the effect that improves anti-increased devitrification resistance.But, if surpassing 15% anti-increased devitrification resistance, import volume descends, meltbility also has a declining tendency.Therefore, ZrO ₂The ideal range of content generally is 0～15%, 1～10% better, and further comparatively ideal scope is 2～10%, and 4～8% is better, and in addition, 5～7.5% is more satisfactory, and further 5.5～7.5% is better.

In above-mentioned optimal morphology, B ₂O ₃, SiO ₂, La ₂O ₃, TiO ₂, Nb ₂O ₅, BaO, WO ₃, ZrO ₂And Sb ₂O ₃Total content to surpass 95% glass relatively good, it is better to surpass 98% glass, it is further better to surpass 99% glass, 100% glass is desirable especially.

The glass of above-mentioned optimal morphology as any composition, if represent with the percentage ratio of quality, can comprise 0～20% Gd ₂O ₃, 0～15% Y ₂O ₃, 0～15% Yb ₂O ₃, 0～18% Ta ₂O ₅, 0～20% Bi ₂O ₃, 0～10% Ga ₂O ₃, 0～10% GeO ₂, total content is 0～10% MgO, CaO and SrO, 0～15% ZnO, 0～10% Al ₂O ₃, total content is 0～5% Li ₂O, Na ₂O and K ₂O.

Gd ₂O ₃With La ₂O ₃Displacement can import 20% at most, if surpass the trend that 20% anti-increased devitrification resistance has deterioration.Therefore, Gd ₂O ₃The scope of content generally is 0～20%, 0～15% better, and 1～10% is further better, and 0～5% is the most desirable.

Y ₂O ₃And La ₂O ₃Equally work to improve specific refractory power, but when import volume surpassed 15%, anti-increased devitrification resistance there was the trend of deterioration.Therefore, Y ₂O ₃The ideal range of content generally is 0～15%, 0～5% better, and further comparatively ideal scope is 0～3%, and is better less than 2% more than or equal to 0%, and 0～1.5% is the most desirable.

Yb ₂O ₃And La ₂O ₃Equally work to improve specific refractory power, but when import volume surpassed 15%, anti-increased devitrification resistance there was the trend of deterioration.Therefore, Yb ₂O ₃The ideal range of content generally is 0～15%, 0～10% better, and further comparatively ideal scope is 0～5%, and 0～4% is better, and in addition, 0～3% is better.

Ta ₂O ₅Play a part to make glass to have high refractive index, but when import volume surpassed 18%, meltbility had a declining tendency with low dispersed.Therefore, Ta ₂O ₅The more satisfactory scope of content generally is 0～18%, 0～10% better, and further comparatively ideal scope is 0～5%, and 0～3% is better, and 0～1% is better.Never use the viewpoint of valuable raw material, preferably do not import Ta ₂O ₅

Bi ₂O ₃The effect of the tansition temperatures reduction that makes glass is played in a small amount of importing, but when import volume surpasses 20%, the trend that makes anti-increased devitrification resistance decline, painted reinforcement is arranged.Therefore, Bi ₂O ₃The ideal range of content generally is 0～20%, 0～10% better, and further comparatively ideal scope is 0～5%, and 0～3% is better, and in addition, 0～1% is better.Have again, when paying the utmost attention to painted can decline, preferably do not import Bi ₂O ₃

Ga ₂O ₃Though can import 10% at most, yet be more valuable composition, and when excessive importing, the anxiety that makes anti-increased devitrification resistance decline arranged.Therefore, Ga ₂O ₃The scope of content preferably 0～10%.Better scope is 0～5%, and further comparatively ideal scope is 0～3%, and 0～1% is better.If never use the viewpoint of valuable raw material to set out, preferably do not import Ga ₂O ₃

GeO ₂Rise and SiO ₂Same effect is being compared SiO aspect the effect that improves specific refractory power ₂Also strong.But raw material is valuable, and when import volume surpasses 10%, the anxiety that makes anti-increased devitrification resistance decline is arranged.Therefore, GeO ₂The ideal range of content generally is 0～10%, 0～5% better, and further comparatively ideal scope is 0～3%, and 0～1% is better.If never use the viewpoint of valuable raw material to set out, preferably do not import GeO ₂

MgO, CaO and SrO are any compositions of replaceable BaO, if total content surpasses the anxiety that 10% specific refractory power has decline.Therefore, the ideal range of the total content of MgO, CaO and SrO generally is 0～10%, 0～5% better, and further comparatively ideal scope is 0～2%, and 0～1% is the most desirable.Have again, when paying the utmost attention to the raising specific refractory power, preferably do not import MgO, CaO and SrO.

ZnO makes glass have the composition of high refractive index dispersing characteristic effect, is again to have the composition that improves anti-increased devitrification resistance, reduces the temperature effect of VISCOUS FLOW.But, but when import volume surpassed 15%, anti-increased devitrification resistance had a declining tendency.Therefore, the ideal range of ZnO content generally is 0～15%, 0～12% better, and further comparatively ideal scope is 0～7%, and 0～5% is better, and 0～3% is the most desirable.Precipitous when the positive rise of the short wavelength end that in above-mentioned scope, makes spectral transmission, and preferentially make λ 70 and λ 5 near the time, when perhaps paying the utmost attention to the glass tansition temperatures and descending, preferably import and surpass 0% ZnO.On the other hand, when further paying the utmost attention to when keeping glass stable, preferably do not import ZnO.Through making one of them preferential, can determine to have or not ZnO.

Have, ZnO works as TiO again ₂And Nb ₂O ₅The content composition of effect a little less than of keeping stability, glass when increasing than BaO.Therefore; Further when improving glass stable when paying the utmost attention to, the scope of the ratio (ZnO/BaO) of ZnO content and BaO content generally is 0～0.120,0～0.090 better, and further comparatively ideal scope is 0～0.080; 0～0.050 is better, and optimal situation is 0.

Al ₂O ₃Though a small amount of the importing can work to improve anti-increased devitrification resistance, when import volume surpasses 10%, makes anti-increased devitrification resistance downward trend.Therefore, Al ₂O ₃The scope of content generally is 0～10%, 0～5% better, and further comparatively ideal scope is 0～3%, and 0～1% is better.When paying the utmost attention to the raising specific refractory power, preferably do not import Al ₂O ₃

Li ₂O, Na ₂O and K ₂O has the effect of the tansition temperatures decline that makes glass, wherein, and Li ₂The above-mentioned effect of O is maximum.But, if total content surpasses the trend that 5% anti-increased devitrification resistance has deterioration.Therefore, Li ₂O, Na ₂O and K ₂The scope of the total content of O generally is 0～5%, and better less than 1.5% more than or equal to 0,0～1% is better, preferably do not import.

Secondly, the composition of opticglass II is described.

[opticglass II]

The optimal morphology of opticglass II if represent with the percentage ratio of quality, is to comprise 1～45% B ₂O ₃, 0～30% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂Glass.

In opticglass II, B ₂O ₃And SiO ₂Play network and be formed into branch.

B ₂O ₃Be the very resultful composition of temperature reduction, preferably import and be not less than 1% glass melting property and mobile viscosity.But, if surpass 45% tendency that has specific refractory power to descend.Therefore, B ₂O ₃Content generally in 1～45% scope, 1～24% scope is better, further comparatively ideal scope is 1～20%, 1～15% is better, in addition, comparatively ideal scope is 2～10%, special ideal scope is 3～8%.

SiO ₂Produce effect to keeping anti-increased devitrification resistance,, the tendency that the meltbility of making worsens, specific refractory power reduces is arranged then if surpass 30%.Therefore, SiO ₂Content generally in 0～30% scope, 0～18% scope is better, and then comparatively ideal scope is 0～10%, 1～8% scope is better, better scope is 2～6%.

For La ₂O ₃, TiO ₂, Nb ₂O ₅, BaO, WO ₃And ZrO ₂, the same with situation illustrated in aforesaid opticglass I.

In above-mentioned optimal morphology, B ₂O ₃, SiO ₂, La ₂O ₃, TiO ₂, Nb ₂O ₅, BaO, WO ₃, ZrO ₂And Sb ₂O ₃Total content to surpass 95% glass relatively good, it is better to surpass 98% glass, it is further better to surpass 99% glass, 100% glass is best.

The glass of above-mentioned optimal morphology is the glass that comprises following composition: as any composition, if represent with the percentage ratio of quality, can comprise 0～20% Gd ₂O ₃, 0～15% Y ₂O ₃, 0～15% Yb ₂O ₃, 0～18% Ta ₂O ₅, 0～20% Bi ₂O ₃, 0～10% Ga ₂O ₃, 0～10% GeO ₂, total content is 0～10% MgO, CaO and SrO, 0～15% ZnO, 0～10% Al ₂O ₃, total content is 0～5% Li ₂O, Na ₂O and K ₂O.

For these any composition Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃, Ta ₂O ₅, Bi ₂O ₃, Ga ₂O ₃, GeO ₂, MgO, CaO, SrO, ZnO, Al ₂O ₃, Li ₂O, Na ₂O and K ₂O is the same with situation illustrated in aforesaid opticglass I.

As previously mentioned, opticglass II is high because of specific refractory power, so hope to pay close attention to the stability of keeping glass.In above-mentioned optimal morphology, following to the stable comparatively ideal form of keeping glass.

[better form]

La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃, TiO ₂, Nb ₂O ₅, WO ₃Work to improve the high refractive index composition of specific refractory power.In order to improve specific refractory power, be necessary to increase the import volume of high refractive index composition, still, and when the import volume of high refractive index composition increases, the stability decreases of glass, the trend that has devitrification to increase.Therefore,, import a kind of composition among MgO, CaO, SrO and the BaO at least, simultaneously, make the total content of high refractive index composition and form the B of composition as network at the import volume that suppresses to increase when devitrification increases the high refractive index composition ₂O ₃And SiO ₂The ratio of total content of total content and MgO, CaO, SrO, BaO of ratio and high refractive index composition of total content be set within the scope of regulation.

In order when devitrification is increased, to increase the La in the high refractive index composition ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃Import volume, the total content of high refractive index composition and form the B of composition as network ₂O ₃And SiO ₂The ratio of total content have great importance, in order when devitrification is increased, to increase the TiO in the high refractive index composition ₂, Nb ₂O ₅, WO ₃Import volume, the ratio of the total content of the total content of high refractive index composition and MgO, CaO, SrO, BaO has great importance.

Therefore, in comparatively ideal form, if represent B with the percentage ratio of quality ₂O ₃And SiO ₂Total content be 1～25%, B ₂O ₃And SiO ₂Total content and La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃, TiO ₂, Nb ₂O ₅And WO ₃The ratio [(B of total content ₂O ₃+ SiO ₂)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃)] be 0.05～0.3, the total content of MgO, CaO, SrO, BaO and La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃, TiO ₂, Nb ₂O ₅And WO ₃Total content ratio [(MgO+CaO+SrO+BaO)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃)] be 0.1～0.4.

If B ₂O ₃And SiO ₂Total content less than 1%, the trend that then has the devitrification of stability decreases, the glass of glass to increase, if surpass 25%, then specific refractory power improves very difficulty.Therefore, B ₂O ₃And SiO ₂The scope of total content generally be 1～25%, 2～18% better, 3～14% is best.

In the high refractive index composition, if ask to import how many La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃Just can not damage the stability of glass, then B ₂O ₃And SiO ₂The ratio of total content of total content and high refractive index composition be the important factor that will consider, if ask to import how many TiO ₂, Nb ₂O ₅, WO ₃Just can not damage the stability of glass, then the ratio of the total content of the total content of MgO, CaO, SrO, BaO and high refractive index composition is the important factor that will consider.

In above-mentioned 2 factors, if (B ₂O ₃+ SiO ₂)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃) less than 0.05, the stability decreases of glass, the trend that devitrification increases are arranged then, if greater than 0.3, then be difficult to specific refractory power is brought up to desired scope, so, preferably make (B ₂O ₃+ SiO ₂)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃) within 0.05～0.3 scope.

In addition, if (MgO+CaO+SrO+BaO)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃) less than 0.1, the stability decreases of glass, the trend that devitrification increases are arranged then, if greater than 0.4, then be difficult to when keeping good anti-increased devitrification resistance, specific refractory power brought up to desired scope, so preferably make (MgO+CaO+SrO+BaO)/(La ₂O ₃+ Gd ₂O ₃+ Y ₂O ₃+ Yb ₂O ₃+ TiO ₂+ Nb ₂O ₅+ WO ₃) within 0.1～0.4 scope.

La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃Being the high refractive index composition, is to make glass have the composition of low dispersing characteristic simultaneously.If La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃Total content less than 25%; Then have to be difficult to the trend not only keeping the stability of glass but also keep desirable optical characteristics, if surpass 45%, the stability decreases of glass and be difficult to glass is stably produced in batches then; So; Above-mentioned total content generally is 25～45%, 28～40% better, and 30～38% is best.

TiO ₂, Nb ₂O ₅, WO ₃To improving the specific refractory power role all than La ₂O ₃, Gd ₂O ₃, Y ₂O ₃, Yb ₂O ₃Greatly.In addition, also work to improve chemical durability and anti-increased devitrification resistance.TiO particularly ₂, because of in the high refractive index composition, its molecular weight is minimum, so even the per-cent of import volume is high, also can not damage the stability of glass.

In the high refractive index composition, play the TiO that pretends very much usefulness to improving specific refractory power ₂, Nb ₂O ₅Molecular weight is little, and from the aspect of the stability that improves glass, also hopes to import to compare Nb ₂O ₅More TiO ₂But, Nb ₂O ₅There is the stability that more can improve glass as glass ingredient, through improving Nb ₂O ₅Content, even TiO ₂Content not superfluously also can reach desirable specific refractory power, so, because of can reducing the painted of glass, thus in opticglass I, Nb ₂O ₅Content and TiO ₂The ratio (Nb of content ₂O ₅/ TiO ₂) preferably more than or equal to 0.1 less than 0.5.If Nb ₂O ₅/ TiO ₂Less than 0.1, the stability decreases of glass then, painted enhancing is if above-mentioned ratio more than or equal to 0.5, then is difficult to accomplish not only kept the stability of glass but also improved specific refractory power.

In opticglass II, in order not only to keep the stability of glass but also further improve specific refractory power, improve glass melting property, plasticity simultaneously, reduce glass coloring, SiO ₂Content and B ₂O ₃The ratio (SiO of content ₂/ B ₂O ₃) preferably 0.3～02.

As ₂O ₃Though with Sb ₂O ₃Play a part same, but toxic because of it, so consider preferably not use from the environment aspect.

In above-mentioned opticglass I, II, lead and compound thereof are to improve the painted composition that enlarges markedly that specific refractory power does not make glass again, but environmental pollution is bigger, so should reduce its import volume, does not preferably import.

Cd and compound thereof, Cr and compound thereof and Tl and compound thereof are also toxic, should from glass ingredient, get rid of.Equally, radioactive substances such as U, Th, Ra also should be got rid of.In addition, except having a mind to make the situation of glass coloring, Cu, Cr, V, Fe, Ni, Co, Pr, Nd, Er, Ho etc. preferably do not import yet.In addition, consider that the influence to environment should avoid the use of Te and Se.The material composition that Cs, Rb, Hf etc. are valuable increases because of making manufacturing cost, so, preferably do not use.

And then, even opticglass I, II do not import Lu ₂O ₃Also can high refractive indexization, because of Lu ₂O ₃Cost an arm and a leg, so consider preferably not import Lu from economy ₂O ₃

In addition, owing to F exerts an adverse impact to the homogeneity of glass, so preferably also do not import F.

Opticglass I, II are because of comprising an amount of Sb ₂O ₃, pretend and be glass of high refractive index, except painted few, be difficult to the characteristic that changes in case also have the glass coloring that obtains.That is, even the method for stating after utilizing is not added Sb ₂O ₃And obtained painted less glass, and as if being placed on, heats in non-oxidized gas environment or the reducing gas environment in such glass, and then the painted of glass can increase.For example, when the combustion gas heating glass, contact with high temp glass, make the glass reduction through making combustion gas.As a result, the glass coloring degree increases, and when in non-oxidized gas environment or reducing gas environment, making the glass die forming, heating back glass is reduced in gas, and the degree of staining of the glass after the shaping is increased.But,, add an amount of Sb if as opticglass I, II ₂O ₃, can prevent to make the painted increase of glass because of heating glass in non-oxidized gas environment or reducing gas environment.As a result, can solve the inconsistent problem of glass coloring through manufacturing process.And then, because of not needing heat treatment step to reduce the glass coloring that in manufacturing process, produces, so manufacturing process is simplified.

[opticglass III]

Opticglass III is the TiO that comprises as glass ingredient having ₂The opticglass of borate-based composition in, when refractive index n d more than or equal to 2.01 and to establish thickness be the outside transsmissivity of 10.0mm when becoming 70% wavelength and being λ 70nm, have the following formula of satisfying (1)

The glass of transmission characteristics of relation.

Have, in opticglass III, the definition of boratory composition, λ 70, λ 5 and opticglass I, II are identical again.

Opticglass III comprises additive Sb ₂O ₃, refractive index n d more than or equal to 1.95 opticglass II in, except comprising that refractive index n d more than or equal to 2.01 the form (being called opticglass III-1), also comprises not comprising Sb ₂O ₃And As ₂O ₃And specific refractory power (nd) is more than or equal to 2.01 form (being called opticglass III-2).Opticglass III-1 except refractive index n d more than or equal to identical with the opticglass I, the II that have explained 2.01, therefore, below only explanation do not comprise Sb ₂O ₃And As ₂O ₃And refractive index n d is more than or equal to 2.01 opticglass III-2.

Opticglass III-2 can obtain through near the temperature province that glass is remained on the tansition temperatures.Specifically, can by after method of manufacture I, II or the III of the opticglass of the present invention stated make.

During near glass being remained on tansition temperatures temperature province, atmosphere surrounding is the oxidizing gas environment preferably.The oxidizing gas environment is the atmosphere surrounding that in atmosphere, air and rare gas element, has mixed oxidizing gas such as oxygen, in air, has added the atmosphere surrounding of oxidizing gas such as oxygen etc.Wherein, preferably above-mentioned glass is remained in the easy to handle atmospheric environment.

In addition; The content of moisture content is influential to painted reduction effect in the oxidizing gas environment; So, preferably using the oxidizing gas under the dryness, it is more satisfactory that dew point is not higher than-10 ℃ oxidizing gas environment; It is desirable more that dew point is not higher than-25 ℃ oxidizing gas environment, and it is the most desirable that dew point is not higher than-30 ℃ oxidizing gas environment.

The manufacturing of the borate opticglass in past takes to make melten glass chilling, shaping, does not remain near the glass tansition temperatures and with certain cooling rate, for example with 30 ℃ speed refrigerative method per hour.Though reduce painted mechanism and imperfectly understand through borate opticglass being remained near the tansition temperatures humidity province, the present inventor thinks to make painted minimizing from glass surface to the diffusion phenomena of inside because of certain.And, think that the environment when glass keeps is relevant with diffusion phenomena.Its reason is; When the glass sample that will change the above-mentioned hold-time cuts in half and observe its section; Though can find out that short sample of hold-time is painted few near sample surfaces, inner painted very serious, and along with the part of the painted severity of prolongation of hold-time is concentrated to centre portions gradually; If further prolong the hold-time again, then the part of painted severity can disappear.

Therefore, can make time that glass keeps under near the temperature the tansition temperatures more than or equal to the needed time of painted minimizing that makes center of glass portion because of diffusion, and then, can set the hold-time to make transmission characteristics satisfy above-mentioned (1) formula.The concentration etc. that plays the gas of redoxomorphism in the temperature that this time keeps because of the volume of glass, shape, glass, the environmental gas changes, so, be preferably in to begin to produce to wait according to experiment in advance before the glass and decide the hold-time.

Here; Near the glass tansition temperatures temperature can with more than or equal to ' glass tansition temperatures (Tg)-100 ℃ ' and smaller or equal to the scope of ' glass tansition temperatures (Tg)+100 ℃ ' as design objective; Preferably and in the scope smaller or equal to ' glass tansition temperatures (Tg)+50 ℃ ' more than or equal to ' glass tansition temperatures (Tg)-50 ℃ '; If the said temperature scope then need not glass is remained on fixed temperature.

Usually, in the said temperature scope, glass was kept 8 hours or more than 8 hours, kept 9 hours or more satisfactory more than 9 hours, keeps 10 hours perhaps ideals more than 10 hours.

The best of opticglass III-2 is formed except not containing Sb ₂O ₃And As ₂O ₃Outside, other are the same with opticglass I, II, but preferably make B ₂O ₃And SiO ₂Total content below 20% or 20%, TiO ₂Content more than 20% or 20%.

Opticglass III-1 is not because of containing Sb ₂O ₃So, the same with opticglass I, II, have the operation after melten glass forms glass, can not increase painted characteristic even glass heat-treated also.On the other hand, opticglass III-2 is not because of containing Sb ₂O ₃And As ₂O ₃So glass is painted sometimes when in reducing gas, glass being heat-treated, still, through after heat-treat in the oxidizing gas stated can reduce painted.

Have, the optimal morphology of opticglass III and opticglass I, II are the same, (1-a) formula below satisfying again.

If according to above-mentioned optimal morphology; Can be as aforementioned; Picture information in the visible region of the body that is taken had no to send to semiconductor camera elements such as CCD or mos sensor with omitting; Carry out look accordingly with the output data of above-mentioned imaging apparatus in case of necessity and proofread and correct, thereby can obtain the view data of reproducing colors verily etc.

Have, the same with opticglass I, II, the optimal morphology of opticglass III is the glass with the transmission characteristics that satisfies following formula (1-b), and then is the glass with the transmission characteristics that satisfies following formula (1-c) again.

For opticglass I, II and opticglass III-1; No matter under near the temperature whether tansition temperatures glass is remained in the oxidizing gas environment; Can make; But opticglass III-2 then need utilize method of manufacture I, II, the III of following opticglass of the present invention to make.

[the method for manufacture I of opticglass]

The method of manufacture I of opticglass of the present invention has the TiO that comprises as glass ingredient ₂The method of manufacture of opticglass of borate-based composition, it is characterized in that, comprise following operation:

If represent, can obtain B with the percentage ratio of quality ₂O ₃And SiO ₂Total content below 20% or 20%, GeO ₂Content be 0～10%, TiO ₂Content at the glass more than 20% or 20%, in the blending raw material, add Sb as additive ₂O ₃And/or As ₂O ₃,

In the method, when the blending raw material, preferably do not add As ₂O ₃, and with Sb ₂O ₃Addition be controlled in the scope of 0.004～0.09 quality %, in addition, preferably make the content of BaO be not less than 5 quality %.

When the blending raw material,, preferably can obtain comprising 1～20% B if represent with the percentage ratio of quality ₂O ₃, 0～18% SiO ₂, 10～50% La ₂O ₃, 20～40% TiO ₂, 0～30% Nb ₂O ₅, 5～35% BaO, 0～7% WO ₃With 0～15% ZrO ₂Glass.Have, the definition of λ 70 as stated again.

When embodiment of the present invention, the setting of each condition preferably makes it can satisfy above-mentioned (1-a) formula, and it is better to satisfy above-mentioned (1-b) formula, and it is the most desirable to satisfy above-mentioned (1-c) formula.

[the method for manufacture II of opticglass]

The method of manufacture II of opticglass of the present invention has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have and satisfy following relational expression (1)

The method of manufacture of opticglass of transmission characteristics, it is characterized in that:

Near the tansition temperatures, the definition of oxidizing gas and λ 70 as stated.In addition, time that keeps near the oxidizing gas of the temperature being equivalent to tansition temperatures and set above-mentioned time method also as stated.

[the manufacturing side III of opticglass]

The method of manufacture III of opticglass of the present invention has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength during as λ 70nm, have and satisfy following relational expression (1)

To comprise TiO ₂Borate glass be kept near the oxidizing gas of temperature the tansition temperatures that is equivalent to this glass, after thermal treatment, cool off.

The method of manufacture II of the present invention and aforementioned opticglass of the present invention is basic identical, so, its difference only is described below.

The glass that is in than is equivalent to after method of manufacture III of the present invention is shaped to melten glass under near the low temperature of the temperature tansition temperatures of glass heats, and it is remained under near the temperature that is equivalent to the glass tansition temperatures.

This method of manufacture III is very suitable as the method that obtains opticglass III-2 of the present invention.

[glass shaping body and method of manufacture thereof]

Secondly, the glass shaping body and the method for manufacture thereof that are formed by opticglass of the present invention are described.

Glass shaping body of the present invention is formed by opticglass of the present invention.Opticglass of the present invention as previously mentioned, the viscosity pole of the melten glass that is used to be shaped is low.This be because, when being shaped in order to prevent the glass devitrification, must make that the glass that is placed under the also high temperature environment of the not too high melten glass of temperature specific refractivity sharply cools off, is shaped, therefore, the viscosity of melten glass.In addition, when making glass from pipe, flow out shaping, even simultaneously from the effusive glass of pipe, along the effusive glass of tube wall with along the effusive glass of the hub of pipe, it forms more or less difference.When the viscosity of effusive glass was hanged down, the difference of this composition increased thereupon.Like this, when the glass of forming difference more or less mixed, forming of glass was known from experience and is produced brush line.That is the opticglass that, outflow viscosity of the present invention is low is easy to produce brush line when being shaped.

In order when forming such glass, brush line not to take place, make not mix to get final product along the effusive glass of tube wall with along the effusive glass of the hub of pipe as far as possible.That is, can make the surface that forms glass shaping body along the effusive glass of tube wall, make the inside that forms glass shaping body along the effusive glass of the hub of pipe.A method that realizes above-mentioned design is exactly the method for manufacture of following glass shaping body.

Promptly; The method of manufacture of glass shaping body is used the mold of the communicating pores with joint access and outlet; Melten glass is flowed into from the inlet of above-mentioned communicating pores, and be full of in the above-mentioned communicating pores, take out glass shaping body continuously at above-mentioned communicating pores internal shaping from the outlet of communicating pores; Thus, produce the glass shaping body that forms by opticglass of the present invention.

The optimal morphology of aforesaid method is to use the mold with communicating pores; Inlet from the effusive melten glass of pipe from above-mentioned communicating pores is continuously flowed into; And take out from the outlet of above-mentioned communicating pores continuously; Forming the method for manufacture of the glass shaping body of solid glass, is at least a portion zone (cooled region) in above-mentioned communicating pores, and the glass sides in the above-mentioned communicating pores is contacted with the inwall of above-mentioned communicating pores; The heat of above-mentioned glass is distributed from above-mentioned side; Simultaneously, make glass through above-mentioned cooled region be in low 150 ℃ of tansition temperatures Tg than above-mentioned glass, promptly more than or equal to the temperature environment of (Tg-150 ℃), make above-mentioned center of glass portion and the approaching method of lateral temperature thus.

In the method for manufacture of above-mentioned glass shaping body, use mold with communicating pores, make the inlet that continuously flows into above-mentioned communicating pores from the effusive melten glass of pipe, and take out continuously from the outlet of above-mentioned communicating pores, form solid bar-shaped glass.

In order to produce uniform glass shaping body on the optics, do not make melten glass careless mobile very important in mold.In order to form the glass of hollow form, the mechanism that part stops glass flow is set in mold, do not make melten glass flow into the part of hollow space, i.e. not filling glass.For example, partly become when hollow at the hub that makes bar-shaped glass shaping body, along the high rod of the central shaft arrangement of the mold thermotolerance the same with mold, flowing into melten glass should surround by rod.At this moment, stop glass can upset flowing of glass to the mechanism that the hollow space that is equivalent to above-mentioned rod is filled.On the other hand, uniform glass shaping body is a purpose to above-mentioned method of manufacture on the optics to obtain, and therefore, glass shaping body also is the solid glass molding that does not have hollow space.

The mold that the method for manufacture of above-mentioned molding is used has communicating pores, and this communicating pores has inlet that flows into melten glass and the outlet of taking out solid glass.In the present invention, make the inlet that continuously flows into communicating pores from the effusive melten glass of melten glass outflow pipe.And; In at least a portion zone (cooled region) in above-mentioned communicating pores; Side through making at least the glass of surface before solidifying from molten state, promptly the face towards the direction vertical direction that moves with whole glass contacts with the inside of above-mentioned communicating pores, thereby the heat of glass is distributed from the side.Thus, can reduce or prevent to take place easily low glass of the glass of brush line, the viscosity when particularly flowing out or fluorine-containing glass and produce brush line.Particularly, contact with the inwall of communicating pores, make between side and the communicating pores inwall very close to each otherly, can cool off glass effectively through making whole side.

As after state, in order to prevent the glass devitrification, the temperature that flows out the melten glass that flows into the communicating pores inlet again from pipe is preferably near the liquidus temperature or the temperature more than it.Specifically, the surface temperature that flows into the melten glass of communicating pores inlet is preferably in the scope of (liquidus temperature+10 ℃)～(liquidus temperature+100 ℃).The surface temperature that flows into the molten glass flow of communicating pores inlet can regard identical with the temperature that flows out the pipe lower end as, and the temperature that flows out the pipe lower end can be used thermocouple measurement.In addition, the temperature that flows into the melten glass central part of communicating pores inlet can be measured through thermopair being inserted into melten glass inside.The temperature head of the surface temperature of the molten glass flow of measuring like this and the temperature of central part is preferably within 120 ℃, and is more satisfactory within 60 ℃, the most desirable within 50 ℃.

Decision again after the factors such as the temperature of mold (communicating pores inwall) is preferably in that consideration (1) glass does not melt, (2) melten glass is poured in the communicating pores very close to each otherly.In order to carry out temperature control, in case of necessity, well heater or water cooler can be set in mold.When the temperature of the forming of glass surface of communicating pores outlet is too high, cool off through carrying out air-cooled to mold or water cooling plate etc. being set, in addition, when temperature is too low, heat through using well heater, can carry out temperature regulation.

The temperature of the communicating pores upper inside wall of above-mentioned cooling zone for example can be the temperature than low 50 ℃～150 ℃ of the glass tansition temperatures of the glass that is shaped.As after state; When with the path of the whole glass flow in the communicating pores during as the cooling zone, the temperature of communicating pores inwall can be the temperature than low 20 ℃～50 ℃ of the glass tansition temperatures of the glass that is shaped near inlet, when use shaping stove; Near outlet; Can be the temperature than low 100 ℃～400 ℃ of glass tansition temperatures, the pars intermedia between entrance and exit can be smaller or equal near the temperature of the temperature outlet more than or equal near the temperature inlet.Have, the temperature of communicating pores inwall can be measured near again thermopair being inserted the communicating pores inwall behind the mold opening through making again.

Like this,, make glass sides contact to dispel the heat and compare, can promote glass cools, reduce or prevent the generation of brush line with the communicating pores inwall in the cooling zone.But, as illustrated just now, in the glass that particularly viscosity is lower when flowing out, when the inner temperature head with the surface of the glass that takes out from mold is excessive, make glassbreak or breakage because of internal stress sometimes.Therefore, in above-mentioned method of manufacture, make glass through the cooling zone through than low 150 ℃ of the tansition temperatures (Tg) of above-mentioned glass, promptly more than or equal to the temperature environment of (Tg-150 ℃), make the temperature and the lateral temperature of above-mentioned center of glass portion approaching thus.Therefore, in order to reduce or prevent brush line and the glass of cool quickly takes place to destroy because of internal stress or is damaged in the cooling zone after through the cooling zone.

Above-mentioned cooling zone can be the flowing-path of the whole glass in the communicating pores.At this moment, above-mentioned environment more than or equal to (Tg-150 ℃) can be the residing environment of glass that takes out from communicating pores.Like this, when make the glass that takes out from communicating pores through more than or equal to the environment of (Tg-150 ℃) and make center of glass portion and lateral temperature near the time, preferably make from the glass of communicating pores taking-up to get into immediately the above-mentioned environment.

In addition; In the method for manufacture of above-mentioned glass shaping body; With roughly being divided into 2 zones of inlet side and outlet side in the communicating pores; The operation that the side of glass is contacted with the communicating pores inwall and the heat of glass is distributed from the side simultaneously, can be controlled at the temperature of the communicating pores inwall in outlet side zone low 150 ℃ of tansition temperatures Tg than glass, promptly in the TR more than or equal to (Tg-150 ℃).At this moment, above-mentioned temperature environment more than or equal to (Tg-150 ℃) is the environment in the outlet side zone after said temperature control.Here, also can make inlet side zone and outlet side zone adiabatic, so that easily temperature control is carried out in two zones.

For above-mentioned any situation; Make the approaching operation of center of glass portion and lateral temperature preferably make glass pass through to hang down 100 ℃, promptly carry out more than or equal to the temperature environment of (Tg-100 ℃) than the tansition temperatures of glass; Make glass pass through to hang down 50 ℃, promptly better more than or equal to the temperature environment of (Tg-50 ℃) than the tansition temperatures of glass, it is the most desirable that glass is passed through under the environment of the tansition temperatures Tg of glass.

If the temperature under the above-mentioned environment is too low, then when in the shaping stove, making the approaching operation of center of glass portion and lateral temperature, must do stove not only high but also big.In addition, when in mold, making the approaching operation of center of glass portion and lateral temperature, must increase the size of mold.Consequently, need very big space, be difficult to control the speed of taking out glass from the outlet of communicating pores.

In addition, when cutting off glass shaping body, if the temperature of glass is too low, then the Young's modulus of elasticity because of glass increases, so be difficult to cut off.In the present invention; Be a continuum from the melten glass to the glass shaping body, when cutting off glass shaping body with very big power, the impact that is produced can have influence on the melten glass in the mold; Make the mobile generation disorder of glass etc., may can not get high-quality glass shaping body.Though can use wire saw or emery wheel to cut, must make glass cools near room temperature, such cooling because need reach tens meters be used for carry out slow refrigerative space, so undesirable.In order to carry out cutting off of glass shaping body well; The temperature of glass is generally near the tansition temperatures or below it; Smaller or equal to tansition temperatures but better more than or equal to the situation of (tansition temperatures-150 ℃); Smaller or equal to tansition temperatures but more than or equal to the better off of (tansition temperatures-100 ℃), and then comparatively ideal is smaller or equal to tansition temperatures but more than or equal to the situation of (tansition temperatures-50 ℃).Near tansition temperatures situation is the most desirable.Consider above each point, in the method, perhaps make center of glass portion and the approaching operation of lateral temperature under the environment more than (Tg-150 ℃) at (Tg-150 ℃).After carrying out the approaching operation of center of glass portion and lateral temperature, through carrying out cutting off or cutting off of glass shaping body, can be on desirable position the separation of glasses molding, and be unlikely to make its breakage.

Be used for making that glass is inner and the upper temperature limit of the operation that lateral temperature is approaching can be the temperature that because of the rapid cooling of glass sides the external diameter shape (with the vertical cross-sectional shape of removing direction) of the glass after the shaping is not out of shape; Preferably under the softening temperature of glass or its, if then better less than softening temperature.

When in environmental gas, carrying out aforesaid operations, the stove that is called the shaping stove is connected with the outlet of communicating pores, the glass that takes out continuously from the outlet of communicating pores directly gets in the stove, under the approaching state of central part and lateral temperature, comes out of the stove.In addition, through the time in the stove be the following time, that is: the internal stress of glass shaping body is reduced to can not cause unexpected destructive degree or because slight thermal shocking or physical shock and the time of damaged degree.For this reason, consider the take-off speed of glass and through the time in the stove, can be through the suitable length along the glass removing direction of decision shaping stoves such as test.The control of furnace gas temperature for example can be spent the time that the current value that is configured in the well heater in the stove or electric current flow through through controlling flow and carried out.

In the method for manufacture of above-mentioned glass shaping body, through making center of glass portion and the approaching operation of lateral temperature, can center of glass portion and lateral temperature head be located at for example 0～150 ℃, 0～100 ℃ is better, 0～50 ℃ of the best.Have, above-mentionedly make the approaching operation of center of glass portion and lateral temperature and make near the annealing operation the slow cool to room temperature of glass different, being in more than room temperature under high a lot of state in the temperature of glass is end operation.

Secondly, the mold of the method for manufacture use of above-mentioned glass shaping body is described.

From preventing viewpoints such as glass heat fusion, broadening, bending, in mold, the ratio (internal diameter/length) of the internal diameter of communicating pores and length is preferably in 1/50～3 times the scope.1/20～2 times scope is best.The internal diameter of communicating pores should be considered to decide according to the external diameter of the glass shaping body that will obtain, and for example, can be 10～100mm.But, be not that this size is limited.

In order to prevent that glass from moving in mold, preferably make the arbitrary portion that glass passed through identical with cross-sectional shape of mold perpendicular to the travel direction of glass shaping body perpendicular to the cross-sectional shape of glass travel direction.When not controlling the temperature distribution of mold; The temperature of the inlet side of the mold in the forming process is higher than the temperature of outlet side, so, when the internal diameter one that at room temperature makes communicating pores regularly; Because of the thermal expansion of mold, the internal diameter along the communicating pores of glass travel direction during shaping can not keep certain.In this manufacturing process; Along the direction of inlet to outlet, the internal diameter of communicating pores becomes greatly gradually, and perhaps the above-mentioned internal diameter along the glass travel direction keeps necessarily when being shaped in order to make; Consider thermal expansion again; Preferably communicating pores is made cone shape, Way out will be more greatly, and the tapering of decision circular cone.Particularly, when making the lower forming of glass of viscosity when flowing out or using the mold that forms by the high glass material of wettability, adhere on the mold, preferably make tapering greatly in order not make glass.

As the material of employed mold, thermotolerance metals such as carbon, foundry goods, nickel preferably.In addition, from preventing the viewpoint of mold deterioration, the operation of processing glass shaping body from melten glass is preferably in the rare gas element carries out.

When the quality of gases affect glass shaping body, preferably control environment wherein surrounds its flowing-path with the melten glass between the inlet of pipe spout and communicating pores.In this manufacturing process; The area that is exposed to the face in the gas of high temp glass is so big unlike existing manufacturing process; So; Even with the front end of pipe and the sealing of whole shaping appts, do not replace the atmosphere surrounding of the inside,, then can reach the purpose that controls environment if as above-mentioned, the minimal space encloses of necessity is replaced as desired gas with internal gas again.In order to suppress volatilization from high temp glass surface, reduce or prevent the wettability of glass the periphery of pipe front end, improve the quality of glass shaping body, above-mentioned gas is the rare gas element under exsiccant gas, rare gas element or the dryness preferably.

When making the molding that forms by the glass that comprises volatile component, for example fluorine composition; Make glass through the cooling zone through being not less than environment than low 150 ℃ of the tansition temperatures of above-mentioned glass; And no matter when whether making the approaching operation of center of glass portion and lateral temperature; This method is as the method that reduces or prevent brush line, and is very suitable.

The preferred example of the method for manufacture of this glass shaping body is to use the method for the mold of the communicating pores with straight line joint access and outlet.In the method, be preferably in, make the liquid level of the melten glass in the communicating pores certain, carry out the inflow of melten glass like this than disposing mold on the high position of entrance and exit.

Fig. 1 illustrates above-mentioned preferred example.Fig. 1 is the synoptic diagram of the routine manufacturing installation that uses in the method for manufacture of above-mentioned glass shaping body.As shown in Figure 1, make the melten glass 2 that in pipe 1, flows down flow into mold 3 and make glass from the higher position to the process that lower position moves, glass shaping body 4 is shaped.As shown in Figure 1, if the part that glass passed through that flows into is the communicating pores of straight line joint access and outlet, melten glass flows more smooth and easy in mold, is not easy to occur sinuous flow, and the result can stably produce uniform glass shaping body on the optics.

In addition, in the method for manufacture of this glass shaping body, best that kind as shown in Figure 1 disposes mold 3, makes the hub vertical (consistent with plummet) of communicating pores.But, also can be configured to above-mentioned hub is tilted with respect to plummet.When configuration mold 3 makes its hub vertical, flow to Way out in mold from the effusive vertically downward molten glass flow of pipe 1, so, can further reduce the sinuous flow in the mold, further improve the effect that reduces brush line.

In addition, flow into melten glass through the communicating pores that connects to the entrance and exit straight line, thereby can obtain straight glass shaping body.Straight glass shaping body can be used for glass shaping body is processed and produced the glass gob that die forming uses or processes optical element.Have the hub of linearity and the glass shaping body that all equates with respect to the size on vertical cross-sectional shape of hub and the optional position in order to obtain like this; Preferably use the mold of communicating pores with the connection of entrance and exit straight line; Simultaneously, the glass that from mold, takes out is evenly cooled off.Through even cooling, glass is evenly shunk, and it is straight to keep glass shaping body.In addition, in this manufacturing process, through as aforementioned, making center of glass portion and the approaching operation of lateral temperature, thereby can make glass shaping body straight.

For the stable formation condition, preferably make the height of the molten glass level in the communicating pores certain.For this reason, as long as make melten glass necessarily from the discharge of pipe 1.But As time goes on the discharge of melten glass has small change sometimes, so, preferably control the speed of from mold, taking out glass, so that it is certain to remain the height of liquid level.

Secondly, the method for taking out glass from the communicating pores outlet is described.

In the method for manufacture of this glass shaping body; As the method for taking out glass from the communicating pores outlet; Also can use utilization to make method that glass draws from the communicating pores outlet downwards and except the gravity that glass is applied, also glass applied any removing method in the method for the power of drawing because of moving of causing of the deadweight of glass.In addition, glass does not almost extend during because of taking-up, so the take-off speed of glass is equivalent to the translational speed of the glass shaping body of above-mentioned taking-up.The control of take-off speed is meant that the power of drawing of feed glass molding makes take-off speed become desirable speed; Perhaps; When the deadweight because of glass makes glass when moving than desirable fireballing speed downwards; Apply the power that glass shaping body is slowed down, make take-off speed reach desirable speed.

When the speed of taking out glass from the communicating pores outlet was excessive or too small, the liquid level of the melten glass in the communicating pores can not keep necessarily the gap occurring between communicating pores inwall and the glass, and the size of glass shaping body is unstable.Under the extreme case, melten glass overflows from mold, or the shape of glass shaping body is bad.Therefore, preferably above-mentioned take-off speed is controlled.

An example as the take-off speed of feed glass molding; Can enumerate method as shown in Figure 1; That is, come the method for velocity from the outlet taking-up of feed glass molding from the face (side) that utilizes the communicating pores inwall to form of the glass of communicating pores taking-up through maintenance.For example, use a plurality of cylinders 5 that the side of glass shaping body is clamped, do not produce under the state of slip, come the mobile speed of feed glass molding downwards through the velocity of rotation of index drum 5 in the side 6 of cylinder 5 and glass shaping body.Preferably along the above-mentioned a plurality of cylinders 5 of the many groups of mobile route configuration of glass shaping body, thereby the gravity that utilizes many series cylinders to make to act on the glass shaping body disperses the support glass molding.Like this, can prevent reliably to take place because of the glass shaping body situation that to control take-off speed of between cylinder, sliding.Above-mentioned cylinder preferably is configured in the above-mentioned shaping stove 7.Distortion through the glass shaping body in the shaping stove 7 reduces, and cylinder 5 following glass shaping bodies are the state of downward suspension through the maintenance of cylinder 5.Therefore, even the glass support below the cylinder 5 is separated with the glass on top, can not produce bad influence to the speed control that glass takes out yet.In addition, because of the distortion of the glass shaping body that comes out from shaping stove 7 reduces, so can not make glass breakage because of the separation of glass shaping body.And then, if on through the position above-mentioned holding position after, cut off or cut off and carried out the annealed glass shaping body, though do not interrupt melten glass to mold also flow can, so very convenient.Like this; As long as the weight of the glass shaping body that should keep is not too greatly; So, be favourable from the take-off speed aspect of feed glass, and; Can when glass shaping body is shaped, the glass shaping body that cuts off be sent to next process, and can improve the generation efficient of glass shaping body.

On the other hand, going to control in the method for take-off speed through the side that keeps glass, when the power of clamping glass was excessive, glass can be damaged, so added power can not be more than or equal to prescribed value.Therefore, when the weight of glass shaping body was excessive, glass shaping body slided between cylinder, was difficult to carry out speed control.For fear of such state of affairs, can use the method for velocity of coming feed glass to take out from communicating pores through the leading section that supports the glass that takes out from communicating pores.Fig. 2 illustrates an example of this method, and Fig. 2 is the synoptic diagram of another example of the manufacturing installation that uses in the manufacturing process of this glass shaping body.This method is different with the lateral method of maintenance, because of not being utilizes friction to keep glass shaping body, so be well suited for the manufacturing of the heavier glass shaping body of weight.

In above-mentioned any one take-off speed control method, all be the control of carrying out take-off speed like this, promptly; Utilize the height of the molten glass level in the level sensor 8 monitoring molds; According to above-mentioned monitor signal, when the aspect ratio altitude datum of liquid level is high, increase take-off speed; When the aspect ratio altitude datum of liquid level hangs down, reduce take-off speed.For example, above-mentioned monitor signal is imported taking-up and is input to speed controller 9, liquid level and altitude datum with monitoring in unit 9 compare, and take out its result and feed back to take-off speed.Through utilizing cylinder 5 (with reference to Fig. 1) clamping glass sides to control in the method for take-off speed, can import the wave that unit 9 is exported, the velocity of rotation of index drum 5 to the unit of the motor that cylinder 5 is rotated.Going to control the method (with reference to Fig. 2) of take-off speed through the leading section of support from the glass of communicating pores taking-up; Wave to the actuator input unit 9 of the mechanism's (supporting mechanism 10) that supports leading section is exported can make the translational speed of the parts of support glass leading section reach desirable speed.Monitoring method to the molten glass level height in the mold has no particular limits, and can enumerate methods such as use temperature meter or laser sensor.

When the angle of the hub of communicating pores and plummet increased, the lateral friction increase of mold communicating pores and glass shaping body was even the heavier lateral method of glass shaping body that also keeps of the weight of glass shaping body also can be controlled take-off speed.Therefore, the extremely low glass of viscosity is produced under the situation of heavy weight glass shaping body from outflow the time, also can be configured to make the relative plummet of hub of communicating pores to tilt mold.

Secondly, the separation method of the glass shaping body in the taking-up process is described.

The glass that takes out from communicating pores outlet has innerly reduced internal stress with the approaching operation of lateral temperature because of making, and has eliminated unexpected destruction perhaps produces breakage because of very little thermal shocking or physical shock danger.And then in order to make glass cools to room temperature, it is very long one section that glass is pulled out from mold.For this reason, must there be very big space the below of mold, and, the speed that when the preponderance of glass shaping body, is difficult to critically control taking-up.Therefore, in this manufacturing process, when being near the glass tansition temperatures, the temperature that is preferably in glass shaping body carries out the cutting of glass shaping body.

Fig. 3～Fig. 5 illustrates the object lesson of cutting method.Fig. 3, Fig. 4 and Fig. 5 are the explanatory views that is illustrated respectively in the form of the cutting method of glass shaping body in the formation method of above-mentioned each glass shaping body.As shown in Figure 3, preferably adopt following method: utilize line processing, on the prescribed position of the lateral part of glass shaping body; With the vertical direction of the removing direction of glass shaping body on form line, the hub of clamping glass shaping body is placed fulcrum, this fulcrum is used for local support is carried out in the side of an opposite side of having implemented the position after the above-mentioned line processing; Utilize moving of above-mentioned fulcrum restriction top glass molding; Simultaneously, apply the pressure of horizontal direction to the below of the lateral line Working position of glass shaping body, as shown in Figure 4; Glass shaping body cuts off glass shaping body thus from being the part disconnection that line processing has been implemented at the center with the fulcrum.

In addition; When the bigger glass shaping body of cutting external diameter, as shown in Figure 5, the inner metal sleeve that has formed the water route is contacted with line working position part; Utilize thermal shocking to make it produce crack [(b) figure] to glass inside from line; The hub of clamping glass shaping body, and utilize and to name a person for a particular job and the lateral support [(c) figure] of the opposite side of ruling, afterburning from line to the below of glass shaping body, it is applied a moment; Make the crack to the position expansion of supporting by fulcrum, at last glass shaping body is cut off [(d) figure].

The size of the internal stress that in process of cooling, produces changes because of the shape or the size of glass shaping body.For example, when being very thin glass shaping body, be difficult to occur the temperature head inner and surface as optical fiber.In addition, even thickness foliated glass as thin as a wafer also is difficult to occur the temperature head inner and surface.On the contrary, bar-shaped glass that external diameter is bigger or very thick plate glass, inner temperature head with the surface is big, in process of cooling, is easy to generate bigger internal stress.As such glass shaping body, can enumerate such as having more than or equal to the plate glass of 3mm thickness or having bar-shaped glass more than or equal to the external diameter of 3mm.Therefore, the present invention is suitable for having the shaping more than or equal to the plate glass of 3mm thickness, is more suitable in the shaping that has more than or equal to the plate glass of the thickness of 5mm.In addition, the present invention is suitable for the shaping of external diameter more than or equal to the bar-shaped glass of 3mm, is more suitable in the shaping of external diameter more than or equal to the bar-shaped glass of 5mm, and then is more suitable for the shaping of external diameter more than or equal to the bar-shaped glass of 10mm.

Have again, in this manual, ' bar-shaped glass ' be meant have circle, ellipse, square, long-width ratio (length/width) be smaller or equal to 2 the rectangle and the glass shaping body of Polygons prismatic shapes.In addition, ' plate glass ' be finger widths with the ratio (width/thickness) of thickness greater than 2 sheet glass.

In addition, the external diameter of bar-shaped glass be meant with the vertical cross section of the hub of bar-shaped glass in the length of the thinnest part of the thickness of glass.For example, for cylindric glass, because of with the vertical cross section of the hub of cylinder be round; So external diameter is above-mentioned circular diameter, for oval column glass, because of with the vertical cross section of hub be oval; So external diameter is the minor axis of above-mentioned ellipse, for square column glass, because of with the vertical cross section of hub be square; So external diameter is the above-mentioned foursquare length of side; For square column glass, because of with the vertical cross section of hub be rectangle, so external diameter is equivalent to the length of above-mentioned rectangular minor face.

The method of front explanation is the situation that continuously flows into mold from the effusive melten glass of pipe midway without a break, through mold of configuration below the spout of the pipe that flows out melten glass, can make glass shaping body continuously.

Secondly, the example that uses a plurality of molds is described.

In this example, can carry out following two procedures repeatedly, the first is prepared a plurality of above-mentioned molds; Simultaneously, one of them is configured in the below of above-mentioned pipe, injects melten glass continuously to the mold that is configured in the pipe below; Form glass shaping body, then, interrupt flowing into melten glass to mold; The mold that injects melten glass is taken out of from the below of above-mentioned pipe, and from the mold that this is taken out of, take out glass shaping body; It two is after above-mentioned taking out of, and will the mold different with the mold that injects above-mentioned melten glass moves into the below of above-mentioned pipe, after putting well, injects melten glass to the above-mentioned mold of moving into.

The situation of the glass shaping body that the weight that the low glass of viscosity formed when this method was suitable for making by outflow is heavier.Though this method needs a plurality of molds, these molds is shifted to the mechanism of pipe below successively and are used for interrupting the mechanism to mold inflow melten glass; But, have the advantage that when melten glass flows into mold, can not carry out from same mold, taking out fully the operation of glass shaping body simultaneously.Therefore, the moment that reaches the length of regulation in the length of glass shaping body interrupts injecting melten glass to mold, by mold glass shaping body is taken out of from the pipe below, can not need cut off or cuts off glass shaping body and it is taken out from mold.Therefore, the leading section (bottom) that can the support glass molding and the take-off speed of feed glass molding, so, keep the lateral method of glass shaping body different with utilizing friction, can control the take-off speed of very heavy glass shaping body accurately.

In order to interrupt the inflow of above-mentioned melten glass; For example; Can between pipe spout and communicating pores inlet, insert one the parting tool that constitutes by the blade that is suitable for cutting off the molten glass flow that viscosity is low when flowing out; Cut off molten glass flow, move into, take out of the moment of end at mold and withdraw from parting tool, restart the injection of melten glass.The time of this method outside the inflow of interrupting above-mentioned melten glass, preferably also inject from the effusive melten glass of pipe to mold without a break midway.

The handover of mold for example can be used 2 molds; Alternately mold is moved into the spout of pipe or therefrom take out of; Also can 3 or mold more than 3 be placed on turntable etc. makes in the mechanism that a plurality of molds transfer synchronously; Calibration (index) rotates above-mentioned estrade, and makes mold can rest on the below of pipe spout successively.

No matter be method of use, still, preferably make the pipe arranged perpendicular for the method for using a plurality of molds for 1 mold, mold is placed on the pipe spout the center under, be located at the center of molten glass level.Like this, can under inlet side and state that outlet side aligns, melten glass be flowed in the mold, and help to obtain on the optics glass shaping body uniformly.

The preferred example of aforesaid method is to be applicable to that moving coefficient of viscosity that the viscosity under the metal level temperature obtains divided by the density under the room temperature is less than 7 * 10 ^-5m ²The shaping of the glass of/s.When being main purpose with the brush line that reduces or prevent glass shaping body; The hub that uses communicating pores is the straight line mold of (inlet is communicated with the outlet straight line); Placing mold makes the hub of mold communicating pores vertical; Flow into melten glass continuously from the inlet of mold communicating pores, this is for making by above-mentioned moving coefficient of viscosity less than 7 * 10 ^-5m ²The glass shaping body that the glass of/s constitutes is very effective.Material for shape, size and the mold of mold communicating pores can be directly applied for aforementioned condition.And, in communicating pores, the whole circumference of glass sides is contacted with the communicating pores inwall, the heat of glass is distributed from above-mentioned side.In this example, as previously mentioned, preferably make the pipe that flows out melten glass vertical.Like this, can make the direction that glass moves in the flow direction, mold of glass in the pipe consistent with the direction that acts on gravity on glass.Therefore, glass surface and inside are not mixed, can improve the effect that reduces or prevent brush line.According to improving the viewpoint that reduces or prevent the effect of brush line, preferably adjust the position relation of pipe and mold, make the hub of pipe consistent with the hub of mold communicating pores, carry out the inflow of melten glass then.

Moving coefficient of viscosity is less than 7 * 10 ^-5m ²Not only liquid phase viscosity is low but also density is big for the glass of/s; So in glass shaping body, form brush line easily; But if according to the method described above, the upper layer that can obtain making brush line be confined to glass shaping body and inner does not contain uniform, bulky glass shaping body on the optics of brush line.The glass shaping body that obtains like this as after state; Can be processed into the glass gob that die forming is used; Or be processed into optical element; Thereby or the glass gob that above-mentioned die forming is used heated make its die forming produce optical element parison or optical element, also can process and produce optical element to above-mentioned optical element base.

In existing method, if will make coefficient of viscosity less than 3 * 10 ^-5m ²The forming of glass of/s, the high-quality glass shaping body that then is difficult to obtain opticglass He is used for other optical applications.Equally, move coefficient of viscosity smaller or equal to 4 * 10 ^-5m ²It is exceedingly difficult that the glass of/s will obtain above-mentioned high-quality glass shaping body, and moving coefficient of viscosity is smaller or equal to 5 * 10 ^-5m ²It is also very difficult that the glass of/s will obtain above-mentioned high-quality glass shaping body.Equally, move coefficient of viscosity smaller or equal to 6.5 * 10 ^-5m ²The glass of/s causes bad part to increase because of the reason of brush line.

Relative therewith, even the method for manufacture of this glass shaping body, also is suitable for moving coefficient of viscosity for opticglass of the present invention smaller or equal to 6.5 * 10 ^-5m ²The shaping of the glass of/s is more suitable in smaller or equal to 5 * 10 ^-5m ²The shaping of the glass of/s is to smaller or equal to 4 * 10 ^-5m ²The shaping of the glass of/s is more suitable for, and is particularly suitable for smaller or equal to 4 * 10 ^-5m ²The shaping of the glass of/s.Like this, even the moving less glass of coefficient of viscosity also can obtain big volume, high-quality glass shaping body.

If according to the method for manufacture of such glass shaping body, can not have damaged ground and with very high production efficiency produce forms by above-mentioned opticglass, uniform glass shaping body on the optics.

[glass cup for die pressing and method of manufacture thereof]

Glass cup for die pressing of the present invention is formed by opticglass of the present invention.

An example making the method for glass cup for die pressing of the present invention is that the glass shaping body to the method for manufacture made that utilizes aforementioned glass shaping body of the present invention carries out method for processing.

Central part that makes glass in the method for manufacture of this glass shaping body and the approaching operation of lateral temperature are to destroy because of bigger internal stress makes glass shaping body in order to prevent; Neither make the critically consistent such fine annealing of optical characteristics, not again to make glass in stove, slowly drop to the annealing of room temperature with target value with the glass headed by the specific refractory power.For the glass shaping body that takes out from mold is directly carried out above-mentioned annealing, long and big lehre must be set below mold, this is unpractical.In addition, as previously mentioned, if after the glass shaping body cool to room temperature, it is cut, because of the Young's modulus increase of glass, so be not easy to cut off.

Therefore; The aforesaid central part of glass and the temperature (temperature of glass sides) that the approaching operation of lateral temperature is preferably in glass of making finishes than before low 150 ℃ of the tansition temperatures of glass; Tansition temperatures than glass finishes better for low 100 ℃ before; More more satisfactory, finish the most desirable in the time of near the tansition temperatures of glass than finishing before low 50 ℃ of the tansition temperatures of glass.As cut-off method, can use aforesaid method, promptly; The side that utilizes line to be processed in glass shaping body forms line, to the glass shaping body applied moment, makes the crack to the molding internal extended from line; At last glass shaping body is cut off, still, when the external diameter of glass shaping body reaches 40mm or 40mm when above; If an applied moment is difficult to glass is cut off.At this moment, preferably utilize the higher characteristic of temperature of glass shaping body, it carried out thermal shocking through making the local cooling of line working position, make the crack from the line working position to the glass internal extended, applied moment is cut off glass shaping body then.Like this, can be easy to cut off the glass shaping body of external diameter more than or equal to 40mm.For to the glass shaping body applied moment, can utilize the lateral support with the opposite side of line working position of the glass shaping body of naming a person for a particular job to get up and it is carried out reinforcing, make the sideways expansion of line working position to the glass shaping body of fulcrum front.

The central part by making glass and the approaching operation of temperature of side can be cut off under the state that the inner distortion of glass is reduced, so by applying moment or use thermal shock in the lump, thereby can cut well.

Like this, will move in the slow cooling stove, it slowly is cooled near the room temperature with the glass of the isolating fore-end of glass shaping body that from mold or shaping stove, takes out.

The method of a plurality of molds of aforesaid use also will make the central part of glass and the glass shaping body of the operation that lateral temperature is close move at leisure in the slow cooling stove, and it slowly is cooled near the room temperature.

Glass shaping body can use mechanisms such as robot to carry out to the handover of slow cooling stove.At this moment; If the glass of retaining part sharply cools off; Then glass maybe be damaged because of thermal shocking, so, preferably use the specific heat materials with smaller to constitute the part that keeps glass shaping body; Or the mechanism that utilizes well heater that retaining part is heated is set, or when using the specific heat materials with smaller to constitute the part that keeps glass shaping body, utilize well heater that retaining part is heated.

In the slow cooling stove, be cooled to glass shaping body near the room temperature and eliminate distortion.As the slow cooling stove, can use the continous way slow cooling stove that is called Lehr or be referred to as to be interrupted slow cooling stove of cooling type etc.

Secondly, the glass shaping body of eliminating after being out of shape is divided into desirable size.As dividing method, can use the method for cutting off of utilizing wire saw and emery wheel etc., thereby perhaps use the position cut apart has been applied that line is processed to form line and pressurization makes method that the crack cuts off glass from the line expansion etc. to glass shaping body.

If according to this method; No matter glass shaping body is bar-shaped glass or plate glass; Can obtain having hub and with the vertical cross-sectional shape of hub be the glass shaping body of same shape along hub; So best and hub vertically cuts off or cuts off processing to glass shaping body.If the position that cuts off or cut off uniformly-spaced, then can easily obtain the glass gob that volume equates.In addition, if the interval of the position that cuts off or cut off changes, then can and the ratio at this interval carry out the volume distribution between glass block accordingly.If bar-shaped glass then through such processing of cutting hub from vertical direction, then can obtain the sheet glass that is referred to as to cut into slices.In addition, if plate glass through further the glass compact that obtains as stated being cut off or cuts off, can obtain the sheet glass that is referred to as to cut into slices.

Can rely on above-mentioned various sheet glass with its glass gob of using as die forming, still, preferably grinding, grinding, grinding and attrition process carried out in section, make the glass gob that die forming is used again.Because of section has sharp keen edge, thus through above-mentioned mechanical workout, can be with the edge rounding, in order to utilize infrared rays that glass gob is carried out even heating when the die forming, preferably utilize above-mentioned processing to make the surface coarsening of glass gob.Through alligatoring processing, the Powdered remover that uses in the time of can be with die forming is coated on the whole surface of glass gob equably, and cylinder grinds and is suitable for such surface coarsening processing.

When glass cup for die pressing was used for precision moulded formation, the face that the forming face of the precision moulded formation at least of glass gob is duplicated, preferably attrition process was carried out on whole surface, thereby was processed into level and smooth face.

Like this, can produce glass cup for die pressing from glass shaping body.

Secondly, as the cut-off method of cooled glass shaping body gradually, a kind of special ideal cut-off method is described, i.e. the side pressure process of chopping.This method is: establishing glass shaping body is bar-shaped glass; To the processing of ruling of bar-shaped glass part side; The side of the bar-shaped glass of the both sides that are clipped in the middle to the position of having carried out line processing with above-mentioned position; Under the state of the mutual isolating action of bar-shaped glass that does not hinder the both sides that above-mentioned position is clipped in the middle, pressurize, on above-mentioned position of carrying out line processing, cut off bar-shaped glass.

According to Fig. 6 and Fig. 7 the example that it is concrete is described.Fig. 6 and Fig. 7 are the figure that the side pressure process of chopping is described respectively.

At first, as shown in Figure 6, prepared on lateral position of wanting to cut off, to carry out the bar-shaped glass (glass shaping body) 11 and high pressure vessel 12 of line processing.This high pressure vessel 12 is provided with peristome and the liquid introducing port 13 that inserts bar-shaped glass, except above-mentioned peristome and liquid introducing port, all is sealed structure.And, again peristome is clogged after bar-shaped glass is inserted into above-mentioned peristome, simultaneously, the line working position is near the central authorities of high pressure vessel 12.With sealing between the high pressure vessel of above-mentioned peristome and the bar-shaped glass, when the pressure that in high pressure vessel, injects liquid and aforesaid liquid raises, liquid is let out from high pressure vessel.Have, above-mentioned sealing should not hinder bar-shaped glass to move at its long side direction again.The chuck that above-mentioned sealing for example can use rubber to do waits and carries out.

Secondly, from the liquid introducing port 13 of high pressure vessel 12, import liquid, make liquid be full of said vesse, and then, liquid is pressurizeed with the pressure in the high pressure vessel that improves sealing.Though the uncrossed part to the bar-shaped glass sides in the high pressure vessel is evenly pressurizeed; But; At the line working position; Above-mentioned pressure has the effect that above-mentioned working position is drawn back, with the vertical direction of the hub of bar-shaped glass on make progress of fracture, will the rule both sides of working position of that kind as shown in Figure 7 are broken off.

Utilize the side pressure process of chopping can be easier to cut off the glass of pole shape; Be bar-shaped glass such as circle, ellipse, Long Circle for example with the vertical cross-sectional shape of hub; Utilize the side pressure process of chopping to cut off difficulty of square rod shape glass, thereby the side pressure process of chopping is preferably used in cutting off of pole shape glass.

In order to use the side pressure process of chopping and central shaft vertically to cut off bar-shaped glass, the distortion that fully reduces in the bar-shaped glass by slow cooling is effective.The section of the bar-shaped glass that cuts off like this becomes minute surface, in addition, need as cutting off, not cut off, and does not also have chip, so can effectively utilize glass.Be not limited to the side pressure process of chopping, the method for cutting off is different with the method that grinding glass cuts off, and does not produce chip when cutting off glass, can effectively utilize glass, can reduce the amount of waste simultaneously.

The glass block that obtains like this as section, can be obtained the glass gob that die forming is used as above-mentioned.

Have again; The employed liquid that can not of the side pressure process of chopping makes glass surface, high pressure vessel, sealing material and is connected the pressurizing device deterioration of the pressure that is used for improving liquid on the liquid introducing port of high pressure vessel; And the surface tension that is filled in the liquid in the line working position fully is less; So, preferably use easy to handle liquid.As aforesaid liquid, water is optimum.

In addition; The pressure of the liquid when carrying out side pressure and cutting off can suitably be adjusted according to the mechanical characteristics of glass, shape and size etc.; Can also use to have enough high pressure vessels of the resistance to pressure of anti-maximal pressure (for example withstand voltage 50Mpa) with about 20Mpa as target.

The weight of glass cup for die pressing can with being equal in weight of purpose glass molded article, shape and size can wait suitably decision according to the shape of above-mentioned die-formed product, the shape of model forming module.

[optical element and method of manufacture thereof]

Secondly, optical element of the present invention and method of manufacture thereof are described.

Optical element of the present invention is formed by opticglass of the present invention.

In addition, the method for manufacture of optical element of the present invention has 2 kinds of forms.

The 1st form (to call the method for making I of optical element in the following text) is that the glass cup for die pressing that utilizes aforementioned method of manufacture to make is heated, and through using model forming module to carry out the method that die forming is made optical element.

The method for making I of optical element and then be divided into 2 forms, the 1st method is that glass cup for die pressing is heated, and makes it softening; And in the importing model forming module; Die forming makes die-formed product slowly carry out grinding, grinding after the cooling, thereby is processed into the method for optical element again.In the method, be the shape of wanting grinding, grinding to form the shape of optical element with the glass gob die forming.Operation before heating, soften to slow cooling can be carried out atmosphere.In the method, use through cylinder grinding etc. and make the glass gob behind the whole surface coarsening, the whole surface of glass gob is applied pulverous removers such as SP 1 equably.Then, import and heat, make it softening in the process furnace, import in the model forming module again.Then, in the use behind mould and the counterdie press molding, open mould and take out die-formed product, put into the slow cooling stove, when reducing to be out of shape, make the specific refractory power of glass consistent with the target value height.After with the molding cool to room temperature, use well-known grinding, the polishing that is used for making glass optical component to carry out grinding, attrition process, accomplish the making of optical element.Like this, produce various optical elements such as spherical lens, prism.In case of necessity, also can form optical multilayers such as antireflection film on the surface of optical element.

The 2nd method of the method for making I of optical element is that ganoid glass cup for die pressing after processing is heated, precise form, thus be processed into the method for optical element.Precision moulded formation is called mold pressing optics again! モー Le De オプディ Network ス) be shaped; Has the section bar that comprises precision machined forming face; Be to use the global shape that the model forming module after the above-mentioned section bar assembled with high precision is formed optical element; Simultaneously above-mentioned forming face is critically copied on glass, thereby form the method for optical function face.In the method, the positional precision of a plurality of optical function faces also can high precision form.For example, a kind of lens that can be shaped can suppress inclination and the deviation of above-mentioned hub of hub of the optical function face on lens two sides.In the 2nd method; Can be without mechanical workouts such as grinding, grindings; Just can form the optical function face; The surface of the optical element that just makes light refraction, diffraction, reflection or see through, so, can produce not only time-consuming cost but also high optical element in mechanical workouts such as non-spherical lens expeditiously.Precision moulded formation can use well-known method to carry out.For example; In order to improve the demoulding property of carbon film etc.; The whole surface of the glass gob of using at die forming forms has the film that makes the function that glass and section of mould molding surface slide easily, in non-oxidizing gas, above-mentioned glass gob is heated precision moulded formation in identical atmosphere surrounding.Secondly, open model forming module, take out die-formed product, slowly obtain optical element after the cooling.The optical element that obtains so also can carry out the mechanical workout of centering of lens for example etc. in case of necessity to a peripheral part of optical function face.Utilize such method, can produce optical elements such as non-spherical lens, spherical lens, set of lenses, microlens, diffraction grating, prism expeditiously.In case of necessity, also can form optical multilayers such as antireflection film on the surface of optical element.

In aforesaid method, when die forming glass gob in non-oxidizing gas, if use the glass gob that forms by opticglass III-2, because in non-oxidizing gas, (also comprise reducing gas) to not containing Sb ₂O ₃Glass heat-treat, so, the painted increase of glass sometimes.Therefore, when die forming in non-oxidizing gas, preferably use the glass gob that forms by opticglass I, II or opticglass III-2., in non-oxidizing gas die forming by not containing Sb ₂O ₃Glass, the glass gob that for example forms by opticglass III-2, even glass coloring increases,, also can reduce the painted of glass if utilize heat treating method of the present invention.But; If the maintenance temperature of die-formed product is too high in the oxidizing gas; Then molding deforms; Form accuracy may reduce, thus keep temperature to be preferably in more than or equal in ' glass tansition temperatures (Tg)-100 ℃ ' and the scope smaller or equal to ' glass tansition temperatures (Tg)-5 ℃ ', then better in more than or equal to ' glass tansition temperatures (Tg)-60 ℃ ' and scope smaller or equal to ' glass tansition temperatures (Tg)-20 ℃ '.

The 2nd form of the method for manufacture of optical element of the present invention (to call the method for making II of optical element in the following text) is that the glass shaping body that utilizes aforesaid manufacturing process to make is shaped, and makes the method for optical element through mechanical workout.

At first, the same with the operation of the method for manufacture of above-mentioned glass cup for die pressing, glass shaping body is carried out fine annealing, make specific refractory power accurately consistent with desirable value, simultaneously, reduce the distortion of glass, cut off or cut off glass shaping body, produce section.As the shape of glass shaping body, can enumerate bar-shaped glass and plate glass etc.The same with the method for manufacture of glass cup for die pressing, when the hub with pole shape glass vertically carries out cutting off of glass, preferably use the side pressure process of chopping.

Secondly, the shape optical element base that grinds to form optical element is produced in the grinding stripping and slicing, and this blank is ground, and accomplishes optical element at last.

In the method for making II of optical element, when using bar-shaped glass, preferably make the external diameter of external diameter and optical element of bar-shaped glass equal, perhaps form the external diameter after external diameter to optical element has carried out grinding or attrition process.Have, at the method for making I of optical element, when using bar-shaped glass, the external diameter of bar-shaped glass and the external diameter that is shaped with glass gob are equated, perhaps, the external diameter of the glass gob that formation is used die forming has carried out the external diameter after grinding or the attrition process.

Like this, various optical elements such as prism can be high-level efficiency made and glass breakage can be do not made.Also can on the surface of optical element, form optical multilayers such as antireflection film.

[embodiment]

Below, explain in further detail through embodiments of the invention, still, the invention is not restricted to these examples.

Embodiment 1

In the present embodiment, the method that illustrates below the utilization forms that refractive index n d is 2.08313, Abbe number (vd) is 22.23, liquidus temperature is that viscosity in 1270 ℃, liquidus temperature is that 0.824dPas, glass tansition temperatures are that density under 701 ℃, room temperature is 4.780, moving coefficient of viscosity is 1.724 * 10 ^-5m ²/ s, and if represent with the percentage ratio of quality, by the SiO that comprises 3.59% ₂, 6.24% B ₂O ₃, 32.44% La ₂O ₃, 26.73% TiO ₂, 11.12% Nb ₂O ₅, 6.14% ZrO ₂, 13.74% BaO and 0.00% Sb ₂O ₃The glass shaping body of the pole shape that forms of opticglass.

At first, frit is carried out weighing, obtain the opticglass I shown in the table 1, behind the thorough mixing, import in the melt container, the heating fusion.Secondly; Abundant clarification, uniform melten glass are flowed out with the viscosity of 0.6dPas and with the pipe spout of certain take-off rate (15ml/ branch) from arranged perpendicular continuously, continuously flow into without interruption and be located at the inlet central authorities that are disposed at the communicating pores in the locational carbon system mold shown in Figure 1.The temperature that flows into the melten glass of communicating pores inlet is 1320 ℃.The internal diameter of the communicating pores of mold is φ 12mm, makes the hub of communicating pores consistent with vertical, and the hub of pipe is consistent with the hub of above-mentioned communicating pores.If the length of mold communicating pores is 100mm, in order to be shaped well, around mold, to twine not shown band heater and heat, the temperature of communicating pores inwall is controlled at 520～600 ℃.Use 2 cylinders will export the side clamping of the pole shape glass that takes out, and control the take-off speed of pole shape glass from communicating pores.Use the liquid level of the melten glass in the laser sensor monitoring mold communicating pores, the monitor signal that the sensor is exported is input to the cylinder unit, and control makes the power input of cylinder motor rotating, makes the height of above-mentioned liquid level certain.In the present embodiment, the take-off speed of pole shape glass is set in the 2.2mm/ branch, accordingly the speed of rotation of cylinder is fed back, the height of liquid level is kept necessarily with the height change of above-mentioned liquid level.

Like this, take out the glass stick of the pole shape of φ 12mm continuously from the communicating pores outlet.Configuration shaping stove is transplanted in the shaping stove pole shape glass that from mold, takes out immediately under mold.The not shown well heater of configuration in the shaping stove, the temperature maintenance that makes furnace gas is at 780 ℃.The above-mentioned cylinder of configuration in the shaping stove.The length of the travel direction of the pole shape glass in the shaping stove is 360mm; Pole shape glass is through wherein needing the time; Because of the central part of pole shape glass in the meantime approaching with the temperature on surface; Event can not make pole shape glass destructive internal stress suddenly itself, can not have to make pole shape forming of glass damagedly.

Secondly, on a part of side of the pole shape glass that comes out from the shaping stove, through with the vertical direction of hub of pole shape glass on rule and be processed to form line.And, make internal flow have the metal sleeve of water to contact with line, with the local cooling of the part that forms line, the crack is extended to the center of line.At this moment, make metal sleeve follow moving of pole shape glass, keep and the line state of contact.With respect to the hub of pole shape glass, utilize and name a person for a particular job and the position of the opposite side in position that forms of ruling supports; Side pressurization in moment of progress of fracture to the glass shaping body below ruling; Push the forming of glass body side surface of line below, will separate with following pole shape glass than the pole shape glass that the height that forms line also will lean on.Have, the pole shape glass of present embodiment is 12mm because of external diameter, and is thinner again, so even it is contacted with metal sleeve and apply thermal shocking, also can well separate.

During separation, use the robots arm that the side of isolating pole shape glass is kept, after the separation, under the state that keeps with above-mentioned robots arm, pole shape glass transfer is entered the mouth to the continous way slow cooling stove that is placed on mold and shaping stove next door.The travelling belt of configuration well heater and conveyance glass in continous way slow cooling stove; The pole shape glass that is positioned on the travelling belt is moved; And slowly cool off to eliminate distortion; When cutting off the pole shape glass that takes out from continous way slow cooling stove, cut surface being ground observe it again when inner, only surperficial 0.5mm with interior extremely shallow layer in just discovery brush line is arranged, brush line is can't see in dark again place.That is, the major part of pole shape glass optically is uniform.

Equally, can there be the pole shape forming of glass that each glass by the opticglass shown in the table 1 2～9 is formed.After these pole shape glass being placed in the continous way slow cooling stove slowly cooling; From stove, take out again and cut off; And cut surface ground observes it again when inner, only surperficial 0.5mm with interior extremely shallow layer in just discovery brush line is arranged, brush line is can't see in dark again place.That is, the major part of pole shape glass optically is uniform.

Table 1 illustrates the composition of the glass of each opticglass 1～9, and table 2 and table 3 illustrate its characteristic.

[table 1]

[table 2]

[table 3]

Have again, in atmosphere, under 700 ℃ temperature, Sb ₂O ₃Be that 0.00% opticglass 1 and 8 kept 40 hours, reduce painted thermal treatment.

Comparative example 1

Be shaped with the embodiment 1 the same pole shape glass shaping body that forms by the opticglass of forming 10～12 that makes with the glass shown in the table 4.Table 4 illustrates its characteristic.

[table 4]

Fig. 8 be the opticglass 1～9 of expression among the embodiment 1 with comparative example 1 in the figure of relation of specific refractory power (nd) and λ 70 of opticglass 11～12; Can know by Fig. 8; The λ 70 of the opticglass 1～9 of embodiment 1 is little than the value of being obtained by formula (1);

Opticglass

5,6,8,9 equates with the value of being obtained by formula (1-b) or is littler than it that opticglass 5 is littler than the value of being obtained by formula (1-c).Relative therewith, the opticglass 11 of comparative example 1 and 12 λ 70 are bigger than the value of being obtained by formula (1).Have, shown in Fig. 8, λ 70 for the opticglass 10 of comparative example 1 again>700nm, specific refractory power (nd) is 2.0425, and is bigger than the value of being obtained by formula (1).

Have, various characteristics is measured according to following method again.

(1) specific refractory power (nd) and Abbe number (vd) are to measuring with the opticglass that obtains after per hour 30 ℃ cooling rate is cooled off.

(2) density utilizes Archimedes's method to measure.

(3) tansition temperatures uses the thermo-mechanical analysis device, under 4 ℃/minute heat-up rate, measures.

(4) liquidus temperature of the expression opticglass below the moving coefficient of viscosity utilization is measured with the method for viscosity under this liquidus temperature, and this viscosity is obtained moving coefficient of viscosity divided by the density under the room temperature.

(a) liquidus temperature is prepared a plurality of platinum crucibles, puts into 50cm in each crucible ³Glass, add a cover, put into the stove that temperature is set in 10 ℃ again, under different design temperatures, kept 2 hours, measure non crystallized minimum temperature through range estimation, with it as liquidus temperature.

(b) viscosity under the liquidus temperature (liquid phase viscosity) adopts the method by JIS Z8803 regulation, uses coaxial cylinder viscometer to measure.

(5) λ 70 and λ 5 be in the spectral transmission of measuring according to the method for this specification sheets, is that 70% wavelength is made as λ 70 with transsmissivity, and transsmissivity is that 5% wavelength is made as λ 5.

(6) Pt concentration utilizes the icp analysis method to measure.

Embodiment 2

Each pole shape glass behind the slow cooling that use is made by embodiment 1 has been made glass cup for die pressing.At first, the position of cutting off that utilizes line to be processed in pole shape glass sides forms line.Then, pole shape glass is inserted in the high pressure vessel, make the position that forms line be positioned at the central authorities of container; In order to limit moving of central axis direction; Utilize rubber seal that pole shape glass is stuck in the peristome of container, fills with water in the container makes inside not have bubble.

Pressurization under this state makes the hydraulic pressure in the container reach 20Mpa, on scribing position, vertically glass is blocked with the hub of pole shape glass.Like this, pole shape glass is cut off, process stripping and slicing by the interval of regulation.

Secondly, cylinder is carried out in above-mentioned section grind, weight is adjusted to the equiponderant weight with the target die-formed product, simultaneously, the edge rounding with sharp keen makes surface coarsening, becomes glass cup for die pressing.

Embodiment 3

The section of being made by embodiment 2 is carried out grinding, ground and process ganoid glass cup for die pressing.

Embodiment 4

Secondly, will be coated in equably by pulverous remover that SP 1 forms on the whole surface of the glass cup for die pressing of making by embodiment 2, put into process furnace, and make it in stove, move heating in atmosphere, softening on one side on one side.

Glass gob after softening is imported in the model forming module that is made up of upper die and lower die and middle mould, and die forming in atmosphere is opened mould and is taken out die-formed product again, puts into the slow cooling stove and carries out fine annealing, makes its cool to room temperature, processes the optical element blank.

Secondly, grinding, grind above-mentioned blank, process the spherical lens that each glass by opticglass 1～9 forms.

Devitrification and brush line can't see in lens inside, have obtained uniform optical element on the optics.

Embodiment 5

Secondly; On the whole surface of the glass cup for die pressing of making by embodiment 3, form carbon film; In the mixed gas of nitrogen and oxygen, heat, the model forming module that use has on the forming face of the section bar of SiC system as the carbon film of remover carries out precision moulded formation.Secondly, precision moulded formation article are slowly cooled off, obtain the non-spherical lens that each glass by opticglass 1～9 forms.

Embodiment 6

Utilize the side pressure process of chopping, vertically will block, process section by each the pole shape glass behind the fine annealing of embodiment 1 making with hub.Secondly, grinding, grinding are carried out in section, processed the spherical lens that each glass by opticglass 1～9 forms.

Opticglass of the present invention has the high refractive index that can adapt with the small-sized and high-performance of optical device, can carry out colour balance and proofread and correct, and is specially adapted to various optical elements.

Claims

1. the method for manufacture of an opticglass, it is characterized in that: this opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have and satisfy following relational expression (1)

Transmission characteristics,

In the process that makes the melten glass cooling forming, it is kept near the oxidative environment of the temperature the tansition temperatures that is equivalent to above-mentioned glass, then this glass is cooled off.

2. the method for manufacture of an opticglass, this opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, refractive index n d is more than or equal to 1.95, and, when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm, have and satisfy following relational expression (1)

Transmission characteristics,

To comprise TiO ₂Borate glass be kept near the oxidative environment of temperature the tansition temperatures that is equivalent to above-mentioned glass, after thermal treatment, cool off.

3. the method for manufacture of opticglass according to claim 1 and 2 is made and is not contained Sb in fact ₂O ₃And As ₂O ₃Opticglass.

4. the method for manufacture of opticglass according to claim 1 and 2 is made following opticglass, that is: if represent B with the percentage ratio of quality ₂O ₃And SiO ₂Total content smaller or equal to 20%, TiO ₂Content more than or equal to 20%.

5. the method for manufacture of the optical element of a glass is characterized in that: utilize the method for claim 1 or 2 records to make opticglass, use said opticglass to come manufacturing optical elements.

6. the method for manufacture of the optical element of a glass is characterized in that, has following operation: utilize the method for claim 1 or 2 records to make opticglass, make glass shaping body from said opticglass, and said glass shaping body is processed.

7. an opticglass has the TiO that comprises as glass ingredient ₂Borate-based composition, it is characterized in that:, have and satisfy following relational expression (1) when the outside transsmissivity that with thickness is 10.0mm is 70% a wavelength when being made as λ 70nm

Transmission characteristics.