CN101172757A

CN101172757A - Method for producing optical component

Info

Publication number: CN101172757A
Application number: CNA2007101634911A
Authority: CN
Inventors: 邹学禄
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2006-10-25
Filing date: 2007-10-25
Publication date: 2008-05-07
Also published as: KR20080037541A; JP2008105899A; JP4958213B2; KR100967298B1

Abstract

The invention provides a method for manufacturing an optical element formed by the fluophosphate glass through accurate compression molding. Through the method, the vagueness or white impurity can be reduced or prevented from occurring on the surface of the optical element and the finished product rate can be improved, thus manufacturing the optical element in a high efficiency. The optical element manufacturing method of the invention is includes heating a prefabricated piece formed by the fluophosphate glass and then conducting accurate compression molding to manufacture the optical element with the help of a compression molding mold. The optical element manufacturing method is characterized in that at least one part of the molding surfaced of the compression molding mold is made of a molding surface material away from the carbon system.

Description

The manufacture method of optical element

Technical field

The present invention relates to the manufacture method of optical element.

Background technology

The precision moulded formation method is also referred to as the moulded optical moulding method, this method is: the glass that will have desired optical is configured as the shape that is called as performing member in advance, heating, softening this performing member, use model forming module to carry out precision moulded formation and make optical element (for example, with reference to patent documentation 1).

According to above-mentioned precision moulded formation method, can supply optical elements such as grinding by in the past, glass non-spherical lens that abrasive method is difficult to produce in batches, diffraction grating, micro lens, set of lenses in large quantities with cheaper cost.

Patent documentation 1: the Japanese documentation spy opens the 2002-249337 communique.

Yet, in the time will making, preferably use fluophosphate glass to the near infrared light suction strainer that has low dispersed lens etc. or the response colour relation of semiconductor camera elements such as CCD or CMOS is calibrated etc.

It is lower to consider that fluophosphate glass is compared normal conditions lower-glass tansition temperature with borate glass or silicate glass, therefore can reduce the die forming temperature, helps precision moulded formation.

; though the precision moulded formation of the performing member that is formed by fluophosphate glass is compared with the performing member that is formed by borate glass or silicate glass and can be set the die forming temperature lower; but, thereby the surface that exists in resulting optical element produces problem fuzzy or gonorrhoea reduction yield rate.

Summary of the invention

The present invention In view of the foregoing finishes, thereby its purpose is to provide the surface that can reduce or be suppressed at optical element when the optical element that formed by fluophosphate glass by the precision moulded formation manufacturing to produce the method that fuzzy or gonorrhoea etc. are made optical element expeditiously.

When the optical element that forms by fluophosphate glass by the precision moulded formation manufacturing, can produce fuzzy or gonorrhoea etc. from the teeth outwards, after the inventor studies the reason of its generation, obtain following opinion (a) and (b).

(a) in precision moulded formation, use model forming module to be shaped from the glass of die forming temperature to the various glass of the glass that the die forming temperature is lower as fluophosphate glass above 600 ℃.As the model forming module of the temperature province that can tackle such broadness, use the mould as section bar with SiC, on the forming face of this model forming module,, applied akin carbon mold release film with SiC as mold release film.

But, when using above-mentioned model forming module precision moulded formation fluophosphate glass system performing member, sometimes fluorine that glass contained or fluorine cpd can react with the carbon mold release film that is coated on the section of mould molding surface, thereby produce fuzzy or gonorrhoea on the surface of optical element.

Further reduce the die forming temperature though also may be thought of as the described reaction of inhibition,, if reduce the die forming temperature, then glass viscosity can rise, thereby can destroy glass when being shaped.

(b) when fluophosphate glass comprises the Cu ion, except the fluorine composition, the Cu ion is also relevant with the fuzzy or gonorrhoea that produces at optical element surface.Because the Cu ion ratio is easier to be reduced, and in glass, move easily, therefore by being that mold release film contacts with the carbon on model forming module surface under the high temperature when the precision moulded formation, Cu ion in the glass is reduced, the precipitate of this reduction reaction blurs thereby produce attached to glass surface.

Based on above-mentioned cognition, the inventor further studies the back and finds, at least a portion by forming face is carried out precision moulded formation in be tied to form the model forming module that the shape flooring forms by non-carbon, can address the above problem, thereby finish the present invention.

That is, the invention provides the manufacture method of following optical element,

(1) a kind of manufacture method of optical element, the performing member that is formed by fluophosphate glass is heated, make optical element by carrying out precision moulded formation with model forming module, the manufacture method of described optical element is characterised in that at least a portion of the forming face of model forming module is tied to form the shape flooring by non-carbon and forms.

As the manufacture method of above-mentioned (1) described optical element, it is characterized in that (2) fluophosphate glass comprises the Li ion as cation constituent.

(3) as the manufacture method of above-mentioned (2) described optical element, it is characterized in that, fluophosphate glass also comprise as cation constituent, from Mg ion, Ca ion, Sr ion and Ba ion, select the composition more than 2 kinds.

As the manufacture method of above-mentioned (2) or (3) described optical element, it is characterized in that (4) the glass tansition temperature (Tg) of fluophosphate glass is below 470 ℃.

As the manufacture method of each described optical element in above-mentioned (1)～(3), it is characterized in that (5) fluophosphate glass comprises the Cu ion as cation constituent.

As the manufacture method of above-mentioned (5) described optical element, it is characterized in that (6) the glass tansition temperature (Tg) of fluophosphate glass is below 400 ℃.

As the manufacture method of each described optical element in above-mentioned (1)～(6), it is characterized in that (7) it is at least a for what select that non-carbon is tied to form the shape flooring from transition metal, silicon and lead.

According to the present invention, when the optical element that forms by fluophosphate glass by the precision moulded formation manufacturing, owing to use at least a portion of forming face to be tied to form the model forming module that the shape flooring forms by non-carbon, therefore can reduce or be suppressed at optical element surface and produce fuzzy or gonorrhoea etc., thereby make optical element expeditiously.

Embodiment

The manufacture method of optical element of the present invention is for to heat the performing member that is formed by fluophosphate glass, carry out precision moulded formation with model forming module, make the method for optical element thus, it is characterized in that at least a portion of the forming face of model forming module forms for being tied to form the shape flooring by non-carbon.

(performing member that forms by fluophosphate glass) as basic material

At first, the performing member that employed fluophosphate glass in the manufacture method of optical element of the present invention is formed describes.

As performing member, for example can use the performing member that in the method for following (1)～(3), obtains, that is:

(1) when frit is fused produce melten glass after, this melten glass is flowed out from spout, pouring into moulding is vitreum, after the annealing, to vitreum cut off, grinding, grinding, become performing member (below, be called the method for making I of performing member).

(2) when frit is fused produce melten glass after, this melten glass is flowed out from spout, from molten glass flow, isolate the fused glass block that is equivalent to a performing member weight, in glass cooling process, be configured as performing member (below, be called performing member method for making II).

(3) when frit is fused produce melten glass after, this melten glass is flowed out from spout, from molten glass flow, isolate fused glass block, in glass cooling process, be configured as glass block, this glass block is ground, be configured as performing member (below, be called performing member method for making III).

In method for making II, the III of performing member, preferred limit makes glass float the limit to cool off, be shaped.Like this,, can prevent from glass surface, to produce fold, also can prevent from the vitrification process, to crack the crack by being shaped while floating.

Performing member is made according to the mode that has with corresponding shape of objective optics element and weight.For example, when the lens made as optical element, preferably the shape of performing member is done globulate or had the shape of a rotation axes of symmetry.By such performing member is being carried out mold pressing on the direction of rotation axes of symmetry, glass is evenly stretched, be configured as the lens that do not have uneven gauge.

For performing member, also can apply in its surface and contain carbon film, so that glass is fully spread out in shaping dies when precision moulded formation.But, consider that fluorine composition in carbon film and the glass reacts and produce fuzzy or gonorrhoea etc. on the surface of optical element because this contains, therefore preferred the use on the surface do not apply the performing member that contains carbon film and glass is exposed.

As the fluophosphate glass that constitutes above-mentioned performing member, roughly divide into and utilize not containing Cu ionic fluophosphate glass and adding the Cu ion and given the fluophosphate glass of near-infrared absorbing characteristic of low dispersing characteristic.

As the optimal way that does not contain Cu ionic fluophosphate glass that utilizes low dispersing characteristic, can list following fluophosphate glass (below, be called glass I).That is:

% represents with positively charged ion, contains:

P ⁵⁺：10～45％，

Al ³⁺：5～30％，

Mg ²⁺：0～20％，

Ca ²⁺：0～25％，

Sr ²⁺：0～30％，

Ba ²⁺：0～33％，

Li ⁺：0～30％，

Na ⁺：0～10％，

K ⁺：0～10％，

Y ³⁺：0～5％，

B ³⁺：0～15％，

And, F ^-Content with respect to F ^-And O ^2-The mol ratio F of total amount ^-/ (F ^-+ O ^2-) be 0.25～0.85.

Glass I preferably realizes specific refractory power (n _d) be 1.40～1.58, Abbe number (vd) is the glass of the optical characteristics more than 67.Consider the manufacturing security, glass I is carried out the component adjustment, and to make its Abbe number (vd) be better below 90.

In addition, from making the viewpoint of stability, as divalent cation composition (R ²⁺), preferably comprise Ca ²⁺, Sr ²⁺, and Ba ²⁺Among two or more.

In addition, preferably as divalent cation composition (R ²⁺) Mg ²⁺, Ca ²⁺, Sr ²⁺, and Ba ²⁺Total content be more than the 1 positively charged ion %, more preferably Mg ²⁺, Ca ²⁺, Sr ²⁺, and Ba ²⁺Content be respectively more than the 1 positively charged ion %.

Below, the composition of above-mentioned glass I is elaborated, be that the positively charged ion % of benchmark represents with the ratio of each cation constituent in order to mol ratio, and be that the negatively charged ion % of benchmark represents also in order to mol ratio with the ratio of each anionic component.

P ⁵⁺Be important cation constituent,, import P with oxide raw material and surpass 45% o'clock needs if the stability of 10% glass of less than can reduce as the network structure of glass ⁵⁺, thereby can make the oxygen ratio become big, can't meet the desired optical characteristics.Therefore, this amount is controlled to be 10%～45%, P ⁵⁺Preferred range is 10%～45%, and the scope that is more preferably is 10%～40%.Wherein, importing P ⁵⁺The time use PCl ₅Can corrode the platinum as the constituent material of glass melting container etc., perhaps volatilization is also stronger, from the angle of the stability made and improper, so preferably import with phosphoric acid salt.

Al ³⁺It is the composition that improves the stability of fluophosphate glass, the stability of glass can reduce during less than 5%, and surpass at 30% o'clock because glass tansition temperature (Tg) and liquidus temperature (LT) rise bigger, therefore forming temperature rises, when being shaped, can and produce striped strongly owing to the surface volatilization, therefore, its amount is controlled to be 5%～30%.Al ³⁺Preferred range is 7%～28%.

Importing is as divalent cation composition (R ²⁺) Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Help to improve the stability of glass.But, preferably among these ions, import more than two kinds, more preferably import Ca ²⁺, Sr ²⁺And Ba ²⁺In more than two kinds.From more improving divalent cation composition (R ²⁺) importing effect aspect consider preferred Mg ²⁺, Ca ²⁺, Sr ²⁺And Ba ²⁺Total content be more than the 1 positively charged ion %.In addition, if import the higher limit that surpasses separately, then stability can descend sharp.Ca ²⁺, Sr ²⁺Can import relatively largely, but Mg ²⁺, Ba ²⁺The a large amount of importing can especially be reduced stability., because Ba ²⁺For can therefore preferably in the scope of not damaging stability, import morely keeping low dispersive to realize the composition of high refractive index simultaneously.

For the foregoing reasons, with Mg ²⁺Amount be controlled to be 0～20%, be preferably 1～15%, with Ca ²⁺Amount be controlled to be 0～25%, be preferably 1～20%, with Sr ²⁺Amount be controlled to be 0～30%, be preferably 1～25%, with Ba ²⁺Amount be controlled to be 0～33%, more preferably 1～25%.

Li ⁺For not damaging the composition that stability can reduce glass tansition temperature (Tg), still, its amount surpasses the weather resistance of 30% meeting infringement glass, and processibility also can reduce simultaneously.Therefore, its amount is controlled to be 0～30%.

As mentioned above, because fluophosphate glass normal conditions lower-glass tansition temperature is lower, so the precision moulded formation temperature also can be set lowlyer.But, because this glass contains easily and the fluorine composition of model forming module surface reaction, therefore need reduce to a certain degree the die forming temperature, and note not producing the fuzzy or gonorrhoea of the optical element surface that the surface reaction because of forming mould surface and glass causes.From such viewpoint, preferably import the Li more than 1% with the effect that reduces the die forming temperature ⁺Therefore, preferably its content is 1～30%, more preferably 2～30%, more preferably 3～30%, further preferred 4～30%.

I contains Li when glass ⁺The time, owing in alkalimetal ion, contain Li more ⁺Therefore, it is smaller and show better water-proof glass to obtain coefficient of thermal expansion.

In addition, contain Li more than 1% as glass I ⁺The time since with do not contain Li ⁺The glassy phase ratio, the glass melting temperature (Tm) can be reduced about 50 ℃, dissolve in platinum and the glass coloring that causes, sneak into unfavorable conditions such as bubble, generation striped from container in the time of therefore also can reducing, eliminate fusion.

In addition, contain Li as glass I ⁺The time, by reducing the glass tansition temperature, the Heating temperature of glass also can obtain relaxing the reaction of glass and model forming module or the effects such as life-span of prolongation model forming module in the time of can reducing the precision moulded formation of performing member.

Na ⁺, K ⁺Respectively with Li ⁺Identical have the effect that reduces glass tansition temperature (Tg), but while and Li ⁺Compare, have the tendency of further increasing coefficient of thermal expansion.In addition, owing to the solubleness to water of NaF, KF is compared with LiF greatly a lot, thereby also can cause water-proof deterioration, therefore with Na ⁺, K ⁺Amount be controlled to be 0～10% respectively.Na ⁺, K ⁺All be preferably 0～5%, more preferably do not import.

Y ³⁺Have the stability that improves glass, the effect of weather resistance, still, can worsen on the contrary if surpass 5% stability, glass tansition temperature (Tg) also can significantly rise, and therefore its amount is controlled to be 0～5%.Y ³⁺Amount be preferably 0～3%, more preferably 0.5～3%.

B ³⁺Be the vitrifying composition, have the effect that makes stabilizationization, still, excessive importing can cause the deterioration of weather resistance, in addition, is accompanied by B ³⁺Increase, the O in the glass ^2-Also can increase, therefore be difficult to reach the objective optics characteristic, thereby its amount is controlled to be 0～15%.But, as BF ₃, therefore easily volatilization and cause the generation of striped in dissolving preferably is controlled to be 0～10% with its amount, and more preferably 0～5%.When the volatility of preferential reduction glass, be preferably 0～0.5%, more preferably do not import.

In addition, consider from the stable aspect of making high-quality opticglass, in glass I, preferred P ⁵⁺, Al ³⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Li ⁺And Y ³⁺Total amount surpass 95% when representing with positively charged ion %, more preferably surpass 98%, more preferably surpass 99%, further be preferably 100%.

Except above-mentioned cation constituent, in the scope of not damaging purpose of the present invention, glass I can comprise cation constituents such as lanthanon such as Ti, Zr, Zn, La, Gd.

In addition, can so that stabilization turn to purpose and import Si ⁴⁺, still, if reduction melting temperature (Tm) and excessively importing, it is remaining then can to produce fusion, or volatilization becomes many during fusion, thus stability is made in infringement.Therefore, preferably with Si ⁴⁺Amount be controlled to be 0～10%, more preferably 0～8%, more preferably 0～5%.

For the ratio of anionic component, for accomplished desired optical and opticglass, with F with excellent stability ^-Content with respect to F-and O ^2-The mol ratio F of total amount ^-/ (F ^-+ O ^2-) be controlled to be 0.25～0.85.Preferably with the F in the negatively charged ion ^-And O ^2-Overall control be 100%.

Specific refractory power (the n of glass I _d) be 1.40～1.58, Abbe number (vd) is more than 67, is preferably 67～90, more preferably 70～90.

Glass I shows high transmittance in the visible region except the situation of adding tinting material.Glass I shows following optical transmittance characteristic: when the sample at two sides thickness 10mm smooth and parallel to each other, inject the light time from the direction perpendicular to described two sides, the transmissivity of wavelength 400nm～2000nm (except the reflection loss of sample surfaces) is more than 80%, preferred more than 95%.

The glass tansition temperature (Tg) of glass I is preferably below 470 ℃, more preferably below 430 ℃.

Because glass I shows good water tolerance, chemical durability, therefore after manufacturing performing member to in during the precision moulded formation, even prolonged preservation, the performing member surface also undergoes no deterioration.In addition, because the surface of optical element also is difficult to go bad, therefore also can use optical element with the unambiguous good order and condition in long-term surface.

Can be by for example using phosphatic raw materials, fluoride raw material etc., weighing, concoct these raw materials, provide it to the melt container of platinum alloy system, after heating, the fusion, clarify, homogenizing, from conduit flow out, being shaped obtains glass I.

On the other hand, the fluophosphate glass that add the Cu ion, applies the near-infrared absorbing characteristic is suitable for as the colorific adjustment of semiconductor camera elements such as CCD or CMOS filtering material, can use this glass, make performing member, come to have on the profiled surface various lens such as the strainer of diffraction grating or non-spherical lens by precision moulded formation.Strainer with diffraction grating is to possess low-pass filter with interference fringe removal function and the optical element with these two kinds of functions of near infrared ray cut-off filter of colorific adjustment function, and lens such as non-spherical lens are the optical element that possesses imaging function and these two kinds of functions of near infrared ray cut-off filter.

Give the optimal way of the fluophosphate glass of near-infrared absorbing characteristic as adding the Cu ion, can exemplify out following fluophosphate glass (below, be called glass II).

% represents with positively charged ion, and glass II contains 11～45% P ⁵⁺, 0～29% Al ³⁺, amount to 0～43% Li ⁺, Na ⁺And K ⁺, amount to 14～50% Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺And Zn ²⁺, 0.5～13% Cu ²⁺, and % represents with negatively charged ion, glass II contains 17～80% F ^-In above-mentioned composition, preferred remaining anionic component all is O ^2-

Below, the composition of glass II is elaborated, be that the positively charged ion % of benchmark represents with the ratio of each cation constituent in order to mol ratio, and be that the negatively charged ion % of benchmark represents also in order to mol ratio with the ratio of each anionic component.

In glass II, P ⁵⁺Being the basal component of fluophosphate glass, is to cause Cu ²⁺Absorb the important component of region of ultra-red.If P ⁵⁺Contain quantity not sufficient 11%, then color worsens and has green, on the contrary, if surpass 45%, then worsens weathering resistance, devitrification resistance.Therefore, preferred P ⁵⁺Content be 11～45%, more preferably 20～45%, more preferably 23～40%.

Al ³⁺It is the composition that improves the devitrification resistance of fluophosphate glass and thermotolerance, resistance to sudden heating, physical strength, chemical durability.But,, then can worsen the near infrared absorption characteristic if surpass 29%.Therefore, preferred Al ³⁺Content be 0～29%, more preferably 1～29%, more preferably 1～25%, further be preferably 2～23%.

Li ⁺, Na ⁺And K ⁺Be to improve glass melting, devitrification resistance, improve the composition of the transmissivity of visible region, still,, then worsen weather resistance, the processibility of glass if total amount surpasses 43%.Therefore, preferred Li ⁺, Na ⁺And K ⁺Total content be 0～43%, more preferably 0～40%, more preferably 0～36%.

In the alkali composition, Li ⁺Above-mentioned comparatively outstanding on, more preferably Li ⁺Amount be 15～30%, more preferably 20～30%.Like this, can be by importing Li ⁺Become to assign to reduce glass tansition temperature (being preferably below 400 ℃).

Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺And Zn ²⁺Be the useful composition of the devitrification resistance that improves glass, weather resistance, processibility, still, because excessive importing can reduce devitrification resistance, therefore preferred Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺And Zn ²⁺Total amount be 14～50%, more preferably 20～40%.

Mg ²⁺Content is preferred 0.1～10%, and more preferably 1～8%.Ca ²⁺Content is preferred 0.1～20%, and more preferably 3～15%.

Sr ²⁺Content is preferred 0.1～20%, and more preferably 1～15%.

Ba ²⁺Content is preferred 0.1～20%, and more preferably 1～15%, further preferred 1～10%.

Cu ²⁺Be the main undertaker of near infrared light absorption characteristic.If its quantity not sufficient 0.5%, then near infrared absorption diminishes, and on the contrary, if surpass 13%, then devitrification resistance worsens.Therefore, preferred Cu ²⁺Content be 0.5%～13%, more preferably 0.5～10%, more preferably 0.5～5%, further be preferably 1～5%.

In glass II, F ^-Be the fusing point that reduces glass, the important anionic component that improves weathering resistance.Owing to contain F ^-, therefore can reduce the glass melting temperature, suppress Cu ²⁺Reduction, thereby obtain desired optical.If less than 17% then worsens weathering resistance, on the contrary,, then can reduce O if surpass 80% ^2-Content, therefore produce because the Cu of 1 valency ⁺Near the 400nm that causes painted.Thereby, preferred F ^-Content be 17～80%.Consider from the above-mentioned characteristic of further raising aspect, more preferably F ^-Amount be 25～55%, more preferably 30～50%.

In glass II, O ^2-Be important anionic component, preferred whole anionic component is removed F ^-After remainder all with O ^2-Composition constitutes.Therefore, O ^2-Preferably measure to deduct above-mentioned F from 100% ^-The scope of preferred amount.If O ^2-Very few, the Cu of divalent then ²⁺Being reduced into is the Cu of 1 valency ⁺, so the short wavelength zone especially near the absorption the 400nm can become big and present green.On the contrary, if excessive, then the viscosity of glass is higher, and melt temperature uprises, so transmissivity worsens.In addition, because Pb, As hazardous property are stronger, preferably do not use.

For glass II, preferred glass tansition temperature (Tg) is below 400 ℃, more preferably below 390 ℃, more preferably below 380 ℃.As mentioned above, owing to consider when die forming contains Cu ionic fluophosphate glass because Cu ionic reduction reaction can produce fuzzy at optical element surface, therefore the preferred die forming temperature that reduces, the surface reaction that suppresses forming mould surface and glass, and be made as below 400 ℃ by the glass tansition temperature with glass II, also can reduce the die forming temperature.

The preferred transmission characteristics of glass II is as follows.

In the spectral transmission of wavelength 500～700nm, the wavelength that demonstrates 50% transmissivity is scaled the thickness of 615nm, and the spectral transmission of wavelength 400～1200nm demonstrates characteristic as described below.

Wavelength 400nm is more than 78%, and is preferred more than 80%, more preferably more than 83%, further preferred more than 85%,

Wavelength 500nm is more than 85%, and is preferred more than 88%, more preferably more than 89%,

Wavelength 600nm is more than 51%, and is preferred more than 55%, more preferably more than 56%,

Wavelength 700nm is below 12%, and is preferred below 11%, more preferably below 10%,

Wavelength 800nm is below 5%, and is preferred below 3%, more preferably below 2.5%, further preferred below 2.2%, further preferred below 2%,

Wavelength 900nm is below 5%, and is preferred below 3%, more preferably below 2.5%, further preferred below 2.2%, further preferred below 2%,

Wavelength 1000nm is below 7%, and is preferred below 6%, more preferably below 5.5%, further preferred below 5%, further preferred below 4.8%,

Wavelength 1100nm is below 12%, and is preferred below 11%, more preferably below 10.5%, further preferred below 10%,

Wavelength 1200nm is below 23%, and is preferred below 22%, more preferably below 21%, further preferred below 20%.

That is, the near infrared absorption of wavelength 700～1200nm is bigger, and the absorption of the visible rays of wavelength 400～600nm is less.Here, so-called transmissivity is: suppose to have and be parallel to each other and two planar glass samples of optical grinding, when to a described plane vertically during incident light, the light intensity that penetrates from described another plane is also referred to as outside transmissivity divided by the resulting value of intensity before the described incident light incident sample.

By above-mentioned characteristic, can carry out the colorific adjustment of semiconductor camera elements such as CCD or CMOS well.

For glass II, can heat by forming the melt container etc. of the platinum alloy system that offers after corresponding raw material weighing, the blending, fusion, clarification, homogenizing etc. and obtain with the glass of wanting to obtain.

(employed model forming module)

Below, employed model forming module in the manufacture method of optical element of the present invention is described.

For employed model forming module in the manufacture method of optical element of the present invention, at least a portion of its forming face is tied to form the shape flooring by non-carbon and constitutes.

Constitute and get final product though at least a portion of the forming face of model forming module is tied to form the shape flooring by non-carbon,, preferred whole forming face is tied to form the shape flooring by non-carbon and constitutes.

Non-carbon is tied to form the shape flooring and preferably selects at least a from transition metal, silicon and lead.

As transition metal, preferably from platinum, tungsten, palladium, rhodium, ruthenium, iridium, osmium, rhenium, tantalum, nickel, chromium, titanium, niobium, vanadium and molybdenum, select at least a.

Non-carbon is tied to form the shape flooring also can be alloy, can list as alloy and select at least a from Pt-Ir-Cr alloy, Pt-It alloy, Ir-Re alloy, Pd-W alloy, Rh-Ta alloy, W-Ru alloy, Ru-Re alloy, Os-Rh alloy, Pt-Re alloy, Pt-Ru alloy, Re-Ta alloy, Ir-Ru-Ta alloy, Ru-Re-W alloy, Pt-W alloy, Pt-Ta alloy, Ru-W-Re-Ta alloy, Pt-Rh alloy, Pt-Pd-Ru alloy, Pt-It-Ru-Pd alloy, Pt-Ir-Pd-Rh alloy and Pt-Ir-Rh-Pd-Ru alloy etc.

As mentioned above, when the performing member that is made of fluophosphate glass is heated, in model forming module during precision moulded formation, because the carbon mold release film of forming mould surface and the fluorine composition in the glass reacts or glass in the Cu ion be reduced, therefore produce fuzzy or gonorrhoea on the surface of resulting optical element easily, but, since above-mentioned non-carbon be tied to form shape flooring glass be difficult to glass in fluorine composition or Cu ion react, therefore can reduce, prevent the generation of fuzzy, the gonorrhoea of optical element surface.

As the method that forms that is tied to form forming face that the shape flooring forms by above-mentioned non-carbon, can exemplify out following method, that is: the material forming with high heat resistance, high rigidity, high working property that will be called as section bar is the mold shape that has critically the face corresponding with the surface shape of the optical element of target, on above-mentioned, directly or via middle layer formation be tied to form the film that the shape flooring forms by non-carbon.

As above-mentioned moulding stock, can use superhard alloy, sintering metal, pottery, quartz etc.As superhard alloy, can example to illustrate with the wolfram varbide be the superhard alloy of main component, be the superhard alloy of main component with the titanium carbide, be the superhard alloy of main component with the titanium nitride, with the free synthetic superhard alloy of above-mentioned superhard alloy, as sintering metal, can example to illustrate with the titanium nitride be the sintering metal of main component, be the sintering metal of main component with the titanium carbide, as pottery, the sintered compact of wolfram varbide can routine be shown.

The middle layer plays the fusible effect that improves die main body and be tied to form the film that the shape flooring forms by non-carbon.Therefore, the material that constitutes the middle layer considers that employed section bar and non-carbon are tied to form the shape flooring and suitably select to get final product.For example, preferably comprise alloy of being tied to form shape flooring common element with employed non-carbon etc.The middle layer is not limited to one deck, also can constitute with multilayer.

Intermediate coat and be tied to form the film that the shape flooring forms by non-carbon and for example can wait and form by sputter (sputter) method, vapour deposition method.

Be tied to form preferred 0.05～100 μ m of thickness of the film that the shape flooring forms, more preferably 0.05～50 μ m, further preferred 0.1～50 μ m by non-carbon.

(precision moulded formation)

Below, employed precision moulded formation in the manufacture method of optical element of the present invention is described.

In the manufacture method of optical element of the present invention, the performing member that is formed by fluophosphate glass is heated, in above-mentioned model forming module, carry out precision moulded formation.

When using above-mentioned glass I as fluophosphate glass, precision moulded formation atmosphere can be blended in the reducing atmospheres such as shaping gas in the rare gas element any for inert atmospheres such as oxygen-containing atmosphere, nitrogen and with hydrogen.In addition, when using above-mentioned glass II as fluophosphate glass, consider that from preventing Cu ionic reduction aspect preferred precision moulded formation atmosphere is carried out precision moulded formation in the air that oxygen-containing atmosphere for example cleans.

As the optimal way of precision moulded formation, can express precision moulded formation method 1 and 2 shown below.

(precision moulded formation method 1)

Precision moulded formation method 1 is: performing member is imported model forming module, model forming module and performing member are heated together, carry out precision moulded formation.

In precision moulded formation method 1, preferably the temperature of model forming module and described performing member all is heated to the glass display that constitutes performing member and goes out 10 ⁶～10 ¹²After the temperature during viscosity of dPas, carry out precision moulded formation.

In addition, described glass cools is extremely preferably demonstrated 10 ¹²DPas is above, more preferably demonstrate 10 ¹⁴DPas is above, further preferably demonstrate 10 ¹⁶Temperature during the above viscosity of dPas then, is taken out the precision moulded formation product from model forming module.

According to above-mentioned condition, can also optical element can be taken out indeformablely simultaneously by the glass shape of transfer printing die forming section of mould molding surface critically.

(precision moulded formation method 2)

Precision moulded formation method 2 is: the performing member of heating is imported in the model forming module of preheating, carry out precision moulded formation.

According to precision moulded formation method 2, owing to before above-mentioned performing member is imported model forming module, heat in advance, therefore can shorten the cycle, produce the optical element of good surface accuracy simultaneously with free of surface defects.

Wherein, the preheating temperature of model forming module is preferably set to the preheating temperature that is lower than performing member.So, by reducing the preheating temperature of model forming module, can reduce the consumption of model forming module.

In precision moulded formation method 2, the glass that constitutes performing member preferably is preheated to and demonstrates 10 ⁹DPas is following, more preferably demonstrate 10 ⁹Temperature during the viscosity of dPas.

In addition, preferred limit makes described performing member float the limit to carry out preheating, and, more preferably be preheated to the glass display that constitutes performing member and go out 10 ^5.5～10 ⁹Temperature during the viscosity of dPas further preferably is preheated to and demonstrates 10 ^5.5Above and the less than 10 of dPas ⁹Temperature during the viscosity of dPas.

In addition, begin the cooling of glass or begin the cooling of glass from mold pressing midway in the time of preferably with the beginning mold pressing.

Wherein, though the temperature of model forming module is adjustable to the temperature of the preheating temperature that is lower than described performing member, can go out 10 with described glass display ⁹～10 ¹²Temperature during the viscosity of dPas is a benchmark.

In precision moulded formation method 2, behind the die forming, the viscosity that preferably is cooled to glass is 10 ¹²After dPas is above, carry out the demoulding.

To carry out the optical element that precision moulded formation obtains by precision moulded formation method 1 or 2 and from model forming module, take out, carry out slow cooling as required.When optical element is lens etc., also can forms on the surface as required and prevent reflectance coating or coating near-infrared reflection film.

In resulting optical element, light sees through with making, the face of refraction, diffraction, reflection is called the optical function face (with lens is example, the lens face of the aspheric surface of non-spherical lens and the sphere of spherical lens etc. is equivalent to the optical function face), according to die forming methods such as above-mentioned precision moulded formation method 1 or precision moulded formation methods 2, promptly, critically be transferred to by forming face and form the optical function face on the glass, thereby need not to apply mechanical workouts such as grinding and grinding for the face shape of making the optical function face with model forming module.

Therefore, method of the present invention is suitable for the manufacturing of lens, set of lenses, diffraction grating, the lens that have diffraction grating, bevelled mirror, the bevelled mirror that has lens, diffraction grating and strainer optical elements such as (strainers that also comprises subsidiary diffraction grating), especially, can on large-duty basis, make non-spherical lens.

Embodiment

Below, by embodiment the present invention is described in further detail, still, the present invention is not limited to these examples.

Embodiment 1

(1) manufacturing of glass

Come suitable weighing phosphoric acid salt, fluorochemical, oxide compound, carbonate, oxyhydroxide according to each fluophosphate glass that obtains having the composition shown in table 1～table 3, carry out thorough mixing, be mixed into frit.Frit after the blending is put in the platinum crucible, and cover lid carries out fusion, clarification, homogenizing in 800～1250 ℃, obtain each melten glass.

Table 1

No.		1	2	3	4	5	6
No.		1	2	3	4	5	6	(positively charged ion %)
	P ⁵⁺	26.0	27.0	29.0	25.9	24.9	14.0	(positively charged ion %)
	P ⁵⁺	26.0	27.0	29.0	25.9	24.9	14.0	Al ³⁺	20.0	21.0	11.0	21.0	20.0	29.4
	Mg ²⁺	10.0	7.3	8.0	7.5	6.5	3.9	Al ³⁺	20.0	21.0	11.0	21.0	20.0	29.4
	Mg ²⁺	10.0	7.3	8.0	7.5	6.5	3.9	Ca ²⁺	14.0	9.1	10.0	9.4	8.1	22.4
	Sr ²⁺	15.0	15.6	17.0	15.9	13.8	14.5	Ca ²⁺	14.0	9.1	10.0	9.4	8.1	22.4
	Sr ²⁺	15.0	15.6	17.0	15.9	13.8	14.5	Ba ²⁺	10.0	11.0	12.0	11.3	9.7	8.2
	Li ⁺	4.0	8.0	12.0	8.0	16.0	5.0	Ba ²⁺	10.0	11.0	12.0	11.3	9.7	8.2
	Li ⁺	4.0	8.0	12.0	8.0	16.0	5.0	Y ³⁺	1.0	1.0	1.0	1.0	1.0	2.6
	La ³⁺	0.0	0.0	0.0	0.0	0.0	0.0	Y ³⁺	1.0	1.0	1.0	1.0	1.0	2.6
	La ³⁺	0.0	0.0	0.0	0.0	0.0	0.0	Gd ³⁺	0.0	0.0	0.0	0.0	0.0	0.0
	Add up to	100.0	100.0	100.0	100.0	100.0	100.0	Gd ³⁺	0.0	0.0	0.0	0.0	0.0	0.0
	Add up to	100.0	100.0	100.0	100.0	100.0	100.0	(negatively charged ion %)
	F ^-	64.1	62.1	56.5	63.5	63.4	81.5	(negatively charged ion %)
	F ^-	64.1	62.1	56.5	63.5	63.4	81.5	O ^2-	35.9	37.9	43.5	36.5	36.6	18.5
	F ^-/(F ^-+O ^2-)	0.641	0.621	0.565	0.635	0.634	0.815	O ^2-	35.9	37.9	43.5	36.5	36.6	18.5
	F ^-/(F ^-+O ^2-)	0.641	0.621	0.565	0.635	0.634	0.815	The glass tansition temperature (℃)		429	417	375	406	375	404
Refractive index n d		1.50098	1.50674	1.52147	1.50204	1.49885	1.4679	The glass tansition temperature (℃)		429	417	375	406	375	404
Refractive index n d		1.50098	1.50674	1.52147	1.50204	1.49885	1.4679	Abbe number vd		81.2	80.2	76.7	81.0	81.0	89.1

Table 2

No.		7	8	9	10	11
No.		7	8	9	10	11	(positively charged ion %)
	P ⁵⁺	38.0	38.0	29.0	29.0	29.0	(positively charged ion %)
	P ⁵⁺	38.0	38.0	29.0	29.0	29.0	Al ³⁺	9.0	9.0	9.0	9.0	9.0
	Mg ²⁺	6.0	6.0	6.0	6.0	6.0	Al ³⁺	9.0	9.0	9.0	9.0	9.0
	Mg ²⁺	6.0	6.0	6.0	6.0	6.0	Ca ²⁺	4.0	4.0	4.0	4.0	4.0
	Sr ²⁺	5.0	5.0	5.0	5.0	5.0	Ca ²⁺	4.0	4.0	4.0	4.0	4.0
	Sr ²⁺	5.0	5.0	5.0	5.0	5.0	Ba ²⁺	16.0	16.0	23.0	23.0	23.0
	Li ⁺	21.0	21.0	21.0	21.0	21.0	Ba ²⁺	16.0	16.0	23.0	23.0	23.0
	Li ⁺	21.0	21.0	21.0	21.0	21.0	Y ³⁺	1.0	1.0	3.0	1.0	1.0
	La ³⁺	0.0	0.0	0.0	2.0	0.0	Y ³⁺	1.0	1.0	3.0	1.0	1.0
	La ³⁺	0.0	0.0	0.0	2.0	0.0	Gd ³⁺	0.0	0.0	0.0	0.0	2.0
	Add up to	100.0	100.0	100.0	100.0	100.0	Gd ³⁺	0.0	0.0	0.0	0.0	2.0
	Add up to	100.0	100.0	100.0	100.0	100.0	(negatively charged ion %)
	F ^-	33.5	27.4	42.9	42.9	42.9	(negatively charged ion %)
	F ^-	33.5	27.4	42.9	42.9	42.9	O ^2-	66.5	72.6	57.1	57.1	57.1
	F ^-/(F ^-+O ^2-)	0.335	0.274	0.429	0.429	0.429	O ^2-	66.5	72.6	57.1	57.1	57.1
	F ^-/(F ^-+O ^2-)	0.335	0.274	0.429	0.429	0.429	The glass tansition temperature (℃)		374	374	367	366	368
Refractive index n d		1.55490	1.5549	1.55067	1.55276	1.55221	The glass tansition temperature (℃)		374	374	367	366	368
Refractive index n d		1.55490	1.5549	1.55067	1.55276	1.55221	Abbe number vd		71.0	71.0	72.1	71.8	71.8

Table 3

No.			12	13
No.			12	13	Glass is formed
	(positively charged ion %)	P ⁵⁺	27.8	28.8	Glass is formed
		P ⁵⁺	27.8	28.8	Al ³⁺	18.2	13.9
		Ba ²⁺	6.1	4.0	Al ³⁺	18.2	13.9
		Ba ²⁺	6.1	4.0	Sr ²⁺	10.9	4.7
		Ca ²⁺	9.4	6.5	Sr ²⁺	10.9	4.7
		Ca ²⁺	9.4	6.5	Mg ²⁺	6.0	3.1
		Zn ²⁺	0.0	5.3	Mg ²⁺	6.0	3.1
		Zn ²⁺	0.0	5.3	Li ⁺	20.4	23.3
		Na ⁺	0.0	7.4	Li ⁺	20.4	23.3
		Na ⁺	0.0	7.4	K ⁺	0.0	0.0
		La ³⁺	0.0	0.0	K ⁺	0.0	0.0
		La ³⁺	0.0	0.0	Y ³⁺	0.0	0.0
		Yb ³⁺	0.0	0.0	Y ³⁺	0.0	0.0
		Yb ³⁺	0.0	0.0	Gd ³⁺	0.0	0.0
		Si ⁴⁺	0.0	0.0	Gd ³⁺	0.0	0.0
		Si ⁴⁺	0.0	0.0	B ³⁺	0.0	0.0
		Zr ⁴⁺	0.0	0.0	B ³⁺	0.0	0.0
		Zr ⁴⁺	0.0	0.0	Ta ⁵⁺	0.0	0.0
		Cu ²⁺	1.2	3.0	Ta ⁵⁺	0.0	0.0
		Cu ²⁺	1.2	3.0	Sb ³⁺	0.0	0.0
		(negatively charged ion %)	F ^-	48	Sb ³⁺	0.0	0.0	40.9
	O ^2-		F ^-	48	52	59.1		40.9
	O ^2-		The glass tansition temperature (℃)			59.1	370	330
Specific refractory power (nd)			The glass tansition temperature (℃)			1.51314	370	330	1.52115

(2) manufacturing of performing member

The melten glass that obtains is like this poured in the mould of preheating, carries out slow cooling, obtain glass shaping body, with this glass shaping body cut off, grinding, grinding, produce each performing member for precise compression moulding with spherical form.In addition, also melten glass can be dripped from conduit, make glass drop under the situation of floating on the shaping dies, be configured as performing member, can also will separate requirement from the effusive melten glass of conduit, obtain glass block, make this glass block under the situation of floating on the shaping dies, be configured as performing member.

Do not contain the coating of carbon film etc. on the performing member surface, whole surface is the state that glass exposes.

(3) make non-spherical lens by precision moulded formation

Shaping dies as above-mentioned performing member being carried out precision moulded formation is ready to a plurality of shaping dies that comprise mold, bed die, phantom.The main body of each shaping dies is made of the section bar shown in the table 4 respectively, and in addition, its forming face forming face material shown in the use table 4 respectively forms film shape by sputtering method on section bar, and thickness is the scope of 0.1～50 μ m.

Table 4

No.	Section bar	The forming face material
No.	Section bar	The forming face material	1	The WC superhard alloy	Pt(40at％)-Ir(40at％)-Cr(20at％)
2	Pottery	Pt(40at％)-Ir(40at％)-Cr(20at％)	1	The WC superhard alloy	Pt(40at％)-Ir(40at％)-Cr(20at％)
2	Pottery	Pt(40at％)-Ir(40at％)-Cr(20at％)	3	The TiN sintering metal	Pt(40at％)-Ir(40at％)-Cr(20at％)
4	The TiC sintering metal	Pt(40at％)-Ir(40at％)-Cr(20at％)	3	The TiN sintering metal	Pt(40at％)-Ir(40at％)-Cr(20at％)
4	The TiC sintering metal	Pt(40at％)-Ir(40at％)-Cr(20at％)	5	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-ZrO2(0.5wt％)
6	The TiN sintering metal	Pt(89.8wt％)-Rh(9.7wt％)-TiO2(0.5wt％)	5	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-ZrO2(0.5wt％)
6	The TiN sintering metal	Pt(89.8wt％)-Rh(9.7wt％)-TiO2(0.5wt％)	7	The TiC sintering metal	Pt(89.8wt％)-Rh(9.7wt％)-Ta2O5(0.5wt％)
8	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-La2O3(0.5wt％)	7	The TiC sintering metal	Pt(89.8wt％)-Rh(9.7wt％)-Ta2O5(0.5wt％)
8	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-La2O3(0.5wt％)	9	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-Nb2O5(0.5wt％)
10	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-V2O5(0.5wt％)	9	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-Nb2O5(0.5wt％)
10	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-V2O5(0.5wt％)	11	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-HfO2(0.5wt％)
12	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-BeO(0.5wt％)	11	The WC superhard alloy	Pt(89.8wt％)-Rh(9.7wt％)-HfO2(0.5wt％)
12	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-BeO(0.5wt％)	13	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-Y2O3(0.5wt％)
14	The WC superhard alloy	Pt(80wt％)-Pd(15wt％)-Ru(15wt％)-ZrO2(0.5wt％)	13	Pottery	Pt(89.8wt％)-Rh(9.7wt％)-Y2O3(0.5wt％)

(notes) at% represents atomic percentage, and wt% represents quality percentage

(making non-spherical lens) by precision moulded formation method 1

Each performing member that will obtain in (2) imports in above-mentioned each shaping dies, model forming module and performing member is heated to the glass display that constitutes performing member together goes out 10 ⁶～10 ¹²Temperature during the viscosity of dPas is carried out precision moulded formation.

Then, the glass display that is cooled in the shaping dies goes out 10 ¹⁶After the temperature during viscosity of dPas, from model forming module, take out non-spherical lens.

(making non-spherical lens) by precision moulded formation method 2

Performing member is preheating to the glass display that is formed in each performing member that obtains in (2) goes out 10 ⁹Temperature during the viscosity of dPas.This performing member is imported to the glass heats of formation performing member to demonstrating 10 ¹⁰～10 ¹²In each shaping dies of temperature during the viscosity of dPas, carry out precision moulded formation.

In addition, in above-mentioned each method, precision moulded formation atmosphere is the air of cleaning.

So, then produce the non-spherical lens that constitutes by fluophosphate glass and by containing the non-spherical lens that Cu ionic fluophosphate glass with near infrared light absorption characteristic constitutes with low dispersing characteristic.All can't see fuzzy or gonorrhoea on the surface of resulting lens.

So, then produce have protruding crescent shape, the non-spherical lens of the different shape of recessed crescent shape, concave-concave shape, biconvex shape, plano-convex shape, plano-concave shape.

Similarly, the data that also can produce the formation optical recording formula medium of DVD or CD etc. write, read in the micro lens with optical system.

The lens that produce like this can be got core processing, also can not need to get core processing, and the reference plane when making fixed lens becomes with the position relation of optical axis regulation, the mode of angle and limits precision moulded formation.

In addition, in above-mentioned example, made lens, still, also can make diffraction grating, strainer (strainer that also comprises subsidiary diffraction grating), bevelled mirror etc. by precision moulded formation.

Also can on resulting optical element surface, form optical thin films such as preventing reflectance coating as required.

Industrial applicibility

According to the present invention, can provide when the optical element that formed by fluophosphate glass by the precision moulded formation manufacturing, reduce or be suppressed at fuzzy or gonorrhoea that optical element surface produces etc., thereby make expeditiously the method for optical element.

Claims

1. the manufacture method of an optical element by the performing member that is formed by fluophosphate glass is heated, is carried out precision moulded formation with model forming module and is made optical element, and the manufacture method of described optical element is characterised in that,

At least a portion of the forming face of model forming module is tied to form the shape flooring by non-carbon and forms.

2. the manufacture method of optical element as claimed in claim 1 is characterized in that, fluophosphate glass comprises the Li ion as cation constituent.

3. the manufacture method of optical element as claimed in claim 2 is characterized in that,

Fluophosphate glass also comprises as the composition more than 2 kinds cation constituent, that select from Mg ion, Ca ion, Sr ion and Ba ion.

4. as the manufacture method of claim 2 or 3 described optical elements, it is characterized in that the glass tansition temperature (Tg) of fluophosphate glass is below 470 ℃.

5. as the manufacture method of each described optical element in the claim 1～3, it is characterized in that fluophosphate glass comprises the Cu ion as cation constituent.

6. the manufacture method of optical element as claimed in claim 5 is characterized in that, the glass tansition temperature (Tg) of fluophosphate glass is below 400 ℃.

7. as the manufacture method of each described optical element in the claim 1～6, it is characterized in that it is at least a for what select that non-carbon is tied to form the shape flooring from transition metal, silicon and lead.