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CN102898001A - Processes for the production of glass preform and optical element - Google Patents

Processes for the production of glass preform and optical element Download PDF

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Publication number
CN102898001A
CN102898001A CN201210301860XA CN201210301860A CN102898001A CN 102898001 A CN102898001 A CN 102898001A CN 201210301860X A CN201210301860X A CN 201210301860XA CN 201210301860 A CN201210301860 A CN 201210301860A CN 102898001 A CN102898001 A CN 102898001A
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China
Prior art keywords
glass
performing member
temperature
precision moulded
moulded formation
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Pending
Application number
CN201210301860XA
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Chinese (zh)
Inventor
邹学禄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoya Corp
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Hoya Corp
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Publication date
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Publication of CN102898001A publication Critical patent/CN102898001A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B9/00—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor
    • B24B9/02—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground
    • B24B9/06—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground of non-metallic inorganic material, e.g. stone, ceramics, porcelain
    • B24B9/08—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground of non-metallic inorganic material, e.g. stone, ceramics, porcelain of glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
    • C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

A method for producing a glass preform is provided to obtain a high-quality preform free from loss of transparency and cord generation even when using unstable glass or highly volatile glass. A method for producing a glass preform for use in precision press molding comprises the steps of: separating molten glass mass from molten glass ejected from an ejection port and carrying out press molding of the molten glass to manufacture a glass body having a shape similar to the shape of a glass preform; and forming a glass preform from the glass body at least through a grinding process. The glass preform is formed of fluorine-containing glass or borate glass.

Description

The manufacture method of glass-made performing piece and the manufacture method of optical element
The application be that October 19, application number in 2007 are 200710163290.1 the applying date, denomination of invention divides an application for the patent application of " manufacture method of glass-made performing piece and the manufacture method of optical element ".
Technical field
The present invention relates to the manufacture method of glass-made performing piece and the manufacture method of optical element.
Background technology
The precision moulded formation method is also referred to as the moulded optical moulding method, the method is: glass is preshaped for being called as the shape of performing member, heating, softening performing member use model forming module to carry out precision moulded formation (for example, with reference to patent documentation 1).
According to above-mentioned precision moulded formation method, can supply in large quantities the optical elements such as glass manufacture-illegal spherical lens that the method for grinding by in the past, grinding is difficult to produce in batches with cheaper cost.
For for precision moulded formation performing member, can produce with method for hot forming, that is, from melten glass, separate the fused glass block of the amount of a performing member, in the process of glass cools, curing, it is configured as performing member.
Owing in method for hot forming, being performing member by the melten glass direct forming, although therefore have good production, but want the very not high glass of stability in use or under the state of liquation, have high-volatile glass to produce performing member without defectives such as devitrification, stripeds, need very superb technology.
Patent documentation 1: Japanese documentation JP 2002-249337 communique.
Summary of the invention
The present invention In view of the foregoing finishes, even its purpose is to provide the not too high glass of stability in use and has high-volatile glass under the state of liquation to make without the method for the high-quality performing member of devitrification and striped and use the method for making optical element by the performing member of aforesaid method manufacturing.
The inventor is through conscientiously finding after the research, (1) produces vitreum by the die forming fused glass block, this vitreum is carried out milled processed make performing member, perhaps (2) are cut apart the sheet glass that glass workpiece obtains by die forming and are made vitreum, this vitreum is carried out milled processed make performing member, can address the above problem thus, finish the present invention based on this opinion.
That is, the invention provides following manufacture method.
(1) a kind of manufacture method of glass-made performing piece, described glass-made performing piece be for precision moulded formation, the manufacture method of described glass-made performing piece (below, be called the method for making I of performing member) be characterised in that,
Isolate fused glass block by the melten glass that flows out from spout, carry out die forming, manufacture the vitreum with the shape that is similar to described performing member,
And pass through at least grinding step, make performing member by described vitreum.
(2) a kind of manufacture method of glass-made performing piece, described glass-made performing piece be for precision moulded formation, the manufacture method of described glass-made performing piece (below, be called the method for making II of performing member) be characterised in that,
Melten glass is poured into mold, is configured as glass workpiece,
Cut apart this glass workpiece, produce a plurality of sheet glass,
Heating, softening this sheet glass carry out die forming, make the vitreum with the shape that is similar to described performing member,
And pass through at least grinding step, make performing member by described vitreum.
(3) such as the manufacture method of above-mentioned (1) or (2) described glass-made performing piece, it is characterized in that,
The performing member that manufacturing is formed by fluorine-containing composition glass or borate glass.
(4) a kind of manufacture method of optical element is characterized in that,
Heating is carried out precision moulded formation by a certain the glass-made performing piece that described method produces in above-mentioned (1)～(3).
According to the present invention, following method can be provided, namely, to the vitreum made by the die forming fused glass block or cut apart the vitreum that sheet glass that glass workpiece obtains makes by die forming and carry out milled processed, even also can make high-quality performing member without devitrification and striped for the not high glass of stability in use and the situation that under the liquation state, has high-volatile glass thus.In addition, can provide the method for making optical element by the performing member of aforesaid method manufacturing of using.
Embodiment
At first, the manufacture method of glass-made performing piece of the present invention described.
The manufacture method of glass-made performing piece of the present invention comprises the method for making I of performing member and the method for making II of performing member.
The method for making I of performing member for for precision moulded formation the manufacture method of glass-made performing piece, it is characterized in that,
Fractional melting glass block from the melten glass that is flowed out by spout with its die forming, manufactures the vitreum with the shape that is similar to described performing member, and passes through at least grinding step, makes performing member by described vitreum.
Can obtain melten glass by the known methods such as method of heating, molten raw.For example, in order to obtain the objective optics characteristic, can concoct frit, it be imported in the melt containers such as crucible, tank, heat, after the melting, make through the clarification operation that is used for eliminating foam, the agitating procedure that is used for homogenizing.Above-mentioned frit can use and be called as the in batches not vitrifying raw material of raw material, also can use the vitrifying raw material that is called as glass cullet.
Resulting melten glass is flowed down in the conduit that links with melt container etc., flow out from spout, isolate the so heavy fused glass block of weight that adds the grind in the aftermentioned grinding step in the weight of the amount of a performing member.When the fractional melting glass block, can cut off molten glass flow by the cutting knife that is called as stapling machine, and for not residual cutting vestige, for example also can adopt following method, that is: from the spout of the conduit melten glass that drips, the molten glass flow top of perhaps flowing out by the supporting mass supporting reduces supporting mass rapidly in the moment of fused glass block that can separate targets weight, utilize the surface tension of melten glass, isolate fused glass block from the molten glass flow top.
With above-mentioned fused glass block die forming in shaping dies, thereby produce the vitreum with the shape that is similar to performing member.
Preferably by utilizing universal stage to make continuously above-mentioned vitreum.
For example, on universal stage, the bed die of a plurality of shaping dies equally spaced is configured on the circumference centered by the platform turning axle.Universal stage rotates by the transposition rotating mechanism.By transposition rotation each bed die is transported, is docked on the position that adjacent bed die stops before the rotation.With a bed die stop place be configured in as casting position above-mentioned spout under.In the lower end that rests on bed die on the casting position and catch the molten glass flow that flows out from conduit, with the cutting knife that is called as stapling machine with molten glass flow from cut off etc. midway, thus fused glass block is separated on the bed die.In the moment that finishes to separate, by with universal stage transposition rotation, the bed die that holds fused glass block is transported to next stop place from casting position.Make mold standby above this stop place of the shaping dies relative with bed die, the moment decline mold in the stop of bed die carries out mold pressing with the fused glass block on the bed die with bed die thus.Around each bed die, set in advance respectively mould, by mold pressing fused glass block is spread out in the space that is surrounded by upper/lower die and mould and to be configured as vitreum, the heat of glass is sucked rapidly by upper/lower die and mould and cools off simultaneously, and viscosity rises (stop place that will carry out this mold pressing is called the mold pressing position) rapidly.On the forming face of bed die, also can be coated with in advance the thermotolerance powder agent by spraying method etc., such as Powdered releasing agents such as boron nitride powders, prevent the bonding of glass and improve the at present smooth finish of the glass on the section of mould molding surface of mold pressing with this.
Then, the rising mold is waited for it above the mold pressing position, will hold Vitrea bed die and be sent to next stop place.Vitreum is cooled to the external force that applies when taking out also after the indeformable temperature at bed die, and the use suction device that (is called taking-ups (take-out) position) in the stop place of taking out etc. takes out it from bed die, carries out slow cooling.
Take out the transposition rotation of Vitrea bed die by universal stage and be sent to casting position, and received the fused glass block that be shaped next time.
Like this, each bed die is delivered to casting position, mold pressing position, extracting position successively by the transposition rotation, and repeatedly carries out aforesaid operations on each stop place.
According to the method for making I, fused glass block is configured as vitreum by shaping dies, is promptly sucked heat and rapidly cooling simultaneously.As a result, for high-volatile glass, the temperature province that can promptly volatilize by volatile component, thus reduction is as the volatilization of the glass ingredient of the major cause that produces striped.Even the extremely low glass of viscosity during for outflow is also owing to glass in the die forming operation is cooled off rapidly and can easily make vitreum.
The vitreum of taking-up, slow cooling passes through grinding step at least from shaping dies, makes the performing member that precision moulded formation is used.
The reason of carrying out above-mentioned grinding step is in order to remove the inevitable fold that produces, surface imperfection, depression etc. when the die forming fused glass block is made the vitreum with the shape that is similar to performing member.For this point, in following (1)～(3), be elaborated.
(1) in the die forming of fused glass block, for burning, the glass that does not make high temperature is bonded on the mould, need to reduce in advance the temperature of mould.But owing to having reduced the temperature of mould, glass is cooled off rapidly and is produced local contraction when contact, so the contact area of glass and mould temporarily reduces, and amount of thermal conduction also reduces.As a result, cause the temperature of glass surface to rise, when the temperature of glass surface rose, the viscosity of glass reduced, and the contact area of glass and mould increases, and therefore, glass is cooled off again, produces local contraction.In this wise, can before mold pressing, repeatedly occur because the contraction of glass and viscosity reduce, therefore produce fold on the surface of glass sometimes, but, in the method for making I, by resulting vitreum is added grinding step, can remove above-mentioned fold, obtain having the performing member of smooth surface.
(2) as mentioned above, in order to prevent that glassy bond is on the shaping dies and improve the at present smooth finish of the glass on the section of mould molding surface of mold pressing, and carry out die forming at Powdered releasing agents such as forming mould surface coating boron nitride powders, in the case, the vestige of residual powder on resulting vitreous surface sometimes, but, remove because the surface imperfection that the vestige of this powder causes by above-mentioned grinding step, can obtain having thus the performing member of smooth surface.
(3) when section of cooling rear center of glass surface section delayed quench, because the difference of speed of cooling, produce sometimes the phenomenon that is called as pore (ヒ ケ) that resulting Vitrea central part shrinks, produces from the teeth outwards small depression, but, remove above-mentioned depression by grinding step, can obtain having thus the performing member of smooth surface.
In addition, by above-mentioned grinding step, can critically regulate the quality of performing member.
In addition, in the method for making I, also can before or after above-mentioned grinding step, carry out other treatment process, as such treatment process, can list the grinding process or the matting of behind grinding step, carrying out, the drying process etc. that before grinding step, carry out.
Below, the method for making II of performing member is described.
The method for making II of performing member for for precision moulded formation the manufacture method of glass-made performing piece, it is characterized in that,
Melten glass is poured in the mold, is configured as glass workpiece,
Cut apart this glass workpiece, produce a plurality of sheet glass,
Heating, softening this sheet glass carry out die forming, produce the vitreum with the shape that is similar to described performing member,
At least pass through grinding step, make performing member by described vitreum.
The method that is manufactured on employed melten glass in the method for making II of performing member is identical with above-mentioned performing member method for making I, in addition, makes the method for performing member through grinding step at least by vitreum also identical with performing member method for making I.Therefore, below, the aspect different from the method for making I of performing member described.
As melten glass being poured into the method that moulding is glass workpiece, for example have following method, that is: below the outflow conduit, configure mold, will pour into continuously mold from the melten glass that conduit flows out.Preferred mould has smooth bottom surface and surrounds the sidewall on described bottom surface periphery three limits, and a direction opening of side.The relative sidewall sections by the clamping bottom surface comes the width of regulation glass workpiece.In mold with the forming of glass that pours into, and its peristome by above-mentioned mold pulled out in the horizontal direction with constant speed, import in the leer of the formula of transporting continuously and carry out slow cooling, thereafter, with its cut-out or cut off and be suitable length, be configured as glass workpiece (the method is called the A method).
Be method beyond the A method of glass workpiece as melten glass being poured into moulding, for example can list the method for using the mold with communicating pores straight (below, the method is called the B method).In this law, become vertical mode that mold is arranged on the conduit below according to communicating pores.The horizontal section of preferred communicating pores is similar shape, the also from top to bottom taper that increases gradually of (the outflow direction of glass) sectional area along the central shaft of communicating pores in short transverse (the outflow direction of glass).Pour into the melten glass that flows out from spout by the upside peristome from communicating pores, the temperature on mold top is higher than temperature of lower, expansion by mold enlarges cross section, communicating pores top, the vertical cross-section that therefore can make communicating pores when running well is At The Height is constant arbitrarily, thus movable glass successfully.
Expanded in communicating pores by the melten glass that the upside peristome of communicating pores pours into, promptly suck heat by mold simultaneously and rapidly cooling.So, the glass workpiece that is configured as the shape corresponding with the shape of communicating pores is pulled out from the peristome of communicating pores below, carry out slow cooling.Above-mentioned B method is suitable for making the situation of the bar-shaped glass workpiece such as cylindrical, prismatic.
The A method sucks heat by mold from three directions in bottom and side, and the B method is from the all-round heat that sucks of the travel direction of removing glass, therefore comparatively effective when forming to flowing out viscosity glass low, that devitrification resistance is low.In addition, the area that is exposed in the atmosphere owing to high temp glass also diminishes, so the B method is also comparatively effective in the shaping of high-volatile glass.
So, cool off rapidly to make glass workpiece by the surface to melten glass, can reduce the volatilization as the glass ingredient of the major cause that produces striped in deep layer section.In addition, also can carry out with comparalive ease the shaping of the low glass of viscosity.
Then, produce a plurality of sheet glass by cutting off or cutting off the resulting glass workpiece of Equal.Because the sheet glass that obtains like this exists edge or corner angle, therefore in heating described later, may fold into edge or corner angle when softening and become the product of inferior quality, thereby preferably remove the rounding processing of edge or corner angle.For rounding processing, preferred barreling.
Then, heating, softening above-mentioned sheet glass import in the model forming module and carry out die forming, produce the vitreum of the shape of the performing member with the target of being similar to.
In this die forming, can at the above-mentioned Powdered releasing agent of forming face coating of model forming module before importing sheet glass, also can be coated with above-mentioned Powdered releasing agent in glass sheet surface.
After the vitreum with the shape that is similar to the performing member shape that obtains like this carried out slow cooling, through grinding step, produce performing member.
In the method for making II of performing member, as mentioned above, because Powdered releasing agent is the residual surface imperfection that causes because of the vestige of powder on vitreous surface sometimes, in addition, because the cause of pore produces depression at vitreous surface sometimes, but, by above-mentioned grinding step, can obtain having the performing member of smooth surface.
In addition, in the method for making II, also can before or after above-mentioned grinding step, carry out other treatment process, as such treatment process, can list the grinding process or the matting of behind grinding step, carrying out, the drying process etc. that before grinding step, carry out.
In the method for making I of performing member, II, also can be as required contain carbon film or self-assembled film etc. in the surface-coated of performing member.
The method for making I of performing member, II are particularly suitable for making the situation of the performing member that is made of fluorine-containing composition glass or borate glass.Below, fluorine-containing composition glass and borate glass are described.
(fluorine-containing composition glass)
As fluorine-containing composition glass, especially can list fluophosphate glass.Because this glass contains fluorine, at high temperature shows high volatile volatile, therefore especially effective as the glass of the method for making I of using performing member of the present invention, II.Because the fluophosphate glass knoop hardness is little, wear intensity is large, therefore also be the glass of the kind that is difficult to grind in opticglass, but, in the method for making I of performing member, II, owing to by the vitreum that die forming manufacturing has the shape that is similar to performing member, therefore can in the work that reduces grinding step, make performing member.
In addition, viscosity when fluophosphate glass generally flows out is higher, when the fused glass block that is separated desired wt by the melten glass that flows out was shaped, glass can be drawn fine rule at separate part, produced sometimes this linear parts and remained in unfavorable conditions such as forming projection on the glass block surface of shaping.When the outflow temperature by rising glass, when reducing this outflow viscosity and eliminating above-mentioned unfavorable condition, as mentioned above, easily produce and encourage fluorine from volatilization, the obvious problem of generation striped of glass surface, but, method for making I, II according to performing member, owing to removing the projection of glass surface etc. by milled processed, therefore can eliminate the problems referred to above.
As the object lesson of fluophosphate glass, can exemplify out glass I shown below.
% represents with positively charged ion, and the glass I 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.
This glass is preferably realized specific refractory power (n d) be 1.40～1.58, glass that Abbe number (v d) is 67～90 optical characteristics.
The glass I is 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 amount be more than the 1 positively charged ion %, be more preferably Mg 2+, Ca 2+, Sr 2+, and Ba 2+Amount 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 in order to mol ratio also with the ratio of each anionic component.
P 5+Be the important cation constituent as the network structure of glass, if the stability of 10% glass of less than can reduce, and need to import P with oxide raw material when surpassing 45% 5+, thereby can make the oxygen ratio become large, can't meet the desired optical characteristics.Therefore, this amount is controlled to be 10%～45%, P 5+Preferred scope 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 the melt container of glass, perhaps volatilization is also stronger, from the angle of the stability made and improper, therefore 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 when surpassing 30% because glass tansition temperature (Tg) and liquidus temperature (LT) rising are larger, therefore forming temperature rises, when being shaped, can and strongly produce striped owing to the surface volatilization, thereby in the method for making I of performing member, be difficult to make uniform vitreum, in the method for making II of performing member, also be difficult to make uniform glass workpiece.Therefore, its amount is controlled to be 5%～30%.Al 3+Preferred scope 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 amount be 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 when keeping low the dispersion, realizing the composition of high refractive index, therefore preferably in the scope of not damaging stability, more import.Therefore, make Mg 2+Amount be 0～20%, Mg 2+The preferred scope of amount be 1～15%.In addition, make Ca 2+Amount be 0～25%, be preferably 1～20%.Make Ba 2+Amount be 0～33%, be preferably 1～25%.
Li +Can reduce the composition of glass tansition temperature (Tg) for not damaging stability, still, surpass the weather resistance of 30% meeting infringement glass, processibility also can reduce simultaneously.Therefore, this amount is controlled at 0～30%.Fluophosphate glass normal conditions lower-glass tansition temperature and precision moulded formation temperature all can be set lowlyer.But, because this glass contains easily and the fluorine composition of model forming module reaction, therefore need further to reduce the die forming temperature, and note not producing the fuzzy or gonorrhoea of the optical element surface that the surface reaction because of mould and glass causes, thereby preferably import the Li with above-mentioned effect more than 1% +Therefore, preferably this content is 1～30%, more preferably 2～30%, more preferably 3～30%, further preferred 4～30%.
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, because that the solubleness to water of NaF, KF is compared with LiF is much larger, thereby also can cause the deterioration of water tolerance, therefore with Na +, K +Amount be controlled to be respectively 0～10%.Na +, K +Preferred scope is 0～5%, does not more preferably import.
Y 3+Have the stability that improves glass, the effect of weather resistance, if but surpassing 5% stability can worsen on the contrary, and glass tansition temperature (Tg) also can rise on a large scale, therefore this 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 of the stabilization of making, but 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 this amount is controlled to be 0～10%.But, as BF 3, easily volatilization and cause the generation of striped in dissolving, therefore preferred this amount is 0～10%, more preferably 0～5%.When the volatility of preferential reduction glass, be preferably 0～0.5%, more preferably do not import.
In addition, consider preferred P from the stable aspect of making high-quality opticglass 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, the opticglass I can comprise the cation constituents such as lanthanon such as Ti, Zr, Zn, La, Gd in the scope of not damaging purpose of the present invention.
In addition, can so that stabilization turn to purpose and import Si 4+, still, if reduction melting temperature (Tm) and excessively importing, then can produce and melt remainingly, or volatilization becomes many when melting, thereby stability is made in infringement.Therefore, preferred Si 4+Amount be 0～10%, more preferably 0～8%, more preferably 0～5%.
For the ratio of anionic component, for the optical characteristics of accomplished expectation and the opticglass with excellent stability, with F -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.F in the preferred anionic -And O 2-Total amount be 100%.
Specific refractory power (the n of above-mentioned glass d) be 1.40～1.58, Abbe number (vd) is 67～90, is preferably 70～90.
The glass I shows higher transmissivity in the visible region except the situation of adding tinting material.The glass I shows following optical transmittance characteristic: for the sample of two sides thickness 10mm smooth and parallel to each other, when injecting 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%.
In the glass I, for the Li that contains more than 1% +Glass, the tansition temperature (Tg) of glass is controlled to be below 470 ℃, be preferably below 430 ℃.
For containing Li +Glass owing in alkalimetal ion, containing more Li +, so coefficient of thermal expansion is smaller, shows in addition better water tolerance, thereby can make smooth and high-quality performing member by the abrading glass body.
Because the glass I shows good water tolerance, weather resistance chemically, 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.
In addition, in the glass I, for the Li that contains more than 1% +Glass since with do not contain Li +The glassy phase ratio, the glass melting temperature (Tm) can be reduced about 50 ℃, therefore also can reduce, eliminate when melting from container and dissolve in platinum and the glass coloring that causes, sneak into the unfavorable conditions such as bubble, generation striped.
In addition, importing Li +Glass in, 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 life-span texts of prolongation model forming module in the time of can reducing the precision moulded formation of performing member.
Can be by using phosphatic raw materials, fluoride raw material etc., weighing, concoct these raw materials, offer platinum alloy melt container processed, heat, melting, clarification, homogenizing etc., obtain the glass I.
In addition, as fluorine-containing composition glass, can exemplify out and comprise Cu 2+Fluophosphate glass.Because therefore this glass absorption near infrared ray is suitable for the colorific adjustment filtering material as semiconductor camera elements such as CCD or CMOS.Thereby, can use this glass manufacture performing member, come on the profiled surface the various lens such as the strainer of subsidiary diffraction grating or non-spherical lens by precision moulded formation.
The strainer of subsidiary diffraction grating is to possess the 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.In addition, lens are the optical element that possesses imaging function and these two kinds of functions of near infrared ray cut-off filter.
As containing Cu 2+The object lesson of fluophosphate glass, can exemplify out following glass II.
% represents with positively charged ion, and the 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, the glass II contains 17～80% F -In above-mentioned composition, the surplus of preferred anionic composition all is O 2-
Below, the composition of above-mentioned 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 in order to mol ratio also with the ratio of each anionic component.
In the 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 worsen color and with green, on the contrary, if P 5+Surpass 45%, then worsen weathering resistance, devitrification resistance.Therefore, preferred P 5+Content be 11～45%, more preferably 20～45%, more preferably 23～40%.
Al 3+To improve the intensity of the devitrification resistance of fluophosphate glass and thermotolerance, resistance to sudden heating, machinery, the composition of weather resistance chemically.But, if surpass 29%, then can worsen the near infrared absorption characteristic.Therefore, preferred Al 3+Content be 0～29%, more preferably 1～29%, further preferred 1～25%, further preferred 2～23%.
Li +, Na +And K +Be meltbility, the devitrification resistance of improving glass, improve the composition of the transmissivity of visible region, still, if total amount surpasses 43%, then worsen weather resistance, the processibility of glass.Therefore, preferred Li +, Na +And K +Total content be 0～43%, more preferably 0～40%, further preferred 0～36%.
In the alkali composition, Li +Above-mentioned comparatively outstanding on, more preferably Li +Amount be 15～30%, further preferred 20～30%.
Mg 2+, Ca 2+, Sr 2+, Ba 2+And Zn 2+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+The preferred scope of content is 0.1～10%, and preferred scope is 1～8%.Ca 2+The preferred scope of content is 0.1～20%, and preferred scope is 3～15%.
Sr 2+The preferred scope of content is 0.1～20%, and preferred scope is 1～15%.
Ba 2+The preferred scope of content is 0.1～20%, and preferred scope is 1～15%, and further preferred scope is 1～10%.
Cu 2+The main undertaker of near-infrared absorption characteristic.If this 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 the glass II, F -The fusing point that reduces glass, the important anionic component that improves weathering resistance.Because the glass II contains F -, therefore can reduce the melt temperature of glass, suppress Cu 2+Reduction, thereby the optical characteristics that obtains expecting.If less than 17% then worsens weathering resistance, on the contrary, if surpass 80%, then can reduce O 2-Content, therefore produce because the Cu of 1 valency 1+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 the glass II, O 2-Be important anionic component, preferred whole anionic component is removed F -After remainder all with O 2-Composition consists of.Therefore, O 2-Preferably measure as 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 1+, so the short wavelength zone especially near the absorption the 400nm can become large and present green.On the contrary, if excessive, then the viscosity of glass is higher, and melt temperature uprises, so transmissivity worsens.And, because Pb, As hazardous property are stronger, preferably do not use.
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 following characteristic.
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 larger, 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 the glass sample on two planes 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 well the colorific adjustment of the semiconductor camera elements such as CCD or CMOS.
Can be by weighing, concoct with the glass wanting to obtain and form corresponding raw material, offer the melt container of platinum alloy system, heat, melting, clarification, homogenizing etc., obtain the glass II.
In addition, the fluorine-containing composition glass as the method for making I that is suitable for performing member, II can list the fluoborate glass that contains high-volatile fluorine composition.
(borate glass)
Because borate glass also contains high-volatile boric acid component, therefore comparatively effective as the glass of the method for making I of using performing member of the present invention, II.Especially, contain B more than 20 % by mole 2O 3Borate glass under the liquation state, demonstrate high volatile volatile.
An example as such borate glass is containing B 2O 3, La 2O 3And in ZnO and the opticglass as the glass material of precision moulded formation, following glass (below, be called the glass III) can example be shown, that is, with % by mole representing, contain 20～60% B 2O 3, 0～20% SiO 2, 5～42% ZnO, 0～10% Li 2O, 5～24% La 2O 3, 0～20% Gd 2O 3, 0～10% ZrO 2, 0～10% Ta 2O 5, 0～10% WO 3, 0～10% Nb 2O 5, 0～10% TiO 2, 0～10% Bi 2O 3, 0～10% GeO 2, 0～10% Ga 2O 3, 0～10% Al 2O 3, 0～10% BaO, 0～10% Y 2O 3And 0～10% Yb 2O 3The glass III preferably can realize specific refractory power (n d) be more than 1.75, more preferably more than 1.80, further preferred glass more than 1.85.For Abbe number (vd), preferably can realize the glass of 30～50 scope.
Because this glass contains high-volatile B 2O 3Therefore, in the method for hot forming of performing member, need to take into full account and prevent because the striped that volatilizees and produce.And because the glass III given high refractive index and this two specific character of low tansition temperature simultaneously, so liquidus temperature is elevated to more than 950 ℃ or more than 1000 ℃, and in order to prevent devitrification, must at high temperature flow out melten glass.Therefore, when the thermoforming performing member, within the long time that flows out to the performing member shaping from glass, must under the high state of volatility, process glass.On the other hand, if by method of the present invention by such glass manufacture performing member, then can make with comparalive ease high-quality performing member.
Below, each composition of glass III is described.Wherein, in the situation that without specifying, the content of each composition and total amount are with % by mole representing, the ratio of the content of composition also represents with mol ratio.
B 2O 3Be essential component, play the effect that mesh forms oxide compound.When more importing La 2O 3When the high refractive index composition, need to import the B more than 20% in order to form glass 2O 3As main network constituent, in the sufficient stability of giving devitrification, keep the meltbility of glass, still, surpass 60% if import, then can reduce the specific refractory power of glass, thereby can't obtain glass of high refractive index.Therefore, this import volume is controlled to be 20～60%.From improving B 2O 3The above-mentioned effect aspect that imports is considered, preferably imports 22～58%, more preferably imports 24～56%.
SiO 2Any composition, with respect to more containing La 2O 3And Gd 2O 3Glass, can reduce the liquidus temperature of glass, improve high temperature viscosity, and greatly improve the stability of glass, still, because excessive importing, can reduce the specific refractory power of glass, the glass tansition temperature uprises, the precision moulded formation difficulty is therefore with SiO 2Import volume be controlled to be 0～20%, preferred 0～18%.
ZnO is essential component, can reduce melt temperature and liquidus temperature and the tansition temperature of glass, also can regulate specific refractory power.Therefore, import more than 5%, still, surpass 42% if import, then can worsen the stability to devitrification, reduce weather resistance chemically, therefore, this import volume is controlled to be 5～42% scope.Preferred scope is 5～41%.
Li 2O is the composition that the effect of reduction glass tansition temperature is large, be difficult to reduce specific refractory power in alkali metal component most, still, because excessive importing can reduce specific refractory power, also can reduce the stability of glass, therefore this import volume is controlled to be 0～10%, is preferably 0～8%.
La 2O 3Be essential component, it can not reduce the stability of the devitrification of glass or can not increase dispersion, and can increase specific refractory power, improves chemical durability yet.But, if less than 5% then can not obtain sufficient effect, on the other hand, if surpass 24%, then worsen significantly the stability to devitrification, therefore this import volume is controlled to be 5～24%.Consider preferred La from the above-mentioned effect of further raising aspect 2O 3Content be 6～23%, more preferably 7～22%.
Gd 2O 3With La 2O 3Identical, be to improve the specific refractory power of glass and chemical durability and can not worsen stability and low dispersed composition to glass devitrification.If Gd 2O 3Import above 20%, worsen the stability of devitrification and the tendency of glass tansition temperature rising deterioration precision moulded formation thereby then have, therefore import 0～20%.In order to give high refractive index and to improve chemical durability, preferred Gd 2O 3Import 1～19%.Preferred scope is 2～18%.In addition, in order to improve stability, glass, preferred La 2O 3And Gd 2O 3Composition as the glass ingredient coexistence.
In addition, the glass aspect that from obtaining Abbe number (vd) be more than 40, specific refractory power is higher is considered, preferred La 2O 3And Gd 2O 3Total content is 10～24%, is preferably 12～23%.
ZrO 2Be as high refractive index, hang down the composition that disperses and any composition that uses.By importing ZrO 2, the high temperature viscosity that can improve and to the effect of the stability of devitrification, and can not reduce the specific refractory power of glass, but, surpass 10% if import, then liquidus temperature sharply rises, also can worsen the stability to devitrification, therefore its import volume is controlled to be 0～10%, be preferably 0～8%.
Ta 2O 5Be as high refractive index, hang down the composition that disperses and any composition that uses.By importing a small amount of Ta 2O 5, can have and improve high temperature viscosity and to the effect of the stability of devitrification, and can not reduce the specific refractory power of glass, but, surpass 10% if import, then liquidus temperature sharply rises, disperse also can increase, therefore its import volume is controlled to be 0～10%, be preferably 0～8%.
WO 3The composition that suitably imports for the stability of improving glass and meltbility, raising specific refractory power, still, if this import volume surpasses 10%, then disperse to become large, can't obtain the low dispersing characteristic of needs, therefore its import volume is controlled to be 0～10%, be preferably 0～8%.
Nb 2O 5Be any composition that keeps the stability of glass and improve specific refractory power, because excessive importing can increase dispersion, therefore its import volume be controlled to be 0～10%, be preferably 0～8%.
TiO 2Be any composition that can import for regulating optical constant, because excessive importing can increase dispersion, can't obtain the optical constant of target, therefore its import volume is controlled to be 0～10%, be preferably 0～8%, more preferably do not import.
Bi 2O 3The stability that play a part to increase specific refractory power, improves glass, but because excessive importing can reduce the stability of glass, rising liquidus temperature.Therefore, its import volume is controlled to be 0～10%, is preferably 0～6%.
GeO 2Be any composition that plays a part to increase specific refractory power and improve the stability of glass, its import volume is controlled to be 0～10%, be preferably 0～8%.But, because to compare price very expensive with other compositions, therefore more preferably do not import.
Ga 2O 3Also be any composition that plays a part to increase specific refractory power and improve the stability of glass, its import volume is controlled to be 0～10%, be preferably 0～8%.But, because to compare price very expensive with other compositions, therefore more preferably do not import.
Al 2O 3Play a part to improve the high temperature viscosity of glass and reduce liquidus temperature, improve the plasticity of glass, also play a part to improve chemical durability.But, because excessive importing can reduce specific refractory power and to the stability of devitrification, therefore import volume is controlled to be 0～10%, be preferably 0～8%.
BaO is any composition that uses as the composition of high refractive index, low dispersion, when a small amount of importing, can improve stability and the chemical durability of glass, but, surpass 10% if import, then can greatly damage the stability to the devitrification of glass, rising tansition temperature and yield point temperature, therefore its import volume is controlled to be 0～10%, is preferably 0～8%.
Y 2O 3And Yb 2O 3Be as high refractive index, hang down the composition that disperses and any composition that uses.When a small amount of importing, can improve stability and the chemical durability of glass, still, and if excessive importing then can damage the stability to the devitrification of glass greatly, rising glass tansition temperature and yield point temperature, therefore, with Y 2O 3Content be controlled to be 0～10%, be preferably 0～8%.With Yb 2O 3Content be controlled to be 0～10%, be preferably 0～8%.
In addition, preferred La 2O 3, Gd 2O 3, Y 2O 3And Yb 2O 3Total content be 10～24%.
In addition, Sb 2O 3As deaerating agent and the composition that adds arbitrarily, still, if with respect to the total content of all glass ingredients Sb 2O 3Addition surpass 1 quality %, then the forming face of model forming module may sustain damage when precision moulded formation, therefore, preferably adds the Sb of 0～1 quality % with respect to the total content of all glass ingredients 2O 3, more preferably add 0～0.5 quality %.
On the other hand, the composition for preferably not importing as glass ingredient has exemplified PbO.PbO is objectionable constituent, and can produce following problem, namely, when performing member that precision moulded formation in non-oxidizing gas is made of the glass that contains PbO, lead can be separated out in surface at molding, thereby the transparency of infringement optical element, the metallic lead of perhaps separating out is attached on the model forming module.
Lu 2O 3As general optics composition, to compare frequency of utilization less with other compositions, in addition, its rareness and price is high, expensive as Optical Glass Materials, therefore consider from the cost aspect, preferably do not import.
Cadmium, tellurium etc. can cause that the poisonous elements such as radioelement, arsenic such as the element, thorium of environmental problem preferably do not comprise yet.The glass III is to realize the glass of high refractive index.Therefore, preferably do not comprise the fluorine that reduces specific refractory power yet.
For the glass that obtains target forms, can be by weighing, blending as the oxide compound of raw material, carbonate, vitriol, nitrate, oxyhydroxide etc., fully mix, become to mix and criticize, in melt container, heat, melting, deaeration, stirring etc., as evenly and not containing frothy melten glass, obtain above-mentioned glass III.Specifically, can use known scorification.
Below, the manufacture method of optical element of the present invention is described.
The manufacture method of optical element of the present invention is characterised in that, heats the glass-made performing piece of making by method for making I or the II of performing member, carries out precision moulded formation.
In optical element, light sees through with making, the face of refraction, diffraction, reflection is called the optical function face (take lens as 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 precision moulded formation, namely, critically be transferred on glassly by the forming face with the precision moulded formation mould, can form the optical function face by die forming, need not to apply in order to make the optical function face mechanical workouts such as grinding and grinding.
Therefore, the manufacture method of optical element of the present invention is suitable for the manufacturing of the optical elements such as lens, set of lenses, diffraction grating, bevelled mirror, is particularly suitable as the method for making non-spherical lens on large-duty basis.
As the model forming module that in precision moulded formation, uses, can use known the mould that is provided with mold release film such as the forming face of section bar such as pottery such as the thermotolerance of silicon carbide, zirconium white, aluminum oxide etc. arranged, among these moulds, the model forming module of preferred silicon carbide system.In addition, as mold release film, can use to contain carbon film etc., but consider from weather resistance, cost aspect, particularly preferably carbon film.
In precision moulded formation, for the forming face with the precision moulded formation mould remains good state, the atmosphere when preferably being shaped is non-oxidizing gas.As non-oxidizing gas, the mixed gas of preferred nitrogen, nitrogen and hydrogen etc.
Optimal way as the manufacture method of optical element of the present invention can list following precision moulded formation 1 and 2 these dual modes.
(precision moulded formation 1)
Precision moulded formation 1 is: import above-mentioned performing member in the precision moulded formation mould, above-mentioned precision moulded formation mould and performing member are heated together, carry out precision moulded formation.
In precision moulded formation 1, preferably the temperature of precision moulded formation mould and described performing member all is heated to the glass display that consists of 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 16Then temperature during the above viscosity of dPas, takes out the precision moulded formation product from the precision moulded formation mould.
According to above-mentioned condition, can by the glass forming face shape of transfer printing precision moulded formation mould critically, also the precision moulded formation product can be taken out indeformablely simultaneously.
(precision moulded formation 2)
Precision moulded formation method 2 is: the performing member of heating is imported to the precision moulded formation mould of preheating, carry out precision moulded formation.
According to precision moulded formation 2, owing to before described performing member is imported the precision moulded formation mould, heating in advance, therefore can shorten the cycle, can produce the optical element of the good surface accuracy with free of surface defects simultaneously
Wherein, the preheating temperature of precision moulded formation mould 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 precision moulded formation mould.
In precision moulded formation 2, the glass that consists of described performing member preferably is preheated to and demonstrates 10 9DPas is following, more preferably demonstrate 10 9Temperature during viscosity about dPas.
Preferred limit makes described performing member float the limit to carry out preheating, and, more preferably be preheated to the glass display that consists of described 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, although the temperature of precision moulded formation mould 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 benchmark.
In the method, behind the die forming, the viscosity that preferably is cooled to described glass is 10 12After dPas is above, carry out the demoulding.
The optical element that precision moulded formation is obtained takes out from the precision moulded formation mould, carries out as required slow cooling.When molding is the optical elements such as lens, also can be as required at the surface coated optical thin film.
As mentioned above, according to the manufacture method of optical element of the present invention, use the performing member that is consisted of by the glass that as fluophosphate glass and borate glass, comprises the high volatile volatile composition, can make with comparalive ease the optical elements such as 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.
(Production Example of melten glass)
As frit, use the phosphoric acid salt corresponding with each glass ingredient, fluorochemical, carbonate, nitrate, oxyhydroxide, oxide compound etc., come each frit of weighing according to becoming the composition glass that has shown in table 1～table 6, after fully mixing, put in the platinum crucible, heat, melting, clarification, homogenizing, obtain each melten glass.
Use above-mentioned each melten glass, make the physical property measurement sample of glass, estimate according to following method.
(1) specific refractory power (n d) and Abbe number (vd)
Measure for-30 ℃ of/hour opticglass that obtain making the slow cooling cooling rate.
(2) glass tansition temperature (Tg)
Thermo-mechanical analysis device (サ-モ プ ラ ス TMA8310) by Rigaku Denki Co., Ltd is measured as 4 ℃/minute take heat-up rate.
(3) viscosity under liquidus temperature and the liquidus temperature
In being provided with the devitrification test furnace of thermograde, put into sample, keep lowering the temperature after 1 hour, come to have or not in the confirmatory sample crystallization with 80 times opticmicroscopes.Can not see that the minimum temperature of crystallization is as liquidus temperature.
Viscosity Measurement Methods by JIS specification Z8803, use coaxial double rotational circle cartridge type rotational viscosimeter (Tokyo Industrial Co., Ltd system, high temperature viscosity measuring apparatus RHEOTRONIC II (modified form)), change the temperature of glass, viscosity under temperature is separately measured, finish the graphic representation of expression viscosity and temperature relation, use this graphic representation to calculate viscosity under the liquidus temperature.
Embodiment 1 (Production Example of the performing member of being made by the method for making I of performing member)
On universal stage, lay the bed die of a plurality of moulds of configuration and shaping dies, above-mentioned each melten glass with the composition shown in table 1～table 6 is flowed out continuously from conduit.Catch the lower end of molten glass flow with the bed die forming face of shaping dies, cut off molten glass flow midway with stapling machine, obtain fused glass block in the bed die forming face thus.Each fused glass block is adjusted to weight after the weight of the performing member that obtains of want adds the weight of removing by aftermentioned grinding, milled processed.In addition, on the bed die forming face, spray equably in advance the coating boron nitride powder.
Then, by universal stage being carried out the transposition rotation, the mold that the bed die that is contained with fused glass block is transported to shaping dies is the position of standby up, by falling mold, with mold and bed die fused glass block is carried out mold pressing, in the space that is surrounded by upper/lower die and mould, spread glass out.
Pass through aforesaid operations, fused glass block is configured as the shape that is similar to the target performing member, and, glass surface is cooled off rapidly, interrupted in fact the volatilization of the fluorine composition, B2O3 composition or the alkali metal component that comprise in the glass, thereby can prevent at the inner striped that forms of die forming thing.
Then, mold is risen, again await orders up.Behind cooling frame pressing formation thing on the bed die that transports by the rotation of universal stage, take out from bed die, in leer, carry out slow cooling.So, then can obtain having the shape that is similar to the performing member shape.
Then, the performing member with desired wt through grinding, grinding step and cleaning, drying process, is made in above-mentioned Vitrea surface.Can be coated with carbon film on the performing member surface as required.
Resulting each performing member forms by having the optical-quality homogeneous glass that forms shown in table 1～table 6, its smooth surface, and striped also be can't see in surface, inside.
Table 1
Figure BSA00000767588400221
Table 2
Table 3
Figure BSA00000767588400231
Table 4
Figure BSA00000767588400232
Table 5
Figure BSA00000767588400241
Table 6
Figure BSA00000767588400242
Embodiment 2 (Production Example of the performing member of being made by the method for making II of performing member)
(making glass workpiece by the A legal system)
The mold that will have smooth base plate and the sidewall that surrounds three directions of base plate becomes the mode of level to be configured in the conduit below according to base plate, injects continuously above-mentioned each melten glass with the composition shown in table 1～table 6 with constant rate respectively to the part with base plate and side walls enclose.
Then, be configured as the sheet glass with width and thickness of one, extract continuously in the horizontal direction each sheet glass from the peristome of mold side out with constant speed, import in the leer.After in the leer, the sheet glass of slow cooling with respect to extracting the cut-out of perpendicular direction ground out, is configured as each glass workpiece with writing board shape.
(making glass workpiece by the B legal system)
The mold that will have a columniform communicating pores is that vertical mode is configured in the conduit below that melten glass flows out according to communicating pores, and above-mentioned each melten glass that will have a composition shown in table 1～table 6 injects in the communicating pores continuously from the conduit spout.
Each melten glass is configured as cylindrically in communicating pores, the speed that simultaneously remains constant altitude with the liquid level with the melten glass in the communicating pores is extracted cylindrical glass downwards out from the outlet of communicating pores.At near the stove that connects temperature with inside under the communicating pores outlet and remain on the glass tansition temperature of each glass, inside by reducing the cylindrical glass of extracting out continuously in this stove and the temperature head of near surface prevent the self-destruction that the thermal contraction because of cylindrical glass causes.
Cylindrical glass cut off or cut off extraction by the position of above-mentioned stove is configured as glass workpiece.The columniform glass workpiece that obtains is like this put into leer carry out slow cooling.
To be divided into a plurality of sheet glass by each glass workpiece of above-mentioned A method or the manufacturing of B method, so that their shape, weight are mutually the same.The weight of each melten glass sheet is adjusted to the weight of gained after the weight of the performing member that obtains of want adds the weight of removing by aftermentioned grinding, milled processed.
Then, a plurality of sheet glass of barreling evenly are coated with boron nitride powder last from the teeth outwards, are configured on the basin that refractory body makes, and import in the heating unit that is used for heating, soften glass that is called as softening furnace.
The sheet glass that will heat in softening furnace, soften imports and comprises in the model forming module of mold, bed die, mould, die forming is after having the vitreum of the shape that is similar to performing member in atmosphere, from model forming module, take out, carry out slow cooling.
The process grinding of Vitrea surface, grinding step and cleaning, drying process to obtaining like this produce the performing member with desired wt.As required, can be coated with carbon film on the performing member surface.
Resulting each performing member forms by having the optical-quality homogeneous glass that forms shown in table 1～table 6, its smooth surface, and striped also be can't see in surface, inside.
Embodiment 3 (manufacture method of optical element)
(Production Example of being made by precision moulded formation 1)
Each performing member that to make in embodiment 1,2 imports in the precision moulded formation mould that comprises mold, bed die, mould, performing member and precision moulded formation mould are heated together, are aspheric lens shape with the performing member precision moulded formation between upper/lower die.
From mould, take out the lens that are shaped, carry out slow cooling, produce the non-spherical lens that is formed by each glass shown in table 1～table 6.For the shape of resulting lens, can by suitably selecting the shape of precision moulded formation mould, make the various lens such as protruding crescent lens, recessed crescent lens, biconcave lens, biconvex lens, plano-convex lens, plano-concave lens.
(Production Example of being made by precision moulded formation 2)
Below, will separate heating with the precision moulded formation mould at above-described embodiment 1,2 each performing member of making, and import in the precision moulded formation mould, also can pass through precision moulded formation, make above-mentioned various lens.
Also can prevent the optical thin films such as reflectance coating in the optical element coating that produces as required.
Industrial applicibility
According to the present invention, even can provide as the not high glass of stability in use and under the liquation state, have the situation of high-volatile glass, also can make without the method for the high-quality performing member of devitrification and striped and use the method for making optical element by the performing member of aforesaid method manufacturing.

Claims (4)

1. the manufacture method of a glass-made performing piece, described glass-made performing piece be for precision moulded formation, and the manufacture method of described glass-made performing piece is characterised in that,
Isolate fused glass block from the melten glass that flows out from spout, carry out die forming, make the vitreum with the shape that is similar to described performing member,
At least pass through grinding step, make performing member by described vitreum.
2. the manufacture method of a glass-made performing piece, described glass-made performing piece be for precision moulded formation, and the manufacture method of described glass-made performing piece is characterised in that,
Melten glass is poured into mold, is configured as glass workpiece,
Cut apart this glass workpiece, produce a plurality of sheet glass,
Heating, softening this sheet glass carry out die forming, manufacture the vitreum with the shape that is similar to described performing member,
At least pass through grinding step, make performing member by described vitreum.
3. the manufacture method of glass-made performing piece as claimed in claim 1 or 2 is characterized in that,
The performing member that manufacturing is formed by fluorine-containing composition glass or borate glass.
4. the manufacture method of an optical element is characterized in that,
Heating is carried out precision moulded formation by the glass-made performing piece that each described method in the claim 1～3 produces.
CN201210301860XA 2006-10-19 2007-10-19 Processes for the production of glass preform and optical element Pending CN102898001A (en)

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