CN101244890B

CN101244890B - Method for manufacturing optical glass, glass base stock for press forming, and method for manufacturing the glass base stock for press forming, and method for manufacturing optical element

Info

Publication number: CN101244890B
Application number: CN 200710151742
Authority: CN
Inventors: 池西干男
Original assignee: Hoya Corp
Current assignee: Hoya Corp
Priority date: 2006-09-29
Filing date: 2007-09-27
Publication date: 2012-06-06
Anticipated expiration: 2027-09-27
Also published as: CN101244890A; JP2008081383A; JP4229334B2

Abstract

The invention provides an optical glass manufacturing method through the fusion method to make the optical glass formed by the fluorophosphoric acid glass to reduce the foreign body mixed into the glass, the glass materials for the shaping of the optical glass manufacturing, the manufacturing method of the glass materials for the shaping of the die and the manufacturing method of the optical elements. The manufacturing method of the optical glass uses the fluorophosphoric acid glass shaping method which uses the phosphate materials and the fluorid glass, characterized by including: a first working procedure to fuse the phosphate materials in the nonmetal container to get the phosphate glass and a second working procedure to fuse with the fluorid materials in the platinum or platinum alloy container in the state of melt phosphate glass or after the curing of the melts.

Description

The method of manufacture of opticglass, die forming are with the method for manufacture of glass material and method of manufacture and optical element

Technical field

The method of manufacture, die forming that the present invention relates to opticglass with glass material, die forming with the method for manufacture of glass material and the method for manufacture of optical element.

Background technology

Fluophosphate glass is as low dispersive glass and very useful, and for example, the fluophosphate glass that has imported cupric ion etc. has obtained as near-infrared absorbing glass using widely.

Have as the method for manufacture of the opticglass that is formed by above-mentioned fluophosphate glass is known: phosphatic raw materials and fluoride raw material are heated, melt and obtain glass; The method of under molten state, this glass being clarified, being homogenized (below, be called scorification).This method is an efficient and simple method when being known in mass production glass.

In above-mentioned scorification, in the crucible of platinum with erosion resistance or platinum alloy system, carry out melting and the clarification of glass, the processing that homogenizes of frit usually, so that impurity can not be added in the melten glass that is in the ultrahigh-temperature state.

But because fluophosphate glass has extremely strong aggressiveness, even therefore use the crucible of platinum or platinum alloy system, crucible also can be etched, so its constituent can enter into glass.The platinum or the platinum alloy that are blended in the glass can be separated out as foreign matter, become the source at random of light, thereby cause the downgrade (for example, with reference to patent documentation 1) of opticglass.

Patent documentation 1: the Japanese documentation spy opens 2002-128528 communique (the right hurdle the reciprocal the 4th of page 2 walks to hurdle, a page 3 left side the 2nd row).

Summary of the invention

Invent problem to be solved

In view of the foregoing; First purpose of the present invention is to provide a kind of method of manufacture that when making the opticglass that is formed by fluophosphate glass through scorification, can reduce the opticglass that is blended into the foreign matter in the glass; Second purpose of the present invention is to provide a kind of die forming that is formed by the opticglass of making through aforesaid method to use the glass material, and it is a kind of by make the method for die forming with glass material and optical element through the opticglass of aforesaid method manufacturing that the 3rd purpose of the present invention and the 4th purpose are respectively to provide.

The means that are used to deal with problems

Contriver of the present invention has studied that foreign matter is blended into the mechanism in the fluophosphate glass when using phosphatic raw materials to make fluophosphate glass with fluoride raw material and through scorification, and the result has obtained the conclusion of following (a)～(b).

(a) melt when above-mentioned phosphatic raw materials and can corrode platinum or platinum alloy crucible during vitrifying, thereby cause platinum or platinum alloy to be added in the glass.

(b) when attempting using the silicon crucible to replace platinum or platinum alloy system crucible for the erosion that prevents phosphatic raw materials; The silicon crucible can be corroded by fluoride raw material specifically; Can be added in the glass from the silicon in the crucible, thereby cause the optical characteristics of glass such as specific refractory power to depart from expected value out and away.

According to above-mentioned conclusion; Inventor of the present invention has further carried out finding after the research: at first; Fusion phosphatic raw materials in nonmetal container mades such as silicon crucible and obtain phosphate glass is under the state of melts or after this melts is solidified at the phosphate glass that obtains then, in the container of platinum or platinum alloy system with it with the fluorochemical fusion; Can prevent the erosion of fluoride raw material thus to the silicon crucible; Thereby not only can give the opticglass desired optical that obtains, but also can reduce platinum or the platinum alloy that is blended in the fluophosphate glass, thereby can reduce this platinum or platinum alloy the amount of separating out as foreign matter.Contriver of the present invention has accomplished the present invention on the basis of above-mentioned discovery.

That is, the present invention provides:

(1): a kind of method of manufacture of the opticglass that forms by the fluophosphate glass that has used phosphatic raw materials and fluoride raw material, it is characterized in that, comprising: first operation, fusion phosphatic raw materials in nonmetal container made and obtain phosphate glass; And second operation, be under the state of melts or after this melts solidifies at the phosphate glass that obtains, in the container of platinum or platinum alloy system with it with the fluoride raw material fusion.

(2): a kind of die forming is used the glass material, it is characterized in that, is formed by the opticglass that obtains through above-mentioned (1) described method.

(3): use the glass material like above-mentioned (2) described die forming, it is characterized in that, be performing member for precise compression moulding.

(4): a kind of die forming is with the method for manufacture of glass material; It is characterized in that; The melten glass that is formed by the opticglass that obtains through above-mentioned (1) described method is flowed out; Isolate fused glass block, this fused glass block is configured as performing member for precise compression moulding in the refrigerative process.

(5): a kind of die forming is with the method for manufacture of glass material; It is characterized in that; To be cast in the casting mould by the melten glass that the opticglass that obtains through above-mentioned (1) described method forms, after producing glass shaping body, this glass shaping body is carried out mechanical workout.

(6): a kind of method of manufacture of optical element, it is characterized in that, above-mentioned (3) described die forming is carried out precision moulded formation with glass material or the die forming that obtains through above-mentioned (4) described method with the glass material.

(7): a kind of method of manufacture of optical element; It is characterized in that; Above-mentioned (2) or (3) described die forming with the glass material or carry out die forming through the die forming that above-mentioned (4) or (5) described method obtain with the glass material and make the optical element base substrate, are ground this base substrate and cut, grind.

(8): a kind of method of manufacture of optical element, it is characterized in that, comprise that the glass shaping body to being formed by the opticglass that obtains through above-mentioned (1) described method grinds the operation of cutting, grinding.

(9): a kind of method of manufacture of optical element; It is characterized in that, the melten glass that is formed by the opticglass that obtains through above-mentioned (1) described method is flowed out, carry out die forming; Make the optical element base substrate thus, then this base substrate is ground and cut, grind.

The effect of invention

According to the present invention; The method of manufacture of following opticglass can be provided: when using phosphatic raw materials and fluoride raw material and making the opticglass that forms by fluophosphate glass through scorification; Not only the opticglass desired optical can be given, but also platinum or the platinum alloy foreign matter that is blended in the glass can be reduced.In addition,, can provide the die forming that forms by the opticglass of making through aforesaid method to use the glass material, can also provide by making the method for die forming respectively with glass material and optical element through the opticglass of aforesaid method manufacturing according to the present invention.

Description of drawings

Fig. 1 is the simplified diagram of the precision moulded formation device that uses in an embodiment of the present invention;

Fig. 2 is the photo of the glass block that obtains in an embodiment of the present invention;

Fig. 3 is the photo of the glass block that in comparative example of the present invention, obtains.

Embodiment

(method of manufacture of opticglass)

The method of manufacture of opticglass of the present invention at first, is described.

The method of manufacture of opticglass of the present invention is the method for manufacture of the opticglass that formed by the fluophosphate glass that has used phosphatic raw materials and fluoride raw material, it is characterized in that, comprising:

First operation, fusion phosphatic raw materials in nonmetal container made and obtain phosphate glass; With second operation, be under the state of melts or after this melts solidifies at the phosphate glass that obtains, in the container of platinum or platinum alloy system with it with the fluoride raw material fusion.

In the present invention, phosphatic raw materials is meant in the manufacturing processed of glass and can forms Al (PO ₃) ₃, Ba (PO ₃) ₂, Ca (PO ₃) ₂, Sr (PO ₃) ₂Etc. the material of various metal phosphates, comprising: above-mentioned various phosphoric acid salt itself, and H ₃PO ₄, P ₂O ₅Deng with the resultant of reaction of oxide compounds such as basic metal, alkaline-earth metal etc.In addition, in the present invention, fluoride raw material is meant AlF ₃, MgF ₂, CaF ₂, SrF ₂In fluorochemical, and the mixture of above-mentioned fluorochemical.Can suitably select above-mentioned frit according to the glass ingredient that will obtain.

As the nonmetal container made of fusion phosphatic raw materials, preferably by the formed container of more than one materials in silicon, aluminum oxide, graphite, silit, the glassy carbon etc.

In the method for the invention, first operation is a fusion phosphatic raw materials and obtain the operation of phosphate glass in above-mentioned nonmetal container made.Heating temperature during fusion is preferably 900～1300 ℃, is more preferably 900～1200 ℃.Be preferably 30～240 minutes heat-up time, be more preferably 60～180 minutes.In addition, atmosphere is preferably non-oxidizing atmosphere, as non-oxidizing atmosphere, can enumerate out rare gas atmosphere, vacuum atmospheres etc. such as nitrogen atmosphere, argon.Atmosphere when making fusion is non-oxidizing atmosphere, the container that can use the material by low resistivity against fire to form.

The fusion of above-mentioned phosphatic raw materials proceeds to raw material at least and melts and vitrifying.Can further continue to heat the processing that homogenizes of oozy glass of going forward side by side, but consider also will through after the platinum stated or the container of platinum alloy system carry out that homogenizing of glass handled etc., therefore preferably finish heat treated at the vitrified time point of raw material.

As stated; Fluoride raw material can corrode the container that forms as nonmetal container made, by silicon; But in the present invention since in nonmetal container made fusion phosphatic raw materials only, the constituent that therefore can prevent or reduce the silicon container made is blended in the glass.

In the method for the invention, second operation be the phosphate glass that obtains be under the state of melts or after this melts solidifies in the container in platinum or platinum alloy system with it with fluorochemical fused operation.

Fusion in above-mentioned second operation was carried out after both can having made the phosphate glass former state that in nonmetal container made, makes flow out in the container of platinum or platinum alloy system at the container through nonmetal container made and platinum or platinum alloy system with pipe coupling, also can be to the phosphate glass cooling of in nonmetal container made, making, solidify and the vitreum that obtains carries out carrying out in the container in platinum or platinum alloy system after the reheat.

As the platinum alloy that constitutes container, for example can enumerate out platinum/zirconia alloy, platinum/au-alloy, platinum/iridium alloy, platinum/rhodium alloy etc.

Melt temperature in second operation is preferably 800～1200 ℃, is more preferably 900～1100 ℃.Since pyritous gas easily with atmosphere in reaction of moisture, the quality of gas is understood owing to this reaction reduces, so the atmosphere during fusion is preferably dry atmosphere.Amount of moisture in the dry atmosphere preferably is equivalent to below the dew point-30 ℃, and the kind of gas can be enumerated out rare gas elementes such as nitrogen, argon.

In addition, preferably in melting treatment, carry out stir process, glass is homogenized.

As stated; Phosphatic raw materials can corrode the container of platinum or platinum alloy system when vitrifying; But in the present invention; Because make phosphatic raw materials fusion in nonmetal container made, and fusion in the container of platinum or platinum alloy system after vitrifying, the constituent that therefore can prevent or reduce the container of platinum or platinum alloy system is blended in the glass.

Then, the opticglass that is formed by the fluophosphate glass that obtains through method of the present invention is described.

As preferred first embodiment of the opticglass that forms by fluophosphate glass (below, be called opticglass I), can enumerate following opticglass: when representing, contain 5～50% P with positively charged ion % ⁵⁺, 0.1～40% Al ³⁺, 0～20% Mg ²⁺, 0～25% Ca ²⁺, 0～30% Sr ²⁺, 0～30% Ba ²⁺, 0～30% Li ⁺, 0～10% Na ⁺, 0～10% K ⁺, 0～10% Y ³⁺, 0～5% La ³⁺, 0～5% Gd ³⁺

In above-mentioned opticglass I, anionic component F ^-And O ^2-Proportion optimization be: F ^-Content with respect to F ^-With O ^2-The mol ratio F of total amount ^-/ (F ^-+ O ^2-) be positioned at 0.25～0.95 scope.Through as above setting the amount of anionic component, can give glass low dispersing characteristic.

According to above-mentioned opticglass I, the value nd that can realize specific refractory power is 1.40000～1.60000, Abbe number (υ d) is the optical characteristics more than 67.In addition, do not have special qualification, but from stably making the angle of glass for the upper limit of Abbe number (υ d), preferably with below 100 as benchmark.

In above-mentioned opticglass I, divalent cation composition (R ²⁺) preferably include Ca ²⁺, Sr ²⁺, Ba ²⁺In two or more.

In addition, in above-mentioned opticglass I, as divalent cation constituent (R ²⁺) Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Total content be preferably more than 1% Mg more preferably ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Content separately be more than 1%.

Below, the composition of above-mentioned opticglass I is carried out detailed explanation, containing of each cation constituent proportional (%) means with the mol ratio to be the positively charged ion % on basis, containing of each anionic component proportional (%) also means with the mol ratio to be the negatively charged ion % on basis.

P ⁵⁺Reticulattion formative element as glass is important cation constituent, and when less than 5%, the stability of glass can reduce, and to surpassing at 50% o'clock, owing to need to import oxide raw material, so the oxidation ratio becomes big, can't satisfy the objective optics characteristic.Therefore, preferably making its content is 5%～50%, is more preferably 5%～40%, is preferably 5%～35% especially.In addition, if importing P ⁵⁺The time use PCl ₅Words can corrode platinum, and volatilization is also very violent, thereby is an impediment to stable manufacturing, and is therefore inapplicable, preferably imports as phosphoric acid salt.

Al ³⁺It is the composition that improves the stability of fluorphosphate glass; When less than 0.1%, stability can descend, and when surpassing 40%; Glass tansition temperatures (Tg) and liquidus temperature (LT) can significantly rise; Therefore forming temperature rises, and the surface volatilization during shaping can cause producing very strong striped, thereby can't obtain the performing member that the glass forming body of homogeneous, especially die forming are used.Therefore, preferably making its content is 0.1%～40%, is more preferably 5%～40%, is preferably 10%～35% especially.

Importing is as divalent cation composition (R ²⁺) Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Help to improve the stability of glass.But excessive importing can cause the stability decreases of glass, therefore preferably makes Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Be positioned within the following scope.

At first, Mg ²⁺Preferred content be 0～20%, be more preferably 1～20%, further be preferably 5～15%, be preferably 5～10% especially.Ca ²⁺Preferred content be 0～25%, be more preferably 1～25%, further be preferably 5～20%, be preferably 5～16% especially.Sr ²⁺Preferred content be 0～30%, be more preferably 1～30%, further be preferably 5～25%, be preferably 10～20% especially.Ba ²⁺Preferred content be 0～30%, be more preferably 1～30%, further be preferably 1～25%, further be preferably 5～25%, be preferably 8～25% especially.

Import Mg separately with difference ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺Compare, it is two or more to be more preferably importing, the further preferred Ca that imports ²⁺, Sr ²⁺, and Ba ²⁺In two or more.In order further to improve divalent cation composition (R ²⁺) the importing effect, preferably make Mg ²⁺, Ca ²⁺, Sr ²⁺, and Ba ²⁺Total content be more than 1%.In addition, when import volume surpassed higher limit separately, stability can sharply descend.Ca ²⁺, Sr ²⁺Import volume can be many, but import Mg in a large number ²⁺, Ba ²⁺Especially can cause stability decreases.But, Ba ²⁺Owing to be to keep hanging down the composition that dispersive is realized high refractive index simultaneously, therefore preferably many importings in the scope of not damaging stability.

Li ⁺Be the composition that can under the situation that not damage stability, glass tansition temperatures (Tg) reduced, but as surpass 30% weather resistance that can damage glass, and reduce processibility simultaneously.Therefore, making its content is 0～30%.Preferred range is 0～25%, and the scope that is more preferably is 0～20%.

But, special when hoping further to reduce the glass tansition temperatures when being used for precision moulded formation etc., preferably make Li ⁺Amount be 2～30%, be more preferably 5～25%, be more preferably 5～20%.

Na ⁺, K ⁺Respectively with Li ⁺Equally have the effect that glass tansition temperatures (Tg) is reduced, but also have the Li of ratio simultaneously ⁺The stronger tendency that coefficient of thermal expansion is increased.In addition,, thereby can cause water tolerance to worsen, therefore make Na owing to NaF, KF are far longer than LiF to the solubleness of water ⁺, K ⁺Amount be respectively 0～10%.Na ⁺, K ⁺Preferable range separately is 0～5%, is more preferably not import.

Y ³⁺, La ³⁺, Gd ³⁺The effect that has stability and the weather resistance that improves glass and specific refractory power is risen, but when surpassing 5%, can cause stability to worsen on the contrary, glass tansition temperatures (Tg) is risen, therefore making its amount is 0～5%.Preferred range is 0～3%.

In addition, in order stably to make high-quality opticglass, preferably make the P that representes with positively charged ion % ⁵⁺, Al ³⁺, Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Li ⁺, Y ³⁺, La ³⁺, Gd ³⁺Total amount surpass 95%, be more preferably and surpass 98%, further preferably surpass 99%, further be preferably 100%.

Except above-mentioned cation constituent, above-mentioned opticglass I can also contain the cation constituent of cation constituent, B of lanthanon such as Ti, Zr, Zn etc. etc. in the scope of not damaging the object of the invention.

About the ratio of anionic component, the opticglass in order to obtain realizing desired optical and to have advantages of excellent stability makes F ^-Content with respect to F ^-With O ^2-The mol ratio F of total amount ^-/ (F ^-+ O ^2-) be 0.25～0.95.

In addition, above-mentioned opticglass I is for making optical element through precision moulded formation, perhaps is good glass for cutting through grinding, grind to make for the optical element.

Preferred second mode of the opticglass that forms by fluophosphate glass (below, be called opticglass II) be by containing Cu ²⁺The opticglass that forms of fluophosphate glass, this glass plays a role as near-infrared absorbing glass.Opticglass II is particularly useful for the color correct of semiconductor camera elements such as CCD, CMOS and uses spectral filter, when being used for aforementioned applications, preferably makes Cu ²⁺Content be 0.5～13 positively charged ion %.

When representing through positively charged ion %, contain 11～45% P preferred especially composition of opticglass II ⁵⁺, 0～29% Al ³⁺, total amount is 0～43% Li ⁺, Na ⁺, K ⁺, total amount is 14～50% Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, Zn ²⁺, 0.5～13% Cu ²⁺And, when representing, contain 17～80% F through negatively charged ion % ^-

In above-mentioned composition, the residual content of anionic component all is O preferably ^2-

Below, the composition of above-mentioned opticglass II is carried out detailed explanation.Identical with the explanation of above-mentioned composition for opticglass I, containing of each cation constituent proportional (%) means with the mol ratio to be the positively charged ion % on basis, and containing of each anionic component proportional (%) also means with the mol ratio to be the negatively charged ion % on basis.

In above-mentioned composition, P ⁵⁺Be the basal component of fluophosphate glass, Cu ²⁺It is the important component that produces the absorption characteristic of region of ultra-red.Work as P ⁵⁺Contain quantity not sufficient 11% time, color worsens that also band is green, on the contrary when surpassing 45%, weathering resistance, the deterioration of anti-increased devitrification resistance.Therefore, preferably make P ⁵⁺Content be 11～45%, be more preferably 20～45%, further be preferably 23～40%.

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

Li ⁺, Na ⁺, K ⁺Be the composition that improves glass melting property, anti-increased devitrification resistance and improve the transmitance in visible light zone, when total amount surpassed 43%, the weather resistance of glass, processibility descended.Therefore, preferably make Li ⁺, Na ⁺, K ⁺Total content be 0～43%, further be preferably 0～40%, further be preferably 0～36%.

In alkaline components, Li ⁺Have good above-mentioned effect, preferably make Li ⁺Amount be 15～30%, further be preferably 20～30%.

Mg ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, and Zn ²⁺Be the composition of the anti-increased devitrification resistance that helps to improve glass, weather resistance, processibility, but, therefore preferably make Mg because the words of excessive importing can cause anti-increased devitrification resistance to descend ²⁺, Ca ²⁺, Sr ²⁺, Ba ²⁺, and Zn ²⁺Total content be 14～50%, be more preferably 20～40%.

Mg ²⁺The preferable range of content be 0.1～10%, preferred scope is 1～8%.Ca ²⁺The preferable range of content be 0.1～20%, the scope that is more preferably is 3～15%.Sr ²⁺The preferable range of content be 0.1～20%, the scope that is more preferably is 1～15%.Ba ²⁺The preferable range of content be 0.1～20%, the scope that is more preferably is 1～15%, further preferred range is 1～10%.

Cu ²⁺Can make glass produce the near infrared light absorption characteristic.When it contained quantity not sufficient 0.5%, near infrared absorption was little, and when surpassing 13%, anti-increased devitrification resistance can worsen on the contrary.Therefore, preferably make Cu ²⁺Content be 0.5～13%, be more preferably 0.5～10%, further be preferably 0.5～5%, further be preferably 1～5%.

F ^-In opticglass II the melting point that reduces glass, the important anionic component that improves weathering resistance.Opticglass II is through containing F ^-, can reduce the glass melting temperature, suppress Cu ²⁺Reduction, thereby can obtain the optical characteristics that needs.Work as F ^-Contain quantity not sufficient 17% time, weathering resistance can worsen, on the contrary when above 80% the time, O ^2-Content can reduce, thereby can be because the Cu of 1 valency ⁺And near 400nm, produce painted.Therefore, preferably make F ^-Content be 17～80%.In order further to improve above-mentioned characteristic, further preferably make F ^-Amount be 25～55%, be more preferably 30～50%.

O ^2-Be important anionic component in opticglass II, in all anionic components except F ^-Remainder in addition is preferably all by O ^2-Composition constitutes.Therefore, O ^2-Preferred amount be 100% to deduct above-mentioned F ^-Preferred amount after the scope that obtains.Work as O ^2-When very few, the Cu of divalent ²⁺Can be reduced and become the Cu of 1 valency ⁺, so near the absorption short wavelength zone, the especially 400nm can become big and present green.Served as on the contrary for a long time, the viscosity of glass rises, and melt temperature raises, so transmitance can worsen.

In addition, because the hazardous property of Pb, As is strong, therefore preferably do not use.

The preferred light transmission rate of opticglass II is following: when being scaled thickness; The characteristic that the spectrophotometric transmittance of wavelength 400～1200nm shows below, said thickness are that the wavelength that in the spectrophotometric transmittance of wavelength 500～700nm, demonstrates 50% transmitance is the thickness of 615nm.

When wavelength is more than 78% during for 400nm, be preferably more than 80%, when wavelength is more than 85% during for 500nm, be preferably more than 88%; When wavelength is more than 51% during for 600nm, be preferably more than 55%, when wavelength is below 12% during for 700nm, be preferably below 11%; When wavelength is below 5% during for 800nm, be preferably below 3%, when wavelength is below 5% during for 900nm, be preferably below 3%; When wavelength is below 7% during for 1000nm, be preferably below 6%, when wavelength is below 12% during for 1100nm; Be preferably below 11%, when wavelength is below 23%, to be preferably below 22% during for 1200nm.

That is, the near infrared absorption of wavelength 700～1200nm is big, and the absorption of the visible rays of wavelength 400～600nm is little.Here; Transmitance is the value that obtains as follows: imagination has two planar glass samples that are parallel to each other and passed through optical grinding; When light incident in said plane vertically; The light intensity of another ejaculation from said plane is divided by intensity and the value that obtain of said incident light before the sample incident, and this transmitance is called as outside transmitance.

Opticglass II can carry out the color correct of semiconductor camera elements such as CCD, CMOS well owing to this characteristic.

(die forming is used the glass material)

Die forming of the present invention is characterised in that with the glass material: the opticglass that is obtained by the method for manufacture through opticglass of the present invention forms.

Compare with other common opticglass, the opticglass that is formed by fluophosphate glass has the character that stage of wear is big, thermal expansivity is also big, but for attrition process, does not hope to have this character.When stage of wear was big, working accuracy reduced, and the damage when perhaps grinding remains on the glass surface easily.In addition;, grinding in glass when spraying cutting fluid; If spray cutting fluid, or exist on the surface when carrying out ultrasonic cleaning the glass of the scar that causes by grinding to put in the scavenging solution that temperature risen owing to grinding the glass risen to temperature; Therefore glass can be exposed under the very big temperature variation, occurs the big fluophosphate glass of thermal expansivity easily because thermal shocking and damaging problem.Therefore, preferably make die forming and use the glass material through not carrying out abrasive method.From this viewpoint, die forming is preferably performing member for precise compression moulding with the glass material.Here, performing member for precise compression moulding means that the glass that weight is identical with die-formed product is configured as the shape that is suitable for precision moulded formation in advance.

As performing member for precise compression moulding; Preferred its whole surface forms through the vitrification of molten state; Through the face that the whole surface that makes performing member forms for the vitrification by molten state, can prevent or reduce performing member when glass cleaning, or breakage when heating before the precision moulded formation.

(die forming is with the method for manufacture of glass material)

Then, the method for manufacture of die forming with the glass material is described.

Die forming of the present invention with first mode of the method for manufacture of glass material (below; The method of manufacture I that is called the glass material) be characterised in that: the melten glass that the opticglass that obtained by the method for manufacture through opticglass of the present invention is formed flows out; Be separated into fused glass block, in this fused glass block refrigerative process, be configured as performing member for precise compression moulding.

Below, according to the method for manufacture I of the preferred concrete bright glass material of as an exampleBSEMGVR takeN-PSVSEMOBJ.

Melten glass is flowed out from the pipe of the platinum system that is heated to specified temperature or platinum alloy system with the constant flow continuously.Isolate the fused glass block of weight with 1 performing member from effusive melten glass; When the fractional melting glass block; In order not stay the cut-out vestige, preferably avoid the use of cutting knife, for example; The following method of preferred use: melten glass is dripped from the spout of pipe; Perhaps support the top of effusive molten glass flow, and promptly fall supporting mass, utilize the surface tension of melten glass to isolate fused glass block from the top of molten glass flow in the moment of the fused glass block that can isolate target weight through supporting mass.

Isolated fused glass block preferably is configured as intended shape in the process on the recess of performing member shaping dies, in glass cools.At this moment, in order to prevent crackle, fissured breakage to occur being called as producing on the performing member surface in gauffer or the process of cooling, preferably applying blast upwards and under the buoyant state, forming to glass block on the recess at glass.At this moment, in order to reduce, prevent the generation of striped, preferably brush the cooling that gas promotes above-mentioned surface to the glass block surface.

Even be reduced to after performing member applies the temperature province that external force also can not be out of shape, performing member is taken out from the performing member mould and carries out slow cooling in the temperature of glass.

In addition, in order to reduce the glass ingredient from glass surface volatilization, preferably (the dry mixed gas atmosphere of dry nitrogen atmosphere, dry air atmosphere, nitrogen and oxygen etc.) carry out glass outflow and performing member shaping in dry atmosphere.

The method of manufacture I of glass material can make high quality and the high performing member of weight precision, the method for manufacture of the performing member that therefore is suitable for using as precision moulded formation.

Die forming of the present invention with second mode of the method for manufacture of glass material (below; The method of manufacture II that is called the glass material) characteristic is following: the melten glass that the opticglass that will be obtained by the method for manufacture through opticglass of the present invention forms is cast in the casting mould; After producing glass shaping body, this glass shaping body is carried out mechanical workout.

As the preferred concrete example of the method for manufacture II of glass material, at first, melten glass is flowed out continuously from pipe, and it is flow in the casting mould that is configured in the pipe below.Use has smooth bottom and surrounds the casting mould of the sidewall of bottom, a lateral opening of this casting mould from three directions.Side wall portion according to from sandwich open side and bottom is relative in parallel to each other; The central authorities of bottom surface are positioned at the vertical lower of pipe; The mode of bottom surface level disposes in addition, the fixed cast mould; The melten glass that flow in the casting mould is extended with homogeneous thickness in the zone by side walls enclose, after cooling, extract glass from the lateral peristome of casting mould out to horizontal direction with constant speed.The glass shaping body of extracting out is fed in the lehre and is annealed.So just obtained having certain width and thickness and reduced or suppressed the plate glass molding of surperficial striped.

Then, cut off or cut off the plate glass molding, it is divided into a plurality of glass block that are called as section (cutpiece), these glass block are ground cut, grind, it is finish-machined to the preform for press forming of target weight.

In addition, other preferred concrete example is following.

The casting mould that will have columniform through hole disposes, is fixed on the vertical lower of pipe towards the mode of vertical direction according to the hub of through hole.At this moment, the mode that preferably is positioned at the vertical lower of pipe according to the hub of through hole disposes casting mould.Make melten glass with the constant flow from pipe flow in the casting mould through hole and in through hole filling glass; Solidified glass is extracted out and carried out slow cooling to vertical lower from the lower ending opening portion of through hole with constant speed, thereby obtain the glass shaping body of cylindrical bar shape.After the glass shaping body that as above obtains is annealed, cut off or cut off from vertical direction with respect to the hub of cylindrical bar shape, obtain a plurality of sheet glass.Then, sheet glass ground cut, grind, be finish-machined to the preform for press forming of desired wt.In aforesaid method, preferably the same outflow, the shaping of in dry atmosphere, carrying out melten glass with above stated specification.And in aforesaid method, the glass surface in forming process brushes gas also can reduce, prevent the generation of striped effectively to impel its refrigerative mode.

(method of manufacture of optical element)

The method of manufacture of optical element of the present invention then, is described.

The characteristic of first mode of the method for manufacture of optical element of the present invention (below, be called the method for manufacture I of optical element) is following: to carrying out precision moulded formation with the die forming that glass material or the method for manufacture I through the glass material obtain with the glass material as the die forming of the present invention of performing member for precise compression moulding.

Above-mentioned precision moulded formation also is called as moulded optical and is shaped, and is known method in the relevant technologies field.Through precision moulded formation, the forming face of model forming module is critically copied on glass, thereby can form the optical function face through die forming, therefore needn't grind for precision work optical function face cut, mechanical workout such as grinding.

Therefore, the method for manufacture I of optical element of the present invention is suitable for making optical elements such as lens, lens arra, diffraction grating, prism, is particularly suited for as the method for making non-spherical lens with high productivity.

Method of manufacture I according to optical element of the present invention; Because the tansition temperatures (Tg) of the glass of formation performing member is all lower; Therefore can reduce the die forming temperature, alleviate the infringement that the forming face to model forming module causes, thereby can prolong the life-span of shaping dies.In addition, have high stability, therefore in reheat, mold pressing procedure, also can prevent the devitrification of glass effectively owing to constitute the glass of performing member.And, can carry out melting with high productivity from glass to the series of processes that obtains the finished product.

The employed model forming module of precision moulded formation method is known; For example can use the mould that mold release film is set on the forming face of the ceramic section bar of thermotolerances such as silit, zirconium white, aluminum oxide; The wherein preferred model forming module of making by silit that uses; As mold release film, can use to contain carbon film etc.From aspects such as weather resistance, costs, especially preferred carbon film.

In precision moulded formation, for the forming face with model forming module remains good state, preferably making the atmosphere when being shaped is non-oxidizing gas.As non-oxidizing gas, the mixed gas of preferred nitrogen, nitrogen and hydrogen etc.

As the optimal way of the method for manufacture I of optical element of the present invention and can enumerate: the glass material is imported in the model forming module and both heated together the mode of carrying out precision moulded formation; And independent heated glass material imported to the mode of in the model forming module of preheating, carrying out precision moulded formation.

From model forming module, take out the optical element of precision moulded formation, and carry out slow cooling as required.

Second mode of the method for manufacture of optical element of the present invention (below; The method of manufacture II that is called optical element) characteristic is following: the die forming that the die forming of the invention described above is obtained with glass material or the method for manufacture II through above-mentioned glass material carries out die forming with the glass material and makes optical element base substrate (blank), this base substrate is ground cut, grind.

1 the weight that the weight of above-mentioned glass material is preferably the optical element that will obtain adds through grinding cuts, grinds the weight of removing, and cuts as grinding, abrasive method, can use known method in the past.

The characteristic of the Third Way of the method for manufacture of optical element of the present invention (below, be called the method for manufacture III of optical element) is following: comprise that the glass shaping body that opticglass that the method for manufacture by the opticglass through the invention described above is obtained forms grinds the operation of cutting, grinding.

As the concrete mode of the method for manufacture III of optical element, the following method of can giving an example out: melten glass being flowed out form shape is glass shaping body, after annealing, cut off, grind cut, mechanical workout such as grinding, thereby produce optical element.For example, can be with respect to cylinder axis from vertical direction to (slice) processing of cutting into slices of the glass shaping body of above-mentioned cylindrical bar shape, then the columned glass that obtains is ground cut, attrition process, thereby produce optical element such as various lens.

The cubic formula of the method for manufacture of optical element of the present invention (below; The method of manufacture IV that is called optical element) characteristic is following: the melten glass that the opticglass that the method for manufacture by the opticglass through the invention described above is obtained forms flows out; Make the optical element base substrate through die forming, then this base substrate is ground and cut, grind.

1 the weight that the weight of above-mentioned optical element base substrate is preferably the optical element that will obtain adds through grinding cuts, grinds the weight of removing, and cuts as grinding, abrasive method, can use known method in the past.

When the optical element that obtains through above-mentioned various method of manufacture is lens etc., can form antireflection film as required and from the teeth outwards, perhaps cover with the near infrared light reflectance coating.

(embodiment)

Below, come to explain in further detail the present invention through embodiment, but the present invention does not receive any restriction of these embodiment.

Embodiment 1(the manufacturing example of opticglass I)

For the glass of the composition that obtains having the No.1 shown in table 1 and the table 2～11, the raw material that weighing is corresponding with each composition also mixes fully.At this moment, phosphatic raw materials is mixed with fluoride raw material and it is divided into two raw material groups concocts.

The blending raw material that will comprise above-mentioned phosphatic raw materials is put in the silicon crucible, stirs down and carries out 1 hour melt at 1200 ℃, carries out chilling, pulverizing then, obtains glass cullet (cullet).Melt in the operation at this, the supply of nitrogen continuously in the silicon crucible remains non-oxidizing atmosphere with atmosphere.

Then, these glass cullet of 10kg are put into in the airtight platinum system crucible of lid, are put into the blending raw material that 15kg contains fluorochemical simultaneously, be heated to 900 ℃ and stir, fusion.Then, the gas of thorough drying is imported in the platinum system crucible and the atmosphere that keeps dry, under 1100 ℃, melten glass carried out 2 hours clarification simultaneously.As the kind of dry gas, can illustration go out mixed gas, oxygen of rare gas element, rare gas element and oxygen such as nitrogen etc.

After clarification, the temperature that the temperature when making the temperature of glass drop to than clarification is low 850 ℃ makes the pipe outflow of melten glass from being connected with the crucible bottom then, and is cast in the casting mould and is configured as glass blank.

In addition, the gas that imports in above-mentioned silicon system crucible, the platinum system crucible is discharged to the outside after being cleaned through strainer.

Make light to each the bodies incident that obtains, from transverse observation the light path of the said light the glass, the result finds that almost the light cause owing to the platinum foreign matter is at random, so has confirmed to prevent that the platinum foreign matter is blended in the glass blank.From a plurality of glass blanks that obtain, at random select 1, the photo that obtains after the photography (white dot of the glass blank among Fig. 2 is attached to the dust on the glass surface) as shown in Figure 2.

In addition, for opticglass No.1～11 that obtain, specific refractory power (nd), Abbe number (υ d) and glass tansition temperatures (Tg) have been measured as follows.Measure the result shown in table 1～2.

(1) specific refractory power (nd) and Abbe number (υ d)

Measure for-30 ℃ of/hour opticglass that obtain making the slow cooling cooling rate.

(2) glass tansition temperatures (Tg)

Through the thermo-mechanical analysis device of Rigaku Denki Co., Ltd, making heat-up rate is 4 ℃/minute, and (Tg) measures to the glass tansition temperatures.

(table 1)

Table 1

(table 2)

Table 2

Embodiment 2 (the manufacturing example of opticglass II)

For the glass of the composition that obtains having the No.12 shown in the table 3～13, the raw material that weighing is corresponding with each composition also mixes fully.At this moment, phosphatic raw materials is mixed with fluoride raw material and it is divided into two raw material groups concocts.

Then, through having made opticglass No.12～13 with embodiment 1 identical method.Make light to each the opticglass incident that obtains, the light path of the said light from transverse observation glass, result do not find that almost the light that causes owing to the platinum foreign matter is at random, has therefore confirmed to prevent that the platinum foreign matter is blended in the glass blank.

For opticglass No.12～13 that obtain, likewise measured specific refractory power (nd), Abbe number (υ d) and glass tansition temperatures (Tg) with embodiment 1, in addition, measured the transmitance of representative wavelength.The result is as shown in table 3.

Above-mentioned transmitance be wavelength when being 615nm transmitance be the value under 50% the thickness.For opticglass No.12, said thickness is 1.0nm, and for opticglass No.13, said thickness is 0.45nm.In addition, be used for writing board shape and relative face has been carried out optical grinding and made its sample that is parallel to each other, transmitance is measured through spectrophotometer.

(table 3)

Table 3

(notes) R ⁺Be Li ⁺, Na ⁺, and K ⁺Total content

R " ²⁺Be Mg ²⁺, Ca ²⁺, Sr ²⁺, and Ba ²⁺Total content

R " ²⁺Be R ' ²⁺And Zn ²⁺Total content

Comparative example 1(the manufacturing comparative example of opticglass)

For the glass of the composition that obtains having the No.1 shown in table 1 and the table 2～11, the raw material that weighing is corresponding with each composition also mixes fully.At this moment, be regardless of phosphatic raw materials and fluoride raw material and be blended together and concoct sample.

The above-mentioned sample of respectively concocting of 25kg is put into covering in the airtight platinum system crucible, heated 1 hour down, raw material is melted at 1200 ℃.Then, the gas of thorough drying is imported in the platinum system crucible and the atmosphere that keeps dry, and when stirring, under 900 ℃, melten glass carried out 1 hour clarification.

After clarification, the temperature when making the temperature of glass drop to than clarification is low 850 ℃, make the pipe outflow of melten glass then, and be cast in the casting mould and be configured as glass blank from being connected with the crucible bottom.

In addition, the gas that imports in the platinum system crucible is discharged to the outside after being cleaned through strainer.

Make light to the bodies incident that forms by each opticglass that obtains; The light path of the said light from transverse observation glass; It is at random that the result has observed the light that causes owing to the platinum foreign matter significantly, therefore confirmed in glass blank, to have sneaked into more platinum foreign matter.From a plurality of glass blanks that obtain, at random select 1, the photo that obtains after the photography is as shown in Figure 3.

Embodiment 3(making the manufacturing example of lens performing member through the method for manufacture I of glass material)

To be separated into the fused glass block of target performing member weight by each melten glass that opticglass No.1～11 that in embodiment 1, obtain form through following method: melten glass is flowed out with the pipe of constant flow from platinum system; Melten glass is dripped or after the top of using supporting mass supporting molten glass flow, fall supporting mass rapidly and isolate fused glass block, the temperature of the pipe of said platinum system is adjusted to and can makes glass stably effusive temperature province under the situation of devitrification not.Then; The mould of accepting that has gas vent through the bottom is caught each fused glass block that obtains; The glass block buoyant being formed simultaneously, use the lens performing member thereby produce the precision moulded formation that forms by opticglass No.1～11 from gas vent ejection gas.It is spherical or flat spherical through the separation spacing of adjusting, set melten glass the shape of performing member to be become.The weight and the set(ting)value of each performing member that obtains critically are consistent, and the whole surface of all performing members is the vitrification of molten state and slick of forming.

Then, observe the inside of performing member, the result does not all find striped.

Embodiment 4(making the manufacturing example of lens performing member through the method for manufacture II of glass material)

Each melten glass that will be formed by opticglass No.1～11 that in embodiment 1, obtain flows out to the casting mould from the pipe of platinum system with the constant flow and is cast into; And being configured as plate glass simultaneously to impel its refrigerative brushing dry gas to glass surface, the temperature of the pipe of said platinum system is adjusted to and can makes glass stably effusive temperature province under the situation of devitrification not.In this case, do not find striped on the surface of plate glass.After having carried out anneal, cut off each plate glass obtain, and the surface of the sheet glass that obtains thus ground cut, grind, be that the precision moulded formation of shiny surface is used the lens performing member thereby obtain whole surface.

Embodiment 5(making the manufacturing example of various lens through the method for manufacture I of optical element)

Use molding device shown in Figure 1 that each performing member that in embodiment 3 and embodiment 4, obtains is carried out precision moulded formation and obtains various lens.Specifically; Performing member 4 is arranged between the bed die 2 and mold 1 of the model forming module that constitutes by mold 1, bed die 2 and mould 3; Make then that silica tube 11 is inner to be nitrogen atmosphere, and well heater 12 is switched on and silica tube 11 inside are heated.The model forming module temperature inside is set at the glass that is formed demonstrates 10 ⁸～10 ¹⁰The temperature of the viscosity of dPas descends signature bar 13 and pushes mold 1 in the situation of keeping this temperature, thereby the performing member that is arranged in the shaping dies is carried out mold pressing.The pressure that makes mold pressing is 8MPa, and clamp time is 30 seconds.After mold pressing, remove the pressure of mold pressing, the viscosity of slow cooling to said glass becomes 10 under the glass molded article that makes the shaping that is molded and bed die 2 and mold 1 state of contact ¹²The temperature that dPas is above is chilled to room temperature then and from shaping dies, takes out various lens.

In addition, in Fig. 1, reference number 9 expression supporting bars, reference number 10 expression bed dies, sleeve die fixer, reference number 14 expression thermopairs.In addition, the shape of the forming face of mold 1 shown in Figure 1, bed die 2 etc. can be carried out suitable change according to the lens shape that obtains.

The lens of different shapes such as concavees lens, convex lens, biconcave lens, biconvex lens, plano-convex lens, plano-concave lens have been made through aforesaid method.The lens that obtain have high surface accuracy respectively.On above-mentioned various lens, be provided with antireflection film as required.

Embodiment 6(making the manufacturing example of various lens through the method for manufacture II of optical element)

To be cast into by each melten glass that opticglass No.1～11 that in embodiment 1, obtain form in the casting mould and be configured as plate glass.After the plate glass that obtains having been carried out annealing, to spend the cutter shape it is cut into a plurality of sheet glass, carry out cylinder (barrel) then and grind and make surface roughening and make sheet glass become the weight of expectation, thereby manufacture the glass material.

Then, powder release agent such as coating SP 1 etc. on whole of above-mentioned glass material heats in atmosphere, softening and carry out die forming, thereby manufactures the blank that has with the akin shape of shape of various lens.After the blank that obtains is annealed, grind and cut, grind, thereby manufacture the various lens that form by opticglass No.1～11.

The lens of different shapes such as concavees lens, convex lens, biconcave lens, biconvex lens, plano-convex lens, plano-concave lens have been made through aforesaid method.On above-mentioned various lens, be provided with antireflection film as required.

Embodiment 7(making the manufacturing example of various lens through the method for manufacture III of optical element)

Each melten glass that is formed by opticglass No.1～11 that in embodiment 1, obtain is flow into the casting mould from pipe continuously, in dry atmosphere, be configured as plate glass and carry out slow cooling.Then, it is inner to have observed glass, and the result does not find striped.

This plate glass is cut into the size that needs and grinds and cut, grind, thereby obtain the various lens that form by opticglass No.1～11.

Embodiment 8(making the manufacturing example of near-infrared absorbing spectral filter through the method for manufacture III of optical element)

Each melten glass that is formed by opticglass No.12～13 that in embodiment 2, obtain is flow into the casting mould from pipe continuously, in dry atmosphere, be configured as glass blank and carry out slow cooling.Then, it is inner to have observed glass, and the result does not find striped.

To above-mentioned each glass blank cut into slices and the surface ground cut, grind and be processed into lamellar, thereby produce the near-infrared absorbing spectral filter.

Embodiment 9(making the manufacturing example of various lens through the method for manufacture IV of optical element)

Each melten glass of being formed by opticglass No.1～11 that in embodiment 1, obtain is flowed out from the pipe of platinum system continuously, catch this melten glass waiting on the mold pressing bed die below the pipe, cut off molten glass flow, thereby obtain the fused glass block of requirement.The bed die that is loaded with fused glass block is withdrawed from from the pipe below, use the mold relative that above-mentioned fused glass block is carried out die forming, thereby obtain blank with bed die.

Repeat above-mentioned series of processes successively through using a plurality of bed dies, thereby obtain a plurality of blank.

After each blank is annealed, grind and cut, grind, thereby obtain the various lens that form by opticglass No.1～11.

(industrial applicibility)

According to the present invention; The method of manufacture of following opticglass can be provided: when making the opticglass that forms by fluophosphate glass through scorification; Not only the opticglass desired optical can be given, but also platinum or the platinum alloy foreign matter that is blended in the glass can be reduced.In addition,, can provide the die forming that forms by the opticglass of making through aforesaid method to use the glass material, can also provide by making the method for die forming respectively with glass material and optical element through the opticglass of aforesaid method manufacturing according to the present invention.

Claims

1. the method for manufacture of an opticglass that is formed by the fluophosphate glass that has used phosphatic raw materials and fluoride raw material is characterized in that, comprising:

First operation, fusion phosphatic raw materials in nonmetal container made and obtain phosphate glass; With

Second operation is under the state of melts or after this melts solidifies at the phosphate glass that obtains, in the container of platinum or platinum alloy system with it with the fluoride raw material fusion.

2. a die forming is characterized in that with the method for manufacture of glass material,

The melten glass that is formed by the opticglass that obtains through the described method of claim 1 is flowed out, isolate fused glass block, this fused glass block is configured as performing member for precise compression moulding in the refrigerative process.

3. a die forming is characterized in that with the method for manufacture of glass material,

To be cast in the casting mould by the melten glass that the opticglass that obtains through the described method of claim 1 forms, after producing glass shaping body, this glass shaping body is carried out mechanical workout.

4. the method for manufacture of an optical element is characterized in that,

Die forming to obtaining through the described method of claim 2 carries out precision moulded formation with the glass material.

5. the method for manufacture of an optical element is characterized in that,

The die forming that obtains through claim 2 or 3 described methods is carried out die forming with the glass material make the optical element base substrate, this base substrate is ground cut, grind.

6. the method for manufacture of an optical element is characterized in that,

Comprise that the glass shaping body to being formed by the opticglass that obtains through the described method of claim 1 grinds the operation of cutting, grinding.

7. the method for manufacture of an optical element is characterized in that,

The melten glass that is formed by the opticglass that obtains through the described method of claim 1 is flowed out, carry out die forming, make the optical element base substrate thus, then this base substrate is ground and cut, grind.