WO2015046509A1 - 光学素子およびその製造方法 - Google Patents

光学素子およびその製造方法 Download PDF

Info

Publication number
WO2015046509A1
WO2015046509A1 PCT/JP2014/075887 JP2014075887W WO2015046509A1 WO 2015046509 A1 WO2015046509 A1 WO 2015046509A1 JP 2014075887 W JP2014075887 W JP 2014075887W WO 2015046509 A1 WO2015046509 A1 WO 2015046509A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
film
press
oxide
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/075887
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
法一 西村
山本　英明
佐藤　浩一
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
Original Assignee
Hoya Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoya Corp filed Critical Hoya Corp
Priority to KR1020167004994A priority Critical patent/KR102219149B1/ko
Priority to CN201480053466.6A priority patent/CN105579412B/zh
Publication of WO2015046509A1 publication Critical patent/WO2015046509A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • 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
    • C03B11/08—Construction of plunger or mould for making solid articles, e.g. lenses
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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

Definitions

  • the present invention relates to an optical element and a manufacturing method thereof.
  • a method of manufacturing an optical element such as a glass lens
  • a method of press-molding a molding material hereinafter referred to as “a glass material for press molding” or “preform”
  • a glass material for press molding or “preform”
  • the glass material for press molding and the molding surface of the molding die adhere to each other under high temperature conditions, so that a chemical reaction occurs at the interface between them, so that fusion, spider, scratches, etc. Reaction traces or the like may occur, and the optical performance of the optical element obtained by press molding may deteriorate.
  • Patent Document 1 proposes to provide a coating film on the surface of a glass material for press molding to suppress the reaction between the mold and the glass.
  • Patent Document 2 proposes to provide a hydrogen capture film on the surface of a glass material for press molding in order to suppress the generation of linear marks.
  • One embodiment of the present invention provides an optical element manufacturing method capable of suppressing the generation of bubbles in an optical element after press molding.
  • One embodiment of the present invention provides: Oxide glass, A coating film covering at least part of the surface of the oxide glass; Have The above-described coating film is a metal oxide film in which oxygen is lost from the stoichiometric composition, and the metal oxide film is included in the oxide glass at a temperature equal to or higher than the glass transition temperature of the oxide glass. An optical element in which an oxygen atom is incorporated at a rate faster than a rate at which a metal atom contained in the metal oxide film diffuses into the oxide glass; About.
  • a further aspect of the present invention provides: A step of preparing a glass material for press molding having an oxide glass and a coating film that covers at least a part of the surface of the oxide glass and is a metal oxide film in which oxygen is lost from the stoichiometric composition; , A press process for forming a press-molded body by press-molding a glass material for press molding; With The press-molded body described above includes the above-described coating film that has undergone a pressing process, and the coating film that has undergone the pressing process is a metal oxide film having a higher oxygen content than the coating film before the pressing process.
  • Device manufacturing method About.
  • the inventors have provided the above-described coating film on the surface of the glass material for press molding.
  • a metal oxide film in which oxygen is deficient from the stoichiometric composition is in a state where oxygen is easily taken up. Therefore, with the metal oxide film in this state, oxygen that causes foaming during press molding can be removed from the inside of the glass, and generation of bubbles can be suppressed.
  • the movement of oxygen atoms from the oxide glass to the coating film incorporation
  • the movement of metal atoms from the coating film to the oxide glass Diffusion
  • the diffusion rate of the metal atoms is faster than the rate at which oxygen atoms are taken into the coating film
  • the diffusion proceeds in preference to the uptake.
  • a remarkable reduction in film thickness or disappearance of the film occurs due to press molding, and it is difficult to suppress foaming inside the oxide glass.
  • the above-mentioned coating film takes in oxygen atoms in preference to the diffusion of metal atoms, it efficiently takes in oxygen atoms that cause generation of bubbles from oxide glass and suppresses foaming. Can do.
  • the above-described coating film that has undergone a pressing step is present.
  • the coating film included in this optical element takes in oxygen from the oxide glass at the time of press molding, the content of oxygen atoms relative to metal atoms is higher than that contained in the glass material for press molding.
  • the coating film included in the optical element is still in a state in which oxygen is lost from the stoichiometric composition.
  • FIG. 1 shows an example of a press molding apparatus.
  • FIG. 2 shows an optical micrograph of the lens (core glass: I-1 in Table 1) produced in Example 1.
  • FIG. 3 shows an optical micrograph obtained by enlarging and photographing a part of the lens (core glass: I-1 in Table 1) produced in Comparative Example 2.
  • FIG. 4 shows the depth direction analysis results of secondary ion intensity by TOF-SIMS after pressing (lens) for Example 1.
  • FIG. 5 shows the depth direction analysis result of secondary ion intensity by TOF-SIMS before pressing (unpressed product) in Example 1.
  • FIG. 6 shows the result of comparison of the secondary ion intensity ratio of ZrO 2 / ZrO in FIGS.
  • FIG. 1 shows an example of a press molding apparatus.
  • FIG. 2 shows an optical micrograph of the lens (core glass: I-1 in Table 1) produced in Example 1.
  • FIG. 3 shows an optical micrograph obtained by enlarging and photographing a part of the lens (core glass: I-1 in
  • FIG. 7 shows the depth direction analysis result of the secondary ion intensity of the lens produced in Comparative Example 2 by TOF-SIMS.
  • FIG. 8 shows a result of superimposing the result of Example 1 shown in FIG. 4 and the result of Comparative Example 2 shown in FIG.
  • FIG. 9 shows the results of depth direction analysis of secondary ion intensity by TOF-SIMS after pressing (lens) for Comparative Example 1.
  • FIG. 10 shows the depth direction analysis result of the secondary ion strength by TOF-SIMS before pressing (unpressed product) in Comparative Example 1.
  • press molding is performed using a glass material for press molding having a metal oxide film in which oxygen is lost from the stoichiometric composition as a coating film covering at least part of the surface of the oxide glass. I do.
  • the above-mentioned coating film has the above-mentioned press-molding glass material in which the content of oxygen atoms relative to metal atoms is also present in at least a part of the surface of the press-molded body obtained by press-molding this press-molding glass material Is included as a metal oxide film that is higher than the coating film of the film.
  • bubbles generated in the optical element after press molding are oxygen derived from oxide glass.
  • a metal oxide film in which oxygen is deficient from the stoichiometric composition is considered to be in a state where oxygen can be easily taken in so as to approach the stoichiometric composition, which is a more stable state. Therefore, by applying at least a part of the surface of the oxide glass with a metal oxide film in which oxygen is deficient from the stoichiometric composition, the oxygen that causes foaming during the press is converted from the oxide glass to the metal.
  • the metal oxide film remaining on the surface of the press-molded body (optical element) thus formed contains oxygen atoms taken from the oxide glass, the press-molding glass before press molding has it. It contains more oxygen atoms than the metal oxide film. That is, the press-molded body has a metal oxide film having a content rate of oxygen atoms with respect to metal atoms higher than that of the coating film of the press-molding glass material on at least a part of the surface.
  • the metal oxide film is converted into oxide glass at a temperature equal to or higher than the glass transition temperature of the oxide glass.
  • the rate at which oxygen atoms are incorporated is the rate at which metal atoms contained in the metal oxide film diffuse into the oxide glass (hereinafter, “metal atom diffusion rate”). )
  • metal atom diffusion rate is the rate at which metal atoms contained in the metal oxide film diffuse into the oxide glass.
  • the speed at which the above-described metal oxide film takes in oxygen atoms in the oxide glass during press molding depends on whether the metal atoms in the metal oxide film are oxides. Faster than the speed taken into the glass.
  • uptake of oxygen atoms into the coating film during pressing proceeds in preference to the diffusion of metal atoms into the oxide glass. Therefore, after press molding, the metal oxide film in the above-described state can be present on the press-molded body.
  • the glass material for press molding suitably used in the method for manufacturing an optical element according to one aspect of the present invention includes an oxide glass and a coating film that covers at least a part of the surface of the oxide glass.
  • the metal oxide film is in a state where oxygen is deficient from the stoichiometric composition, and the oxygen atom uptake rate and the metal atom diffusion rate satisfy the above relationship.
  • the optical element obtained through the step of press molding the glass material for press molding also has a metal oxide film in which the oxygen atom uptake rate and the metal atom diffusion rate satisfy the above-described relationship.
  • the metal oxide film present on the optical element has a higher oxygen atom content to metal atoms than the metal oxide film before press molding. This is because oxygen atoms are taken from the oxide glass in press molding.
  • the above-described glass material for press molding will be described in more detail.
  • Coating film (metal oxide film)
  • the coating film covering the oxide glass may be formed by a film formation method capable of forming a metal oxide film in which oxygen is lost from the stoichiometric composition.
  • a film formation method capable of forming a metal oxide film in which oxygen is lost from the stoichiometric composition.
  • core glass glass
  • the lower limit of the film forming temperature (core glass temperature) is preferably 150 ° C. or higher, and more preferably 200 ° C. or higher.
  • the upper limit is preferably less than the glass transition temperature of the core glass.
  • the upper limit temperature is, for example, 450 ° C. or less.
  • a plurality of core glasses formed in a predetermined shape are arranged in a tray and placed in a vacuum chamber, and the core glass is heated to about 300 ° C. by a heater while evacuating the vacuum chamber. To do. After evacuating until the degree of vacuum in the vacuum chamber becomes 1 ⁇ 10 ⁇ 5 Torr or less, Ar gas is introduced, the atmosphere gas in the vacuum chamber is replaced with Ar gas, and then a high frequency is applied to the target substrate. The raw material is turned into plasma, and a coating film is formed on the surface of the core glass.
  • the film thickness of the coating film can be controlled to a desired film thickness by adjusting the pressure (vacuum degree) in the vacuum chamber, the power source power, and the film formation time.
  • the coating film should just cover at least one part of the surface of core part glass. Therefore, the core glass after coating film formation may be in a state where a part of the surface is uncoated or the entire surface may be covered.
  • An optical functional surface means a region within an effective diameter in an optical lens, for example.
  • oxygen atoms can be taken from the core glass if the above-described coating film is present in at least a part of the surface of the glass material for press molding. .
  • a metal that can form a metal oxide film in which the oxygen atom uptake rate and the metal atom diffusion rate satisfy the above-described relationship may be used.
  • Specific examples of such metals include zirconium, titanium, niobium, tungsten, and tantalum.
  • a preliminary experiment is performed as appropriate to confirm that the oxide film satisfying the above relationship can be formed by the oxygen atom uptake rate and the metal atom diffusion rate. It is possible to determine a metal that can form a metal oxide film that satisfies the above relationship. As a target in the above-described film forming method, it is preferable to use these metals alone.
  • the film thickness of the coating film is preferably 0.5 nm or more and more preferably 1.5 nm or more in order to efficiently take in oxygen from the oxide glass. From the viewpoint of preventing spiders, the thickness of the coating film is preferably 15 nm or less, and more preferably 10 nm or less.
  • the coating film described above is in a state where oxygen is lost from the stoichiometric composition.
  • the stoichiometric composition is ZrO 2
  • the coating film is a zirconium oxide film
  • the composition is ZrOx (x ⁇ 2).
  • x is not particularly limited as long as it is less than 2. The same applies to other metal oxide films.
  • Oxide glass examples of the core glass whose surface is at least partially covered by the above-described coating film include optical glasses having various compositions that are usually used for producing optical elements.
  • optical glasses having various compositions that are usually used for producing optical elements.
  • Specific examples of such optical glass include boric acid-rare earth glass such as lanthanum borate glass, phosphate glass, and silicate glass.
  • an oxide glass containing a relatively large amount of Nb 2 O 5 , TiO 2 , WO 3 , and Ta 2 O 5 as high refractive index imparting components can be mentioned.
  • one or more high refractive index imparting components selected from the group consisting of Nb 2 O 5 , TiO 2 , WO 3 and Ta 2 O 5 are included, and the high refractive index
  • the oxide glass having a total content (Nb 2 O 5 + TiO 2 + WO 3 + Ta 2 O 5 ) of the rate-imparting component of 10% by mass or more is used as the core glass, and the above-mentioned coating film is provided on the core glass.
  • the total content (Nb 2 O 5 + TiO 2 + WO 3 + Ta 2 O 5 ) is more preferably 15% by mass or more.
  • the total content (N b O 5 + TiO 2 + WO 3 + Ta 2 O 5 ) is 50% by mass or less, which suppresses an increase in press temperature due to a significant increase in the glass transition temperature Tg and the yield point Ts. Moreover, it is preferable from the viewpoint of easiness of vitrification, and more preferably 45% by mass or less.
  • the pressing temperature is usually performed at a temperature equal to or higher than the glass transition temperature of the core glass, the higher the glass transition temperature, the higher the pressing temperature tends to be. On the other hand, a significant increase in the press temperature may promote the generation of bubbles. Therefore, as a preferable specific embodiment of the core glass, an oxide glass containing an appropriate amount of one or more glass components having an action of lowering the glass transition temperature can be exemplified.
  • the glass component having an action of lowering the glass transition temperature include ZnO and an alkali metal oxide selected from the group consisting of Li 2 O, Na 2 O and K 2 O.
  • the total content of ZnO and alkali metal oxide is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the total content (ZnO + Li 2 O + Na 2 O + K 2 O) is preferably 25% by mass or less, and more preferably 20% by mass or less.
  • Specific examples of the core glass include optical glass having a refractive index nd of 1.70 to 2.10 and an Abbe number ⁇ d of 20 to 55 from the viewpoint of the usefulness of the optical element.
  • an optical glass satisfying one or both of glass transition temperature Tg of 630 ° C. or lower and yield point Ts of 680 ° C. or lower can also be illustrated.
  • the method for manufacturing an optical element according to one embodiment of the present invention is not limited to the specific embodiment described above.
  • the optical glass that can serve as the core glass
  • the following glasses I, II, and III can be given, for example.
  • the core glass may be an oxide glass, and the composition thereof is not particularly limited. Glasses I, II, and III are all suitable as optical glasses for producing optical elements. According to one embodiment of the present invention, such an optical glass can be press-molded to provide a high-quality optical element free from bubbles in the glass.
  • B 3+ and Si 4+ in total 5 to 60% (however, B 3+ is 5 to 50%), Zn 2+ and Mg 2+ in total 5% or more, La 3+ , Gd 3+ , Y 3+ and Yb 3+ in total 10 to 50%, Ti 4+ , Nb 5+ , Ta 5+ , W 6+ and Bi 3+ in total 6 to 45% (provided that the total content of Ti 4+ and Ta 5+ exceeds 0% and W 6+ Content over 5%), Including The cation ratio of the Si 4+ content to the B 3+ content (Si 4+ / B 3+ ) is 0.70 or less, Ti 4+ and Ta 5+ content of the cation ratio of Ta 5+ to the total content of (Ta 5+ / (Ti 4+ + Ta 5+)) is not less 0.23 or more, The cation ratio of the W 6+ content to the total content of Nb 5+ and W 6+ (W 6+ / (N
  • the glass I is a high refractive index glass, it can exhibit a low glass transition temperature, and thus is suitable as a glass for precision press molding.
  • the glass transition temperature is 650 ° C. or lower.
  • Optical glass having a glass transition temperature of 650 ° C. or lower can maintain the glass temperature during precision press molding in a relatively low temperature range, suppresses the reaction between the glass during press molding and the press molding surface, and is precise.
  • the press formability can be maintained in a good state.
  • the glass transition temperature is preferably 640 ° C. or less, more preferably 630 ° C. or less, further preferably 620 ° C.
  • the glass transition temperature is preferably 500 ° C. or higher, and is preferably 520 ° C. or higher. More preferably, it is 540 degreeC or more, More preferably, it is 560 degreeC or more, It is still more preferable to set it as 570 degreeC or more.
  • B 2 O 3 La 2 O 3 and ZnO are included, and expressed in mol%, B 2 O 3 20 to 60%, SiO 2 0 to 20%, ZnO 22 to 42%, La 2 O 3 5 to 24%, Gd 2 O 3 0 ⁇ 20% ( provided that the total of La 2 O 3 and Gd 2 O 3 is 10 ⁇ 24%), ZrO 2 0 ⁇ 10%, Ta 2 O 5 0 ⁇ 10%, WO 3 0 ⁇ 10%, Nb 2 O 5 0-10%, TiO 2 0-10%, Bi 2 O 3 0-10%, GeO 2 0-10%, Ga 2 O 3 0-10%, Al 2 O 3 0- 10%, BaO 0 to 10%, Y 2 O 3 0 to 10% and Yb 2 O 3 0 to 10%, and an Abbe number ( ⁇ d ) of 40 or more and substantially free of lithium Glass.
  • ⁇ d Abbe number
  • substantially free of lithium means that the amount of Li 2 O introduced is suppressed to a level that does not cause spiders or burns that hinder the use of the glass surface as an optical element. It is. Specifically, it means that the content is reduced to less than 0.5 mol% in terms of the amount of Li 2 O. Since the risk of spider and burns can be reduced as the amount of lithium is reduced, the amount of Li 2 O is preferably suppressed to 0.4 mol% or less, and more preferably to 0.1 mol% or less. Preferably, no introduction is more preferable.
  • the transition temperature (T g ) is low in order to prevent wear of the press mold and damage to the release film formed on the molding surface of the mold.
  • the temperature (T g ) is preferably 630 ° C. or lower, and more preferably 620 ° C. or lower.
  • the amount of lithium in the glass is limited as described above. Therefore, if the transition temperature (T g ) is excessively decreased, the refractive index decreases or the glass Problems such as a decrease in stability of the product are likely to occur. Therefore, the transition temperature (T g ) is more preferably 530 ° C. or higher, and further preferably 540 ° C. or higher.
  • Glass III exhibits a low-temperature softening property with a glass transition temperature of 650 ° C. or lower.
  • a more preferable range of the glass transition temperature of the glass III is 640 ° C. or less, more preferably 630 ° C. or less, more preferably 620 ° C. or less, and still more preferably 610 ° C.
  • the glass transition temperature is excessively decreased, it is difficult to achieve higher refractive index and lower dispersion and / or the stability and chemical durability of the glass tend to decrease.
  • Is preferably 510 ° C. or higher, preferably 540 ° C. or higher, more preferably 560 ° C. or higher, and even more preferably 580 ° C. or higher.
  • the preferred range of the yield point (Ts) of the glass III is 700 ° C. or less, more preferably 690 ° C. or less, further preferably 680 ° C. or less, more preferably 670 ° C. or less, and still more preferably 660 ° C. or less. .
  • the yield point (Ts) is preferably 550 ° C. or higher, more preferably 580 ° C. or higher, even more preferably 600 ° C. or higher, and even more preferably 620 ° C. or higher.
  • Core Glass Molding can be formed into a known shape as a preform for optical element molding using oxide glass by a known method as a preform molding method.
  • a preform molding method Regarding the shape of the core glass and the forming method, reference can be made, for example, to paragraphs 0087 to 0106 of JP2011-1259A and description of examples, paragraphs 0040 to 0044 of JP2004250295A and description of examples.
  • the glass material for press molding used in the method for producing an optical element according to one embodiment of the present invention is obtained by performing a film forming process for coating the above-described metal oxide film on the core glass described above. be able to.
  • the glass material for press molding thus obtained has a structure in which the metal oxide film is in direct contact with the surface of the core glass. On the glass material for press molding having this configuration, one or more layers can be arbitrarily formed. Such a coating is effective for enhancing the mold releasability of the glass from the mold during press molding.
  • a carbon-containing film can be exemplified.
  • the carbon-containing film provides sufficient slipperiness with the mold when the glass material is supplied to the mold prior to pressing so that the glass material can move smoothly to a predetermined position (center position) of the mold.
  • the glass material is softened and deformed by the press, the glass material is stretched according to the glass deformation on the surface of the glass material, and the glass material can be spread on the mold surface.
  • it is useful in that the glass is easily separated from the surface of the mold when the molded body is cooled to a predetermined temperature after pressing, thereby assisting the mold release.
  • laminating a carbon-containing film on the above-described metal oxide film is also effective in suppressing the occurrence of cracking in press molding.
  • a film containing carbon as a main component is preferable, but a film containing a component other than carbon such as a hydrocarbon film may be used.
  • a method for forming the carbon-containing film a known film forming method such as vacuum deposition using a carbon raw material, sputtering, ion plating method, plasma CVD (Chemical Vapor Deposition) can be used.
  • a carbon-containing film may be formed by thermal decomposition of a carbon-containing material such as hydrocarbon.
  • the film described as the first surface layer and the second surface layer in JP2011-1259A can be formed.
  • the same publication can be referred to.
  • optical element The glass material for press molding described above is prepared, and then the press molded body obtained by press molding itself or by subjecting the press molded body to a post-process such as film formation. An optical element according to one embodiment can be obtained.
  • Press molding can be performed by a known press molding method as a method for molding an optical element.
  • a known press molding method as a method for molding an optical element.
  • a precision material made of a dense material having sufficient heat resistance and rigidity can be used.
  • examples include metals such as silicon carbide, silicon nitride, tungsten carbide, aluminum oxide, titanium carbide, and stainless steel, or those whose surfaces are coated with a film of carbon, refractory metal, noble metal alloy, carbide, nitride, boride, etc. be able to.
  • a film covering the molding surface a film containing carbon is preferable from the viewpoint that a glass material for press molding can be molded into a glass optical element without fusing, spidering, scratching, or the like. JP, 2011-1259, A paragraph 0116 can be referred to about a carbon content film.
  • FIG. 1 shows an example of a press forming apparatus.
  • press molding glass in which a core glass 1 is coated with the above-described coating film 2 in a molding die 6 including an upper die 3, a lower die 4 and a barrel die 5.
  • the material PF is supplied and the temperature is raised to a temperature range suitable for pressing.
  • the heating temperature is appropriately set depending on the type of oxide glass constituting the core glass 1, but the glass material PF and the mold 6 are temperatures at which the viscosity of the glass material PF becomes 10 5 to 10 10 dPa ⁇ s.
  • the pressing temperature is more preferably, for example, a temperature at which the oxide glass constituting the core glass 1 is 10 6 to 10 8 dPa ⁇ s before and after 10 7.2 dPa ⁇ s, and the core glass 1 is equivalent to 10 7.2 dPa ⁇ s. It is more preferable to set the temperature so that Usually, the press temperature is set to a temperature equal to or higher than the glass transition temperature of the core glass.
  • the core glass is covered with a metal oxide film in which oxygen is deficient from the stoichiometric composition and the oxygen atom uptake rate and the metal atom diffusion rate satisfy the above relationship.
  • the glass material PF may be supplied to the mold 6 and the glass material PF and the mold 6 may be heated to a predetermined range, or the glass material PF and the mold 6 may be heated to a predetermined temperature range. Therefore, the glass material PF may be disposed in the mold 6. Further, the glass material PF is heated to a temperature equivalent to 10 5 to 10 9 dPa ⁇ s, the mold 6 is heated to a temperature corresponding to a glass viscosity of 10 9 to 10 12 dPa ⁇ s, and the glass material PF is placed in the mold 6. Then, a method of immediately press forming may be employed.
  • the mold temperature can be relatively lowered, the temperature increase / decrease cycle time of the molding apparatus can be shortened, and deterioration of the mold 6 due to heat can be suppressed, which is preferable.
  • cooling is started at the start or after the start of press molding, and the temperature is lowered while applying an appropriate load application schedule and maintaining the adhesion between the molding surface and the glass. Then, it molds and takes out a molded object.
  • the mold release temperature is preferably 10 12.5 to 10 13.5 dPa ⁇ s.
  • the metal oxide film provided on the glass material for press molding has taken in oxygen atoms from the core glass, so that the coating film has a higher oxygen content than before press molding. That is, there is a metal oxide film in which the content of oxygen atoms with respect to metal atoms is higher than the coating film of the glass material for press molding before press molding.
  • This metal oxide film has been found by the present inventors to be in a state where oxygen is deficient rather than the stoichiometric composition.
  • the obtained glass molded body can be shipped as an optical element as a final product as it is, or post-processing such as centering and film formation for forming an optical functional film such as an antireflection film on the surface. It can also be made into a final product after application.
  • a desired antireflection film can be obtained by appropriately forming a film such as Al 2 O 3 , ZrO 2 —TiO 2 , MgF 2 on the glass molded body having the surface layer as a single layer or a laminated layer. Can be formed.
  • the antireflection film can be formed by a known method such as vapor deposition, ion-assisted vapor deposition, ion plating, or sputtering.
  • the vapor deposition material is heated by an electron beam, direct energization or arc in a vacuum atmosphere of about 10 ⁇ 4 Torr using a vapor deposition apparatus, and the material generated by evaporation and sublimation from the material is used.
  • the antireflection film can be formed by transporting the vapor onto the substrate and condensing / depositing it.
  • the substrate heating temperature can be about room temperature to about 400 ° C. However, when the glass transition temperature (Tg) of the substrate is 450 ° C. or lower, the upper limit temperature of the substrate heating is preferably Tg ⁇ 50 ° C.
  • An optical element is a small-diameter, thin-walled small-mass lens, for example, a small imaging system lens, a communication lens, an optical pickup objective lens, a collimator lens, and the like mounted on a portable imaging device.
  • the lens shape is not particularly limited, and various shapes such as a convex meniscus lens, a concave meniscus lens, a biconvex lens, and a biconcave lens can be taken.
  • the glass transition temperature and yield point described below are values measured at a heating rate of 4 ° C./min with a thermomechanical analyzer of Rigaku Corporation.
  • the refractive index (nd) and the Abbe number ( ⁇ d) were measured for the optical glass obtained at a slow cooling rate of ⁇ 30 ° C./hour.
  • Example 1 Production of glass material for press molding Optical glass I-1 belonging to glass I and optical glass II- belonging to glass II described in Table 1 as optical glass to be core glass 1 of glass material PF for press molding 1 was used to form a zirconia oxide film on the surface by the following process. First, the optical glass to be the core glass 1 was dropped and cooled from a molten state onto a receiving mold, and a glass lump having a shape in which one side was a convex surface and the other side was a concave surface was preformed. A coating film (film thickness: about 5 nm) was formed on the preformed glass block by sputtering at a film forming temperature of 300 ° C.
  • the film thickness was adjusted according to the sputtering conditions.
  • the press-molding glass material thus obtained had an outer dimension of 10 to 11 mm and a center thickness of 7 to 8 mm.
  • the glass material PF for press molding produced in the above (1) was press molded in a nitrogen gas atmosphere by a mold press molding apparatus.
  • the core glass was heated to a temperature at which the viscosity of the core glass was 10 7.2 dPa ⁇ s, and supplied to a mold heated to a temperature equivalent to 10 8.5 dPa ⁇ s as the viscosity of the core glass.
  • the glass material is pressed between the upper and lower molds (press temperature: 675 ° C.), cooled to a temperature below the annealing temperature of the core glass while maintaining the close contact between the glass and the upper and lower molds, and molded from within the mold.
  • the body optical lens
  • the molded body had an outer diameter of 20.0 mm and a center thickness of 0.70 mm.
  • the outer periphery of the press-molded body was centered by grinding to obtain a concave meniscus aspheric glass lens with a diameter of 18 mm.
  • Example 2 In the production of the glass material for press molding (1), a coating film having a film thickness of about 5 nm was formed on each of the core glass I-1 and II-1 using metal titanium (Ti) instead of metal zirconium. Otherwise, a concave meniscus aspheric glass lens was obtained in the same manner as in Example 1.
  • Example 3 In the production of the glass material for press molding (1), a coating film having a film thickness of about 5 nm was formed on the core glass I-1 and II-1 using metal tantalum (Ta) instead of metal zirconium. Otherwise, a concave meniscus aspheric glass lens was obtained in the same manner as in Example 1.
  • Example 4 In the production of the glass material for press molding (1), except that metal tungsten (W) was used instead of metal zirconium, and a coating film having a film thickness of about 5 nm was formed on the core glass II-1. A concave meniscus aspheric glass lens was obtained in the same manner as in Example 1.
  • Example 5 In the production of the glass material for press molding (1), except that metal niobium (Nb) was used instead of metal zirconium, and a coating film having a film thickness of about 5 nm was formed on the core glass II-1. A concave meniscus aspheric glass lens was obtained in the same manner as in Example 1.
  • Example 1 in the production of the glass material for press molding (1) except that a coating film having a thickness of about 5 nm was formed on the core glass I-1 using metal yttrium (Y) instead of metal zirconium. Similarly, a concave meniscus aspheric glass lens was obtained.
  • Y metal yttrium
  • Example 2 Similar to Example 1, except that the ZrO 2 film and the SiO 2 film, which are the surface layers in Examples 1 to 6 of JP 2011-1259 A, were formed in this order on the surface of the core glass I-1. A concave meniscus aspheric glass lens was obtained. The thicknesses of the ZrO 2 film and the SiO 2 film were each about 5 nm.
  • FIG. 2 shows an optical micrograph of the lens (core glass: I-1 in Table 1) produced in Example 1. It can be confirmed that a homogeneous lens having high transparency without bubbles is obtained. On the other hand, in the lenses produced in Comparative Examples 1 and 2, many bubbles having a diameter of 50 ⁇ m or more were confirmed.
  • FIG. 3 shows an optical micrograph obtained by enlarging and photographing a part of the lens (core glass: I-1 in Table 1) produced in Comparative Example 2.
  • the coating film covering the core glass is a film having a stoichiometric composition such as a ZrO 2 film.
  • a metal oxide film permeates oxygen liberated from the oxide glass at the time of press molding and is considered not to be taken into the film. Oxygen that has permeated the membrane is confined in the press mold and is not released to the outside. As a result, it is presumed that the film again passes through the film and returns to the glass, thereby causing foaming in the glass.
  • Example 1 ⁇ Confirmation of coating film state before and after press molding (Example 1, Comparative Example 2)>
  • TOF-SIMS Time-of-flight secondary ion mass spectrometer
  • Depth direction analysis by TOF-SIMS Depth direction measurement was performed using TOF-SIMS300 manufactured by ION-TOF.
  • TOF-SIMS is a technique for irradiating pulsed primary ions and detecting the generated secondary ions.
  • FIG. 4 shows the depth direction analysis results of secondary ion intensity by TOF-SIMS after pressing (lens) for Example 1.
  • FIG. 5 shows the depth direction analysis result of secondary ion intensity by TOF-SIMS before pressing (unpressed product) in Example 1.
  • the unit of secondary ionic strength is an arbitrary unit. The same applies to the drawings described later.
  • the film thickness of the zirconium oxide formed as the coating film on the core glass in Example 1 is about 5 nm.
  • ZrO and ZrO 2 are described as secondary ions derived from zirconium oxide in each sample. Although not shown in the figure, Zr alone is detected in each sample.
  • the coating films before and after pressing are all zirconium oxide.
  • the analysis results of ZrO and ZrO 2 before pressing shown in FIG. 5 two peaks are recognized in the vicinity of the surface.
  • the present inventors presume that the first peak near the surface is a natural oxide film, and the second peak is caused by reaction with glass during film formation.
  • SiO 2 detected by the depth direction analysis of the secondary ion intensity by TOF-SIMS is derived from SiO 2 contained in the glass.
  • Figure 6 is a ZrO 2/2 ion intensity ratio of ZrO (hereinafter. Referred to as "ZrO 2 / ZrO intensity ratio") result of comparison in FIGS.
  • the ZrO 2 / ZrO intensity ratio is an index indicating the degree of oxidation in the zirconium oxide film.
  • the range of about 2 nm from the surface of the zirconium oxide cannot be discussed because of the influence of the natural oxide film.
  • the ZrO 2 / ZrO intensity ratio from the depth range of about 2 nm to about 5 nm is higher after pressing than before pressing. From this result, it can be confirmed that the oxidation of zirconium oxide was promoted by the press.
  • the ZrO 2 / ZrO strength ratio described above is, for example, in the range of 0.5 to 1.9 before pressing.
  • the coating can be a zirconium oxide film having a ZrO 2 / ZrO strength ratio in the range of, for example, 2.0 to 2.3 after pressing.
  • Higher ZrO 2 / ZrO means that it is oxidized and contains more oxygen.
  • the ZrO 2 / ZrO intensity ratio of this film can usually take a value of about 2.4 to 3.2.
  • FIG. 7 shows the depth direction analysis result of the secondary ion intensity by TOF-SIMS of the lens produced in Comparative Example 2.
  • FIG. 8 shows a result of superimposing the result of Example 1 shown in FIG. 4 and the result of Comparative Example 2 shown in FIG. Comparative Example 2 has a SiO 2 / ZrO 2 / glass structure, and it has been confirmed in advance that SiO 2 and ZrO 2 have a stoichiometric composition before and after pressing.
  • the interface between SiO 2 and ZrO 2 is 0, and the SiO 2 portion is indicated by minus. Focusing on the region (depth 0 to 5 nm) showing ZrOx in FIG.
  • the ZrO 2 / ZrO intensity ratio after pressing in Example 1 is smaller than that in Comparative Example 2. From this result, it can be seen that the degree of oxidation by the press of Example 1 is lower than that of Comparative Example 2. That is, it can be confirmed that the zirconium oxide after pressing in Example 1 is deficient in oxygen as compared with ZrO 2 having a stoichiometric composition in Comparative Example 2.
  • Comparative Example 2 since the SiO 2 film was formed on the outermost surface of the press-molding glass material, it is not necessary to consider the influence of the natural oxide film. However, in Example 1, the region of about 2 nm from the surface is the natural oxide film. It is affected and cannot be the subject of discussion.
  • Example 1 the zirconium oxide film had a composition in which oxygen was lost from the stoichiometric composition ZrO 2 both before and after pressing. It can be confirmed that the oxygen content of the zirconium oxide film is higher than that before pressing.
  • Each of the metal oxide films produced on the core glass in Examples 2 to 5 was in a state where oxygen was lost from the stoichiometric composition before and after pressing by the same method. It was confirmed that the oxygen content was higher than before pressing.
  • the glass III-1 shown in Table 2 below corresponding to the oxide glass III was also press-molded in the same manner as in Example 1, and it was confirmed that a homogeneous lens without bubbles was obtained.
  • generation of bubbles after pressing can be suppressed.
  • the total of the diameters of the bubbles does not exceed 50 ⁇ m can be used as an index that is a homogeneous optical element in which the generation of bubbles is suppressed.
  • the number of bubbles having a diameter of 25 ⁇ m or more is less than 1 or the number of bubbles having a diameter of 10 ⁇ m or more is less than 3 when observed with an optical microscope at a magnification of 10 to 50 times, and the total diameter of the bubbles That does not exceed 25 ⁇ m can be used as an index that is a homogeneous optical element without bubbles. All the lenses manufactured in the above-described examples satisfy the preferable index and the more preferable index.
  • the total diameter of the bubbles is, for example, 100 ⁇ m if there are two mills having a diameter of 50 ⁇ m.
  • the diameter here refers to the diameter when the bubble is a circular bubble, the distance in the longitudinal direction when the bubble is elliptical, and the longest possible distance when the bubble is irregular.
  • the diameter In the examples, almost the entire surface of the core glass surface was coated with a metal oxide film, but even if a portion was uncoated, oxygen was deficient from the stoichiometric composition and the oxygen atom uptake rate. Needless to say, the same effect can be obtained if a metal oxide film in which the diffusion rate of metal atoms and the diffusion rate of metal atoms satisfy the above-described relationship exists on the surface of the core glass.
  • an oxide glass and a coating film that covers at least a part of the surface of the oxide glass are included, and the coating film has a stoichiometric composition.
  • the rate at which the metal oxide film takes in oxygen atoms contained in the oxide glass at a temperature higher than the glass transition temperature of the oxide glass in a state where oxygen is more deficient is that the metal atoms contained in the metal oxide film It is possible to provide an optical element that is a metal oxide film faster than the speed of diffusion into oxide glass.
  • the metal oxide is a metal oxide selected from the group consisting of zirconium, titanium, niobium, tungsten, and tantalum.
  • the metal oxide film of the press-molded body obtained by press molding is in a state where oxygen is deficient due to the stoichiometric composition.
  • the above-mentioned oxide glass contains one or more high refractive index imparting components selected from the group consisting of Nb 2 O 5 , TiO 2 , WO 3 and Ta 2 O 5 .
  • the total content (Nb 2 O 5 + TiO 2 + WO 3 + Ta 2 O 5 ) of the high refractive index imparting component is preferably 10% by mass or more and 50% by mass or less.
  • the above oxide glass contains one or more selected from the group consisting of ZnO and alkali metal oxides (Li 2 O, Na 2 O, K 2 O).
  • the total content of ZnO and alkali metal oxide (ZnO + Li 2 O + Na 2 O + K 2 O) is 5% by mass or more and 25% by mass or less.
  • heating during press molding is performed at a heating temperature of 650 ° C. or higher. According to the manufacturing method of the above-mentioned optical element, generation
  • the oxide glass and a coating film covering at least a part of the surface of the oxide glass, the coating film described above is in a state in which oxygen is lost from the stoichiometric composition,
  • the rate at which the metal oxide film takes in oxygen atoms contained in the oxide glass is faster than the rate at which the metal atoms contained in the metal oxide film diffuse into the oxide glass.
  • a glass material for press molding which is a metal oxide film is also provided. This glass material for press molding is suitably used in the method for producing an optical element according to the above-described embodiment.
  • the present invention is useful in the field of manufacturing optical elements such as glass lenses.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
PCT/JP2014/075887 2013-09-30 2014-09-29 光学素子およびその製造方法 Ceased WO2015046509A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020167004994A KR102219149B1 (ko) 2013-09-30 2014-09-29 광학 소자 및 그 제조 방법
CN201480053466.6A CN105579412B (zh) 2013-09-30 2014-09-29 光学元件及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-205497 2013-09-30
JP2013205497A JP6218536B2 (ja) 2013-09-30 2013-09-30 光学素子およびその製造方法

Publications (1)

Publication Number Publication Date
WO2015046509A1 true WO2015046509A1 (ja) 2015-04-02

Family

ID=52743632

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/075887 Ceased WO2015046509A1 (ja) 2013-09-30 2014-09-29 光学素子およびその製造方法

Country Status (5)

Country Link
JP (1) JP6218536B2 (enExample)
KR (1) KR102219149B1 (enExample)
CN (1) CN105579412B (enExample)
TW (1) TWI621594B (enExample)
WO (1) WO2015046509A1 (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12515982B2 (en) 2021-03-19 2026-01-06 Corning Incorporated High-index borate glasses

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI610074B (zh) * 2016-12-16 2018-01-01 由田新技股份有限公司 曲面待測物表面瑕疵檢測系統
CN106772716A (zh) * 2017-02-07 2017-05-31 长沙青波光电科技有限公司 大na非球面柱透镜的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003335549A (ja) * 2002-03-14 2003-11-25 Hoya Corp 光学ガラス、精密プレス成形用プリフォーム、及び光学素子
JP2004091322A (ja) * 2002-08-29 2004-03-25 Eastman Kodak Co 注入された精密ガラス成型ツールを用いたガラスレンズの成型メカニズム
JP2012091951A (ja) * 2010-10-26 2012-05-17 Asahi Glass Co Ltd 光学素材の処理方法及び光学素子の成形方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4255292B2 (ja) 2003-02-21 2009-04-15 Ｈｏｙａ株式会社 光学素子成形用ガラス素材および光学素子の製造方法
CA2556730C (en) * 2004-02-25 2013-12-24 Afg Industries, Inc. Heat stabilized sub-stoichiometric dielectrics
JP4231967B2 (ja) 2006-10-06 2009-03-04 住友金属鉱山株式会社 酸化物焼結体、その製造方法、透明導電膜、およびそれを用いて得られる太陽電池
JP5134893B2 (ja) * 2007-09-07 2013-01-30 キヤノンオプトロン株式会社 光学薄膜の形成材料および光学薄膜の形成方法
CN102428045B (zh) 2009-05-20 2014-02-26 Hoya株式会社 压制成型用玻璃材料、以及使用该玻璃材料的玻璃光学元件的制造方法、以及玻璃光学元件
JP5364568B2 (ja) * 2009-12-28 2013-12-11 Ｈｏｙａ株式会社 プレス成形用ガラス素材、プレス成形用ガラス素材の製造方法、および光学素子の製造方法
JP5555204B2 (ja) * 2011-06-27 2014-07-23 Ｈｏｙａ株式会社 プレス成形用ガラス素材およびその製造方法、ならびに光学素子の製造方法
JP2013127118A (ja) 2011-09-06 2013-06-27 Idemitsu Kosan Co Ltd スパッタリングターゲット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003335549A (ja) * 2002-03-14 2003-11-25 Hoya Corp 光学ガラス、精密プレス成形用プリフォーム、及び光学素子
JP2004091322A (ja) * 2002-08-29 2004-03-25 Eastman Kodak Co 注入された精密ガラス成型ツールを用いたガラスレンズの成型メカニズム
JP2012091951A (ja) * 2010-10-26 2012-05-17 Asahi Glass Co Ltd 光学素材の処理方法及び光学素子の成形方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12515982B2 (en) 2021-03-19 2026-01-06 Corning Incorporated High-index borate glasses

Also Published As

Publication number Publication date
KR102219149B1 (ko) 2021-02-22
CN105579412A (zh) 2016-05-11
KR20160065080A (ko) 2016-06-08
JP6218536B2 (ja) 2017-10-25
JP2015067525A (ja) 2015-04-13
TW201527229A (zh) 2015-07-16
TWI621594B (zh) 2018-04-21
CN105579412B (zh) 2018-09-14

Similar Documents

Publication Publication Date Title
CN102428045B (zh) 压制成型用玻璃材料、以及使用该玻璃材料的玻璃光学元件的制造方法、以及玻璃光学元件
KR101348051B1 (ko) 프레스 성형용 유리 소재, 상기 유리 소재를 이용한 유리 광학 소자의 제조 방법, 및 유리 광학 소자
JP5364568B2 (ja) プレス成形用ガラス素材、プレス成形用ガラス素材の製造方法、および光学素子の製造方法
JP2007269613A (ja) ガラス光学素子の製造方法
JP2007261826A (ja) レンズおよびその製造方法
JP6218536B2 (ja) 光学素子およびその製造方法
JP6633904B2 (ja) プレス成形用ガラス素材、ガラス光学素子およびその製造方法
WO2016159055A1 (ja) プレス成形用ガラス素材、ガラス光学素子およびその製造方法
JP5442420B2 (ja) 精密プレス成形用ガラス素材の肉厚決定方法および製造方法、ならびにガラス光学素子の製造方法
CN104136384B (zh) 压制成形用玻璃材料、玻璃光学元件及它们的制造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480053466.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14847963

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20167004994

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14847963

Country of ref document: EP

Kind code of ref document: A1