WO2014013935A1 - ガラス成形品及びその製造方法、光学素子ブランク、並びに光学素子及びその製造方法 - Google Patents
ガラス成形品及びその製造方法、光学素子ブランク、並びに光学素子及びその製造方法 Download PDFInfo
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- WO2014013935A1 WO2014013935A1 PCT/JP2013/068995 JP2013068995W WO2014013935A1 WO 2014013935 A1 WO2014013935 A1 WO 2014013935A1 JP 2013068995 W JP2013068995 W JP 2013068995W WO 2014013935 A1 WO2014013935 A1 WO 2014013935A1
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- Prior art keywords
- glass
- glass molded
- molded product
- optical element
- lump
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
-
- 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
-
- 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
-
- 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
- C03C17/25—Oxides by deposition from the liquid 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
- C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2215/00—Press-moulding glass
- C03B2215/40—Product characteristics
- C03B2215/46—Lenses, e.g. bi-convex
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
Definitions
- the present invention relates to a glass molded article made of optical glass (fluorophosphate glass) containing phosphorus, oxygen, and fluorine, a manufacturing method thereof, an optical element blank, an optical element, and a manufacturing method thereof.
- optical glass fluorophosphate glass
- a method for producing a glass optical element such as a lens
- a glass molded product having a shape approximating the optical element is produced, ground and polished to finish the optical element.
- a method for producing a glass molded product for example, a method is used in which a glass lump made of homogeneous optical glass is prepared, and the glass lump is heated and softened to form a glass molded product.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2007-210863
- Patent Document 2 an optical element blank having a shape that approximates the shape of an optical element is produced by press molding, and the optical element blank is processed to produce an optical element. How to do is described.
- the inventor of the present invention found that when the glass lump made of optical glass containing phosphorus, oxygen and fluorine is heated and softened, the glass surface selectively crystallizes because the fluorine on the glass lump surface is air. It was thought that this was caused by the phenomenon that the oxygen in the glass was replaced and the fluorine content on the glass lump surface decreased. Therefore, in order to prevent crystallization occurring on the surface of the glass lump, it was found that crystallization on the surface of the glass lump can be suppressed by increasing the phosphorus content on the surface of the glass lump with reduced fluorine content. .
- the present invention provides a glass molded article and a method for producing the glass molded article described below.
- a method for producing a glass molded article comprising:
- the method for producing a glass molded product of the present invention When the method for producing a glass molded product of the present invention is used, generation of a hardened layer on the glass surface due to crystallization during heating and softening can be suppressed. It is possible to prevent the deterioration of the homogeneity. As a result, when the present invention is used, a high-quality glass molded product can be produced. Moreover, the manufacturing method of the glass molded product of this invention has little loss of glass material, and can manufacture a glass molded product and an optical element at low cost.
- the method for producing a glass molded article of the present invention comprises a step A of coating a surface of a glass block made of optical glass containing phosphorus, oxygen and fluorine with a coating agent containing phosphorus, and A step B of heating, softening and molding the glass block coated with the coating agent;
- a glass lump made of optical glass containing phosphorus, oxygen and fluorine used in the present invention can be produced by a known method.
- a glass raw material containing phosphorus, oxygen and fluorine is melted, clarified and stirred to produce a homogeneous molten glass, and cast into a mold to prepare a glass block. After this glass block is annealed, it can be cut into a cubic shape to obtain glass pieces and barrel-polished to produce glass lumps of the same weight and shape made of the respective optical glasses.
- a cylindrical glass column is formed by casting molten glass containing phosphorus, oxygen and fluorine into a cylindrical mold disposed below an outflow pipe.
- the glass column formed in the mold is drawn vertically downward from the opening at the bottom of the mold at a constant speed, and after cooling the glass column shape, it is cut or cleaved to obtain a substantially disc-shaped glass piece.
- the glass piece is polished or barrel-polished to form a glass lump.
- the drawing speed may be set so that the molten glass liquid level in the mold becomes constant.
- a molten glass produced by melting, clarifying and stirring a glass raw material containing phosphorus, oxygen and fluorine is caused to flow out from the outflow pipe, and the tip of the flowing molten glass flow.
- the mold for receiving glass is not particularly limited, and a mold for float molding (a recess for receiving molten glass is formed of a porous body, and gas is ejected from the surface of the recess through the porous body. It may be a mold having a structure in which upward wind pressure is applied to the lump), or may be a tray-shaped mold in which a concave-shaped receiving portion is formed.
- the composition of the glass constituting the glass block used in the glass molded article and the method for producing the same of the present invention is not particularly limited as long as it is an optical glass (so-called “fluorophosphate glass”) containing phosphorus, oxygen and fluorine.
- an optical glass containing phosphorus, oxygen and fluorine a glass containing P 5+ at 3 cation% or more and less than 50 cation%, O 2 ⁇ at 5 to 80 anion%, and F ⁇ at 20 to 95 anion% is exemplified.
- Al 3+ an alkaline earth metal component, an alkali metal component, a rare earth component, and the like may be appropriately contained.
- Step A Step of coating the surface of glass lump with coating agent
- a coating material containing phosphorus is coated on the surface of a glass block made of optical glass containing phosphorus, oxygen and fluorine.
- the coating agent containing phosphorus is not particularly limited as long as it contains phosphorus, and examples thereof include a simple substance of phosphorus, a phosphorus compound, and a composition containing phosphorus.
- phosphorus compounds include phosphoric acid (including phosphoric acids such as pyrophosphoric acid), phosphates (eg, alkali phosphates, ammonium phosphates, etc.), oxides (eg, diphosphorus pentoxide, etc.) , Halides, organophosphorus compounds and the like.
- the composition containing phosphorus include a combination of the above phosphorus compounds, a solution in which phosphoric acid, phosphate, phosphorus oxide, or the like is dissolved in water, an organic solvent, or the like.
- the coating agent contains one or more selected from the group consisting of phosphoric acid, phosphate, and phosphorus oxide.
- the aspect of the coating agent is not particularly limited, and may be solid or liquid.
- liquid coating agent a solution containing at least one selected from the group consisting of phosphoric acid, phosphate, and phosphorus oxide is preferable.
- the solvent for such a solution include water and organic solvents.
- a phosphoric acid aqueous solution is preferable as the liquid coating agent.
- a solid coating When used as a solid coating, it is preferable to use it after it is processed into a powder because it is easy to uniformly adhere to the surface of the glass lump.
- Such powder can be attached to the glass mass using methods such as spraying, spraying and rubbing.
- An example of a solid coating agent is phosphoric acid.
- the particle diameter of the powdery coating material is preferably 5 to 100 ⁇ m, and more preferably 10 to 50 ⁇ m.
- a liquid coating agent it is preferable to use a solution in which a compound such as phosphoric acid, phosphate, phosphorus oxide, or a composition containing at least one of them is dissolved.
- a solution in which phosphoric acid, phosphate, or phosphorus oxide is dissolved in water is preferable.
- the coating agent is a solution, it is preferable to immerse the glass block in a container containing the solution, or to apply the solution to the surface of the glass block by spraying or applying with a brush.
- the concentration of the coating agent which is an aqueous solution is preferably 1 to 30% by weight, more preferably 1 to 20% by weight.
- the coating agent is a phosphoric acid aqueous solution, it is preferably 1 to 20% by weight, more preferably 1 to 10% by weight.
- the surface of the glass lump has a composition with a higher phosphorus content than the inside of the glass lump.
- Such a glass having a high phosphorus content has a property that it is hardly crystallized even when heated. Therefore, crystallization of the glass lump surface can be effectively prevented.
- the coating agent is preferably coated at least on the surface on which crystallization is desired to be suppressed during heating and softening, and more preferably on the entire surface of the glass lump surface.
- the glass lump is a glass lump placing tool (for example, “softening tray 10” described in Patent Document 1) on which the heated glass lump is placed. You may further coat
- the mold release agent may be used by mixing with a coating agent or may be used after coating the coating agent.
- the release agent include powder release agents such as boron nitride, alumina, silicon oxide, and magnesium oxide.
- Process to heat and soften glass lump (Process B)
- the glass lump coated with the coating agent is heated and softened and molded to obtain a glass molded product.
- the step of heating and softening the glass lump is performed by placing the glass lump whose surface is coated with a coating material on a heat-resistant glass lump mounting tool and heating the whole glass lump mounting tool.
- a coating material for example, “softening furnace 30” described in Patent Document 1
- the glass lump coated with the coating is heated, the glass lump is softened, and phosphorus contained in the coating on the surface of the glass lump penetrates into the glass lump, and the surface of the glass lump enters the inside of the glass lump.
- the composition has a higher phosphorus content. In this way, a surface layer having a high phosphorus content is formed on the surface of the glass block.
- the content of phosphorus in the surface layer of the glass lump is preferably 1.2 times or more, and preferably 10% by weight or more higher than the content of phosphorus inside the glass lump.
- Such a glass having a high phosphorus content has the property that it is very difficult to crystallize even when heated, so that the crystallization of the glass lump can be greatly suppressed.
- the thickness of the surface layer is not limited, but it needs to be thick enough to suppress crystallization of the surface of the glass block, preferably 1 to 100 ⁇ m, and more preferably 5 to 50 ⁇ m.
- the heating of the glass prior to molding, softening it is preferably heated to a temperature at which the viscosity of the glass becomes less 10 6 dPa ⁇ s, 10 5 dPa -It is more preferable to heat to the temperature which becomes s or less. According to the present invention, devitrification of the glass surface is suppressed even when the glass is heated and softened to such a viscosity.
- the glass lump surface It is preferable to coat the glass lump surface with an aqueous solution of phosphoric acid, phosphate or phosphorus oxide as a coating agent.
- the coating is a liquid such as an aqueous solution
- the coating is applied to the glass lump using means such as immersing the lump in the liquid, spraying the liquid with a spray, or applying the liquid with a brush or the like. can do.
- After coating it is preferable to use after drying to such an extent that the coating agent does not flow.
- a solid material such as phosphoric acid when coated as a coating agent, it is preferable to coat the glass lump surface with a powder processed into a powder form.
- the coating agent can be coated on the glass mass using a method such as passing the glass mass through the powder, spraying the powder onto the glass mass, spraying, or rubbing.
- a component that promotes adhesion may be added to the surface of the glass lump. For example, when a glass lump is coated with phosphoric acid powder as a coating agent and heated, phosphoric acid melts on the surface of the glass lump.
- the coating containing phosphoric acid, phosphate or phosphorus oxide before heating the glass lump, phosphorus contained in the melted coating penetrates into the glass lump, and the surface of the glass lump is
- the composition has a higher phosphorus content than the inside of the glass lump.
- a surface layer having a high phosphorus content is formed on the surface of the glass lump, and crystallization on the surface of the glass lump can be effectively prevented.
- the yield of manufacture of a glass molded product which can utilize a glass material effectively improves.
- the method of molding the softened glass is not particularly limited, but a known molding method such as a press molding method, a rolling method in which a glass lump is sandwiched between a plurality of rotating rollers and molded into a rod-shaped glass, or a stretching method is used. Can be used.
- the glass lump is softened by heating, and the softened glass lump is pressed by a press mold in a press molding apparatus to be formed into a desired shape.
- the press molding apparatus used when the press molding method a known apparatus can be used.
- the press molding apparatus include an upper mold, a lower mold, or a mold having a barrel mold as necessary, and a pressurizing mechanism that applies a press pressure to the upper mold and the lower mold.
- the number of molds may be set according to the number of glass lumps supplied simultaneously from the glass lumps placing tool. When the glass lump is supplied to the mold, the upper mold is retracted upward, and in this state, the glass lump is supplied onto the lower mold.
- the upper mold After the supply of the glass lump onto the lower mold, the upper mold is lowered, the mold is closed, the softened glass lump is pressed with the upper and lower molds, and the molding surface of the upper and lower molds (using the barrel mold, (Including the case where the inner surface of the mold is transferred to glass) can be transferred to glass, and a glass molded product having a desired shape can be obtained.
- the glass molded product is released from the press mold and annealed.
- the distortion inside the glass is reduced so that the optical characteristics such as the refractive index become a desired value.
- the glass lump heating conditions, molding conditions, materials used for the press mold, etc. may be applied.
- the above steps can be performed in the atmosphere.
- the obtained glass molded article can be suitably used mainly as an optical element blank.
- the optical element blank is a glass blank having a shape that approximates the shape of the target optical element, and the optical element can be finally produced by grinding and polishing the glass blank.
- a glass molded product that can be used as an optical element is obtained.
- the optical element can be obtained without subjecting the glass molded product to polishing or the like, so that productivity is high and material loss due to processing is small.
- a glass molded article by a precision press molding method among the above-described glass lump manufacturing methods, use the glass lump (preform) obtained by float forming described in the third example. Is preferred.
- the glass molded article of the present embodiment is a glass molded article made of optical glass containing phosphorus, oxygen and fluorine, and the phosphorus content in the surface layer of the glass molded article is the interior of the glass molded article. Larger than the phosphorus content.
- the inside is the inside (deep part) in the thickness direction of the glass molded product, and is a portion existing inside the surface layer of the glass molded product.
- the phosphorus content in the surface layer is larger than the phosphorus content in the glass molded product, so that the surface is difficult to crystallize during molding, and the deterioration of homogeneity due to the cured film can be suppressed. it can.
- the phosphoric acid content of the surface layer in the glass molded article is +1 cation% or more, more preferably +10 cation% or more, more preferably +20 cation%, more preferably +30 cation% from the inside of the glass block. That's it.
- the upper limit of the phosphoric acid content of the surface layer in the glass molded article is preferably +90 cation%, more preferably +80 cation%, and further preferably +70 cation% from the inside of the glass block.
- a glass molded article when producing a highly homogenous glass product such as an optical element, the amount of removal of the surface of the glass molded article can be reduced, and material loss and manufacturing cost can be reduced. it can. Moreover, when the whole glass molded article is homogeneous, a glass molded article can also be used as an optical element.
- the glass molded product of the present embodiment can be manufactured, for example, by the above-described glass molded product manufacturing method.
- the thickness of the surface layer of the glass molded product is preferably 1 ⁇ m or more from the viewpoint of suppressing crystallization of the surface.
- the thickness of the surface layer is preferably 100 ⁇ m or less from the viewpoint of reducing the amount of removal when processing a glass molded product.
- the more preferable lower limit of the thickness of the surface layer is 5 ⁇ m, and the more preferable upper limit is 50 ⁇ m.
- the glass molded product of the present embodiment is suitable for an optical element or an optical element blank because the inside is homogeneous and surface crystallization is suppressed.
- Process C The glass molded product obtained through the steps A and B can be further processed by a known processing method such as grinding or polishing.
- the glass molded product is an optical element blank.
- An optical element such as a lens or a prism can be manufactured by forming the glass molded product by approximating the shape of the glass molded product to that of the optical element, and further grinding and / or polishing.
- the grinding and / or polishing method can be performed, for example, through the following steps.
- (i) Grinding process A glass molded product is ground using a diamond grindstone or the like so as to have a shape that approximates the shape of the target optical element.
- (ii) Polishing Step The surface ground in the above grinding step is polished using free abrasive grains such as cerium oxide to smooth the surface.
- (iii) Polishing process The polished surface is polished using zirconia or the like.
- step C it is preferable to remove the surface layer of the glass molded product by polishing or grinding to obtain a homogeneous glass molded product based on the glass lump.
- the process C is not an essential process,
- molded by the process B can also be used as an optical element.
- a glass molded product can be produced with high productivity, and optical elements such as lenses and prisms can be stably produced using the glass molded product.
- optical elements obtained by processing the glass molded product of the present invention include various lenses such as spherical lenses, aspherical lenses, and micro lenses, diffraction gratings, lenses with diffraction gratings, lens arrays, prisms, and the like. be able to. From the application side, digital still cameras, digital video cameras, single-lens reflex cameras, mobile phone cameras, optical lenses for reading and writing data to optical disks such as DVDs and CDs, lenses constituting imaging optical systems The lens etc. which comprise can be illustrated.
- the optical element may be provided with an optical thin film such as an antireflection film, a total reflection film, a partial reflection film, or a film having spectral characteristics.
- an optical thin film such as an antireflection film, a total reflection film, a partial reflection film, or a film having spectral characteristics.
- each glass lump whose surface is coated with a coating agent is placed on a softening basin, which is a glass lump mounting tool, and stored in a softening furnace to heat and soften the glass lump.
- a softening furnace to heat and soften the glass lump.
- the “softening temperature” is a temperature at which the viscosity of the glass becomes 10 7.6 dPa ⁇ s, and is also referred to as “Littleton temperature”.
- the “softening temperature” refers to a temperature measured by a method defined in JIS R 3103-1: 2001.
- the glass lump was taken out from the softening furnace.
- the surface of the glass lump of Examples 1 to 6 heated in the softening furnace is formed so that the melted coating agent covers the surface of the softened glass lump, and the components of the coating penetrate into the glass lump. It was.
- the molding surface of the press mold has a shape obtained by inverting the surface of the glass molded product (optical element blank) to be obtained.
- the heating temperature at the time of molding was as shown in Table 2.
- the glass molded product (optical element blank) obtained by press molding in this manner was taken out from the mold.
- the surfaces of the glass molded products of Examples 1 to 6 were not crystallized, and no cured film was formed by crystallization.
- the cured film was not woven into the glass molded product. Further, the glass molded articles of Examples 1 to 6 were not devitrified.
- boron nitride powder was applied to the surface of the glass block together with the aqueous solution (coating agent) shown in Table 2, and the glass block was heated, softened and pressed as in Examples 1 to 6.
- a glass molded product was produced.
- the surface of the glass molded product thus produced was not crystallized, and no cured film was formed by crystallization.
- the cured film was not woven into the glass molded product.
- the inside of each glass molded product was not devitrified.
- B and N are detected by analyzing the surface of a glass molded article produced by applying boron nitride on the glass lump surface by XPS.
- Boron nitride functions as a mold release agent and does not suppress crystallization of the glass surface, and B and N in the surface layer are also treated as contamination. Therefore, in calculating the phosphorus content from the XPS analysis results, B, N, and C are excluded.
- the measurement conditions by XPS are as follows. Excitation X-ray: Al mono Detection area: ⁇ 100 ⁇ m Extraction angle: 45deg Detection depth: 4-5nm Sputtering conditions: Ar + 2.0 kV Sputtering rate: about 5 nm / min (SiO 2 conversion)
- each glass molded product of Examples 1 to 6 formed by applying only an aqueous phosphoric acid solution although there is variation depending on the location, the amount of P 5+ calculated from the analysis result by XPS exceeds 50 cation%. It was.
- each glass molded product of Examples 1 to 6 was ground by 30 ⁇ m, and the composition of the ground surface was analyzed by XPS. As a result, the amount of P 5+ exceeded 50 cation%.
- each glass molded product of Examples 1 to 6 was ground by 50 ⁇ m, and the composition of the ground surface was analyzed by XPS under the same conditions as the above measurement conditions.
- the composition was almost the same as the composition of the optical glass 1 shown in Table 1.
- the composition was almost the same as the composition of the optical glass 2 shown in Table 1. That is, the amount of P 5+ on the inner side of 50 ⁇ m from the surface of each glass molded product of Examples 1, 3, and 5 is about 28 cation%, and the inside of 50 ⁇ m from the surface of each glass molded product of Examples 2, 4, and 6 The amount of P 5+ on the side was about 6.1 cation%.
- each glass molding of Examples 1, 3, and 5 was analyzed.
- the product was almost the same as the composition of the optical glass 1 shown in Table 1, and the glass molded products of Examples 2, 4, and 6 were almost the same as the composition of the optical glass 2 shown in Table 1.
- the phosphorus content in the outermost surface and the ground surface having a depth of 30 ⁇ m from the outermost surface is larger than the phosphorus content in the deep portion of 50 ⁇ m or more, and in the deep portion of 50 ⁇ m or more. Since the phosphorus content has a constant composition, it can be said that the thickness of the surface layer of the glass molded product is 30 ⁇ m or more and less than 50 ⁇ m.
- Examples 1-6 boron nitride powder was applied to the surface of the glass lump together with an aqueous phosphoric acid solution, and the glass lump was heated and softened in the same manner as in Examples 1-6, followed by press molding.
- the phosphorus content of the product was analyzed by XPS, it was confirmed that the phosphorus content of the surface layer was higher than the phosphorus content inside the glass molded product in any glass molded product.
- the thickness of the surface layer of the glass molded product was 30 ⁇ m or more and less than 50 ⁇ m.
- Example 7 Production of spherical lens
- the glass molded article (lens blank) of Example 1 was annealed to match the optical characteristics with those of the target lens and to reduce distortion in the glass. Thereafter, the lens blank was ground and polished by a known method to produce a spherical lens (Example 7).
- Example 7 In the same manner as in Example 7, the spherical lenses of Examples 8 to 12 were produced from the glass molded articles (optical element blanks) of Examples 2 to 6.
- Examples 7 to 12 spherical lenses were produced, but other optical elements such as prisms can be manufactured from the glass molded articles of Examples 1 to 6.
- the method for producing a glass molded article of the present embodiment includes a step A of coating a surface of a glass block made of optical glass containing phosphorus, oxygen and fluorine with a coating agent containing phosphorus, and A step B of heating, softening and molding the glass block coated with the coating agent;
- step B the glass block is heated at a temperature at which the viscosity of the glass constituting the glass block is 10 6 dPa ⁇ s or less. To do.
- the coating agent includes at least one selected from the group consisting of phosphoric acid, phosphate, and phosphorus oxide. Including.
- the coating agent is a solution.
- the coating agent comprises a phosphoric acid aqueous solution.
- the step B includes a press molding step.
- the glass molded product according to the present embodiment is obtained by the manufacturing method according to any one of [1] to [6].
- the glass molded product of the present embodiment is a glass molded product made of optical glass containing phosphorus, oxygen, and fluorine,
- the phosphorus content in the surface layer of the glass molded product is larger than the phosphorus content inside the glass molded product.
- the thickness of the surface layer is 1 to 100 ⁇ m.
- the optical element blank according to the present embodiment is formed of the glass molded product according to any one of [7] to [9].
- the optical element of the present embodiment is formed of the glass molded product according to any one of [7] to [9].
- the method for manufacturing an optical element according to the present embodiment includes a process C for further processing the optical element blank according to the above [10].
- step C includes a step of removing a surface layer of the optical element blank.
- a method for producing a glass molded article of the present embodiment is a glass made of an optical glass containing phosphorus, oxygen, and fluorine as a coating containing phosphoric acid, phosphate, phosphorus oxide, or a composition containing these.
- step B the glass block is heated at a temperature at which the viscosity of the glass constituting the glass block is 10 6 dPa ⁇ s or less.
- the coating agent is selected from the group consisting of phosphoric acid, phosphate, phosphorus oxide, and an aqueous solution in which these are dissolved. Contains one or more.
- the coating agent is an aqueous phosphoric acid solution.
- the molding in step B is press molding.
- the glass molded article has a surface layer formed on the surface of the glass lump,
- the phosphorus content in the surface layer is larger than the phosphorus content in the center of the glass block.
- the method for producing a glass molded product according to the present embodiment is a step of processing the glass molded product obtained by the method for producing a glass molded product according to any one of [A1] to [A6]. Further includes C.
- the glass molded product obtained by the method for producing a glass molded product described in [A6] above is processed to remove the surface layer C. Further included.
- the glass molded article is an optical element or an optical element blank.
- the glass molded product of the present embodiment in another aspect is a glass molded product that is a glass block made of optical glass containing phosphorus, oxygen, and fluorine, and is a surface formed on the surface of the glass block
- the phosphorus content of the layer is larger than the phosphorus content in the center of the glass lump.
- the thickness of the surface layer is 1 to 100 ⁇ m.
- the glass molded article described in [A10] or [A11] above is an optical element or an optical element blank.
- the glass molded product of the present invention can be used for optical elements such as lenses and prisms.
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Abstract
Description
[1]リンを含む被覆剤を、リン、酸素およびフッ素を含有する光学ガラスからなるガラス塊の表面に被覆する工程A、および、
被覆剤が被覆されたガラス塊を、加熱し、軟化させ、成形する工程B、
を含むガラス成形品の製造方法。
ガラス成形品の表面層におけるリンの含有量は、ガラス成形品の内部のリンの含有量に比べて大きい、ガラス成形品。
被覆剤が被覆されたガラス塊を、加熱し、軟化させ、成形する工程B、を含む。
本発明で用いられるリン、酸素およびフッ素を含有する光学ガラスからなるガラス塊は公知の方法で作製できる。
ガラス塊の製造方法の第一の例としては、リン、酸素およびフッ素を含有するガラス原料を熔解、清澄、撹拌して均質な熔融ガラスを作製し、鋳型に鋳込んでガラスブロックを準備し、このガラスブロックをアニールした後、立方体形状に切断してガラス片を得て、バレル研磨してそれぞれの光学ガラスからなる互いに重量、形状が等しいガラス塊を作製することができる。
本発明の工程Aでは、リンを含む被覆剤を、リン、酸素およびフッ素を含有する光学ガラスからなるガラス塊の表面に被覆する。
本発明の工程Bでは、被覆剤が被覆されたガラス塊を加熱して軟化させて成形して、ガラス成形品を得る。
ガラス塊を加熱して軟化させるステップは、表面に被覆剤が被覆されたガラス塊を耐熱性のガラス塊載置具の上に置き、ガラス塊載置具ごと加熱装置(たとえば、特許文献1に記載された「軟化炉30」)に入れて行うことができる。被覆剤が被覆されたガラス塊が加熱されるとガラス塊は軟化状態となり、ガラス塊の表面上の被覆剤に含まれるリンがガラス塊に浸透し、ガラス塊の表面は、ガラス塊の内部に比べてリンの含有量の多い組成となる。このようにして、ガラス塊の表面にはリンの含有量の多い表面層が形成される。
軟化したガラスを成形する方法は特に限定されないが、プレス成形法、ガラス塊を複数本の回転するローラで挟みロッド状のガラスに成形する圧延法、延伸法など公知の成形法を用いることができる。
本実施形態のガラス成形品は、リン、酸素およびフッ素を含有する光学ガラスからなるガラス成形品であって、ガラス成形品の表面層におけるリンの含有量は、ガラス成形品の内部のリンの含有量に比べて大きい。ここで、内部とは、ガラス成形品の厚み方向における内部(深部)であり、ガラス成形品の表面層よりも内側に存在する部分である。
工程Aと工程Bを経て得られたガラス成形品を、研削、研磨等の公知の加工方法によって、さらに加工できる。ここで、ガラス成形品は、光学素子ブランクである。
(i)研削工程
目的とする光学素子の形状に近似する形状になるように、ダイヤモン砥石等を用いてガラス成形品を研削する。
(ii)研磨工程
上記研削工程で研削された面を、酸化セリウムなどの遊離砥粒を用いて研磨し、表面を平滑にする。
(iii)ポリッシュ工程
研磨された面を、ジルコニアなどを用いてポリッシュする。
このような、工程を行うことによってガラス成形品の加工し、光学素子を製造することができる。
なお、本発明のガラス成形品の製造方法において、工程Cは必須の工程ではなく、たとえば、工程Bで成形されたガラス成形品を光学素子として用いることもできる。
本発明のガラス成形品を加工して光学素子としては、球面レンズ、非球面レンズ、マイクロレンズなどの各種のレンズ、回折格子、回折格子付のレンズ、レンズアレイ、プリズムなどを例示することができる。用途面からは、デジタルスチルカメラ、デジタルビデオカメラ、一眼レフカメラ、携帯電話搭載カメラ、車載カメラなどの撮像光学系を構成するレンズ、DVD、CDなどの光ディスクへのデータ読み書きを行うための光学系を構成するレンズなどを例示することができる。
(1) ガラス塊の作製
表1に組成および特性を示す2種類の光学ガラス(光学ガラス1および2)を作製するため、ガラス原料を準備し、それぞれのガラス原料を熔解、清澄、撹拌して均質な熔融ガラスを作製し、流出パイプから流出させた。流出する熔融ガラス流の先端を成形型で受けた状態で、ガラス成形品の製造に必要な量の熔融ガラス塊を分離して成形型上に受けた。成形型からガスを噴出して成形型上の熔融ガラス塊に上向きの風圧を加え、浮上状態でガラス塊に成形した。このようにして、2種類の光学ガラス1と光学ガラス2のガラス塊を作製した。
光学ガラス1と光学ガラス2の各ガラス塊を表2に示す水溶液(被覆剤)に浸漬して、ガラス塊の表面に被覆剤を被覆した。
ガラス成形品の最表面および内部の組成をX線光電子分光法(XPS)により分析した。
XPSによりガラス成形品の内部の組成を分析する場合、分析しようとする部位が露出するまでガラス成形品を研削し、研削面の組成を分析する。したがって、ガラス成形品の最表面、研削面のいずれの面で分析を行う場合でも、汚染物質としてC、Nなどの元素が検出されることがある。このような場合は、XPSによる分析結果からリンの含有量を算出するにあたり、C、Nなどのコンタミを除外する。
励起X線:Al mono
検出領域:Φ100μm
取出し角:45deg
検出深さ:4~5nm
スパッタリング条件:Ar+ 2.0kV
スパッタリングレート:約5nm/min(SiO2換算)
実施例1のガラス成形品(レンズブランク)をアニールして光学特性を目的のレンズの光学特性に一致させると共に、ガラス中の歪を低減した。その後、レンズブランクを公知の方法で、研削および研磨して加工し、球面レンズを作製した(実施例7)。
[1] 本実施の形態のガラス成形品の製造方法は、リンを含む被覆剤を、リン、酸素およびフッ素を含有する光学ガラスからなるガラス塊の表面に被覆する工程A、および、
被覆剤が被覆されたガラス塊を、加熱し、軟化させ、成形する工程B、を含む。
ガラス成形品の表面層におけるリンの含有量は、ガラス成形品の内部のリンの含有量に比べて大きい。
[A1] 本実施の形態のガラス成形品の製造方法は、リン酸、リン酸塩、酸化リンまたはこれらを含有する組成物を含む被覆剤をリン、酸素およびフッ素を含有する光学ガラスからなるガラス塊の表面に被覆する工程A、および
被覆剤が被覆されたガラス塊を加熱して軟化させて成形する工程B、を含む。
表面層のリンの含有量はガラス塊の中心部のリンの含有量に比べて大きい。
Claims (13)
- リンを含む被覆剤を、リン、酸素およびフッ素を含有する光学ガラスからなるガラス塊の表面に被覆する工程A、および、
前記被覆剤が被覆された前記ガラス塊を、加熱し、軟化させ、成形する工程B、
を含むガラス成形品の製造方法。 - 前記工程Bにおいて、前記ガラス塊を構成するガラスの粘度が106dPa・s以下となる温度にて、前記ガラス塊を加熱する、請求項1に記載のガラス成形品の製造方法。
- 前記被覆剤は、リン酸、リン酸塩、および酸化リンからなる群から選択される1種以上を含む、請求項1または2に記載のガラス成形品の製造方法。
- 前記被覆剤は、溶液からなる、請求項1~3のいずれかに記載のガラス成形品の製造方法。
- 前記被覆剤は、リン酸水溶液からなる、請求項1~4のいずれかに記載のガラス成形品の製造方法。
- 前記工程Bは、プレス成形工程を含む、請求項1~5のいずれかに記載のガラス成形品の製造方法。
- 請求項1~6のいずれかに記載の製造方法により得られる、ガラス成形品。
- リン、酸素およびフッ素を含有する光学ガラスからなるガラス成形品であって、
前記ガラス成形品の表面層におけるリンの含有量は、前記ガラス成形品の内部のリンの含有量に比べて大きい、ガラス成形品。 - 前記表面層の厚さは、1~100μmである、請求項8に記載のガラス成形品。
- 請求項7~9のいずれかに記載のガラス成形品からなる、光学素子ブランク。
- 請求項7~9のいずれかに記載のガラス成形品からなる、光学素子。
- 請求項10に記載の光学素子ブランクを、さらに加工する工程Cを含む、光学素子の製造方法。
- 前記工程Cは、前記光学素子ブランクの表面層を除去する工程を含む、請求項12に記載の光学素子の製造方法。
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US14/415,403 US20150197446A1 (en) | 2012-07-18 | 2013-07-11 | Glass molded article and method for producing same, optical element blank, and optical element and method for producing same |
KR20147035731A KR20150035716A (ko) | 2012-07-18 | 2013-07-11 | 유리 성형품 및 그 제조 방법, 광학 소자 블랭크, 그리고 광학 소자 및 그 제조 방법 |
CN201380037700.1A CN104470861B (zh) | 2012-07-18 | 2013-07-11 | 玻璃成型品及其制造方法、光学元件坯料、以及光学元件及其制造方法 |
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JPS6335423A (ja) * | 1986-07-25 | 1988-02-16 | Minolta Camera Co Ltd | ガラスレンズの成形方法 |
JPS6335424A (ja) * | 1986-07-25 | 1988-02-16 | Minolta Camera Co Ltd | ガラスレンズの成形方法 |
JPH08283042A (ja) * | 1995-04-12 | 1996-10-29 | Central Glass Co Ltd | 親水性物品およびその製造方法 |
JP2007269614A (ja) * | 2006-03-31 | 2007-10-18 | Hoya Corp | モールドプレス用ガラス素材、及びガラス光学素子の製造方法 |
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US20040177648A1 (en) * | 2002-08-02 | 2004-09-16 | Hoya Corporation | Glass material for molding, method of manufacturing same, and method of manufacturing glass articles using same |
US20050188724A1 (en) * | 2004-03-01 | 2005-09-01 | Hoya Corporation | Process for the production of precision press-molding preform and process for the production of optical element |
JP5085049B2 (ja) * | 2006-03-31 | 2012-11-28 | Hoya株式会社 | モールドプレス用ガラス素材、該ガラス素材の製造方法、及びガラス光学素子の製造方法 |
JP5547777B2 (ja) * | 2012-07-17 | 2014-07-16 | Hoya株式会社 | ガラス光学素子の製造方法 |
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JPS6335423A (ja) * | 1986-07-25 | 1988-02-16 | Minolta Camera Co Ltd | ガラスレンズの成形方法 |
JPS6335424A (ja) * | 1986-07-25 | 1988-02-16 | Minolta Camera Co Ltd | ガラスレンズの成形方法 |
JPH08283042A (ja) * | 1995-04-12 | 1996-10-29 | Central Glass Co Ltd | 親水性物品およびその製造方法 |
JP2007269614A (ja) * | 2006-03-31 | 2007-10-18 | Hoya Corp | モールドプレス用ガラス素材、及びガラス光学素子の製造方法 |
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US20150197446A1 (en) | 2015-07-16 |
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