WO2018051754A1 - Lentille trempée et procédé de fabrication de lentille trempée - Google Patents

Lentille trempée et procédé de fabrication de lentille trempée Download PDF

Info

Publication number
WO2018051754A1
WO2018051754A1 PCT/JP2017/030245 JP2017030245W WO2018051754A1 WO 2018051754 A1 WO2018051754 A1 WO 2018051754A1 JP 2017030245 W JP2017030245 W JP 2017030245W WO 2018051754 A1 WO2018051754 A1 WO 2018051754A1
Authority
WO
WIPO (PCT)
Prior art keywords
lens
less
reinforced
glass
main surface
Prior art date
Application number
PCT/JP2017/030245
Other languages
English (en)
Japanese (ja)
Inventor
長嶋　達雄
茂輝 澤村
周作 秋葉
伸一 安間
Original Assignee
旭硝子株式会社
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 旭硝子株式会社 filed Critical 旭硝子株式会社
Publication of WO2018051754A1 publication Critical patent/WO2018051754A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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
    • 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
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the present invention relates to a reinforced lens, and more particularly to a reinforced lens having a high impact strength and a method for manufacturing the reinforced lens.
  • an imaging glass lens having a small and wide imaging angle of view has been used for applications such as an in-vehicle camera, a robot vision sensor, a surveillance camera, and a wearable camera.
  • an imaging glass lens mounted on an in-vehicle camera or the like is more than an imaging lens of a general camera. It is necessary to have extremely high strength.
  • an in-vehicle camera is required not to cause damage or erosion due to impact or wind pressure associated with traveling of an automobile or sand dust splashed by traveling.
  • the lens thus chemically strengthened deforms due to the formation of a compressive stress layer, and when incorporated in the imaging optical system of the camera, the image formation in the peripheral part away from the optical axis is shifted. There was a problem that the image quality deteriorated.
  • the present invention has been made from the above viewpoint, and an object thereof is to provide a reinforced lens having high impact resistance. It is another object of the present invention to provide a method for manufacturing a reinforced lens having high impact resistance, in which the shape does not change greatly even when chemically strengthened.
  • the present invention is a chemically strengthened lens of a glass lens molded body, wherein the glass contains 30 to 65 mol% of SiO 2 , 10 mol% or more of Li 2 O, 0 to 10 mol% of SrO + BaO, and Li 2 O.
  • a reinforced lens having / (Li 2 O + Na 2 O + K 2 O) of 0.5 or more is provided.
  • the falling ball strength indicated as a height at which the reinforced lens does not break is 80 cm or more. It is preferable that
  • the lens molding has a first main surface and a second main surface facing each other, the lens molding has a diameter of 14 mm, a radius of curvature of the first main surface of 12 mm, and The amount of change in the radius of curvature of the first main surface before and after chemical strengthening when the second main surface is molded to a radius of curvature of 3 mm is preferably 10 ⁇ m or less.
  • the reinforced lens of the present invention preferably has a crack initiation load (CIL) of 100 gf or more.
  • the glass preferably has a glass transition point (Tg) of 500 ° C. to 630 ° C.
  • the reinforced lens of the present invention preferably has a refractive index (nd) of 1.73 to 2.10 and an Abbe number ( ⁇ d) of 15 to 45.
  • the reinforced lens of the present invention preferably has a refractive index (nd) of 1.63 or more and less than 1.73 and an Abbe number ( ⁇ d) of 35 to 55.
  • the reinforced lens of the present invention preferably has a refractive index (nd) of 1.50 or more and less than 1.63 and an Abbe number ( ⁇ d) of 45 to 65.
  • the reinforced lens of the present invention preferably has a water resistance of grade 3 or higher and an acid resistance of grade 3 or higher as measured according to JOGIS06-2008 according to the Japan Optical Glass Industry Association standard.
  • the reinforced lens of the present invention preferably includes an antireflection layer on at least one main surface of the first main surface and the second main surface.
  • the reinforced lens of the present invention preferably includes an antifouling coating layer on at least one main surface of the first main surface and the second main surface.
  • the present invention contains 30 to 65 mol% of SiO 2 , 10 mol% or more of Li 2 O, 0 to 10 mol% of SrO + BaO, and Li 2 O / (Li 2 O + Na 2 O + K 2 O) is 0.5 or more.
  • Mold glass into a lens molding The lens molded body is a reinforced molten salt containing at least sodium nitrate, and the reinforced molten salt contains 25% or more of sodium nitrate in terms of mass%, and contains 95% or more of sodium nitrate and potassium nitrate in total.
  • a reinforced lens having excellent impact resistance can be provided.
  • a method for manufacturing a reinforced lens having high impact resistance it is possible to provide a manufacturing method in which the shape does not change greatly even if chemical strengthening treatment is performed.
  • the reinforced lens of the present invention has a strength that can sufficiently withstand a harsh usage environment without deteriorating the image quality when used for an imaging lens of a vehicle-mounted camera, for example.
  • the strengthening lens of the present invention is a chemically strengthened lens of a glass lens molded body, wherein the glass contains 30 to 65 mol% of SiO 2 , 10 mol% or more of Li 2 O, 0 to 10 mol% of SrO + BaO, and Li 2 O / (Li 2 O + Na 2 O + K 2 O) is 0.5 or more.
  • the reinforced lens of the present invention is obtained by using glass having the above-mentioned predetermined composition as a lens molded body, and chemically strengthening the lens molded body.
  • shape correction is basically not performed after the chemical strengthening process. Therefore, in the chemical strengthening treatment, sufficient impact resistance and mechanical characteristics must be obtained under the condition that the lens shape of the lens molded body obtained by molding does not change greatly. Details of a method of using glass as a lens molded body and a method of chemically strengthening the lens molded body will be described later.
  • the reinforced lens of the present invention is suitably used as a lens disposed on the most object side of an imaging lens such as an in-vehicle camera that requires sufficient strength, for example.
  • An imaging lens such as a vehicle-mounted camera usually has a configuration in which a plurality of lenses are arranged so as to intersect the optical axis from the subject side toward the imaging element. Since lenses other than the lens arranged closest to the subject (hereinafter referred to as “other lenses”) are not directly exposed to the outside, the required intensity is smaller than the lens arranged closest to the subject.
  • FIG. 1 is a cross-sectional view of an example of a reinforced lens according to an embodiment of the present invention.
  • a reinforced lens 10 shown in FIG. 1 is a typical example of a lens disposed on the most object side of a vehicle-mounted camera.
  • the strengthening lens 10 has a first main surface 1 disposed on the subject side and a second main surface 2 facing the first main surface 1.
  • the first main surface 1 is a curved surface having a convex shape on the subject side, and the radius of curvature is R1.
  • the diameter of the reinforced lens 10 is D1.
  • the second main surface 2 has a convex curved surface on the subject side having a diameter D2 at the center, and the radius of curvature of the curved surface is R2.
  • the thickness of the convex portion is T1
  • the distance between the apex of the curved surface of the second main surface 2 and the base portion is indicated by T2.
  • the thickness of the reinforced lens 10 is T1 + T2.
  • the specific size of the reinforced lens 10 is, for example, a diameter D1 of the reinforced lens 10 of 5 to 50 mm, a radius of curvature R1 of the first main surface 1 of 5 to 500 mm, and a diameter of a curved surface of the second main surface 2.
  • D2 is 2 to 40 mm
  • its radius of curvature R2 is 2 to 400 mm
  • the thickness T1 of the convex part is 0.1 to 10 mm
  • the distance T2 between the vertex of the curved surface of the second main surface 2 and the base is 1 to 19 mm, strengthening
  • strengthening The thickness of the lens 10 is 2 to 20 mm.
  • the curvature radius R2 of the curved surface of the second main surface 2 is referred to as the curvature radius R2 of the second main surface 2.
  • the reinforced lens of the present invention is not limited to the reinforced lens having the cross-sectional shape shown in FIG.
  • the reinforced lens of the present invention is a plano-convex reinforced lens mainly for convex lenses, having a curved surface on the first main surface disposed on the subject side, and a second main surface having a planar shape. Also good.
  • the present invention obtains a molded lens by molding glass into a predetermined shape, and has sufficient impact resistance even under chemical strengthening conditions in which the shape does not change greatly.
  • a chemical strengthening treatment can be performed so as to obtain mechanical properties.
  • SiO 2 is contained in an amount of 30 to 65 mol%
  • Li 2 O is contained in an amount of 10 mol% or more
  • SrO + BaO is contained in an amount of 0 to 10 mol%
  • Li 2 O / It is found that the above-mentioned problem can be solved by molding glass having a (Li 2 O + Na 2 O + K 2 O) of 0.5 or more into a lens molded body and subjecting the lens molded body to chemical strengthening treatment under predetermined conditions.
  • the invention has been completed.
  • % when referring to the composition of glass is mol% based on oxide unless otherwise specified.
  • (I) In general, chemical strengthening treatment in a glass molded body is performed by replacing alkali ions having a small ion radius with alkali ions having a large ion radius, so that a compression stress layer (hereinafter referred to as “strengthening layer”) is formed on the surface of the molded body. Is formed, and the impact resistance and mechanical properties are enhanced.
  • Alkali ions have larger ionic radii in the order of Li + , Na + and K + , and in the chemical strengthening treatment, Li + is exchanged with Na + or K + , or Na + is exchanged with K + , The exchange speed is clearly faster in the former.
  • the shape changes as the chemical strengthening time increases and the processing temperature increases. It becomes easy. Further, it was found that even when the chemical strengthening treatment is performed under the same conditions, the shape change is large when Na + is replaced with K + .
  • the glass contains 10 mol% or more of Li 2 O because sufficient impact resistance and mechanical properties can be obtained under chemical strengthening conditions in which the lens shape obtained by molding does not change significantly.
  • Li 2 O is preferably 12% or more, and more preferably 15% or more.
  • Li 2 O in the glass is preferably 30% or less, and more preferably 25% or less.
  • the ratio of Li 2 O content to the total content of alkali metal components Li 2 O + Na 2 O + K 2 O), Li 2 O / (Li 2 O + Na 2 O + K 2 O) Is 0.5 or more.
  • Li 2 O / (Li 2 O + Na 2 O + K 2 O) is more preferably 0.6 or more, and further preferably 0.7 or more.
  • SrO + BaO is 10 mol% or less.
  • SrO and BaO are components that impair the impact resistance and mechanical properties that inhibit the chemical strengthening treatment and increase the specific gravity of the glass. More preferably, it is 8% or less, More preferably, it is 6% or less.
  • SrO and BaO are preferably not included from the viewpoint of impact resistance and mechanical properties, but this purpose is lost for reasons such as increasing the Abbe number, increasing the refractive index, and improving the thermal stability of the glass. You may make it contain in the range which is not.
  • SiO 2 is contained in the range of 30 to 65 mol%.
  • SiO 2 is a glass network former, and if it is less than 30%, impact resistance and mechanical properties deteriorate. Preferably it is 35% or more, more preferably 40% or more. If it exceeds 65%, Tg becomes too high and chemical strengthening treatment cannot be carried out efficiently, and the melting temperature rises and productivity may be impaired. Preferably it is 62% or less, More preferably, it is 60% or less.
  • the reinforced lens of the present invention obtained by molding glass having the above composition into a lens molded body and chemically strengthening it preferably has the following impact resistance.
  • the falling ball strength was used as an index of impact resistance in the present invention.
  • FIG. 2 shows a schematic diagram of the falling ball strength test.
  • the falling ball strength in the present invention means, for example, a height that does not break even if a 64.6 g iron ball 12 is dropped on the center C of the reinforced lens 10 placed on the horizontal surface 11 as shown in FIG.
  • the test starts from a height of 10 cm (h), and if it is not broken, it is raised by 10 cm.
  • the test is terminated and the height (h) immediately before breaking.
  • the reinforced lens of the present invention preferably has a falling ball strength of 80 cm or more (corresponding to 0.5 J).
  • the strengthening lens used for the drop-ball strength test has a predetermined shape, that is, in the strengthening lens shown in FIG. 1, the diameter D1 of the strengthening lens 10 is 14 mm, the radius of curvature R1 on the first principal surface 1 is 12 mm, and the second principal
  • the curved surface diameter D2 of the surface 2 is 5.72 mm, the curvature radius R2 thereof is 3 mm, the convex portion thickness T1 is 1.4 mm, and the distance T2 between the vertex of the curved surface of the second main surface 2 and the base portion is 2.
  • the test reinforced lens is 1 mm, and the thickness of the reinforced lens 10 is 3.5 mm.
  • the lens shape change before and after chemical strengthening is in the following range.
  • the lens shape change before and after chemical strengthening can be measured, for example, by the following method.
  • the lens molded body has a first main surface and a second main surface facing each other, and is molded into a diameter of 14 mm, a radius of curvature of 12 mm of the first main surface, and a radius of curvature of 3 mm of the second main surface.
  • the amount of change in the radius of curvature of the first main surface before and after chemical strengthening is measured. More specifically, the shape of the molded lens used for the chemical strengthening treatment is the same as the shape of the strengthened lens used for the falling ball test.
  • the radius of curvature of the first principal surface of the lens molded body and the reinforced lens obtained by chemical strengthening treatment can be measured, for example, with a 3D measuring device (manufactured by KEYENCE, VR-3200).
  • a 3D measuring device manufactured by KEYENCE, VR-3200.
  • conditions for the chemical strengthening treatment in the test for example, using a strengthened molten salt containing 25% by mass of sodium nitrate and 75% by mass of potassium nitrate with respect to the total amount of the strengthened molten salt, Conditions are mentioned.
  • the amount of change in the radius of curvature on the first main surface before and after the chemical tempering treatment is 10 ⁇ m or less as evaluated in this way.
  • the amount of change in the radius of curvature on the first main surface before and after the chemical strengthening treatment is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the load of the Vickers indenter at which the occurrence rate of cracks when the indentation is formed using the Vickers indenter is 50% (this load is referred to as crack initiation load (CIL)).
  • CIL crack initiation load
  • the CIL is an index of crack resistance, and the larger the CIL, the less likely it is to crack.
  • the CIL of the reinforced lens of the present invention is preferably 100 gf or more, more preferably 200 gf or more, and further preferably 300 gf or more.
  • the CIL value of the reinforced lens of the present invention refers to the CIL value in an evaluation sample obtained by molding the glass used for the reinforced lens into a plate shape and chemically strengthened, obtained by the following method. .
  • a Vickers hardness tester was used to push the Vickers indenter for 15 seconds on the surface of the evaluation sample that had been mirror-polished on both sides of a 2 mm thick glass plate and then removed the Vickers indenter. Observe. An average value of the number of cracks generated with respect to the indentation load of the Vickers indenter of 100 gf, 200 gf, 300 gf, 500 gf, 1000 gf, and 2000 gf is calculated for each load. The relationship between the load and the number of cracks is calculated by regression using a sigmoid function. From the regression calculation result, the load at which the number of cracks is two can be used as the CIL (gf) of the sample for evaluation. The occurrence rate is 100% when a total of four cracks are generated from all four corners of the indentation.
  • Compressive stress (CS) of the reinforcing layer in the reinforced lens of the present invention is preferably 50 MPa or more, more preferably 100 MPa or more, and further preferably 150 MPa or more.
  • the depth of the reinforcing layer (DOL; Depth of layer) in the reinforced lens of the present invention is preferably 5 ⁇ m or more from the surface. More preferably, it is 10 micrometers or more, More preferably, it is 20 micrometers or more.
  • the thickness of the reinforced layer is preferably 500 ⁇ m or less.
  • the thickness of the reinforcing layer is more preferably 300 ⁇ m or less, and further preferably 200 ⁇ m or less.
  • the CS and DOL of the reinforced lens in the present invention are preferably measured at the central portion of the first main surface of the reinforced lens.
  • CS and DOL for example, measure the retardation of the surface compressive stress layer by passing light through the reinforcing layer on the cross section of the reinforced lens using a birefringence imaging system Abrio (manufactured by Tokyo Instruments), and use the photoelastic constant of the glass. Can be calculated.
  • the reinforced lens of the present invention has a water resistance (RW) of grade 3 or higher measured according to the “Optical Glass Chemical Durability Measurement Method (Powder Method)” (JOGIS06-2008) according to the Japan Optical Glass Industry Association Standard.
  • the acid resistance (RA) is preferably grade 3 or higher.
  • the RW and RA of the reinforced layer and the RW and RA of the glass inside the reinforced lens are strictly different, but in the present invention, there is no great difference that the grade is different. In the invention, both are treated as substantially the same.
  • RW is measured as follows. For a glass powder having a diameter of 420 to 600 ⁇ m, a mass reduction rate (%) when immersed in 80 mL of pure water at 100 ° C. for 1 hour is measured. A predetermined grade is given according to the mass reduction rate. The smaller the numerical value, the better the RW. In the reinforced lens of the present invention, RW is more preferably grade 2 or more, and 1 is particularly preferred.
  • RA is measured as follows. For a glass powder having a diameter of 420 to 600 ⁇ m, a mass reduction ratio (%) when immersed in 80 mL of a 0.01 N nitric acid aqueous solution at 100 ° C. for 1 hour is measured. A predetermined grade is given according to the mass reduction rate. The smaller the numerical value, the better the RA. In the reinforced lens of the present invention, RA is more preferably grade 2 or more, and 1 is particularly preferred.
  • the glass preferably has a specific gravity of 4.0 g / cm 3 or less.
  • the specific gravity of the reinforced layer and the specific gravity of the glass inside the reinforced lens are substantially the same at the first place after the decimal point and are treated as the same. Thereby, when it is set as a reinforced lens, a crack is hard to generate
  • the specific gravity is preferably 3.7 g / cm 3 or less, and more preferably 3.5 g / cm 3 or less.
  • the glass preferably has a glass transition point (Tg) of 500 ° C. or higher and 630 ° C. or lower.
  • Tg glass transition point
  • the Tg of the reinforced layer and the Tg of the glass inside the reinforced lens are substantially the same and are treated as the same.
  • press molding moldability when producing a reinforced lens by precision press molding with high manufacturing efficiency (hereinafter simply referred to as “press molding”) is good.
  • Tg is too low, it is preferable that the temperature is 500 ° C. or higher because compression stress is likely to be relaxed in a reinforced lens having a reinforced layer.
  • the Tg of the glass is preferably 520 to 600 ° C, more preferably 540 to 590 ° C. Tg can be measured by, for example, a thermal expansion method.
  • the Young's modulus refers to the Young's modulus of the glass inside the reinforced lens.
  • the Young's modulus is preferably 80 GPa or more, more preferably 90 GPa or more, still more preferably 95 GPa or more, and still more preferably 100 GPa or more.
  • the refractive index (nd) and Abbe number ( ⁇ d) of the reinforced lens mean the refractive index and Abbe number of the glass inside the reinforced lens. Strictly speaking, the refractive index of the reinforcing layer is different from the refractive index of the glass inside the reinforcing lens, but the numerical value is different to the third place after the decimal point. In the present invention, both are treated as substantially the same.
  • the reinforced lens in the present invention preferably has a refractive index of 1.50 to 2.10, and is divided into three cases according to the specification.
  • ⁇ Strengthened lens of the first specification> The first type of reinforced lens uses a glass lens with a high Abbe number that can shoot a smaller and wider area and that other lenses placed closer to the image sensor can sufficiently correct chromatic aberration. It is a reinforced lens suitable when possible.
  • the reinforced lens of the first specification preferably has a refractive index (nd) in the range of 1.73 to 2.10 and an Abbe number ( ⁇ d) in the range of 15 to 45. More preferably, nd is in the range of 1.75 to 2.00 and ⁇ d is in the range of 20 to 43, and further preferably, nd is in the range of 1.77 to 1.90 and ⁇ d is in the range of 25 to 41.
  • the reinforced lens of the second specification is a glass with a high Abbe number so that the lens arranged on the side closer to the imaging device can sufficiently correct chromatic aberration when photographing a wide range with high resolution and cost.
  • This lens is a reinforced lens that cannot be used with a lens, and is suitable when a low-cost glass or resin lens is used.
  • the reinforced lens of the second specification preferably has a refractive index (nd) of 1.63 or more and less than 1.73 and an Abbe number ( ⁇ d) of 35 to 55. More preferably, nd is in the range of 1.65 to 1.72, and ⁇ d is in the range of 40 to 53, and further preferably, nd is in the range of 1.67 to 1.70, and ⁇ d is in the range of 45 to 51.
  • the third type of reinforced lens is a reinforced lens that is suitable when high resolution is more important than the viewing angle, or when the lens placed closer to the image sensor can only be used from the viewpoint of cost. It is.
  • the reinforced lens of the third specification preferably has a refractive index (nd) of 1.50 or more and less than 1.63 and an Abbe number ( ⁇ d) of 45 to 65. More preferably, nd is in the range of 1.55 to 1.62 and ⁇ d is in the range of 50 to 63, and further preferably, nd is in the range of 1.57 to 1.61 and ⁇ d is in the range of 55 to 61.
  • the glass used for the reinforced lens of the present invention is further expressed in mol% on an oxide basis.
  • SiO 2 30% to 65%
  • Al 2 O 3 0% to 20%
  • B 2 O 3 0% to 40%
  • P 2 O 5 0% to 20%
  • MgO 0% to 20%
  • CaO 0% to 20%
  • SrO 0% to 10%
  • BaO 0% to 10%
  • ZnO 0% to 20%
  • TiO 2 : 0% to 20%
  • ZrO 2 0% to 15%
  • K 2 O: 0% to 5% Nb 2 O 5 : 0% to 30%
  • Ln 2 O 3 0% to 20%
  • La 2 O 3 : 0% to 20%
  • Y 2 O 3 0% to 20%
  • Gd 2 O 3 0% to 20%
  • the glass used for the reinforced lens of the first specification of the present invention may further include mol% based on oxide.
  • SiO 2 30% to 55%
  • Al 2 O 3 0% to 5%
  • B 2 O 3 0% to 40%
  • P 2 O 5 0% to 20%
  • MgO 0% to 10%
  • CaO 0% to 10%
  • SrO 0% to 10%
  • BaO 0% to 10%
  • ZnO 0% to 20%
  • ZrO 2 0% to 15%
  • Li 2 O + Na 2 O + K 2 O: 10% to 30% Li 2 O: 10% to 30%, Na 2 O: 0% to 15%
  • Nb 2 O 5 : 0% to 30%
  • Ln 2 O 3 0% to 20%
  • La 2 O 3 : 0% to 20%
  • Y 2 O 3 0% to 20%
  • the glass used for the reinforced lens of the second specification of the present invention is further oxide-based.
  • SiO 2 30% to 60%
  • Al 2 O 3 0% to 10%
  • B 2 O 3 0% to 20%
  • P 2 O 5 0% to 20%
  • MgO 0% to 20%
  • CaO 0% to 20%
  • SrO 0% to 10%
  • BaO 0% to 10%
  • ZnO 0% to 20%
  • TiO 2 0% to 5%
  • ZrO 2 0% to 15%
  • Li 2 O + Na 2 O + K 2 O: 10% to 30% Li 2 O: 10% to 30%, Na 2 O: 0% to 10%
  • Nb 2 O 5 0% to 15%
  • Ln 2 O 3 0% to 20%
  • La 2 O 3 : 0% to 20%
  • Y 2 O 3 0% to 20%
  • the glass used for the reinforced lens of the third specification of the present invention is further oxide-based.
  • SiO 2 30% to 65%
  • Al 2 O 3 0% to 20%
  • B 2 O 3 0% to 40%
  • P 2 O 5 0% to 20%
  • MgO 0% to 20%
  • CaO 0% to 20%
  • SrO 0% to 10%
  • BaO 0% to 10%
  • ZnO 0% to 20%
  • TiO 2 0% to 5%
  • ZrO 2 0% to 10%
  • Li 2 O + Na 2 O + K 2 O: 10% to 25% Li 2 O: 10% to 20%, Na 2 O: 0% to 10%
  • K 2 O 0% to 5%
  • Nb 2 O 5 0% to 10%
  • Ln 2 O 3 0% to 10%
  • La 2 O 3 0% to 10%
  • Y 2 O 3 :
  • the glass used for the reinforced lenses of the first to third specifications will be described below.
  • the glass used in the present invention is not limited to the composition of the glass used for the reinforced lenses of the first to third specifications as long as the obtained reinforced lens has the characteristics described above, but is preferably in the following range. .
  • “substantially does not contain” means that it is not contained except for inevitable impurities.
  • the content of inevitable impurities is 0.1% or less in the present invention. Preferably it is 0.05% or less, More preferably, it is 0.02% or less.
  • SiO 2 is an essential component in a glass network former, and if it is less than 30%, impact resistance and mechanical properties are lowered. Preferably it is 35% or more, more preferably 40% or more. If it exceeds 55%, the refractive index may decrease. Preferably it is 54% or less, More preferably, it is 52% or less.
  • Al 2 O 3 is an optional component.
  • Al 2 O 3 is a component that improves chemical durability and improves impact resistance and mechanical properties, but when Al 2 O 3 increases, the refractive index decreases, Tg increases too much, glass May be easily devitrified. Preferably it is 3% or less, More preferably, it is 2% or less.
  • B 2 O 3 is an optional component.
  • B 2 O 3 is a component that lowers the Tg, improves the thermal stability of the glass, and improves impact resistance and mechanical properties. However, if the amount of B 2 O 3 is large, the refractive index decreases. There is a risk that chemical durability tends to decrease. Preferably it is 30% or less, more preferably 20% or less.
  • P 2 O 5 is an optional component.
  • P 2 O 5 is a component that lowers the Tg and is a component for adjusting the Abbe number. However, if the amount of P 2 O 5 is large, the refractive index, impact resistance, and mechanical properties are likely to be lowered. Preferably it is 10% or less, More preferably, it is 4% or less, More preferably, it is 2% or less. Most preferably, P 2 O 5 is not substantially contained.
  • MgO is an optional component.
  • MgO is a component that improves the meltability of glass, suppresses devitrification, and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of MgO increases, devitrification is promoted.
  • it is 5% or less, More preferably, it is 3% or less.
  • CaO is an optional component.
  • CaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of CaO is large, the chemical strengthening treatment is hindered, and the impact resistance and mechanical properties are likely to deteriorate. Therefore, when CaO is contained, it is preferably 5% or less, more preferably 3% or less.
  • SrO is an optional component.
  • SrO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of SrO is large, the impact resistance and mechanical properties, which impede the chemical strengthening treatment and increase the specific gravity of the glass, are significantly reduced. Therefore, when SrO is contained, it is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less. Most preferably, SrO is not substantially contained.
  • BaO is an optional component.
  • BaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of BaO is large, the impact resistance and mechanical properties that inhibit the chemical strengthening treatment and increase the specific gravity of the glass are remarkably lowered. Therefore, when BaO is contained, it is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less. Most preferably, BaO is not substantially contained.
  • ZnO is an optional component that adjusts optical constants such as the Abbe number and refractive index of glass to improve mechanical properties.
  • optical constants such as the Abbe number and refractive index of glass.
  • it is 15% or less, More preferably, it is 10% or less, More preferably, it is 5% or less.
  • TiO 2 is an optional component, and can be expected to increase the refractive index of the glass and improve the mechanical properties. On the other hand, when TiO 2 is too much, it is easy to be colored, the transmittance is lowered, and in order to reduce the Abbe number, it is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. When TiO 2 is contained, it is preferably 0.5% or more, more preferably 1% or more, and further preferably 1.5% or more.
  • ZrO 2 is an optional component, and is a component that increases the refractive index of the glass and increases the chemical durability of the glass. Inclusion of ZrO 2 can be expected to improve mechanical properties. On the other hand, when there is too much ZrO 2 , devitrification tends to occur, so it is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. When ZrO 2 is contained, it is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more.
  • Li 2 O is an essential component and is contained at 10% or more. In order to make the chemical strengthening treatment efficient, Li 2 O is preferably 12% or more, more preferably 15% or more. Further, from the viewpoint of suppressing stress relaxation in the chemically strengthened glass due to devitrification and a decrease in Tg, Li 2 O in the glass is preferably 30% or less, more preferably 25% or less.
  • Na 2 O is an optional component that suppresses devitrification, lowers Tg, and enhances the efficiency of replacement with K + when the strengthened molten salt is a mixed salt of sodium nitrate and potassium nitrate. If it is too high, impact resistance and mechanical properties are likely to deteriorate. Preferably it is 15% or less, More preferably, it is 10% or less.
  • Na 2 O is contained, it is preferably 1.5% or more, more preferably 2% or more, and further preferably 2.5% or more.
  • K 2 O is an optional component and is a component that improves the meltability of the glass and suppresses devitrification. However, if it is too much, impact resistance and mechanical properties are likely to deteriorate. Preferably it is 5% or less, More preferably, it is 3% or less.
  • Nb 2 O 5 is an optional component that increases the refractive index of glass and can be expected to improve impact resistance and mechanical properties. On the other hand, if Nb 2 O 5 is too much, it tends to be devitrified, and the transmittance is lowered. In order to reduce the Abbe number, it is preferably 30% or less, more preferably 25% or less, and further preferably 20% or less. is there. When Nb 2 O 5 is contained, it is preferably 5% or more, more preferably 7% or more, and further preferably 10% or more.
  • La 2 O 3 is an optional component.
  • La 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjusting the optical constant, etc., but it is lost if the amount of La 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing La 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Y 2 O 3 is an optional component.
  • Y 2 O 3 is a component that improves the refractive index of glass and can be expected to improve mechanical properties. However, if the amount of Y 2 O 3 is too large, it tends to be devitrified. Therefore, when they contain Y 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Gd 2 O 3 is an optional component.
  • Gd 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjustment of the optical constant, etc., but it is lost if the amount of Gd 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing Gd 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Ln 2 O 3 (Ln is at least one selected from the group consisting of Y, La, Gd, Yb, and Lu. That is, Ln 2 O 3 is La 2 O 3 + Y 2 O 3 + Gd 2 O 3 Is an optional component. Ln 2 O 3 is a component that improves the refractive index of the glass. However, if the amount of Ln 2 O 3 is too large, it tends to devitrify. Therefore, if containing Ln 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Ta 2 O 5 is an optional component.
  • Ta 2 O 5 is a component that improves the refractive index of the glass. However, if the amount of Ta 2 O 5 is too large, it tends to devitrify and the specific gravity also increases. Therefore, if containing Ta 2 O 5, preferably 20% or less, more preferably 15% or less.
  • WO 3 is an optional component.
  • WO 3 is a component that improves the refractive index of the glass and improves the thermal stability of the glass. However, if the amount of WO 3 is too large, it tends to devitrify, reduce the Abbe number, and increase the specific gravity. . Therefore, if containing WO 3, preferably 20% or less, more preferably 15% or less.
  • Bi 2 O 3 and TeO 2 may be contained in less than 10%. These are not essential components, but can be expected to increase the refractive index and improve the meltability. When these components are contained, the total content is preferably 5% or less, and more preferably 3% or less.
  • As 2 O 3 is a harmful chemical substance, it tends to be refrained from use in recent years, and measures for environmental measures are required. Therefore, when importance is placed on the environmental impact, it is preferable that the substance is not substantially contained except for inevitable mixing.
  • Sb 2 O 3 and SnO 2 are not essential components, but can be added for the purpose of adjusting refractive index characteristics, improving meltability, suppressing coloring, improving transmittance, clarifying, and improving chemical durability.
  • the total content is preferably 1% or less, and more preferably 0.5% or less.
  • F is contained.
  • F is not essential, it can be added for the purpose of improving meltability, improving transmittance, improving clarity, and the like.
  • the content ratio is preferably 5% or less, and more preferably 3% or less.
  • SiO 2 is an essential component in a glass network former, and if it is less than 30%, impact resistance and mechanical properties are lowered. Preferably it is 35% or more, more preferably 40% or more. If it exceeds 60%, the refractive index may decrease. Preferably it is 58% or less, More preferably, it is 56% or less.
  • Al 2 O 3 is an optional component.
  • Al 2 O 3 is a component that improves chemical durability and improves impact resistance and mechanical properties, but when Al 2 O 3 increases, the refractive index decreases, Tg increases too much, glass May be easily devitrified. Preferably it is 5% or less, More preferably, it is 3% or less.
  • B 2 O 3 is an optional component.
  • B 2 O 3 is a component that lowers the Tg, improves the thermal stability of the glass, and improves impact resistance and mechanical properties. However, if the amount of B 2 O 3 is large, the refractive index decreases. There is a risk that chemical durability tends to decrease. Preferably it is 20% or less, More preferably, it is 15% or less.
  • P 2 O 5 is an optional component.
  • P 2 O 5 is a component that lowers the Tg and is a component for adjusting the Abbe number. However, if the amount of P 2 O 5 is large, the refractive index, impact resistance, and mechanical properties are likely to be lowered. Preferably it is 20% or less, More preferably, it is 15% or less, More preferably, it is 10% or less. Most preferably, P 2 O 5 is not substantially contained.
  • SiO 2 + Al 2 O 3 + B 2 O 3 + P 2 O 5 is 30% or more and less than 65%.
  • the Abbe number becomes small.
  • it is 35% or more, more preferably 40% or more.
  • the refractive index is low.
  • it is 62% or less, More preferably, it is 60% or less.
  • MgO is an optional component.
  • MgO is a component that improves the meltability of glass, suppresses devitrification, and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of MgO increases, devitrification is promoted. Preferably it is 15% or less, More preferably, it is 10% or less.
  • CaO is an optional component.
  • CaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of CaO is large, the chemical strengthening treatment is hindered, and the impact resistance and mechanical properties are likely to deteriorate. Therefore, when CaO is contained, it is preferably 15% or less, more preferably 10% or less.
  • SrO is an optional component.
  • SrO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of SrO is large, the impact resistance and mechanical properties, which impede the chemical strengthening treatment and increase the specific gravity of the glass, are significantly reduced. Therefore, when SrO is contained, it is preferably 8% or less, more preferably 5% or less, and further preferably 3% or less.
  • BaO is an optional component.
  • BaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of BaO is large, the impact resistance and mechanical properties that inhibit the chemical strengthening treatment and increase the specific gravity of the glass are remarkably lowered. Therefore, when BaO is contained, it is preferably 8% or less, more preferably 5% or less, and further preferably 3% or less.
  • ZnO is an optional component that adjusts optical constants such as the Abbe number and refractive index of glass to improve mechanical properties.
  • optical constants such as the Abbe number and refractive index of glass.
  • it is 15% or less, More preferably, it is 10% or less, More preferably, it is 5% or less.
  • TiO 2 is an optional component, and can be expected to increase the refractive index of the glass and improve the mechanical properties. On the other hand, when TiO 2 is too much, it is easy to be colored, the transmittance is lowered, and in order to reduce the Abbe number, it is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less.
  • ZrO 2 is an optional component, and is a component that increases the refractive index of the glass and increases the chemical durability of the glass. Inclusion of ZrO 2 can be expected to improve mechanical properties. On the other hand, if there is too much ZrO 2 , devitrification tends to occur, so it is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. When ZrO 2 is contained, it is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more.
  • Li 2 O is an essential component and is contained at 10% or more. In order to make the chemical strengthening treatment efficient, Li 2 O is preferably 12% or more, more preferably 15% or more. Further, from the viewpoint of suppressing stress relaxation in the chemically strengthened glass due to devitrification and a decrease in Tg, Li 2 O in the glass is preferably 30% or less, more preferably 25% or less.
  • the value obtained by dividing B 2 O 3 by Li 2 O, B 2 O 3 / Li 2 O, is preferably 0.75 or less, more preferably 0.7 or less. If it exceeds 0.75, the volatilization of the glass becomes intense when the glass is melted, and the variation in the refractive index when the reinforced lens is made increases. More preferably, it is 0.6 or less, More preferably, it is 0.5 or less.
  • Na 2 O is an optional component that suppresses devitrification, lowers Tg, and enhances the efficiency of replacement with K + when the strengthened molten salt is a mixed salt of sodium nitrate and potassium nitrate. If it is too high, the refractive index will be low, the Abbe number will be small, and the impact resistance and mechanical properties will tend to deteriorate. Preferably it is 10% or less, More preferably, it is 5% or less. When Na 2 O is contained, it is preferably 1.5% or more, more preferably 2% or more, and further preferably 2.5% or more.
  • K 2 O is an optional component that improves the meltability of the glass and suppresses devitrification. However, if it is too much, the refractive index decreases, the Abbe number decreases, and the impact resistance. And mechanical properties are likely to deteriorate. Preferably it is 5% or less, More preferably, it is 3% or less.
  • Nb 2 O 5 is an optional component that increases the refractive index of glass and can be expected to improve impact resistance and mechanical properties. On the other hand, if Nb 2 O 5 is too much, it tends to be devitrified, and the transmittance is lowered. In order to reduce the Abbe number, it is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less. is there.
  • La 2 O 3 is an optional component.
  • La 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjusting the optical constant, etc., but it is lost if the amount of La 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing La 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Y 2 O 3 is an optional component.
  • Y 2 O 3 is a component that improves the refractive index of glass and can be expected to improve mechanical properties. However, if the amount of Y 2 O 3 is too large, it tends to be devitrified. Therefore, when they contain Y 2 O 3, preferably 10% or less, more preferably 5% or less.
  • Gd 2 O 3 is an optional component.
  • Gd 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjustment of the optical constant, etc., but it is lost if the amount of Gd 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing Gd 2 O 3, preferably 10% or less, more preferably 5% or less.
  • Ln 2 O 3 (Ln is at least one selected from the group consisting of Y, La, Gd, Yb, and Lu. That is, Ln 2 O 3 is La 2 O 3 + Y 2 O 3 + Gd 2 O 3 Is an optional component. Ln 2 O 3 is a component that improves the refractive index of the glass. However, if the amount of Ln 2 O 3 is too large, it tends to devitrify. Therefore, if containing Ln 2 O 3, preferably 20% or less, more preferably 15% or less.
  • Ta 2 O 5 is an optional component.
  • Ta 2 O 5 is a component that improves the refractive index of the glass. However, if the amount of Ta 2 O 5 is too large, it tends to devitrify and the specific gravity also increases. Therefore, if containing Ta 2 O 5, preferably 10% or less, more preferably 5% or less.
  • WO 3 is an optional component.
  • WO 3 is a component that improves the refractive index of the glass and improves the thermal stability of the glass. However, if the amount of WO 3 is too large, it tends to devitrify, reduce the Abbe number, and increase the specific gravity. . Therefore, if containing WO 3, preferably 10% or less, more preferably 5% or less.
  • the glass used for the reinforced lens of the second specification contains Bi 2 O 3 , TeO 2 , Sb 2 O 3 , SnO 2 , and F in addition to the above components in the same manner as the glass used for the reinforced lens of the first specification. May be.
  • the content ratio of these components can be the same as that of the glass used for the reinforced lens of the first specification including the preferred embodiment.
  • SiO 2 is an essential component in a glass network former, and if it is less than 30%, impact resistance and mechanical properties are lowered. Preferably it is 35% or more, more preferably 40% or more. If it exceeds 65%, Tg tends to be too high. Preferably it is 63% or less, More preferably, it is 62% or less.
  • Al 2 O 3 is an optional component.
  • Al 2 O 3 is a component that improves chemical durability and improves impact resistance and mechanical properties, but when Al 2 O 3 increases, Tg becomes too high and the glass tends to devitrify. There is a fear. Preferably it is 15% or less, More preferably, it is 13% or less.
  • B 2 O 3 is an optional component.
  • B 2 O 3 is a component that lowers the Tg, improves the thermal stability of the glass, and improves impact resistance and mechanical properties. However, if the amount of B 2 O 3 is large, chemical durability is increased. It tends to decrease. Preferably it is 40% or less, More preferably, it is 35% or less.
  • P 2 O 5 is an optional component.
  • P 2 O 5 is a component that lowers the Tg and is a component that increases the Abbe number. However, if the amount of P 2 O 5 is large, impact resistance and mechanical properties are likely to deteriorate. Preferably it is 20% or less, More preferably, it is 15% or less.
  • SiO 2 + Al 2 O 3 + B 2 O 3 + P 2 O 5 is 65% or more and less than 80%.
  • the Abbe number becomes small.
  • it is 66% or more, More preferably, it is 67% or more.
  • melting of the glass becomes difficult.
  • it is 78% or less, More preferably, it is 76% or less.
  • MgO is an optional component.
  • MgO is a component that improves the meltability of glass, suppresses devitrification, and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of MgO increases, devitrification is promoted. Preferably it is 15% or less, More preferably, it is 10% or less.
  • CaO is an optional component.
  • CaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of CaO is large, the chemical strengthening treatment is hindered, and the impact resistance and mechanical properties are likely to deteriorate. Therefore, when CaO is contained, it is preferably 15% or less, more preferably 10% or less.
  • SrO is an optional component.
  • SrO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of SrO is large, the impact resistance and mechanical properties, which impede the chemical strengthening treatment and increase the specific gravity of the glass, are significantly reduced. Therefore, when SrO is contained, it is preferably 8% or less, more preferably 5% or less, and further preferably 3% or less.
  • BaO is an optional component.
  • BaO is a component that suppresses devitrification and adjusts optical constants such as the Abbe number and refractive index of glass.
  • the amount of BaO is large, the impact resistance and mechanical properties that inhibit the chemical strengthening treatment and increase the specific gravity of the glass are remarkably lowered. Therefore, when BaO is contained, it is preferably 8% or less, more preferably 5% or less, and further preferably 3% or less.
  • ZnO is an optional component that adjusts optical constants such as the Abbe number and refractive index of glass to improve mechanical properties.
  • optical constants such as the Abbe number and refractive index of glass.
  • it is 15% or less, More preferably, it is 10% or less, More preferably, it is 5% or less.
  • TiO 2 is an optional component, and can be expected to increase the refractive index of the glass and improve the mechanical properties. On the other hand, when TiO 2 is too much, it is easy to be colored, the transmittance is lowered, and in order to reduce the Abbe number, it is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less.
  • ZrO 2 is an optional component, and is a component that increases the refractive index of the glass and increases the chemical durability of the glass. Inclusion of ZrO 2 can be expected to improve mechanical properties. On the other hand, if there is too much ZrO 2 , devitrification tends to occur, so it is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. When ZrO 2 is contained, it is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more.
  • Li 2 O is an essential component and is contained at 10% or more. In order to make the chemical strengthening treatment efficient, Li 2 O is preferably 11% or more, more preferably 12% or more. Further, from the viewpoint of suppressing stress relaxation in the chemically strengthened glass due to devitrification and Tg reduction, Li 2 O in the glass is preferably 20% or less, more preferably 18% or less.
  • Na 2 O is an optional component that suppresses devitrification, lowers Tg, and enhances the efficiency of replacement with K + when the strengthened molten salt is a mixed salt of sodium nitrate and potassium nitrate. If it is too high, the Abbe number becomes small, and the impact resistance and mechanical properties are likely to deteriorate. Preferably it is 10% or less, More preferably, it is 5% or less. When Na 2 O is contained, it is preferably 1.5% or more, more preferably 2% or more, and further preferably 2.5% or more.
  • K 2 O is an optional component that improves the meltability of the glass and suppresses devitrification. However, if it is too large, the Abbe number decreases, impact resistance and mechanical properties decrease. Easy to do. Preferably it is 5% or less, More preferably, it is 3% or less.
  • Nb 2 O 5 is an optional component that increases the refractive index of glass and can be expected to improve impact resistance and mechanical properties. On the other hand, if Nb 2 O 5 is too much, it tends to be devitrified, and the transmittance is lowered. In order to reduce the Abbe number, it is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less. is there.
  • La 2 O 3 is an optional component.
  • La 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjusting the optical constant, etc., but it is lost if the amount of La 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing La 2 O 3, preferably 10% or less, more preferably 8% or, more preferably not more than 5%.
  • Y 2 O 3 is an optional component.
  • Y 2 O 3 is a component that improves the refractive index of glass and can be expected to improve mechanical properties. However, if the amount of Y 2 O 3 is too large, it tends to be devitrified. Therefore, when they contain Y 2 O 3, preferably 5% or less, more preferably 3% or less.
  • Gd 2 O 3 is an optional component.
  • Gd 2 O 3 is a component that does not reduce the Abbe number for improving the refractive index of the glass, so it can be used for adjustment of the optical constant, etc., but it is lost if the amount of Gd 2 O 3 is too large. It becomes easy to see through, the specific gravity increases, and the impact resistance and mechanical properties are lowered. Therefore, if containing Gd 2 O 3, preferably 5% or less, more preferably 3% or less.
  • Ln 2 O 3 (Ln is at least one selected from the group consisting of Y, La, Gd, Yb, and Lu. That is, Ln 2 O 3 is La 2 O 3 + Y 2 O 3 + Gd 2 O 3 Is an optional component. Ln 2 O 3 is a component that improves the refractive index of the glass. However, if the amount of Ln 2 O 3 is too large, it tends to devitrify. Therefore, if containing Ln 2 O 3, preferably 10% or less, more preferably 5% or less.
  • Ta 2 O 5 is an optional component.
  • Ta 2 O 5 is a component that improves the refractive index of the glass. However, if the amount of Ta 2 O 5 is too large, it tends to devitrify and the specific gravity also increases. Therefore, if containing Ta 2 O 5, preferably 5% or less, more preferably 3% or less.
  • WO 3 is an optional component.
  • WO 3 is a component that improves the refractive index of the glass and improves the thermal stability of the glass. However, if the amount of WO 3 is too large, it tends to devitrify, reduce the Abbe number, and increase the specific gravity. . Therefore, if containing WO 3, preferably 5% or less, more preferably 3% or less.
  • TiO 2 + Nb 2 O 5 + WO 3 is 10% or less. If it exceeds 10%, the Abbe number becomes small. More preferably, it is 8% or less, More preferably, it is 5% or less.
  • the glass used for the strengthened lens of the third specification contains Bi 2 O 3 , TeO 2 , Sb 2 O 3 , SnO 2 , and F in addition to the above components in the same manner as the glass used for the strengthened lens of the first specification. May be.
  • the content ratio of these components can be the same as that of the glass used for the reinforced lens of the first specification including the preferred embodiment.
  • the reinforced lens of this invention can be manufactured by the method including the following process A and process B, for example.
  • Step A 30 to 65 mol% of SiO 2 , 10 mol% or more of Li 2 O, 0 to 10 mol% of SrO + BaO, and Li 2 O / (Li 2 O + Na 2 O + K 2 O) is 0.5 or more Mold glass into a lens molding.
  • Step B The lens molding is subjected to chemical strengthening treatment. Thereby, a reinforced lens excellent in impact resistance and mechanical properties is produced.
  • the chemical strengthening treatment can be performed by a conventionally known method. Specifically, the lens molding is brought into contact with a melt of an alkali metal salt containing an alkali metal ion having an ionic radius larger than that of the alkali metal ion in the lens molding by immersion or the like.
  • the reinforced lens of the present invention in which the metal ions having a small ion radius are replaced with the metal ions having a large ion radius only in the surface layer portion of the lens molding, and the surface layer portion is given compressive stress.
  • the chemical strengthening treatment of the lens molded body in the step B is a strengthened molten salt containing at least sodium nitrate, and the strengthened molten salt contains 25% or more of sodium nitrate in terms of mass%.
  • a strengthened molten salt containing 95% or more of sodium nitrate and potassium nitrate hereinafter referred to as “strengthened molten salt (X)”
  • the chemical strengthening treatment temperature is T (unit: ° C.)
  • the treatment time is t.
  • process B2 the chemical strengthening treatment process according to the production method of the present invention is referred to as process B2.
  • the lens molded body obtained in the above step A can be made into a strengthened lens with almost no change in shape.
  • the amount of change in the radius of curvature of the first main surface before and after the chemical strengthening treatment in the lens molded body having a predetermined shape can be set to 10 ⁇ m or less by the above method.
  • the amount of change is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • ⁇ Process A (Lens molding process)>
  • raw materials are weighed so as to have the predetermined glass composition and mixed uniformly.
  • the prepared mixture is put into a platinum crucible, a quartz crucible or an alumina crucible and roughly melted. Thereafter, it is placed in a gold crucible, platinum crucible, platinum alloy crucible or iridium crucible and melted at a temperature range of 1200 to 1400 ° C. for 2 to 10 hours, clarified and homogenized by degassing, stirring, etc.
  • a glass ingot or further molding is performed to produce a lens preform.
  • a lens molded body can be produced using means such as reheat press molding or precision press molding. That is, after the glass raw material is melted, a lens molded body is produced by a direct press method, or a preform for mold press molding is produced, and after the reheat press molding is performed on the preform, polishing is performed.
  • reheat press molding for example, by performing precision press molding on a preform produced by polishing, to produce a lens molded body, or by directly polishing from the optical glass ingot to form a lens
  • the body can be made.
  • the means for producing the lens molded body is not limited to these means.
  • the chemical strengthening treatment in the present invention is characterized in that sufficient impact resistance and mechanical properties can be obtained under chemical strengthening conditions in which the lens shape of the lens molded body obtained by molding does not change greatly, and the exchange of main alkali metal ions Is the replacement of Li + ions with Na + ions.
  • step B2 chemical strengthening treatment is performed using the strengthened molten salt (X) under conditions of a chemical strengthening treatment temperature T (unit: ° C.) and a treatment time t (unit: time) that satisfy the above formula (1). .
  • the strengthened molten salt (X) As the melt of the alkali metal salt used for the chemical strengthening treatment, the strengthened molten salt (X) is used. Unless otherwise specified, the content of each component is expressed as a percentage by mass with respect to the total amount of the strengthened molten salt (X).
  • Sodium nitrate is essential in the strengthened molten salt (X).
  • the content of sodium nitrate in the strengthened molten salt (X) is 25% or more.
  • the content of sodium nitrate is preferably 30% or more, more preferably 50% or more.
  • the upper limit of the content of sodium nitrate is 100%, preferably 95% or less, more preferably 90% or less.
  • Potassium nitrate is mainly strengthened because the rate at which K + in the molten molten salt (X) is ion exchanged with Li or Na in the glass is slower than the ion exchange between Li + ions and Na + ions. It is not an ion but an optional component. Potassium nitrate, the freezing point depression, lowering the melting point of the reinforcing molten salt (X), and as the lithium nitrate, is not that difficult and enhanced too much content, further Li + ions and Na + ions Since ion exchange, ion exchange of Na + ions and K + ions and mutual diffusion are promoted and strengthening can be promoted more than sodium nitrate single molten salt, they may be mixed.
  • the content of potassium nitrate in the reinforced molten salt (X) is preferably 10% or more, and more preferably 20% or more.
  • the content of potassium nitrate is 75% or less in relation to the content of sodium nitrate. If the content exceeds 75%, the ion exchange rate may be slow.
  • the content of potassium nitrate is preferably 70% or less, more preferably 50% or less.
  • the total amount of sodium nitrate and potassium nitrate is 95% or more.
  • the total amount is preferably 98% or more, more preferably 99% or more.
  • the strengthened molten salt (X) used for the chemical strengthening treatment of the lens molded body consists essentially of the above components, but may contain other components as required while maintaining the above essential composition range.
  • other components include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium sulfate, strontium sulfate, barium sulfate, calcium sulfate, strontium chloride, and barium chloride, and other alkali sulfates, alkali chlorides, and alkaline earths. Examples thereof include sulfates and alkaline earth chlorides.
  • the content of these other components in the strengthened molten salt (X) is 5% or less, preferably 1% or less. If it is in the said range, another component has an effect which prevents volatilization in melt
  • the heating temperature of the strengthened molten salt (X), that is, the chemical strengthening treatment temperature is T (unit: ° C.)
  • the immersion time of the lens molded body in the strengthened molten salt (X), that is, the processing time is
  • T and t are processes satisfying the above formula (1), that is, 30000 ⁇ T 1.8 ⁇ t 0.5 ⁇ 50000.
  • the lens molded body obtained by using the predetermined glass in the step A is subjected to a chemical strengthening treatment using a strengthened molten salt (X) under the conditions where T and t satisfy the above formula (1).
  • the reinforced lens obtained in this way is a reinforced lens that has sufficient impact resistance and has little shape change due to chemical strengthening treatment. That is, the lens is a reinforced lens that can be evaluated by the above method and has a falling ball strength of 80 cm or more and a change amount of the radius of curvature of the first main surface of 10 ⁇ m or less.
  • T 1.8 ⁇ t 0.5 In the reinforced lens obtained when T 1.8 ⁇ t 0.5 is 30000 or less, sufficient impact resistance and mechanical properties cannot be obtained. Further, if T 1.8 ⁇ t 0.5 is 50000 or more, the lens shape, particularly the radius of curvature of the first main surface, greatly changes.
  • the chemical strengthening treatment temperature T is preferably less than (Tg-100) ° C. of the glass constituting the lens molding. If the chemical strengthening treatment temperature T is (Tg-100) ° C. or more, there is a possibility that the strengthened lens of the present invention cannot be obtained without sufficient strengthening of the molded lens body even if ion exchange occurs due to stress relaxation. is there.
  • the treatment time t is preferably 0.25 hours or more. If it is less than 0.25 hours, when the immersion time is too short and a large number of lens molded bodies are arranged side by side and subjected to chemical strengthening treatment, unevenness may be caused in some places.
  • the chemical strengthening treatment step of the lens molded body in the step B2 may include the following (1) preheating step before the immersion treatment of the lens molded body in the reinforced molten salt (X). You may have the following (2) cooling and washing
  • a sample holder dedicated to the lens molded body is prepared, and the sample holder in which a large number of the lens molded bodies obtained in the process A are arranged is continuously used in the preheating furnace and the reinforced molten salt (X).
  • It may be a step in which a preheating step, a chemical strengthening treatment step, a cooling step, and a washing step are successively performed by passing through the filled strengthening tank, cooling tank, and washing tank.
  • the lens molded body is preheated so that the temperature of the lens molded body is equal to or higher than the melting point of the reinforced molten salt (X). It is preferable to keep it. This prevents solidification of the molten salt on the surface of the lens molded body when immersed in the reinforced molten salt (X), reduces the ion exchange rate, and uneven distribution in the glass surface of the surface layer portion to which compressive stress is applied. It is for suppressing becoming.
  • the preheating temperature of the lens molding is preferably less than 400 ° C, more preferably 350 ° C or less. If it is 400 ° C. or higher, the shape may change due to the influence of residual stress during preheating or due to nonuniformity of the glass in-plane temperature at the point of contact with the sample holder.
  • the reinforced lens of the present invention in which the lens molded body is immersed in the reinforced molten salt (X) under the above-described predetermined conditions to form a reinforced layer having a compressive stress applied to the lens molded body. can get.
  • the reinforced lens is usually pulled up from the reinforced molten salt (X) and gradually cooled.
  • the reinforced lens pulled up from the reinforced molten salt (X) is kept waiting for 30 seconds to 2 minutes, and after the tempered lens temperature becomes 300 ° C. or lower, the reinforced lens is brought into contact with the refrigerant. It is preferable to cool rapidly.
  • the cooling rate of the reinforced lens is preferably 100 ° C./min or more.
  • 4000 degrees C / min or less is preferable and 3000 degrees C / min or less is more preferable.
  • the reinforced molten salt (X) adhering to the reinforced lens also undergoes ion exchange only at the contact point in the cooling process, and the reinforced lens is given compressive stress. Since the in-plane distribution of the layers becomes non-uniform, the shape of the obtained reinforced lens, particularly the radius of curvature of the first main surface, may change significantly.
  • the shape of the reinforced lens may change significantly.
  • the reinforced lens may be broken by a heat shock. Further, the shape of the reinforced lens, particularly the radius of curvature of the first main surface, may change greatly.
  • the cleaning liquid is not particularly limited, but a cleaning liquid that has high solubility of the strengthened molten salt (X) and is suitable for cleaning the strengthened lens is selected. For example, in the case of washing in a continuous washing line of a plurality of tanks, after the ion exchange water and IPA (isopropyl alcohol) washing, a drying process is performed.
  • IPA isopropyl alcohol
  • a reinforced lens having sufficient impact resistance and little shape change due to chemical strengthening treatment can be obtained.
  • the first main surface and the second main surface of the reinforced lens are not re-polished after the chemical strengthening treatment step of the B2 step. This is because, according to the manufacturing method of the present invention, the shape of the reinforced lens is sufficiently stable even if the reinforced lens is not re-polished after the chemical strengthening treatment step of the B2 step.
  • the reinforcing lens side surface may be subjected to centering processing or the like as necessary.
  • the reinforced lens of the present invention may include an antireflection layer and / or an antifouling coating layer on at least one main surface of the first main surface and the second main surface.
  • the antireflection layer is provided in order to improve the transmittance by preventing reflection of light incident on the reinforced lens and to efficiently use incident light.
  • the antifouling coating layer can be expected to have functions such as improvement of surface hardness, scratch resistance, and wear resistance, as well as suppression of deterioration in image quality of the camera due to adhesion of dirt such as sebum oil, raindrops, and dust.
  • the reinforced lens produced as described above when the reinforced lens is a lens arranged closest to the subject side of the imaging lens and the first main surface is a main surface arranged on the subject side, at least the first main surface Preferably, an antireflection layer and an antifouling coating layer are formed.
  • the antireflection layer and the antifouling coating layer are usually provided in this order from the reinforced lens side. The same applies to the second main surface.
  • the types and forming methods of the constituent materials for the antireflection layer and antifouling coating layer are shown below.
  • the antireflection layer and the antifouling coating layer are formed by coating the first main surface and / or the second main surface of the reinforced lens obtained after the step B2.
  • Antireflection layer is formed by silica, titania, niobium oxide, tantalum pentoxide, yttria, nitridation formed by sputtering method, vacuum deposition method, ion beam method, ion plating method, plasma CVD method, etc.
  • the thickness of the antireflection layer is usually in the range of 100 to 600 nm.
  • the antireflection layer may be provided on the first main surface and the second main surface of the reinforced lens.
  • the antireflection layer preferably has a reflectance of 1% or less over, for example, 420 to 750 nm.
  • Antifouling coating layer is formed by sputtering, vacuum deposition, ion beam method, ion plating method, plasma CVD method or the like, titania, tin oxide, tungsten oxide, strontium titanate, etc. And a silicate-based, silicone-based, fluorinated methacrylate-based, or fluorine-containing organic compound film containing the photocatalytic metal fine particles formed by a sol-gel method, a coating method, or the like.
  • the thickness of the antifouling coating layer is in the range of 100 to 2000 nm.
  • the antifouling coating layer is not particularly required to be provided on the second main surface, but may be formed on the second main surface when formed by dip coating or the like among the application methods.
  • the reinforced lens produced in this way is useful for various camera applications, and in particular, it is suitably used for applications exposed to harsh environments such as an imaging lens used for a vehicle-mounted camera.
  • the reinforced lens of the present invention described above is a reinforced lens having high impact resistance, and is suitable for an imaging lens used for a vehicle-mounted camera exposed to a harsh environment. Further, according to the production method of the present invention, the lens is a reinforced lens having excellent impact resistance and mechanical properties, and also having good acid resistance and water resistance, and the shape does not change greatly even after chemical strengthening treatment. A lens can be obtained.
  • the raw materials were weighed so as to have chemical compositions shown in Tables 1 to 6 (mol% in terms of oxide).
  • high-purity raw materials used for ordinary lenses such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, and metaphosphate compounds are selected as raw materials for each component. Used.
  • the weighed raw materials are uniformly mixed, put in a platinum crucible with an internal volume of about 300 mL, melted at about 1400 ° C. for about 2 hours, stirred and kept at 1400 ° C. for 0.5 hour for clarification, and the temperature reaches about 650 ° C.
  • the glass was slowly cooled at about 0.5 ° C./min to obtain a glass of length 50 mm ⁇ width 100 mm ⁇ thickness 15 mm.
  • nitrate of NaNO 3 to KNO 3 is 100: 0 nitrate (hereinafter referred to as “100Na”), 75:25 nitrate (hereinafter referred to as “75Na25K”), 50:50 nitrate (hereinafter referred to as “100Na”).
  • “50Na50K”) and 0: 100 nitrate (hereinafter, “100K”) are prepared, heated to 400 ° C., and melted into melts of glass for 30 minutes each. Immersion and chemical strengthening treatment were performed to obtain an evaluation sample for CIL evaluation test. In addition, for 0: 100 nitrate, an evaluation sample for CIL evaluation test obtained by immersion for 4 hours was also prepared. The size of the obtained sample for evaluation was 20 mm ⁇ 20 mm ⁇ 2 mm (thickness).
  • the glass transition point (Tg), refractive index (nd), Abbe number ( ⁇ d), specific gravity (d), Young's modulus (E), devitrification temperature, water resistance (RW), acid resistance of the above glass are as follows. Sex (RA) was measured. Among these physical properties, the refractive index (nd), Abbe number ( ⁇ d), specific gravity (d), water resistance (RW), acid resistance (RA) are as described above when the reinforced lens after chemical strengthening is used. It is substantially the same as refractive index (nd), Abbe number ( ⁇ d), specific gravity (d), water resistance (RW), and acid resistance (RA).
  • the crack initiation load was measured as follows for the evaluation sample in which glass was molded into a plate shape and chemically strengthened.
  • the CIL of the reinforced lens refers to the CIL of the glass plate measured in this way.
  • Tg A glass sample processed into a cylindrical shape having a diameter of 5 mm and a length of 20 mm, and a temperature rising rate of 5 ° C./min by a thermal expansion method using a thermomechanical analyzer (trade name: TMA4000SA, manufactured by Bruker AXS) Measured with
  • Nd Glass was processed into a triangular prism having a side of 30 mm and a thickness of 10 mm, and measured with a refractometer (manufactured by Kalnew, instrument name: KPR-2000).
  • ⁇ nd: nd of a glass prism melted at 1200 to 1400 ° C. for 2 hours to obtain the triangular prism and a glass prism melted at the same temperature for 6 hours to obtain the triangular prism were measured by the above method, and the refraction Rate differences were evaluated.
  • ⁇ d (nd ⁇ 1) / (nF ⁇ nC).
  • Specific gravity The ratio between the mass of the glass sample and the mass of 4 ° C. pure water of the same volume under a pressure of 101.325 kPa (standard atmospheric pressure) is displayed as SG, and JIS Z8807 (1976, in liquid) It measured according to the measuring method to weigh.
  • RW Measured according to the measuring method (powder method) of chemical durability of JOGIS06-2008 optical glass. Specifically, when the glass was made into a glass powder having a diameter of 420 to 600 ⁇ m using an alumina mortar and pestle, the mass reduction ratio (%) when immersed in 80 mL of pure water at 100 ° C. for 1 hour was measured. If the mass reduction ratio is less than 0.05 (%), it is grade 1, if it is 0.05 or more and less than 0.10 (%), it is grade 2, and if it is 0.10 or more and less than 0.25 (%), it is grade 3, 0.25 or more and 0. Less than .60 (%) was grade 4, 0.60 or more and less than 1.10 (%), grade 5 and 1.10 (%) or more, grade 6.
  • RA Measured according to the measuring method (powder method) of chemical durability of JOGIS06-2008 optical glass. Specifically, when the glass was made into a glass powder having a diameter of 420 to 600 ⁇ m using an alumina mortar and pestle, the mass reduction ratio (%) when immersed in 80 mL of a 0.01 N nitric acid aqueous solution at 100 ° C. for 1 hour. ) was measured.
  • Grade 1 if the mass reduction rate is less than 0.20 (%), Grade 2 if it is less than 0.20 and less than 0.35 (%), Grade 3, if it is less than 0.35 and less than 0.65 (%), 0.65 or more and 1 Less than .20 (%), grade 4, 1.20 or more and less than 2.20 (%), grade 5, and 2.20 (%) or more, grade 6.
  • CIL measured by the method described above. When the CIL value was 2000 gf or more, it was expressed as “> 2000”.
  • CIL 100Na-05h the CIL of the glass plate after chemical strengthening treatment at 400 ° C. and 100Na for 30 minutes was expressed as CIL 100Na-05h . The conditions were similarly indicated for the CIL of the glass plate chemically treated under other conditions.
  • Tables 1 to 6 The results are shown in Tables 1 to 6 together with the glass composition.
  • Tables 1-6 Examples 1-31, 41-46 are Examples, Examples 32-35, 37-40 are Comparative Examples, and Example 36 is a Reference Example. “-” In the table means unmeasured.
  • the glass of Example 1 in the glass of Table 7, the glass of Example 1, 7, 16, 18, 23, 25, 42, 44 corresponding to the said Example, and the glass of Example 35, 36, 38 corresponding to a comparative example
  • the raw materials are weighed so as to have the chemical compositions shown in Tables 1 to 6, mixed in the same manner as described above, placed in a platinum crucible having an internal volume of about 700 mL, melted at 1200 to 1400 ° C. for about 6 hours, and stirred.
  • a lens molded body having a thickness of 3.5 mm was processed.
  • the shape of the lens molding was measured with a 3D measuring device (manufactured by KEYENCE, VR-3200).
  • the obtained lens molding was subjected to chemical strengthening treatment under various conditions shown in Table 7 to obtain a strengthened lens.
  • the chemical strengthening treatment includes nitrate with a mass% of NaNO 3 to KNO 3 of 75:25 (indicated as “75% NaNO 3 + 25% KNO 3 ” in Table 7), and nitrate of 0: 100 (in Table 7, “ 100% KNO 3 ”) was prepared, and strengthening was performed at the chemical strengthening treatment temperature T (unit: ° C.) and the treatment time t (unit: time) shown in Table 7.
  • Table 7 also shows T 1.8 ⁇ t 0.5 .
  • Example 7-C Using the glass of Example 7, Example 16, and Example 25, a lens molded body was obtained in the same manner as described above, and the obtained lens molded body was obtained by adding 400% at 30 ° C. with nitrate of NaNO 3 to KNO 3 of 75: 25% by mass. Reinforced lenses were obtained.
  • a total of 7 layers of SiO 2 and Si 3 N 4 are alternately laminated on the first main surface by a sputtering process to form an antireflection layer with a total thickness of 0.5 ⁇ m.
  • a reinforced lens with an antireflection layer was obtained.
  • the reflectance was 1% or less over 420 to 750 nm.
  • the falling ball strength was also evaluated for the three types of reinforced lenses with an antireflection layer. The results are shown in Table 7 in Example 7-C, Example 16-C, and Example 25-C.
  • Falling ball strength [cm] measured by the method described above.
  • Change in shape before and after chemical strengthening The amount of change [ ⁇ m] in the radius of curvature of the first principal surface of the molded lens and the strengthened lens was calculated by the method described above.
  • the glass in each Example are both the Li 2 O and containing at least 10 mol%, and Li 2 O / (Li 2 O + Na 2 O + K 2 O) ⁇ 0.5, SrO + BaO is less 10 mol%, SiO 2 30 Since it is ⁇ 65 mol%, CIL has a high strength of 100 gf or more.
  • CIL is any one of CIL 100Na-0.5h , CIL 75Na25K-0.5h , CIL 50Na50K-0.5h , that is, any of CIL of a glass plate chemically strengthened using reinforced molten salt (X). May be 100 gf or more.
  • Example 34 glass in which B 2 O 3 / Li 2 O greatly exceeds 0.75 has a high ⁇ nd of 0.003 or more and a process margin at the time of manufacture is narrow.
  • the strengthened lens using the glass of this example of Examples 1, 7, 16, 18, 23, 25, 42, 44 is nitrate (strengthened molten salt (X)) in which the mass% of NaNO 3 to KNO 3 is 75:25. ),
  • the falling ball strength is 80 cm or more even under the chemical strengthening condition at 400 ° C. for 30 minutes, and the shape change is suppressed to 10 ⁇ m or less.
  • the tempering time is extended or the tempering temperature is increased to 500 ° C. with the reinforced lens using the glass of Examples 7 and 16, the shape change becomes large. This is because T 1.8 ⁇ t 0.5 is out of the range of the production method of the present invention.
  • the falling ball strength is 80 cm or less in the chemical tempering treatment at 400 ° C. for 30 minutes.
  • the shape change is 10 ⁇ m or more, and it can be seen that the shape change is large despite the slow K ion strengthening speed.
  • the reinforced lens using the glass of Example 7 when the tempering time is extended to 4 hours at 100% KNO 3 and 400 ° C., the falling ball strength reaches 80 cm or more, but the shape change is further increased.
  • the processing time is such that the shape does not change greatly even when chemically strengthened. It can be seen that a reinforced lens having sufficiently high impact resistance and a high refractive index can be obtained.
  • Example 35 CIL is less than 100 gf.
  • Example 36 CIL 100K-4h is 100 gf or more, but any of CIL 100Na-0.5h , CIL 75Na25K-0.5h , and CIL 50Na50K-0.5h does not satisfy the condition of 100 gf or more.
  • the falling ball strength is 75% NaNO 3 + 25% KNO 3 strengthened molten salt or 100% KNO 3 strengthened molten salt at 400 ° C. for a strengthening time of 30 minutes.
  • the falling ball strength is more than 80 cm at 100% KNO 3 at 400 ° C. for 4 hours strengthening time, but the shape change due to strengthening is 10 ⁇ m. Become super.
  • the glass of Example 37 has Li 2 O / (Li 2 O + Na 2 O + K 2 O) of less than 0.5, the efficiency of chemical strengthening is poor, and the CIL is less than 100 gf, so the falling ball strength is less than 80 cm. It is guessed. In Examples 38 to 40, SrO + BaO is more than 10 mol%, the chemical strengthening efficiency is poor, and the CIL is less than 100 gf. Therefore, it is estimated that the falling ball strength is less than 80 cm. When the glass of Example 38 was made into a reinforced lens, it was a 75% NaNO 3 + 25% KNO 3 reinforced molten salt, and even when tempered at 400 ° C. for 30 minutes, the falling ball strength was as low as 10 cm.
  • the reinforced lens of the present invention is excellent in impact resistance, and has a strength that can sufficiently withstand harsh usage environments without deterioration in image quality when used for an imaging lens of an in-vehicle camera, for example. It is. Therefore, it is suitable for an imaging lens used for a vehicle-mounted camera that is exposed to a harsh environment. In addition to in-vehicle cameras, it is also suitable for applications such as robot vision sensors, surveillance cameras, and wearable cameras.
  • a reinforced lens having high impact resistance and suppressed shape change due to chemical strengthening treatment can be obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une lentille trempée présentant une résistance élevée aux chocs. L'invention concerne également un procédé de fabrication d'une lentille trempée présentant une résistance élevée aux chocs, un traitement de trempe chimique ne modifiant pas de manière significative la forme de la lentille. La lentille trempée est une lentille trempée chimiquement d'un corps moulé de lentille à partir d'un verre, le verre contenant 30 à 65 % molaire de SiO2, 10 % molaire ou plus de Li2O, et 0 à 10 % molaire de SrO+BaO, et Li2O/(Li2O+Na2O+K2O) est au moins de 0,5. Le procédé de fabrication d'une lentille trempée comprend les étapes consistant : à mouler un verre ayant la composition ci-dessus en un corps moulé de lentille ; et à réaliser un traitement de trempe chimique, dans des conditions répondant à une température de traitement et un temps de traitement prédéterminés, sur le corps moulé de lentille à l'aide d'un sel fondu trempé contenant au moins du nitrate de sodium, le sel fondu trempé contenant 25 % en masse ou plus de nitrate de sodium et 95 % en masse ou plus de nitrate de sodium et de nitrate de potassium.
PCT/JP2017/030245 2016-09-14 2017-08-24 Lentille trempée et procédé de fabrication de lentille trempée WO2018051754A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016179818 2016-09-14
JP2016-179818 2016-09-14

Publications (1)

Publication Number Publication Date
WO2018051754A1 true WO2018051754A1 (fr) 2018-03-22

Family

ID=61619187

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/030245 WO2018051754A1 (fr) 2016-09-14 2017-08-24 Lentille trempée et procédé de fabrication de lentille trempée

Country Status (1)

Country Link
WO (1) WO2018051754A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655322A (zh) * 2018-06-29 2020-01-07 Hoya株式会社 再加热压制用玻璃材料、再加热压制完成的玻璃材料、抛光完成的玻璃、及其制造方法
WO2021193176A1 (fr) * 2020-03-24 2021-09-30 株式会社 オハラ Verre optique renforcé chimiquement
CN115010363A (zh) * 2022-06-01 2022-09-06 河北光兴半导体技术有限公司 高折射率玻璃组合物和高折射率玻璃及其制备方法和应用
WO2023026715A1 (fr) * 2021-08-27 2023-03-02 株式会社 オハラ Verre optique renforcé chimiquement

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58145638A (ja) * 1982-02-20 1983-08-30 シヨツト・グラスヴエルケ 屈折率▲きごう▼１．５６、アツベ数▲きごう▼４０および密度▲きごう▼２．７０ｇ／ｃｍ↑３を有する光学および眼科用ガラス
JPS6364941A (ja) * 1986-09-05 1988-03-23 Nippon Sheet Glass Co Ltd 光集束性レンズ
JPS63288930A (ja) * 1987-05-22 1988-11-25 Canon Inc 屈折率分布型レンズ用ガラス組成物
JPH01133956A (ja) * 1987-11-20 1989-05-26 Canon Inc 屈折率分布型レンズ用ガラス組成物
JP2002121048A (ja) * 2000-10-11 2002-04-23 Nippon Sheet Glass Co Ltd 屈折率分布型レンズ用母材ガラス組成物
JP2004250279A (ja) * 2003-02-19 2004-09-09 Nippon Sheet Glass Co Ltd 屈折率分布型レンズ用母材ガラス組成物、それを用いた屈折率分布型レンズおよびその製造方法
JP2012240907A (ja) * 2011-05-24 2012-12-10 Ohara Inc 光学ガラス、プリフォーム及び光学素子
JP2015206880A (ja) * 2014-04-18 2015-11-19 旭硝子株式会社 光学素子、および光学素子の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58145638A (ja) * 1982-02-20 1983-08-30 シヨツト・グラスヴエルケ 屈折率▲きごう▼１．５６、アツベ数▲きごう▼４０および密度▲きごう▼２．７０ｇ／ｃｍ↑３を有する光学および眼科用ガラス
JPS6364941A (ja) * 1986-09-05 1988-03-23 Nippon Sheet Glass Co Ltd 光集束性レンズ
JPS63288930A (ja) * 1987-05-22 1988-11-25 Canon Inc 屈折率分布型レンズ用ガラス組成物
JPH01133956A (ja) * 1987-11-20 1989-05-26 Canon Inc 屈折率分布型レンズ用ガラス組成物
JP2002121048A (ja) * 2000-10-11 2002-04-23 Nippon Sheet Glass Co Ltd 屈折率分布型レンズ用母材ガラス組成物
JP2004250279A (ja) * 2003-02-19 2004-09-09 Nippon Sheet Glass Co Ltd 屈折率分布型レンズ用母材ガラス組成物、それを用いた屈折率分布型レンズおよびその製造方法
JP2012240907A (ja) * 2011-05-24 2012-12-10 Ohara Inc 光学ガラス、プリフォーム及び光学素子
JP2015206880A (ja) * 2014-04-18 2015-11-19 旭硝子株式会社 光学素子、および光学素子の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655322A (zh) * 2018-06-29 2020-01-07 Hoya株式会社 再加热压制用玻璃材料、再加热压制完成的玻璃材料、抛光完成的玻璃、及其制造方法
WO2021193176A1 (fr) * 2020-03-24 2021-09-30 株式会社 オハラ Verre optique renforcé chimiquement
WO2023026715A1 (fr) * 2021-08-27 2023-03-02 株式会社 オハラ Verre optique renforcé chimiquement
CN115010363A (zh) * 2022-06-01 2022-09-06 河北光兴半导体技术有限公司 高折射率玻璃组合物和高折射率玻璃及其制备方法和应用

Similar Documents

Publication Publication Date Title
JP6879215B2 (ja) 光学ガラス
US20210179479A1 (en) Optical glass and optical component
JP6321312B1 (ja) 光学ガラスおよび光学部品
JP6922741B2 (ja) 光学ガラス
CN107082562B (zh) 光学玻璃、光学元件以及精密加压成形用预成形品
WO2018051754A1 (fr) Lentille trempée et procédé de fabrication de lentille trempée
US11964904B2 (en) Glass substrate with antireflection film, and optical member
JP5445197B2 (ja) 近赤外線カットフィルタガラスおよび近赤外線カットフィルタガラスの製造方法
US20200325063A1 (en) Optical glass and optical member
JP5919595B2 (ja) 光学ガラス、光学素子およびプリフォーム
JP2010024101A (ja) 光学ガラス、ガラス成形体及び光学素子
JP2015094785A (ja) 光学素子
JP2002211947A (ja) 屈折率分布型レンズ用母材ガラス組成物
JPWO2019082616A1 (ja) 光学ガラス、光学部材およびウェアラブル機器
TW202400532A (zh) 光學玻璃及光學元件

Legal Events

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

Ref document number: 17850658

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 17850658

Country of ref document: EP

Kind code of ref document: A1