WO2018021221A1 - 光学ガラスおよび光学部品 - Google Patents
光学ガラスおよび光学部品 Download PDFInfo
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- WO2018021221A1 WO2018021221A1 PCT/JP2017/026639 JP2017026639W WO2018021221A1 WO 2018021221 A1 WO2018021221 A1 WO 2018021221A1 JP 2017026639 W JP2017026639 W JP 2017026639W WO 2018021221 A1 WO2018021221 A1 WO 2018021221A1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- 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
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- 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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0012—Arrays characterised by the manufacturing method
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- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/18—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical projection, e.g. combination of mirror and condenser and objective
Definitions
- the present invention relates to an optical glass and an optical component.
- Glasses used for wearable devices such as glasses with projectors, glasses-type and goggles-type displays, virtual reality augmented reality display devices, virtual image display devices, etc., widening the angle of images, increasing brightness and contrast, improving light guide characteristics, A high refractive index is required from the viewpoint of ease of processing of the diffraction grating.
- imaging glass lenses that are small and have a wide imaging angle of view have been used for applications such as in-vehicle cameras and robot vision sensors. Therefore, a high refractive index is required.
- optical glass used for the above-mentioned applications in order to make the user's wearing feeling preferable, automobiles and robots are required to be lightweight, and in order to reduce the weight of the entire apparatus, low density is required. . Furthermore, in consideration of use in an external environment, it is also important that there is little surface deterioration and alteration due to acid rain and chemicals such as detergents and waxes used in cleaning.
- glass lenses for in-vehicle use for example, by using a lens glass material for in-vehicle cameras having a predetermined acid resistance, an attempt is made to increase the refractive index and strength, and further improve the acid resistance and water resistance.
- Patent Document 1 For example, refer to Patent Document 1).
- glass that is formed into a plate shape may be used for wearable devices, and may be produced by a molding method such as a float method, a fusion method, or a roll-out method with high manufacturing efficiency.
- a molding method such as a float method, a fusion method, or a roll-out method with high manufacturing efficiency.
- the relationship between the manufacturing temperature and the viscosity of the glass is important.
- the visible light transmittance is also an important parameter, and in the case of a high refractive index glass, when it is melted at a high temperature, the visible light transmittance particularly on the short wavelength side may be lowered. When the viscosity curve is steep, it becomes difficult to control the viscosity in manufacturing.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide an optical glass having a high refractive index and a low density and good manufacturing characteristics.
- the optical component of the present invention uses the optical glass of the present invention.
- the optical glass of the present invention has a predetermined refractive index (n d ), density (d), and dissolution characteristics as described above. Each of these characteristics will be described in turn.
- the optical glass of the present invention has a high refractive index (n d ) in the range of 1.68 to 1.85. Since the refractive index (n d ) is 1.68 or more, the optical glass of the present invention is an optical glass used for wearable devices, widening the image, increasing the brightness and contrast, improving the light guide characteristics, and processing the diffraction grating. It is suitable in terms of ease.
- a small imaging glass lens having a wide imaging angle of view which is used for applications such as an in-vehicle camera and a robot vision sensor, is suitable for photographing a wider range.
- This refractive index (n d ) is preferably 1.70 or more, more preferably 1.73 or more, still more preferably 1.74 or more, and even more preferably 1.75 or more.
- glass having a refractive index (n d ) exceeding 1.85 tends to have a high density and a high devitrification temperature.
- This refractive index (n d ) is preferably 1.83 or less, more preferably 1.82 or less, still more preferably 1.81 or less, and still more preferably 1.80 or less.
- the optical glass of the present invention has a density (d) of 4.0 g / cm 3 or less.
- the density (d) of is preferably 3.8 g / cm 3 or less, more preferably 3.6 g / cm 3 or less, more preferably 3.5 g / cm 3 or less, still more preferably 3.4 g / cm 3 It is as follows.
- the density (d) is preferably 2.0 g / cm 3 or more in order to make it difficult to damage the glass surface. More preferably, it is 2.2 g / cm 3 or more, still more preferably 2.3 g / cm 3 or more, and still more preferably 2.4 g / cm 3 or more.
- T 2 are a reference temperature of solubility, the T 2 of the glass is too high, since it becomes necessary to dissolve at elevated temperature, in the case of the high refractive index glass, possibly especially visible light transmittance on the short wavelength side decreases is there.
- T 2 is preferably 1180 ° C. or lower, more preferably 1150 ° C. or lower, further preferably 1130 ° C. or lower, and still more preferably 1110 ° C. or lower.
- T 2 is preferably 970 ° C. or higher, more preferably 990 ° C. or higher, further preferably 1010 ° C. or higher, and still more preferably 1030 ° C. or higher.
- the optical glass of the present invention preferably has a devitrification temperature of 1200 ° C. or lower. With such characteristics, devitrification of the glass at the time of molding can be suppressed, and the moldability is good.
- This devitrification temperature is more preferably 1175 ° C. or less, further preferably 1150 ° C. or less, even more preferably 1125 ° C. or less, and particularly preferably 1100 ° C. or less.
- the devitrification temperature is the lowest temperature at which crystals having a long side or a long diameter of 1 ⁇ m or more are not observed on the glass surface and inside when the heated and melted glass is cooled by natural cooling.
- the glass of the present invention may have a lower transmittance on the shorter wavelength side than 400 nm by melting at a high temperature. is there.
- in-vehicle cameras and robot vision sensors sometimes use near-ultraviolet images to recognize objects that are difficult to distinguish with visible light, and the glass used in the optical system has transmittance in the near-ultraviolet region. Is required to be high. Therefore, when the optical glass of the present invention is a glass plate having a thickness of 1 mm, the light transmittance (T 360 ) at a wavelength of 360 nm is preferably 40% or more.
- T 360 is more preferably 50% or more, still more preferably 60% or more, still more preferably 65% or more, and particularly preferably 70% or more. T 360 can be measured, for example, using a spectrophotometer for glass plates obtained by mirror polishing both surfaces having a thickness of 1 mm.
- the Young's modulus (E) is preferably 60 GPa or more. With such characteristics, there is an advantage that there is little deflection when used in a wearable device as a thin glass plate, or when used as a lens in a vehicle-mounted camera, a robot vision sensor, or the like. In particular, when the light guide is attached to a frame of glasses or a display device, it is possible to prevent ghost phenomenon and distortion of images and videos.
- This E is more preferably 70 GPa or more, further preferably 80 GPa or more, still more preferably 85 GPa or more, and particularly preferably 90 GPa or more.
- the water resistance (RW) measured in accordance with the method of measuring chemical durability (powder method) of JOGIS06-2008 optical glass, which is the Japan Optical Glass Industry Association standard is preferably grade 2 or higher. .
- RW is measured as follows. For a glass powder having a particle size of 420 to 600 ⁇ m, a mass reduction ratio (%) 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.
- the acid resistance (RA) measured according to the chemical durability measurement method (powder method) of JOGIS06-2008 optical glass is preferably grade 1 or higher.
- RA is measured as follows. For a glass powder having a particle size 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.
- the glass transition point (Tg) is preferably in the range of 500 to 700 ° C. Since the optical glass of the present invention has Tg in the above-described range, the moldability in press molding and redraw molding is good.
- the Tg is more preferably 520 ° C. to 680 ° C., further preferably 540 ° C. to 660 ° C., still more preferably 560 ° C. to 640 ° C., and particularly preferably 570 ° C. to 620 ° C.
- Tg can be measured by, for example, a thermal expansion method.
- the optical glass of the present invention preferably has an Abbe number (v d ) of 50 or less.
- v d is more preferably 46 or less, still more preferably 42 or less, still more preferably 38 or less, and particularly preferably 34 or less.
- the lower limit of the Abbe number of the optical glass of the present invention is not particularly limited, but is generally about 10 or more, specifically 15 or more, and more specifically 20 or more.
- the thermal expansion coefficient ( ⁇ ) at 50 to 350 ° C. is preferably in the range of 50 to 150 ( ⁇ 10 ⁇ 7 / K). Since the optical glass of the present invention has ⁇ in the above-described range, expansion matching with peripheral members is good.
- This ⁇ is more preferably 60 to 135 ( ⁇ 10 ⁇ 7 / K), still more preferably 70 to 120 ( ⁇ 10 ⁇ 7 / K), still more preferably 80 to 105 ( ⁇ 10 ⁇ 7 / K). ), Particularly preferably 90 to 100 ( ⁇ 10 ⁇ 7 / K).
- the optical glass of the present invention is preferably a glass plate having a thickness of 0.01 to 2.0 mm. If the thickness is 0.01 mm or more, damage during handling or processing of the optical glass can be suppressed. Moreover, the deflection
- the area of one main surface is preferably 8 cm 2 or more. If this area is 8 cm 2 or more, a large number of optical elements can be arranged and productivity is improved. This area is more preferably 30 cm 2 or more, further preferably 170 cm 2 or more, still more preferably 300 cm 2 or more, and particularly preferably 1000 cm 2 or more. On the other hand, if the area is 6500 cm 2 or less, handling of the glass plate is facilitated, and breakage during handling or processing of the glass plate can be suppressed. The area is more preferably not 4500Cm 2 or less, further preferably not more 4000 cm 2 or less, more further preferably 3000 cm 2 or less, particularly preferably 2000 cm 2 or less.
- the LTV “Local Thickness Variation) at 25 cm 2 on one main surface is preferably 2 ⁇ m or less.
- a nanostructure having a desired shape can be formed on one main surface using an imprint technique or the like, and desired light guide characteristics can be obtained.
- the light guide can prevent a ghost phenomenon or distortion due to a difference in optical path length.
- the LTV is more preferably 1.8 ⁇ m or less, further preferably 1.6 ⁇ m or less, still more preferably 1.4 ⁇ m or less, and particularly preferably 1.2 ⁇ m or less.
- the warp is preferably 50 ⁇ m or less. If the warpage of the glass plate is 50 ⁇ m or less, a nanostructure having a desired shape can be formed on one main surface using an imprint technique or the like, and desired light guide characteristics can be obtained. When trying to obtain a plurality of light guides, a product with stable quality is obtained.
- the warp of the glass substrate is more preferably 40 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the warp is preferably 30 ⁇ m or less. If the warpage of the glass plate is 30 ⁇ m or less, a nanostructure having a desired shape can be formed on one main surface using an imprint technique or the like, and desired light guide characteristics can be obtained. When trying to obtain a plurality of light guides, a product with stable quality is obtained.
- the warp of the glass plate is more preferably 20 ⁇ m or less, further preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- FIG. 1 is a cross-sectional view when the optical glass of the present invention is a glass plate G1.
- “Warpage” refers to a reference line G1D of the glass plate G1 and the glass plate G1 in an arbitrary cross section passing through the center of the main surface G1F of the glass plate G1 and orthogonal to the main surface G1F of the glass plate G1.
- intersection line between the arbitrary cross section orthogonal to the main surface G1F of the glass plate G1 is defined as a bottom line G1A.
- An intersection line between the arbitrary cross section orthogonal to the other main surface G1G of the glass plate G1 is defined as an upper line G1B.
- the center line G1C is a line connecting the centers in the thickness direction of the glass plate G1. The center line G1C is calculated by obtaining a midpoint of the bottom line G1A and the top line G1B with respect to the laser irradiation direction described later.
- the reference line G1D is obtained as follows. First, the bottom line G1A is calculated based on a measurement method that cancels the influence of its own weight. A straight line is obtained from the bottom line G1A by the method of least squares. The obtained straight line is the reference line G1D. A known method is used as a measurement method for canceling the influence due to its own weight.
- one main surface G1F of the glass plate G1 is supported at three points, a laser is irradiated to the glass plate G1 by a laser displacement meter, the one main surface G1F of the glass plate G1 and another one from an arbitrary reference plane The height of the main surface G1G is measured.
- the glass plate G1 is inverted, three points of the other one main surface G1G opposite to the three points supporting the one main surface G1F are supported, and one glass substrate G1 from an arbitrary reference plane is supported.
- the heights of the main surface G1F and the other main surface G1G are measured. By calculating the average height of each measurement point before and after reversal, the influence of its own weight is cancelled.
- the height of one main surface G1F is measured as described above.
- the height of the other main surface G1G is measured at a position corresponding to the measurement point of the one main surface G1F.
- the height of the other main surface G1G is measured before inversion.
- the height of one main surface G1F is measured at a position corresponding to the measurement point of the other main surface G1G.
- the warpage is measured by, for example, a laser displacement meter.
- the surface roughness Ra of one main surface is preferably 2 nm or less.
- a nanostructure of a desired shape can be formed on one main surface using an imprint technique or the like, and desired light guide characteristics can be obtained.
- This Ra is more preferably 1.7 nm or less, still more preferably 1.4 nm or less, still more preferably 1.2 nm or less, and particularly preferably 1 nm or less.
- the surface roughness Ra is an arithmetic average roughness defined in JIS B0601 (2001). In this specification, it is the value which measured the area of 10 micrometers x 10 micrometers using atomic force microscope (AFM).
- the content ratio of each component is represented by mass% with respect to the total glass mass based on oxide.
- “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.
- composition satisfying the above-described characteristics in the optical glass of the present embodiment include Nb 2 O 5 : 5% to 55%, BaO, TiO 2 , ZrO 2 , WO 3 , and Ln in terms of mass% based on oxide.
- 0% to 30% of at least one selected from the group consisting of 2 O 3 (Ln is at least one selected from the group consisting of Y, La, Gd, Yb and Lu), SiO 2 : 29% to 50 %, Li 2 O + Na 2 O + K 2 O is 2% to 20%, and Li 2 O / (Li 2 O + Na 2 O + K 2 O) is 0.45 or less.
- another component can be contained as needed.
- Li 2 O + Na 2 O + K 2 O indicates the total amount of at least one alkali metal oxide component selected from the group consisting of Li 2 O, Na 2 O and K 2 O.
- Each component in this glass composition will be specifically described below.
- the optical glass of this invention is not limited to the composition of the following embodiment, as long as it has the above-mentioned characteristic.
- SiO 2 is a glass forming component, and is a component that imparts high strength and crack resistance to the glass and improves the stability and chemical durability of the glass.
- the content ratio of SiO 2 is 29% or more and 50% or less.
- the content of SiO 2 is 50% or less, can contain a component for obtaining a high refractive index.
- the content ratio of SiO 2 is preferably 31% or more, more preferably 32% or more, further preferably 33% or more, and particularly preferably 35% or more. Further, the content ratio of SiO 2 is preferably 45% or less, more preferably 42% or less, and further preferably 40% or less.
- Nb 2 O 5 is a component that increases the refractive index of the glass and decreases the Abbe number (v d ).
- the content ratio of Nb 2 O 5 is 5% or more and 55% or less. When the content ratio of Nb 2 O 5 is 5% or more, a high refractive index can be obtained.
- the content ratio of Nb 2 O 5 is preferably 15% or more, more preferably 25% or more, further preferably 35% or more, and particularly preferably 40% or more. Further, Nb 2 O 5 is easily watermarks too large loss. Therefore, 55% or less is preferable, 52% or less is more preferable, and 49% or less is more preferable.
- BaO, TiO 2 , ZrO 2 , WO 3 and Ln 2 O 3 are components that increase the refractive index of the glass. is there. The total content of these components is 0% or more and 30% or less.
- Nb 2 O 5 When Nb 2 O 5 is 15% or less, in order to increase the refractive index of the glass, Nb 2 O 5 and other high refractive index components as BaO, TiO 2 , ZrO 2 , WO 3 and Ln 2 O 3 are included. It is preferable to contain 1% or more of at least one selected from the group consisting of (Ln is at least one selected from the group consisting of Y, La, Gd, Yb and Lu). The content ratio of these components is more preferably 3% or more, still more preferably 5% or more, and particularly preferably 7% or more. On the other hand, when the other high refractive index components exceed 30%, devitrification is likely to occur. The content ratio of these components is more preferably 25% or less, still more preferably 20% or less, and particularly preferably 15% or less.
- Li 2 O + Na 2 O + K 2 O is preferably 4% or more, more preferably 6% or more, still more preferably 8% or more, and particularly preferably 10% or more. Further, Li 2 O + Na 2 O + K 2 O is preferably 18% or less, more preferably 16% or less, further preferably 14% or less, and particularly preferably 12% or less.
- Li 2 O is a component that improves the strength of the glass. 2 tends to be low and easily devitrified. Therefore, in the optical glass of the present embodiment, Li 2 O / (Li 2 O + Na 2 O + K 2 O) is 0.45 or less as a ratio value by mass% based on oxide. If Li 2 O / (Li 2 O + Na 2 O + K 2 O) is more than 0.45, T 2 tends to be low, devitrification tends to occur, and the easy moldability of the glass deteriorates. Li 2 O / (Li 2 O + Na 2 O + K 2 O) is more preferably 0.4 or less, further preferably 0.35 or less, and particularly preferably 0.3 or less.
- Li 2 O is an optional component, and is a component that improves the strength of glass, lowers T 2 , lowers Tg, and improves the meltability of glass.
- the content ratio of Li 2 O is 0% or more and 9% or less.
- strength (Kc) and crack resistance (CIL) can be improved.
- Li 2 O is liable watermarks too large loss.
- the optical glass of the present invention contains Li 2 O, the content ratio is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, and particularly preferably 3% or more.
- the content ratio of Li 2 O is preferably 8% or less, more preferably 7% or less, further preferably 6% or less, and particularly preferably 5% or less.
- the content ratio of Li 2 O is preferably 1.0% or more, more preferably 1.5% or more, further preferably 2.5% or more. 5% or more is particularly preferable.
- Na 2 O is an optional component that suppresses devitrification and lowers Tg.
- the content ratio of Na 2 O is 0% or more and 10% or less. When Na 2 O is contained, an excellent devitrification suppressing effect is obtained. On the other hand, Na 2 O is too large, strength and crack resistance tends to decrease.
- the content ratio is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, and particularly preferably 3% or more. Further, the content ratio of Na 2 O is preferably 9% or less, more preferably 8% or less, and further preferably 7% or less.
- the content ratio of Na 2 O is preferably 1.0% or more, more preferably 1.5% or more, further preferably 2.5% or more. 5% or more is particularly preferable.
- K 2 O is an optional component, a component that improves the meltability of glass, and a component that suppresses devitrification.
- the content ratio of K 2 O is 0% or more and 10% or less. When K 2 O is contained, the devitrification suppressing effect is improved. On the other hand, if there is too much K 2 O, the density tends to increase.
- the content ratio of K 2 O is preferably 0.3% or more, more preferably 0.5% or more, and further preferably 1% or more. Further, the content ratio of K 2 O is preferably 10% or less, more preferably 8% or less, and further preferably 6% or less.
- B 2 O 3 is an optional component.
- B 2 O 3 is a component that lowers Tg and improves mechanical properties such as strength and crack resistance of glass, but if the amount of B 2 O 3 is large, the refractive index tends to decrease. Therefore, the content ratio of B 2 O 3 is preferably 0% or more and 10% or less.
- the content ratio of B 2 O 3 is more preferably 8.5% or less, still more preferably 6.5% or less, and particularly preferably 5% or less. Further, the content ratio of B 2 O 3 is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- 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 content ratio of MgO is preferably 0% or more and 10% or less.
- the content ratio of MgO is more preferably 8% or less, and particularly preferably 6% or less.
- the content ratio of MgO is preferably 0.3% or more, more preferably 0.5% or more, and further preferably 1% or more.
- CaO is an optional component. CaO is a component that suppresses devitrification. However, if the amount of CaO is large, the crack resistance tends to decrease. Therefore, the content ratio of CaO is preferably 0% or more and 15% or less. The content ratio of CaO is more preferably 12% or less, and particularly preferably 10% or less. Further, the content ratio of CaO is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- SrO is an optional component.
- SrO is a component that improves the meltability of the glass, suppresses devitrification, and adjusts the optical constant of the glass. On the other hand, when the amount of SrO increases, devitrification is promoted. Therefore, the content ratio of SrO is preferably 0% or more and 15% or less.
- the content ratio of SrO is more preferably 12% or less, and particularly preferably 10% or less. Further, the content ratio of SrO is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- BaO is an optional component.
- BaO is a component that suppresses devitrification, but if the amount of BaO is large, the density tends to increase. Therefore, when BaO is contained, 0% or more and 15% or less are preferable.
- the content ratio of BaO is more preferably 10% or less, further preferably 8% or less, and particularly preferably 6% or less. Further, the content ratio of BaO is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- Al 2 O 3 is an optional component.
- Al 2 O 3 is a component that improves chemical durability, but when the amount of Al 2 O 3 increases, the glass tends to devitrify. Therefore, the content ratio of Al 2 O 3 is preferably 0% or more and 5% or less.
- the content ratio of Al 2 O 3 is more preferably 3% or less, and particularly preferably 2% or less. Further, the content ratio of Al 2 O 3 is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- TiO 2 is an optional component, and is a component that increases the refractive index of the glass and increases the dispersion of the glass. Further, by containing TiO 2, it is possible to improve the refractive index. On the other hand, when TiO 2 is too much, it is easy to be colored and the transmittance is lowered. Therefore, the content ratio of TiO 2 is preferably 0% or more and 15% or less. When TiO 2 is contained, the content ratio is more preferably 0.5% or more, further preferably 1% or more, and particularly preferably 1.5% or more. Further, the content ratio of TiO 2 is more preferably 12% or less, further preferably 10% or less, and particularly preferably 8% or less.
- WO 3 is an optional component. Addition of WO 3 suppresses the devitrification of the glass. However, if the amount of WO 3 is too large, the glass tends to be devitrified. Therefore, the content ratio of WO 3 is preferably 0% or more and 15% or less. The content ratio of WO 3 is more preferably 12% or less, further preferably 9% or less, and particularly preferably 5% or less. Further, the content ratio of WO 3 is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% 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. By containing ZrO 2 , crack resistance can be improved. On the other hand, if the ZrO 2 is too large, it tends to be devitrified. Therefore, the content ratio of ZrO 2 is preferably 0% or more and 15% or less. When ZrO 2 is contained, the content ratio is more preferably 0.5% or more, further preferably 1% or more, and particularly preferably 2% or more. The content ratio of ZrO 2 is more preferably 15% or less, further preferably 12% or less, and particularly preferably 10% or less.
- ZnO is an optional component and is a component that improves mechanical properties such as strength and crack resistance of glass.
- the content rate is 0-15%.
- the content ratio of ZnO is more preferably 13% or less, further preferably 12% or less, and particularly preferably 10% or less. Further, the content ratio of ZnO is more preferably 0.3% or more, further preferably 0.5% or more, and particularly preferably 1% or more.
- La 2 O 3 is an optional component.
- La 2 O 3 is a component that improves the refractive index of the glass, but if the amount of La 2 O 3 is too large, the mechanical properties are lowered. Therefore, the content ratio of La 2 O 3 is preferably 0% or more and 12% or less. The content ratio of La 2 O 3 is more preferably 10% or less, and further preferably 8% or less. It is preferable that La 2 O 3 is not substantially contained.
- Ln 2 O 3 (Ln is one or more selected from the group consisting of Y, La, Gd, Yb, and Lu) improves the refractive index of the glass.
- Ln 2 O 3 is preferably 15% or less in total, more preferably 10% or less, and particularly preferably 7% or less. It is preferable that Ln 2 O 3 is not substantially contained.
- the optical glass of this embodiment contains at least one of Sb 2 O 3 and SnO 2 .
- Sb 2 O 3 and SnO 2 are not essential components, they can be added for the purpose of adjusting refractive index characteristics, improving meltability, suppressing coloring, improving transmittance, clarifying, and improving chemical durability.
- the total is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less.
- the optical glass of this embodiment contains F.
- F is not essential, it can be added for the purpose of improving solubility, improving transmittance, and improving clarity. When it contains F, 5% or less is preferable and 3% or less is more preferable.
- the optical glass of the present embodiment containing an alkali metal oxide of Li 2 O or Na 2 O is chemically converted by replacing Li ions with Na ions or K ions and Na ions with K ions.
- the optical glass of the present invention is produced, for example, as follows. That is, first, 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. Then put in a gold crucible, platinum crucible, platinum alloy crucible, reinforced platinum crucible or iridium crucible and melt for 2-10 hours at a temperature range of 1200-1400 ° C, homogenize by defoaming, stirring, etc. After that, it is cast into a mold and slowly cooled. Thereby, the optical glass of the present invention is obtained.
- this optical glass can be made into a glass plate by forming molten glass into a plate shape by a molding method such as a float method, a fusion method, or a roll-out method.
- a glass molded object can be produced using means, such as reheat press molding and precision press molding, for example. That is, a lens preform for mold press molding is manufactured from optical glass, and after reheat press molding is performed on the lens preform, a polishing process is performed to manufacture a glass molded body, or a polishing process is performed, for example.
- the glass preform can be produced by precision press-molding the lens preform.
- the means for producing the glass molded body is not limited to these means.
- Residual bubbles of the optical glass of the present invention produced as described above are preferably 10 (10 pieces / kg) or less per kg, more preferably 7 pieces / kg or less, further preferably 5 pieces / kg or less. Part / kg or less is particularly preferable.
- the glass plate is formed by the above-described method, a glass plate free from bubbles can be efficiently formed as long as the residual bubbles are 10 / kg or less.
- the diameter of the circle of the minimum size in which the residual bubbles are enclosed is the individual size of the residual bubbles
- the individual size of the residual bubbles is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 40 ⁇ m or less. 20 ⁇ m or less is particularly preferable.
- L 2 / L 1 is preferably 0.90 or more, more preferably 0.92 or more, and further preferably 0.95 or more.
- L 2 / L 1 is 0.90 or more, the residual bubbles are in a state close to a perfect circle (true sphere), and even if residual bubbles are included, the glass is less than the elliptical residual bubbles.
- the anisotropic scattering of light incident on the glass plate can be suppressed as compared with elliptical residual bubbles.
- the size and shape of the residual bubbles can be obtained from values measured by a laser microscope (manufactured by Keyence Corporation: VK-X100).
- Optical members such as glass plates and glass molded articles produced in this way are useful for various optical elements.
- wearable devices such as glasses with projectors, glasses and goggles
- Light guides used in displays, virtual reality augmented reality display devices, virtual image display devices, filters, lenses, etc.
- Lenses and cover glasses used in in-vehicle cameras, robot vision sensors, etc. .
- it is also suitably used for applications such as an organic EL glass substrate, a wafer level lens array substrate, a lens unit substrate, a lens forming substrate by etching, and an optical waveguide.
- the optical glass of the present embodiment described above has a high refractive index and a low density and good manufacturing characteristics, and is suitable as an optical glass for wearable devices, in-vehicle use, and robot mounting.
- the raw materials were weighed so as to have chemical compositions (mass% in terms of oxide) shown in Tables 1 to 7.
- the raw materials are all high-purity raw materials used for ordinary optical glass such as oxides, hydroxides, carbonates, nitrates, fluorides, hydroxides, and metaphosphate compounds corresponding to the raw materials of each component. Selected and used.
- R 2 O represents the total content of Li 2 O, Na 2 O, and K 2 O.
- Refractive index (n d ) Sample 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). Density (d): Measured according to JIS Z8807 (1976, measurement method for weighing in liquid). Devitrification temperature: About 5 g of a sample was put in a platinum dish, and each sample was held for 1 hour in increments of 10 ° C. from 1000 ° C. to 1400 ° C. After cooling by natural cooling, the presence or absence of crystal precipitation was observed with a microscope. The lowest temperature at which crystals having a long side or long diameter of 1 ⁇ m or more were not recognized was defined as the devitrification temperature.
- Glass transition point (Tg) A value measured using a differential thermal dilatometer (TMA), and determined according to JIS R3103-3 (2001).
- RW Water resistance
- Grade 1 if the mass reduction ratio is less than 0.05%
- Grade 2 if it is 0.05% or more and less than 0.10%
- Grade 3 if it is 0.10% or more and less than 0.25%
- Grade 0.25% or more and 0.60% Less than grade 4, graded 0.60% or more and less than 1.10%, grade 5 and grade 1.6% or more grade 6.
- Acid resistance Measured according to the measuring method (powder method) of chemical durability of JOGIS06-2008 optical glass. Specifically, the mass reduction rate (%) of a glass powder having a particle size of 420 to 600 ⁇ m 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 rate of mass reduction is less than 0.20%, Grade 2 if it is 0.20% or more and less than 0.35%, Grade 3, if it is 0.35% or more and less than 0.65%, Grade 3, 0.65% or more and 1.20% Less than 4.20% or more and less than 2.20%, and grade 6 and above 2.20%.
- LTV The thickness of the glass substrate was measured with a non-contact laser displacement meter (Nanometro manufactured by Kuroda Seiko Co., Ltd.) for a plate-like sample of 50 mm ⁇ 50 mm ⁇ 1 mm at intervals of 3 mm, and LTV was calculated.
- Warpage The height of the two main surfaces of the glass substrate was measured with a non-contact laser displacement meter (Nanometro, manufactured by Kuroda Seiko Co., Ltd.) for a disk-shaped sample having a diameter of 8 inches ⁇ 1 mm and a diameter of 6 inches ⁇ 1 mm at intervals of 3 mm. The warpage was calculated by the method described above with reference to FIG.
- Ra Surface roughness
- Abbe number ( ⁇ d ): Calculated by ⁇ d (n d ⁇ 1) / (n F ⁇ n C ) using the sample used for the refractive index measurement.
- n d is the helium d line
- n F is the hydrogen F line
- n C is the refractive index for the hydrogen C line.
- Thermal expansion coefficient ( ⁇ ) The linear thermal expansion coefficient in the range of 30 to 350 ° C. is measured using a differential thermal dilatometer (TMA), and the average linear thermal expansion coefficient in the range of 30 to 350 ° C. is measured according to JIS R3102 (1995). Asked.
- the light transmittance (T 360 ) at a wavelength of 360 nm is low. Since the glass of Example 64 has Nb 2 O 5 of more than 55%, the refractive index (n d ) is higher than 1.85, the devitrification temperature is higher than 1200 ° C., and the moldability is poor.
- the optical glass obtained from the glass in which the glass composition of each of the above Examples (Examples 1 to 56) is melted has no residual bubbles or has one or two residual bubbles having a size of 14 ⁇ m to 54 ⁇ m. included.
- the aspect ratio (L 2 / L 1 ) of the residual bubbles is approximately 0.9 or more, and includes those having a ratio of 1.0. As described above, even the optical glass containing residual bubbles has a small size and a small number, so that a glass plate free from defects such as bubbles, foreign matter, striae, and phase separation can be obtained.
- an optical glass having an LTV value of 2 ⁇ m or less, a warp value (round glass plate having a diameter of 6 inches) of 30 ⁇ m or less, and an Ra value of 2 nm or less can be obtained. It can. Furthermore, when the water resistance (RW) rating is grade 2 or higher and the acid resistance (RA) rating is grade 1 or higher, surface degradation during polishing or cleaning can be avoided, so the LTV value is 1. It is considered that the warp value (circular glass plate having a diameter of 6 inches) is 18 ⁇ m or less and the Ra value is 1 nm or less.
- the LTV values were 1.1, 1.4, 1.3 ⁇ m
- the warpage values were 45, 36, 42
- Ra values were 0.276, 0.358, 0.362 were obtained. Therefore, an optical glass having an LTV value of 2 ⁇ m or less, a warp value of 50 ⁇ m or less, and an Ra value of 2 nm or less can be obtained by precisely polishing a glass plate that does not have the above-described drawbacks of the embodiments of the present invention.
- the glass can be immersed in a melt obtained by heating and melting sodium nitrate salt at 400 ° C. for 30 minutes and subjected to a chemical strengthening treatment to obtain a strengthened glass.
- the optical glass of the present invention has a high refractive index and a low density and good manufacturing characteristics, and is suitable as an optical glass for wearable devices, in-vehicle use, robot mounting, and the like.
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Abstract
Description
さらに光学部品として用いられる場合、可視光透過率も重要なパラメータであり、高屈折率ガラスの場合、高い温度で溶解すると、特に短波長側の可視光透過率が低下するおそれがあり、一方で粘性カーブが急峻であると、製造するにあたり粘性の制御が困難になる。
本発明の光学部品は、本発明の光学ガラスを用いたことを特徴とする。
本発明の光学ガラスは1.68~1.85の範囲の高い屈折率(nd)を有する。屈折率(nd)が1.68以上であるので、本発明の光学ガラスは、ウェアラブル機器に用いる光学ガラスとして画像の広角化、高輝度・高コントラスト化、導光特性向上、回折格子の加工容易性などの面で好適である。また車載用カメラ、ロボット用視覚センサーなどの用途に用いられる小型で撮像画角の広い撮像ガラスレンズとしては、より小型で広い範囲を撮影するために好適である。この屈折率(nd)は好ましくは、1.70以上であり、より好ましくは1.73以上、さらに好ましくは1.74以上、よりさらに好ましくは1.75以上である。
一方で屈折率(nd)が1.85を超えるガラスは密度が高くなりやすく、また失透温度が高くなりやすい傾向がある。この屈折率(nd)は好ましくは、1.83以下であり、より好ましくは1.82以下、さらに好ましくは1.81以下、よりさらに好ましくは1.80以下である。
一方で本発明の光学ガラスにおいて、ガラス表面に傷を付けにくくするためには、密度(d)は、2.0g/cm3以上が好ましい。より好ましくは2.2g/cm3以上、さらに好ましくは2.3g/cm3以上であり、よりさらに好ましくは2.4g/cm3以上である。
一方でT2が低すぎると、粘性カーブが急峻になり、製造するにあたり粘性の制御が困難になる問題がある。本発明の光学ガラスは、上記した範囲のT2を有することで、製造特性を良好にできる。このT2は好ましくは、970℃以上であり、より好ましくは990℃以上、さらに好ましくは1010℃以上、よりさらに好ましくは1030℃以上である。
本発明の光学ガラスのアッベ数の下限は特に限定しないが、概ね10以上、具体的には15以上、より具体的には20以上であることが多い。
反転前後における各測定点の高さの平均を求めることで自重による影響がキャンセルされる。例えば、反転前に、上述のとおり、一の主表面G1Fの高さを測定する。ガラス板G1を反転後、一の主表面G1Fの測定点に対応する位置で、他の一の主表面G1Gの高さを測定する。同様に、反転前に、他の一の主表面G1Gの高さを測定する。ガラス板G1を反転後、他の一の主表面G1Gの測定点に対応する位置で、一の主表面G1Fの高さを測定する。
反りは、例えば、レーザ変位計により測定される。
次に、本発明の光学ガラスが含有し得る各成分の組成範囲の一実施形態について詳細に説明する。本明細書において、各成分の含有割合は、特に断りのない限り、酸化物基準のガラス全質量に対する質量%で示す。また、本発明の光学ガラスにおいて、「実質的に含有しない」とは、不可避不純物を除き含有しないことを意味する。不可避不純物の含有量は、本発明において0.1%以下である。
このガラス組成における各成分について、以下具体的に説明する。なお、本発明の光学ガラスは、上記した特性を有する限り、下記実施形態の組成に限定されない。
また、Nb2O5は、多すぎると失透し易くなる。そのため、55%以下が好ましく、52%以下がより好ましく、49%以下がさらに好ましい。
本実施形態の光学ガラスを化学強化する場合には、Li2Oの含有割合は、1.0%以上が好ましく、1.5%以上がより好ましく、2.5%以上がさらに好ましく、3.5%以上が特に好ましい。
本実施形態の光学ガラスを化学強化する場合には,Na2Oの含有割合は、1.0%以上が好ましく、1.5%以上がより好ましく、2.5%以上がさらに好ましく、3.5%以上が特に好ましい。
本発明の光学ガラスは、例えば以下のように製造される。すなわち、まず、上記所定のガラス組成となるように原料を秤量し、均一に混合する。作製した混合物を白金坩堝、石英坩堝又はアルミナ坩堝に投入して粗溶融する。その後、金坩堝、白金坩堝、白金合金坩堝、強化白金坩堝又はイリジウム坩堝に入れて1200~1400℃の温度範囲で2~10時間溶融し、脱泡、撹拌などにより均質化して泡切れ等を行った後、金型に鋳込んで徐冷する。これにより本発明の光学ガラスが得られる。
上記で得られた各サンプルについて、屈折率(nd)、密度(d)、失透温度、粘度(粘度ηがlogη=2となる温度T2)、厚さ1mmのガラス板にしたときの波長360nmにおける光の透過率(T360)、耐水性(RW)、耐酸性(RA)を次のように測定した。得られた結果を表1~7に併せて示した。
密度(d):JIS Z8807(1976、液中で秤量する測定方法)に準じて測定した。
失透温度:白金皿にサンプル約5gを入れ、1000℃~1400℃まで10℃刻みにてそれぞれ1時間保持したものを自然放冷により冷却した後、結晶析出の有無を顕微鏡により観察して、長辺又は長径で1μm以上の結晶の認められない最低温度を失透温度とした。
光透過率(T360):10mm×30mm×厚さ1mmの板状に加工し、両表面を鏡面研磨したサンプルについて、分光光度計(日立ハイテクノロジーズ社製 U-4100)で波長360nmにおける光の透過率を測定した。
ヤング率(E):20mm×20mm×1mmの板状のサンプルについて、超音波精密板厚計(OLYMPAS社製、MODEL 38DL PLUS)を用いて測定した(単位:GPa)。
反り:ガラス基板の2つの主表面の高さを非接触レーザ変位計(黒田精工製ナノメトロ)により、直径8インチ×1mmおよび直径6インチ×1mmの円板状のサンプルについて、3mm間隔で測定し、図1を参照して説明した上記方法により反りを算出した。
表面粗さ(Ra):20mm×20mm×1mmの板状のサンプルについて、10μm×10μmのエリアを、原子間力顕微鏡(AFM)(オクスフォードインストゥルメンツ社製)を用いて測定した値である。
アッベ数(νd):上記屈折率測定に使用したサンプルを用いて、νd=(nd-1)/(nF-nC)により算出する。ndはヘリウムd線、nFは水素F線、およびnCは水素C線に対する屈折率である。これらの屈折率も上記した屈折率計を使用して測定した。
熱膨張係数(α):示差熱膨張計(TMA)を用いて30~350℃の範囲における線熱膨張係数測定し、JIS R3102(1995年)により30~350℃の範囲における平均線熱膨張係数を求めた。
Claims (15)
- 屈折率(nd)が1.68~1.85、
密度(d)が4.0g/cm3以下、
かつガラスの粘性がlogη=2となる温度T2が950~1200℃であることを特徴とする光学ガラス。 - 酸化物基準の質量%表示で、
Nb2O5: 5%~55%、
BaO、TiO2、ZrO2、WO3、およびLn2O3(LnはY、La、Gd、YbおよびLuからなる群から選ばれる少なくとも1種である)からなる群から選ばれる少なくとも1種を0%~30%、
SiO2: 29%~50%、
Li2O+Na2O+K2Oが2%~20%であり、
Li2O/(Li2O+Na2O+K2O)が0.45以下である請求項1に記載の光学ガラス。 - 酸化物基準の質量%表示で、
B2O3: 0%~10%、
MgO: 0%~10%、
CaO: 0%~15%、
SrO: 0%~15%、
BaO: 0%~15%、
Li2O: 0%~9%、
Na2O: 0%~10%、
K2O: 0%~10%、
Al2O3: 0%~5%、
TiO2: 0%~15%、
WO3: 0%~15%、
ZrO2: 0%~15%、
ZnO: 0%~15%、
La2O3: 0%~12%、
を含有する請求項2に記載の光学ガラス。 - 失透温度が1200℃以下である、請求項1~3のいずれか1項に記載の光学ガラス。
- 厚さ1mmのガラス板にしたときの、波長360nmにおける光の透過率(T360)が40%以上である、請求項1~4のいずれか1項に記載の光学ガラス。
- ヤング率(E)が60GPa以上である、請求項1~5のいずれか1項に記載の光学ガラス。
- 日本光学硝子工業会規格に準拠して測定される耐水性が等級2以上であり、耐酸性が等級1以上である、請求項1~6のいずれか1項に記載の光学ガラス。
- ガラス転移点(Tg)が500~700℃、アッベ数(vd)が50以下、50~350℃での熱膨張係数αが50~150×10-7/Kである、請求項1~7のいずれか1項に記載の光学ガラス。
- 板厚が0.01~2mmの板状であることを特徴とする請求項1~8のいずれか1項に記載の光学ガラス。
- 一の主表面の面積が8cm2以上である請求項1~9のいずれか1項に記載の光学ガラス。
- 対向する主表面は両面に研磨が施され、一の主表面の面積が25cm2のガラス板としたとき、そのガラス基板のLTVが2μm以下である請求項1~10のいずれか1項に記載の光学ガラス。
- 直径8インチの円形のガラス板としたとき、一の主表面の反りが50μm以下である請求項1~11のいずれか1項に記載の光学ガラス。
- 表面粗さRaが2nm以下である請求項1~12のいずれか1項に記載の光学ガラス。
- 請求項9~13のいずれか1項に記載の板状の光学ガラスを有することを特徴とする光学部品。
- 前記板状の光学ガラスの表面に反射防止膜を有する請求項14に記載の光学部品。
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US (2) | US20180141851A1 (ja) |
JP (2) | JP6321312B1 (ja) |
KR (1) | KR20190038484A (ja) |
CN (1) | CN109476529A (ja) |
TW (1) | TW201808846A (ja) |
WO (1) | WO2018021221A1 (ja) |
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Also Published As
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US20180141851A1 (en) | 2018-05-24 |
TW201808846A (zh) | 2018-03-16 |
JPWO2018021221A1 (ja) | 2018-07-26 |
JP6321312B1 (ja) | 2018-05-09 |
KR20190038484A (ko) | 2019-04-08 |
CN109476529A (zh) | 2019-03-15 |
JP2018118904A (ja) | 2018-08-02 |
US20180194671A1 (en) | 2018-07-12 |
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