JP6315305B2 - Glass laminate and optical imaging member using the same - Google Patents

Glass laminate and optical imaging member using the same Download PDF

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Publication number
JP6315305B2
JP6315305B2 JP2013229202A JP2013229202A JP6315305B2 JP 6315305 B2 JP6315305 B2 JP 6315305B2 JP 2013229202 A JP2013229202 A JP 2013229202A JP 2013229202 A JP2013229202 A JP 2013229202A JP 6315305 B2 JP6315305 B2 JP 6315305B2
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glass
less
film
laminate
laminated
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JP2015083527A (en
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隆 村田
隆 村田
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日本電気硝子株式会社
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Priority to JP2013194730 priority
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/09Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C27/00Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06Joining glass to glass by processes other than fusing
    • C03C27/10Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B17/00Systems with reflecting surfaces, with or without refracting elements
    • G02B17/002Arrays of reflective systems
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B17/00Systems with reflecting surfaces, with or without refracting elements
    • G02B17/006Systems in which light light is reflected on a plurality of parallel surfaces, e.g. louvre mirrors, total internal reflection [TIR] lenses
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23DPLANING; SLOTTING; SHEARING; BROACHING; SAWING; FILING; SCRAPING; LIKE OPERATIONS FOR WORKING METAL BY REMOVING MATERIAL, NOT OTHERWISE PROVIDED FOR
    • B23D57/00Sawing machines or sawing devices not covered by one of the preceding groups B23D45/00 - B23D55/00
    • B23D57/003Sawing machines or sawing devices working with saw wires, characterised only by constructional features of particular parts
    • B23D57/0061Sawing machines or sawing devices working with saw wires, characterised only by constructional features of particular parts of devices for guiding or feeding saw wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/055 or more layers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors

Description

  The present invention relates to a glass laminate, an optical imaging member, a method for producing a glass laminate, and a method for producing an optical imaging member. For example, the light generated from a flat panel display such as a liquid crystal display or an organic EL display is hollowed out. The present invention relates to a glass laminate for imaging, an optical imaging member, a method for producing a glass laminate, and a method for producing an optical imaging member.

  As is well known, from the viewpoint of space saving, flat panel displays such as liquid crystal displays, plasma displays, and organic EL displays are widely used.

  In addition, technology development is progressing to form a hollow image of light generated from a flat panel display. Patent Document 1 proposes an optical imaging member in which a plurality of double-sided reflection bands are arranged at regular intervals so that adjacent reflecting surfaces face each other. However, the optical imaging member described in Patent Document 1 has a problem that it does not necessarily converge to one point after scattered light has passed.

JP 58-21702 A

  In order to solve the above problem, after laminating a large number of transparent plates whose one surface is a reflection surface, the substrate is cut so that a cut surface perpendicular to each reflection surface is formed. An optical imaging member that has been fabricated and closely contacted so that the reflective surface formed on the other laminate is perpendicular to the reflective surface formed on one laminate is studied. ing. In this optical imaging member, the thickness of the transparent plate corresponds to the interval between the reflecting surfaces.

  In the case of the above-mentioned optical imaging member, in order to obtain high-resolution imaging, it is necessary to make the thickness of the transparent plate uniform, but it is difficult to produce such a transparent plate and the cost increases. It was a factor of.

  The present invention has been made in view of the above circumstances, and can create a high-resolution image by creating a laminate that can narrow and uniformize the interval between the reflecting surfaces without causing an increase in cost. An optical imaging member is obtained.

  As a result of diligent efforts, the present inventor can solve the above technical problem by applying a glass laminate in which a reflective film is interposed between glass films and integrating them to an optical imaging member. It is discovered and proposed as the present invention. That is, the glass laminate of the present invention is a glass laminate in which glass films having a thickness of 500 μm or less are laminated, and has a reflective film between the glass films.

  As for the glass laminated body of this invention, the thickness of a glass film is 500 micrometers or less. In this way, since the interval between the reflective films is narrowed, it becomes easy to obtain high resolution imaging. Furthermore, since the glass film can easily improve the surface smoothness and reduce variations in thickness, it is possible to accurately form a reflective film on the surface and to properly perform lamination and integration. Thereby, the space | interval of a reflective surface can be narrowed and equalized, without causing a cost increase.

  Secondly, it is preferable that the glass laminated body of this invention has the strip-shaped glass film laminated | stacked. If it does in this way, it will become easy to apply to an optical image formation member. Here, the “strip-shaped glass film” refers to a glass film having a length dimension / width dimension ratio of 5 or more. The “length dimension” indicates the longer one of the vertical dimension and the horizontal dimension, and the “width dimension” indicates the shorter one of the vertical dimension and the horizontal dimension.

  Thirdly, it is preferable that the glass laminated body of this invention has laminated | stacked the glass film in which the reflective film was formed in at least one surface.

  Fourth, the glass laminate of the present invention preferably has a surface roughness Ra of the surface of the glass film of 100 mm or less. Here, “surface roughness Ra” refers to a value measured by a method based on JIS B0601: 2001.

  Fifth, the glass laminate of the present invention preferably has a glass film undulation of 1 μm or less. Here, “waviness” refers to a value obtained by measuring WCA (filtered centerline waviness) described in JIS B0601: 2001 using a stylus type surface shape measuring apparatus, and this measurement is performed by SEMI STD D15- 1296 “Measurement method of surface waviness of FPD glass substrate” is measured in accordance with a method of measuring 0.8 to 8 mm in the cut-off and 300 mm in the direction perpendicular to the drawing direction of the glass film. Indicates the value.

  Sixth, the glass laminate of the present invention preferably has a difference between the maximum thickness and the minimum thickness of the glass film of 20 μm or less. Here, the “difference between the maximum thickness and the minimum thickness of the glass film” means that the maximum thickness and the minimum thickness of the glass film are obtained by scanning a laser from one side of the glass film in the thickness direction using a laser thickness measuring device. The value obtained by subtracting the value of the minimum thickness from the value of the maximum thickness after measuring the thickness.

  Seventh, in the glass laminate of the present invention, the glass film preferably has an unpolished surface.

  Eighth, the glass laminate of the present invention preferably has a glass film length dimension of 500 mm or less.

  Ninth, the glass laminate of the present invention is preferably formed by a glass film formed by an overflow downdraw method.

  10thly, it is preferable that the glass laminated body of this invention has an contact bonding layer between glass films, and the thickness of this contact bonding layer is 100 micrometers or less. When the adhesive layer is provided, the glass films are easily laminated and integrated. Further, when the thickness of the adhesive layer is reduced, the interval between the reflective films is easily reduced.

  Eleventh, in the glass laminate of the present invention, the reflective film is preferably Al or Ag. These reflective films are advantageous from the viewpoint of obtaining high-resolution imaging.

  12thly, the optical imaging member of this invention is an optical imaging member provided with a pair of glass laminated body, Comprising: Each of a pair of glass laminated body is one of the said glass laminated bodies, and a pair The glass laminates are arranged so that the surfaces on which the reflection films are formed are orthogonal to each other.

  13thly, it is preferable that the optical imaging member of this invention has the glass substrate arrange | positioned on the lamination | stacking outer surface (usually becoming the end surface side of a glass film) of a pair of glass laminated body.

  Fourteenth, the optical imaging member of the present invention preferably has an antireflection film formed on the outer surface of the glass substrate.

  15thly, the manufacturing method of the glass laminated body of this invention prepares the glass film with a reflecting film in which the reflecting film was formed in at least one surface of the glass film of thickness 500 micrometers or less, and the glass film with a reflecting film And laminating and integrating to obtain a glass laminate.

  16thly, it is preferable that the manufacturing method of the glass laminated body of this invention carries out lamination | stacking integration of the glass film with a reflecting film with an adhesive agent.

  Seventeenthly, in the method for producing a glass laminate of the present invention, it is preferable to apply a pressing force to the glass film with a reflective film and laminate and integrate them.

  Eighteenth, the method for producing a glass laminate of the present invention is directed to a direction perpendicular to the surface on which the reflective film is formed (usually a glass film) with respect to the glass laminate in which the glass film with a reflective film is laminated and integrated. (Thickness direction) of cutting into strips.

  Nineteenth, in the method for producing a glass laminate of the present invention, it is preferable to cut the glass laminate with a wire saw.

  20thly, the manufacturing method of the glass laminated body of this invention cut | disconnects in the state which controlled the wire saw at the angle of 45 degrees or less with respect to the surface of the glass film of a glass laminated body.

  Twenty-first, the method for producing an optical imaging member of the present invention comprises a step of preparing a pair of glass laminates in which glass films with a reflection film are laminated and integrated, and a pair of glass laminates formed with a reflection film. And a step of obtaining an optical imaging member by arranging the surfaces to be orthogonal to each other.

  Twenty-second, in the method for producing an optical imaging member of the present invention, the pair of glass laminates is preferably strip-shaped. Here, the “strip-shaped glass laminate” refers to a laminate in which a glass film having a length dimension / width dimension ratio of 5 or more is laminated on the basis of the glass film.

  Twenty-third, the method for producing an optical imaging member of the present invention preferably further includes a step of arranging a glass substrate on the outer surface of the pair of glass laminates.

  Twenty-fourth, the method for producing an optical imaging member of the present invention includes a step of forming a reflective film on at least one surface of a glass film having a thickness of 500 μm or less to obtain a glass film with a reflective film, A step of obtaining a glass laminate by laminating and integrating glass films, and a step of obtaining an optical imaging member by arranging a pair of glass laminates so that the surfaces on which the reflection films are formed are orthogonal to each other. It is characterized by that.

  25thly, the glass film of the present invention has a thickness of 500 μm or less, and a reflective film is formed on at least one surface.

  According to a twenty-sixth aspect, the glass film of the present invention has a thickness of 500 μm or less, has a thickness of 500 μm, has a transmittance of 70% or more at a wavelength of 350 nm, and is used for a glass laminate. The transmittance can be measured with a commercially available transmittance measuring device.

It is a conceptual perspective view which shows an example of the glass laminated body of this invention. It is a conceptual perspective view which shows an example of the glass laminated body of this invention. It is a conceptual perspective view which shows an example of the optical image formation member of this invention. It is a conceptual perspective view which shows an example of the optical image formation member of this invention. It is a conceptual sectional view showing an example of a method of laminating and integrating a glass film with a reflective film. It is a conceptual explanatory drawing which shows an example of the method of cut | disconnecting a large sized glass laminated body into a strip shape with a wire saw.

  In the glass laminate of the present invention, the thickness of the glass film is 500 μm or less, preferably 300 μm or less, 200 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 1 to 20 μm, especially 5 to 10 μm. The thinner the glass film is, the narrower the interval between the reflecting films, so that it becomes easier to obtain a high-resolution image.

  The surface roughness Ra of the surface of the glass film is preferably 100 mm or less, 50 mm or less, 10 mm or less, 8 mm or less, 4 mm or less, 3 mm or less, particularly 0.01 to 2 mm. If the surface roughness Ra of the surface of the glass film is too large, the distance between the reflective films tends to vary. Especially when the glass films are laminated and integrated, the variation in the distance between the reflective films is amplified, and high-resolution imaging is performed. It becomes difficult to obtain. Furthermore, when laminating a glass film, it becomes easy to entrain air and it is difficult to carry out optical carboxylation.

  The surface roughness Ra of the end face of the glass film is preferably 100 mm or less, 50 mm or less, 10 mm or less, 8 mm or less, 4 mm or less, 3 mm or less, particularly 0.1 to 2 mm. If the surface roughness Ra of the end face of the glass film is too large, the glass laminate is easily damaged.

  The waviness of the glass film is preferably 1 μm or less, 0.08 μm or less, 0.05 μm or less, 0.03 μm or less, 0.02 μm or less, particularly 0.01 μm or less. When the undulation of the glass film is too large, the interval between the reflection films tends to vary. In particular, when the glass films are laminated and integrated, the variation in the interval between the reflection films is amplified, making it difficult to obtain a high-resolution image. Furthermore, when laminating a glass film, it becomes easy to entrain air and it is difficult to carry out optical carboxylation.

  The difference between the maximum thickness and the minimum thickness of the glass film is preferably 10 μm or less, 5 μm or less, 2 μm or less, particularly 0.01 to 1 μm. If this difference is too large, the distance between the reflective films tends to vary. In particular, when the glass films are laminated and integrated, the variation in the distance between the reflective films is amplified, making it difficult to obtain a high-resolution image. Furthermore, when laminating a glass film, it becomes easy to entrain air and it is difficult to carry out optical carboxylation.

  The glass film preferably has an unpolished surface. The theoretical strength of glass is inherently very high, but breakage is often caused even by a stress much lower than the theoretical strength. This is because a small defect called Griffith Flow is generated on the surface of the glass film in a process after glass molding, such as a polishing process. Therefore, if the surface of the glass film is unpolished, the original mechanical strength is hardly impaired, and the glass film is difficult to break. Moreover, since a grinding | polishing process can be skipped, the manufacturing cost of a glass film can be reduced. If the entire effective surface of both surfaces is an unpolished surface, the glass film is more difficult to break.

  The length dimension of the glass film is preferably 500 mm or more, 600 mm or more, 800 mm or more, 1000 mm or more, 1200 mm or more, 1500 mm or more, particularly 2000 mm or more. If it does in this way, it will become easy to enlarge an optical image formation member. On the other hand, when the length dimension of a glass film is too large, it will become difficult to cut | disconnect a glass laminated body in the direction orthogonal to the surface in which the reflecting film was formed. Therefore, the length dimension of the glass film is preferably 3500 mm or less, 3200 mm or less, and particularly 3000 mm or less.

  The width dimension of the glass film is not particularly limited as long as it is equal to or less than the length dimension, but when processed into a strip-shaped glass laminate, the ratio of length dimension / width dimension is 5 or more, preferably 10 or more. 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, particularly 100 to 2000. If the ratio of the length dimension / width dimension is too small, the manufacturing efficiency of the optical imaging member tends to be lowered.

  The glass film is preferably formed by an overflow downdraw method. In this way, a glass film that is unpolished and has good surface quality can be produced. The reason is that, in the case of the overflow downdraw method, the surface to be the surface of the glass film does not come into contact with the bowl-like refractory and is molded in a free surface state. Here, the overflow down draw method is a glass film in which the molten glass overflows from both sides of the heat-resistant bowl-shaped structure, and the overflowed molten glass is stretched and formed downward at the lower end of the bowl-shaped structure. It is a method of manufacturing. The structure and material of the bowl-shaped structure are not particularly limited as long as the dimensions and surface accuracy of the glass film are set to a desired state and the quality usable for the glass film can be realized. Moreover, in order to perform the downward stretch molding, any force may be applied to the glass. For example, a method may be adopted in which a heat-resistant roll having a sufficiently large width is rotated and stretched in contact with glass, or a plurality of pairs of heat-resistant rolls are contacted only near the end face of the glass. It is also possible to adopt a method of stretching by stretching. In addition to the overflow downdraw method, for example, a molding method such as a slot down method or a redraw method may be employed.

In the case of molding by the overflow downdraw method, the viscosity of the glass in the portion (lower top end portion) that is not in contact with the bowl-shaped refractory is preferably 10 3.5 to 10 5.0 dPa · s. If no force is applied to the lower top end portion of the bowl-shaped structure, it will drop downward while shrinking due to surface tension. In order to prevent this, it is necessary to stretch the glass fabric in the width direction so that both sides of the glass fabric are sandwiched between the rollers on the roller so that the glass fabric does not shrink. When the glass film is formed, since the amount of heat of the glass itself is small, the cooling rate of the glass is rapidly increased from the moment when the glass film is separated from the bowl-like refractory. Therefore, the viscosity of the glass at the lower top end portion is preferably 10 5.0 dPa · s or less, 10 4.8 dPa · s or less, 10 4.6 dPa · s or less, 10 4.4 dPa · s or less, It is 10 4.2 dPa · s or less, particularly 10 4.0 dPa · s or less. In this way, tensile stress is applied in the width direction to prevent breakage, and the film width can be increased and the film can be stably stretched downward. On the other hand, when the viscosity of the glass at the lower top end portion is too low, the glass is easily deformed, and the quality such as warpage and undulation is likely to be lowered. Further, the subsequent cooling rate is increased, and the thermal shrinkage of the glass film tends to increase. Therefore, the viscosity of the glass at the lower top end portion is preferably 10 3.5 dPa · s or more, 10 3.7 dPa · s or more, 10 3.8 dPa · s or more, particularly 10 3.9 dPa · s or more. It is.

  The crack occurrence rate of the glass film is preferably 70% or less, 50% or less, 40% or less, 30% or less, particularly 20% or less. If it does in this way, it will become difficult to break a glass layered product. Here, the “crack occurrence rate” is a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C., and a Vickers indenter set at a load of 1000 g is driven into the glass surface (optical polishing equivalent surface) for 15 seconds. After counting the number of cracks generated from the four corners of the indentation after 15 seconds (maximum 4 per indentation), this operation was repeated 20 times (that is, the indenter was driven 20 times), and the total number of cracks was counted The value obtained by the total number of cracks / 80.

The liquidus temperature of the glass film is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1130 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, particularly 700 to 1070 ° C. The liquid phase viscosity of the glass film is preferably 10 5.0 dPa · s or more, 10 5.6 dPa · s or more, 10 5.8 dPa · s or more, particularly 10 6.0 to 10 10.0 dPa · s. That's it. If it does in this way, it will become difficult to devitrify glass at the time of fabrication. The “liquid phase temperature” is obtained by passing the standard sieve 30 mesh (500 μm) and putting the glass powder remaining in 50 mesh (300 μm) into a platinum boat and holding it in a temperature gradient furnace for 24 hours to precipitate crystals. Refers to the value measured temperature. “Liquid phase viscosity” refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.

  The Young's modulus of the glass film is preferably 65 GPa or more, 67 GPa or more, 68 GPa or more, 69 GPa or more, 70 GPa or more, 71 GPa or more, 72 GPa or more, particularly 75 to 100 GPa. If it does in this way, after forming a reflecting film in the surface of a glass film, a glass film becomes difficult to warp, As a result, the space | interval of a reflecting film becomes difficult to fluctuate and it becomes easy to obtain high-resolution imaging. “Young's modulus” refers to a value measured by a resonance method.

The density of the glass film is preferably 2.7 g / cm 3 or less, 2.6 g / cm 3 or less, 2.5 g / cm 3 or less, in particular 2.0~2.4g / cm 3. In this way, it becomes easy to reduce the weight of the optical imaging member.

The thermal expansion coefficient of the glass film is preferably 25 to 100 × 10 −7 / ° C., 30 to 90 × 10 −7 / ° C., 30 to 60 × 10 −7 / ° C., 30 to 45 × 10 −7 / ° C., In particular, it is 30 to 40 × 10 −7 / ° C. If it does in this way, it will become easy to match with the thermal expansion coefficient of various functional films. “Thermal expansion coefficient” refers to a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer. As a sample for measuring the thermal expansion coefficient, φ5 mm × with end-face processed R A 20 mm cylindrical sample is used.

  The strain point of the glass film is preferably 600 ° C. or higher, particularly 630 to 750 ° C. If it does in this way, it will become easy to improve heat resistance. The “strain point” refers to a value measured based on the method of ASTM C336-71.

  The transmittance of the glass film in terms of a thickness of 500 μm and a wavelength of 300 nm is preferably 30% or more, 50% or more, 70% or more, 80% or more, 85% or more, particularly 89 to 99%. The transmittance at a thickness of 500 μm and a wavelength of 350 nm is preferably 50% or more, 70% or more, 80% or more, 85% or more, 89% or more, 90% or more, particularly 91% or more. Moreover, the transmittance | permeability in thickness 500micrometer conversion and wavelength 550nm is 85% or more, 89% or more, 90% or more, especially 91 to 99%. In this way, when applied to an optical imaging member or the like, when light is transmitted while repeating reflection, the loss of light is reduced, and high-resolution imaging is easily obtained.

  The haze of the glass film is preferably 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.3% or less. In this way, it becomes possible to reduce the diffuse reflection on the surface, and when applied to an optical imaging member or the like, the light loss is reduced when the light is transmitted while repeating the reflection, and high It becomes easy to obtain a resolution image. Note that “Haze” can be measured with a commercially available Haze meter.

Glass films, as a glass composition, in mass%, SiO 2 35~80%, Al 2 O 3 0~20%, B 2 O 3 0~17%, 0~10% MgO, CaO 0~15%, SrO It is preferable to contain 0 to 15% and BaO 0 to 30%. The reason for limiting the content range of each component as described above is shown below. In addition, in description regarding a glass composition,% display points out the mass%.

The content of SiO 2 is preferably 35 to 80%. When the content of SiO 2 is too large, the melting property, the moldability tends to decrease. Therefore, the content of SiO 2 is preferably 75% or less, 64% or less, 62% or less, and particularly 61% or less. On the other hand, if the content of SiO 2 is too small, it becomes difficult to form a glass network structure, and vitrification becomes difficult, the rate of occurrence of cracks increases, and acid resistance tends to decrease. Therefore, the content of SiO 2 is preferably 40% or more, 50% or more, 55% or more, particularly 57% or more.

The content of Al 2 O 3 is preferably 0 to 20%. When the content of Al 2 O 3 is too large, devitrification crystal glass is precipitated, the liquid phase viscosity tends to decrease. The content of Al 2 O 3 is preferably 18% or less, 17.5% or less, particularly 17% or less. On the other hand, when the content of Al 2 O 3 is too small, the strain point, the Young's modulus tends to decrease. Therefore, the content of Al 2 O 3 is preferably 3% or more, 5% or more, 8.5% or more, 10% or more, 12% or more, 13% or more, 13.5% or more, 14% or more, particularly 14.5% or more.

The content of B 2 O 3 is preferably 0 to 17%. When the content of B 2 O 3 is too large, the strain point, the Young's modulus, acid resistance tends to decrease. Therefore, the content of B 2 O 3 is preferably 15% or less, 13% or less, 12% or less, 11% or less, particularly 10.4% or less. On the other hand, when the content of B 2 O 3 is too small, the high-temperature viscosity becomes high, the meltability is lowered, the crack generation rate is increased, the liquidus temperature is increased, and the density is easily increased. Therefore, the content of B 2 O 3 is preferably 2% or more, 3% or more, 4% or more, 5% or more, 7% or more, 8.5% or more, 8.8% or more, particularly 9% or more. is there.

  MgO is a component that increases the Young's modulus and strain point and decreases the high-temperature viscosity and crack generation rate. However, if the content of MgO is too large, the liquidus temperature rises and the devitrification resistance tends to decrease, and in addition, the BHF resistance tends to decrease. Therefore, the content of MgO is preferably 10% or less, 5% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, particularly 0.5% or less.

  The content of CaO is preferably 0 to 15%. When there is too much content of CaO, a density and a thermal expansion coefficient will become high easily. Therefore, the content of CaO is preferably 12% or less, 10% or less, 9% or less, and particularly 8.5% or less. On the other hand, when there is too little content of CaO, a meltability and a Young's modulus will fall easily. Therefore, the CaO content is preferably 2% or more, 3% or more, 5% or more, 6% or more, 7% or more, particularly 7.5% or more.

  The content of SrO is preferably 0 to 15%. When there is too much content of SrO, a density and a thermal expansion coefficient will become high easily. Therefore, the content of SrO is preferably 12% or less, 10% or less, 6% or less, 5% or less, and particularly 6.5% or less. On the other hand, when there is too little content of SrO, a meltability and chemical resistance will fall easily. Therefore, the content of SrO is preferably 0.5% or more, 1% or more, 2% or more, 3% or more, particularly 3.5% or more.

  When there is too much content of BaO, a density and a thermal expansion coefficient will become high easily. Therefore, the content of BaO is preferably 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 5% or less, 2% or less, 1% or less, particularly 0.5% or less. .

  When a plurality of MgO, CaO, SrO, and BaO components are introduced, the liquidus temperature is lowered, and it is difficult for crystal foreign matter to be generated in the glass. On the other hand, if the total amount of these components is too small, the function as a flux cannot be sufficiently exhibited, and the meltability tends to be lowered. Therefore, the total amount of these components is preferably 5% or more, 8% or more, 9% or more, 11% or more, particularly 13% or more. On the other hand, if the total amount of these components is too large, the density increases and it becomes difficult to reduce the weight of the glass, and the crack generation rate tends to increase. Therefore, the total amount of these components is preferably 30% or less, 20% or less, 18% or less, and particularly 15% or less. In particular, when priority is given to lowering the density of the glass film, the total amount of these components is preferably 5% or more, particularly 8% or more, and 13% or less, 11% or less, particularly 10% or less.

  ZnO is a component that increases meltability and Young's modulus. However, when the content of ZnO is too large, the glass is devitrified, the strain point is lowered, and the density is easily increased. Therefore, the content of ZnO is preferably 15% or less, 10% or less, 5% or less, 3% or less, 1% or less, particularly 0.5% or less.

ZrO 2 is a component that increases the Young's modulus. However, when the content of ZrO 2 is too large, the liquidus temperature rises and zircon devitrification foreign matter is likely to be generated. Therefore, the content of ZrO 2 is preferably 3% or less, 1% or less, 0.5% or less, particularly 0.1% or less.

The upper limit content of Fe 2 O 3 is preferably 1000 ppm (0.1%) or less, 800 ppm or less, 300 ppm or less, 200 ppm or less, 130 ppm or less, 100 ppm or less, 80 ppm or less, 60 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less The lower limit content is preferably 1 ppm or more, particularly 3 ppm or more. The smaller the content of Fe 2 O 3, the higher the transmittance. Therefore, when applied to an optical imaging member or the like, the light loss is reduced when light is transmitted while repeating reflection, and high resolution is achieved. It becomes easier to obtain an image. In order to reduce the content of Fe 2 O 3 , it is preferable to use a high-purity raw material.

Y 2 O 3 , Nb 2 O 3 , and La 2 O 3 are components that increase the strain point, Young's modulus, and the like. However, if the content of these components is too large, the density tends to increase. Therefore, the content of Y 2 O 3 , Nb 2 O 3 and La 2 O 3 is preferably 3% or less.

As a fining agent, As 2 O 3, Sb 2 O 3, CeO 2, SnO 2, F, Cl, selected from the group of SO 3 was one or two or more may be added 0-3%. However, As 2 O 3 , Sb 2 O 3 and F, especially As 2 O 3 and Sb 2 O 3 are preferably refrained from use as much as possible from an environmental point of view, and each content is less than 0.1%. It is preferable to limit to. Preferred fining agents are SnO 2, SO 3 and Cl. The content of SnO 2 is preferably 0 to 1%, 0.01 to 0.5%, particularly 0.05 to 0.4%. Further, the content of SnO 2 + SO 3 + Cl (total amount of SnO 2 , SO 3 and Cl) is preferably 0.001 to 1%, 0.01 to 0.5%, particularly 0.01 to 0.3. %.

  In addition to the above components, other components may be added, and the content of other components is preferably 10% or less, particularly preferably 5% or less.

  As for the glass laminated body of this invention, it is preferable that the glass film in which the reflecting film was formed in at least one surface is laminated | stacked. If it does in this way, it will become easy to reduce the manufacturing cost of a glass laminated body. Further, from the viewpoint of film formation efficiency, it is more preferable that a glass film having a reflective film formed on only one surface is laminated.

  Various materials can be used for the reflective film, and among these, Al or Ag is preferable from the viewpoint of obtaining a high-resolution image.

  There are various methods for forming the reflective film on the surface of the glass film, and examples thereof include vapor deposition, sputtering, and plating. In particular, from the viewpoint of film formation efficiency, it is preferable to form the reflective film by sputtering.

  When a reflective film (particularly an Al reflective film) is formed by sputtering or vapor deposition, the reflective film is preferably electropolished. In this way, the regular reflectance of the reflective film is improved, and the image quality of the image formed can be improved.

  It is also preferable to stick a resin film with a reflective film on the surface of the glass film. In this way, the formation cost of the reflective film can be reduced.

  It is also preferable to apply and dry a metal paste such as an Al paste or an Ag paste on the surface of the glass film, and then laminate and fire the obtained glass film. The metal paste preferably contains glass frit. . If it does in this way, fixation of glass films and formation of a reflective film can be performed simultaneously.

A protective film such as SiO 2 may be formed on the reflective film as necessary. If it does in this way, a reflective film can be protected appropriately.

  In the glass laminate of the present invention, the number of laminated glass films is preferably 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, particularly 700 or more. The larger the number of laminated glass films, the easier it is to produce a large optical imaging member.

  In the glass laminate of the present invention, the glass films are preferably laminated and integrated with each other by an adhesive. That is, it is preferable to have an adhesive layer between the glass films. If it does in this way, glass films can be firmly laminated and integrated. Further, the thickness of the adhesive layer is preferably 100 μm or less, 70 μm or less, 50 μm or less, 40 μm or less, particularly 30 μm or less. If it does in this way, it will become easy to narrow the space | interval of a reflecting film. Although various materials can be used as the adhesive, transparent adhesives such as OCA and cemedine are preferable from the viewpoint of optical properties, and UV curable resin adhesives are also preferable from the viewpoint of production efficiency.

  As the adhesive layer, an EVA resin (ethylene-vinyl acetate copolymer resin) adhesive layer is preferable, and the EVA resin adhesive layer is preferably provided after a reflective film is formed on the surface of the glass film. The thickness of the EVA resin adhesive layer is preferably 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, 0.1 mm or less, 0.05 mm or less, particularly 0.005 to 0.03 mm. . This makes it easy to obtain high resolution imaging.

  In forming the adhesive layer, particularly the EVA resin adhesive layer, it is preferable to heat, and the heating temperature is preferably 50 ° C or higher, 70 ° C or higher, 90 ° C or higher, 100 ° C or higher, particularly 110 to 250 ° C. Thereby, the formation time of the EVA resin layer can be shortened. The heating pressure is preferably 700 torr or less, 70 torr or less, 10 torr or less, 1 torr or less, 0.1 torr or less, particularly 0.01 torr or less. Thereby, foaming at the interface of the adhesive layer, particularly the EVA resin adhesive layer, can be suppressed.

  The adhesive layer is preferably formed by applying an adhesive from the viewpoint of production efficiency. Various methods can be used as the method for applying the adhesive. Among them, dispenser coating and screen printing are preferable from the viewpoint of coating workability.

  As a method of laminating and integrating the glass films, a method of heat treatment in a state where the glass films are superposed is also conceivable. This method eliminates the need for an adhesive layer, so that it is easy to reduce the interval between the reflective films. If adjacent surfaces are smooth, stacking and integration can be performed at a low temperature (about 250 ° C.).

  The optical imaging member of the present invention is an optical imaging member provided with a pair of glass laminates, each of the pair of glass laminates being the above glass laminate, and the pair of glass laminates being a reflection. The surfaces on which the films are formed are arranged so as to be orthogonal to each other.

  The pair of glass laminates are preferably bonded and fixed with an adhesive. That is, it is preferable to have an adhesive layer between the glass laminates. In this way, the pair of glass laminates can be firmly bonded and fixed. The thickness of the adhesive layer is preferably 100 μm or less, 70 μm or less, 50 μm or less, 40 μm or less, particularly 1 to 30 μm in order to minimize the optical influence. In addition, although various materials can be used as the adhesive, a transparent adhesive such as OCA is preferable.

  It is preferable to arrange a glass substrate on the outermost layer side of the pair of glass laminates, and it is preferable to adhere and fix the glass substrate and the glass laminate with an adhesive layer. Specifically, the first glass substrate, the adhesive layer, the first glass laminate, the adhesive layer, the second glass laminate, the adhesive layer, and the second glass substrate are preferably laminated in this order. In this way, it is not necessary to polish the surfaces (preferably cut surfaces) of the pair of glass laminates with high accuracy, and the manufacturing cost of the optical imaging member can be greatly reduced.

  The surface roughness Ra of the surfaces (preferably cut surfaces) of the pair of glass laminates is preferably 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.4 μm or more, particularly preferably It is 7 μm or more, preferably 3 μm or less, 2 μm or less, 1.5 μm or less, 1.2 μm or less, particularly 1 μm or less. If the surface roughness Ra of the surface of the pair of glass laminates is made too small, the necessity for polishing the surface increases, and as a result, the manufacturing cost of the optical imaging member may increase. On the other hand, if the surface roughness Ra of the surface of the pair of glass laminates is too large, air is easily mixed into the adhesive layer.

Refractive index n d of the adhesive layer for bonding and fixing the glass laminate and glass substrate are preferably matched to the refractive index of the glass film of the glass laminate in. The refractive index nd difference between the glass film and the adhesive layer is preferably 0.2 or less, 0.15 or less, 0.12 or less, 0.1 or less, 0.08 or less, 0.05 or less, 0.02 or less, 0.01 or less, 0.008 or less, particularly 0.005 or less. Thereby, the diffuse reflection at the interface between the glass laminate and the adhesive layer can be reduced without polishing the surface of the glass laminate on the adhesive layer side. As a result, the manufacturing cost of the optical imaging member can be significantly reduced. The refractive index n d can be measured by a precision refractometer.

The refractive index of the adhesive layer is preferably matched with the refractive index of the glass substrate. The refractive index nd difference between the glass substrate and the adhesive layer is preferably 0.2 or less, 0.15 or less, 0.12 or less, 0.1 or less, 0.08 or less, 0.05 or less, 0.02 or less, 0.01 or less, 0.008 or less, particularly 0.005 or less. Thereby, the diffuse reflection at the interface between the glass substrate and the adhesive layer can be reduced.

Refractive index n d of the adhesive layer is preferably 1.60 or less, 1.55 or less, 1.54 or less, 1.52 or less, 1.51 or less, particularly 1.50 or less, preferably 1.45 or more 1.48 or more, particularly 1.49 or more. Thereby, it becomes easy to match the refractive index of a glass film or a glass substrate, and diffuse reflection at the interface of the adhesive layer can be suppressed.

  The surface roughness Ra of the glass substrate is preferably 1.0 nm or less, 0.8 nm or less, 0.6 nm or less, 0.5 nm or less, 0.4 nm or less, 0.3 nm or less, 0.2 nm or less, particularly 0.001. ˜0.1 nm is preferred. In this way, the mechanical strength of the optical imaging member can be increased.

  The glass substrate is preferably molded by an overflow downdraw method. In this way, the surface accuracy of the glass substrate is improved and the polishing step can be omitted.

  The glass substrate is preferably tempered glass having a compressive stress layer on the surface. In this case, the compressive stress value of the compressive stress layer is preferably 200 MPa or more, 400 MPa or more, 600 MPa or more, particularly 800 to 1500 MPa, and the stress depth is preferably 10 μm or more, 20 μm or more, 30 μm or more, particularly 40 to 80 μm. It is. In this way, the mechanical strength of the optical imaging member can be increased.

  The glass substrate preferably has an antireflection film (antireflection layer) on the outer surface (the side opposite to the glass laminate). Thereby, reflection of the outer surface is suppressed, and high-resolution imaging is easily obtained.

  The method for producing a glass laminate of the present invention comprises a step of preparing a glass film with a reflective film in which a reflective film is formed on at least one surface of a glass film having a thickness of 500 μm or less, and a glass film with a reflective film is laminated and integrated. And a step of obtaining a glass laminate, and the glass film with a reflective film is preferably laminated and integrated with an adhesive. Here, the technical characteristics of the glass laminate production method of the present invention (for example, glass film, suitable characteristics and modes of the glass laminate) are partially described in the explanation column of the glass laminate of the present invention. Yes. In the present specification, the description of overlapping portions is omitted for convenience.

  In the method for producing a glass laminate of the present invention, it is preferable to apply a pressing force to the glass film with a reflective film to integrate the layers, and the pressing force is applied with an adhesive interposed between the glass films with the reflective film. It is more preferable to apply and laminate and integrate. If it does in this way, while an adhesive agent will spread easily between glass films with a reflecting film, the adhesiveness of an adhesive agent will improve and the integrated strength of a glass laminated body can be raised.

  A roller is preferably used as a means for applying a pressing force. In this way, it is possible to easily apply the pressing force.

  After applying an adhesive on the surface of the glass film with a reflective film with a dispenser or the like and stacking another glass film with a reflective film on it, the roller is rotated across the glass film with the reflective film from one end to the other. While moving, it is preferable to apply a pressing force to the glass film with a reflective film. If it does in this way, while the bending of the glass film with a reflecting film will be suppressed, the adhesiveness of an adhesive agent will improve and the integrated strength of a glass laminated body can be raised.

  After applying an adhesive on the surface of the glass film with the first reflective film with a dispenser or the like and stacking the glass film with the second reflective film thereon, from one end to the other end of the glass film with the second reflective film Then, while rotating the roller, a pressing force is applied to the glass film with the second reflective film, and an adhesive is applied to the surface of the glass film with the second reflective film by a dispenser, etc. After the three glass films with a reflective film are stacked, the roller is rotated and moved in the opposite direction to the glass film with the second reflective film from one end to the other end of the glass film with the third reflective film. However, it is preferable to apply a pressing force to the third glass film with a reflective film, and it is preferable to repeat such processes and sequentially laminate and integrate the glass films with a reflective film. There. If it does in this way, a glass layered product can be produced efficiently.

  The step of applying a pressing force to the glass film with a reflective film is preferably performed before cutting the glass laminate into a strip shape in order to appropriately apply the pressing force, and the length dimension of the glass film in this step The width dimensions are preferably 200 mm or more, 300 mm or more, 500 mm or more, 600 mm or more, 800 mm or more, particularly preferably 1000 to 3000 mm.

  The manufacturing method of the glass laminated body of this invention has the process of cut | disconnecting in strip shape in the direction orthogonal to the surface in which the reflective film was formed with respect to the glass laminated body by which the glass film with a reflective film was laminated | stacked and integrated. Is preferred. If it does in this way, a strip-shaped glass laminated body can be produced simply and the manufacturing efficiency of an optical imaging member will improve.

  Various methods can be used as a method of cutting the glass laminate into strips. Among them, it is preferable to cut using a wire saw, and it is preferable to cut while supplying a slurry containing abrasive grains to the wire saw. Furthermore, the wire saw is regulated at an angle of 45 ° or less, 30 ° or less, 20 ° or less, 10 ° or less, 5 ° or less, 3 ° or less, particularly 1 ° or less with respect to the surface of the glass film of the glass laminate. It is preferable to cut with. The cutting of the glass laminate is different from the cutting of ordinary glass alone, and is the cutting of a composite material having a glass film, a reflective film, an adhesive layer and the like. For this reason, when the glass laminate is cut, if the adhesive strength of each constituent member is insufficient, a part of the constituent member may be peeled off. Therefore, when the above method is used as the cutting means, the stress that leads to the peeling of the various members is reduced, and the above problems can be prevented appropriately.

  The wire width of the wire saw is preferably 500 μm or less, 300 μm or less, 200 μm or less, particularly 10 to 100 μm. If the wire width of the wire saw is too large, the yield of the strip-shaped glass laminate tends to decrease. If the wire width of the wire saw is too small, the wire may be broken during cutting.

  When cutting using a wire saw, in order to precipitate and recover the metal contained in the slurry after cutting, it is preferable to install a slurry circulation device, and it is preferable to additionally provide a metal precipitation tank. In addition, when a metal mixes in a slurry, cutting efficiency will fall easily.

  In the method for producing an optical imaging member of the present invention, a step of preparing a pair of glass laminates in which glass films with reflection films are laminated and integrated, and a pair of glass laminates on which the reflection films are formed are orthogonal to each other. And the step of obtaining an optical imaging member. The glass laminate is preferably produced by the method for producing a glass laminate of the present invention. Here, the technical characteristics of the optical imaging member manufacturing method of the present invention (for example, glass film, glass laminate, suitable characteristics and modes of the glass laminate manufacturing method) are the glass laminate of the present invention and Some are described in the explanation column of the method for producing a glass laminate. In the present specification, the description of overlapping portions is omitted for convenience.

  The method for producing an optical imaging member of the present invention preferably further includes a step of disposing a glass substrate on the outer surface (usually a cut surface) of the pair of glass laminates. In this case, it is not necessary to polish the laminated outer surfaces of the pair of glass laminates with high accuracy, and the manufacturing cost of the optical imaging member can be greatly reduced. Furthermore, in this case, it is preferable that the laminated outer surfaces of the pair of glass laminates are not substantially polished.

  Next, an example of the glass laminate and the optical imaging member of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual perspective view showing an example of the glass laminate 1 of the present invention. The glass laminate 1 is laminated with a glass film 10 having a thickness of 500 μm or less, and has a reflective film 11 between the glass films 10. The reflective film 11 is formed on one surface of the glass film 10, and the reflective film 11 is not formed on the other surface. The glass films 10 are laminated and integrated with an adhesive layer (not shown) so that the reflective films do not overlap. In the drawing, the thickness of the reflective film 11 is exaggerated.

  FIG. 2 is a conceptual perspective view showing an example of the glass laminate 2 of the present invention, in which the glass laminate 1 shown in FIG. 1 is cut into strips in a direction perpendicular to the surface on which the reflective film is formed. is there. If it does in this way, the strip-shaped glass laminated body 2 can be produced efficiently. Note that the cutting width is appropriately determined from the dimensions of the optical imaging member.

  FIG. 3 is a conceptual perspective view showing an example of the optical imaging member 3 of the present invention. A pair of glass laminates 2 shown in FIG. 2 is used for the optical imaging member 3, and the pair of glass laminates 2 is such that the surfaces on which the reflection films 13 are formed are orthogonal to each other. These side surfaces (cut surfaces) are bonded and fixed by an adhesive layer (not shown). In the optical imaging member 3, the interval between the reflection films 13 is narrowed and made uniform by the glass film 12.

  FIG. 4 is a conceptual perspective view showing an example of the optical imaging member 4 of the present invention. A pair of glass laminates 2 shown in FIG. 2 is used for the optical imaging member 4, and the pair of glass laminates 2 is such that the surfaces on which the reflection films 14 are formed are orthogonal to each other. These side surfaces (cut surfaces) are bonded and fixed by an adhesive layer (not shown). In the optical imaging member 4, the interval between the reflective films 14 is narrowed and made uniform by the glass film 15. A glass substrate 16 is disposed on each outer surface of the glass laminate 2. The pair of glass laminates 2 and the glass substrate 16 are bonded and fixed by an adhesive layer (not shown). Here, the refractive index of the adhesive layer matches the refractive index of the glass film 15 and the glass substrate 16.

  Furthermore, an example of the manufacturing method of the glass laminated body of this invention is demonstrated, referring drawings. FIG. 5 is a conceptual cross-sectional view showing an example of a method for laminating and integrating a glass film with a reflective film. FIG. 5A shows a state in which the glass film 21 with a reflective film is sucked and held by the suction device 22 and sequentially laminated, and the glass already laminated by the adhesive application device 23 immediately before lamination. An adhesive is applied to the surface of the outermost layer of the laminate 24. FIG. 5B shows a state in which the glass film 21 with a reflective film 21 is stacked on the glass laminate 24 that has already been laminated, and then the roller 25 is rotated and moved from one end to the other end of the glass film 21 with the reflective film. 1 shows a state in which a pressing force is applied to the glass film 21 with a reflective film, and the outermost glass film 21 with a reflective film is laminated and integrated with the already laminated glass laminate 24. FIG. 5 (c) shows another example in which another glass film 26 with a reflective film is placed on the glass laminate 26 that has already been laminated, and then in the opposite direction to the previous time, from one end to the other end of the glass film 26 with a reflective film. FIG. 2 shows a state where a pressing force is applied to the glass film 26 with a reflecting film while the roller 25 is rotated, and the glass film 26 with a reflecting film is laminated and integrated with the already laminated glass laminate 27. ing.

  FIG. 6 is a conceptual explanatory view showing an example of a method of cutting a large glass laminate into a strip shape with a wire saw. FIG. 6A is a conceptual cross section showing a state immediately before the wire saw 32 is brought into contact with the large glass laminate 31 and the large glass laminate 31 is cut in a direction perpendicular to the surface on which the reflective film is formed. In the figure, the wire saw 32 is inclined by a degree from the surface of the glass film of the large glass laminate 31. FIG.6 (b) is a conceptual abandonment figure which shows the state in the middle of cut | disconnecting the large sized glass laminated body 31 in the direction orthogonal to the surface in which the reflecting film was formed. Here, the angle of the wire saw 32 is maintained in a state inclined by α degrees from the surface of the glass film of the large glass laminate 31. FIG.6 (c) is a conceptual perspective view which shows the state which cut | disconnected the strip-shaped glass laminated body 33 by cut | disconnecting the large sized glass laminated body 31 in the direction orthogonal to the surface in which the reflecting film was formed.

  The glass film of the present invention is characterized in that the thickness is 500 μm or less, and a reflective film is formed on at least one surface. The glass film of the present invention has a thickness of 500 μm or less, has a thickness of 500 μm, has a transmittance of 70% or more at a wavelength of 350 nm, and is used for a glass laminate. The technical characteristics of the glass film of the present invention have already been described, and detailed description thereof is omitted here.

  The present invention will be described in detail based on examples. However, the following examples are merely illustrative. The present invention is not limited to the following examples.

  Table 1 shows the glass composition and characteristics of the glass film (Sample Nos. 1 to 7).

First, glass raw materials were prepared so as to have the glass composition shown in Table 1, and the obtained glass raw materials were supplied to a glass melting furnace and melted at 1500 to 1600 ° C. Next, the obtained molten glass was molded by an overflow down draw method so as to have a thickness and a length dimension of 1500 mm in the table. Subsequently, the glass film immediately after molding was moved to the slow cooling area. At that time, the temperature of the slow cooling area and the film drawing speed were adjusted so that the cooling rate at a temperature of 10 12 to 10 14 dPa · s was 20 ° C./min.

  The density is a value measured by a well-known Archimedes method.

  The strain point is a value measured based on the method of ASTM C336-71.

  The glass transition temperature is a value measured from the thermal expansion curve based on the method of JIS R3103-3.

  The softening point is a value measured based on the method of ASTM C338-93.

The temperature at 10 4.0 , 10 3.0 , 10 2.5 dPa · s is a value measured by a platinum ball pulling method. The lower the temperature, the better the meltability.

  The Young's modulus is a value measured by a resonance method.

  The thermal expansion coefficient is obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer. As a sample for measuring the coefficient of thermal expansion, a cylindrical sample of φ5 mm × 20 mm whose end face was subjected to R processing was used.

  The liquid phase temperature passed through a standard sieve 30 mesh (500 μm), the glass powder remaining in 50 mesh (300 μm) was placed in a platinum boat and held in a temperature gradient furnace for 24 hours, and the temperature at which crystals were precipitated was measured. Is. The liquid phase viscosity is a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.

  HCl resistance and BHF resistance were evaluated by the following methods. First, after optically polishing both surfaces of each sample, a part of the surface was masked. Next, it was immersed in a chemical solution prepared to a predetermined concentration at a predetermined temperature for a predetermined time. Then, the mask was removed, the level difference between the mask portion and the erosion portion was measured with a surface roughness meter, and the value was taken as the erosion amount. Further, both surfaces of each sample were optically polished, and then immersed in a chemical solution prepared to a predetermined concentration at a predetermined temperature for a predetermined time. Thereafter, the surface of the sample was visually observed and evaluated as “X” when the surface became cloudy, rough, or cracked, and “◯” when there was no change.

Here, the amount of erosion of BHF resistance was measured using a 130 BHF solution (NH 4 HF: 4.6 mass%, NH 4 F: 36 mass%) at 20 ° C. for 30 minutes. Appearance evaluation was performed using a 63BHF solution (HF: 6% by mass, NH 4 F: 30% by mass) under treatment conditions at 20 ° C. for 30 minutes. Further, the erosion resistance of HCl resistance was measured using a 10% by mass hydrochloric acid aqueous solution at 80 ° C. for 24 hours. Appearance evaluation was performed under a treatment condition of 80 ° C. for 3 hours using a 10 mass% hydrochloric acid aqueous solution.

  The crack occurrence rate was determined by placing a Vickers indenter set at a load of 1000 g on the sample surface (optical polishing surface) for 15 seconds in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C. The number of cracks generated from the corner is counted (maximum 4 per indentation). The indenter was driven 20 times, and the total number of cracks generated / 80 × 100 was evaluated.

  The surface roughness Ra of the surface is a value measured by a method based on JIS B0601: 2001.

  The surface roughness Ra of the end face is a value measured by a method based on JIS B0601: 2001.

  The waviness is a value obtained by measuring the WCA (filtered center line waviness) described in JIS B0601: 2001 using a stylus type surface shape measuring device. This measurement is based on SEMI STD D15-1296 “FPD glass substrate. The measurement was performed by a method based on “Measurement method of surface waviness”, and the cut-off at the time of measurement was 0.8 to 8 mm, which was a value measured at a length of 300 mm in a direction perpendicular to the drawing direction of the glass film.

  The difference between the maximum thickness and the minimum thickness of the glass film is determined by measuring the maximum thickness and the minimum thickness of the glass film by scanning a laser from one side of the glass film in the thickness direction using a laser thickness measuring device. The value obtained by subtracting the value of the minimum thickness from the value of the maximum thickness.

Refractive index n d is the value measured using a precision refractometer (Shimadzu Corp. KPR-2000).

  As is clear from Table 1, sample No. 1-7 have a small thickness and good surface accuracy. Therefore, sample no. If a reflective film is formed on the surfaces of 1 to 7 and then laminated and integrated, a glass laminate can be produced without causing an increase in cost. If a pair of glass laminates are arranged so that the surfaces on which the reflection films are formed are orthogonal to each other, an optical imaging member capable of forming an image with high resolution can be obtained.

  Sample No. About 1-6, the transmittance | permeability was measured with the thickness and wavelength in a table | surface. As a measuring apparatus, UV-3100PC was used, and measurement was performed under the conditions of slit width: 2.0 nm, scan speed: medium speed, and sampling pitch: 0.5 nm. The results are shown in Table 2.

  As apparent from Table 2, the sample No. Nos. 1 to 6 had high transmittances even at thicknesses and wavelengths.

  Furthermore, about each sample, Haze was measured with the Haze meter (Nippon Denka Kogyo Co., Ltd. Haze Meter NDH-5000). The results are shown in Table 2. As apparent from Table 2, the sample No. Since all of Nos. 1 to 6 have a small haze, diffuse reflection on the surface can be suppressed.

First, sample no. A glass film having a glass composition of 2 was prepared. The thickness of the glass film was 0.25 mm, the refractive index n d is 1.50. Next, after sequentially forming an Al film and an SiO 2 film on one surface of the glass film, 1600 sheets of the obtained glass film were laminated and integrated using LOCTITE 454 (manufactured by Henkel Japan Co., Ltd.) to obtain a glass laminate. Got. Subsequently, using a multi-wire saw (abrasive grain # 600), after cutting the glass laminate in the direction perpendicular to the surface on which the reflective film is formed, that is, in the thickness direction of the glass film, to remove the abrasive grains, etc. Washing was performed to obtain a glass laminate (400 mm × 400 mm × 0.75 mm). When cutting, the angle of the wire saw was adjusted to be parallel to the surface of the glass film of the glass laminate. When the surface roughness of the cut surface of the glass laminate was measured, Ra was 0.7 μm, Rq was 0.89 μm, and Rsm was 63 μm. Furthermore, after dropping UV curable resin (Loctite 3301 manufactured by Henkel Japan Co., Ltd.) on the cut surface of the glass laminate, another glass laminate is arranged so that the surfaces on which the reflective films are formed are orthogonal to each other, and from above. A 365 nm UV lamp (30 mW / cm 2 ) was irradiated for 100 seconds to bond and fix the pair of glass laminates. Sample No. Two glass substrates having a glass composition of 2 were prepared. The glass substrate has a thickness of 0.3 mm and is formed by the overflow down draw method. Finally, a glass substrate was disposed on each outermost layer side of the pair of glass laminates, and was bonded and fixed with the same UV curable resin as described above to obtain an optical imaging member.

DESCRIPTION OF SYMBOLS 1 Glass laminated body 2 Glass laminated body 3 Optical imaging member 4 Optical imaging member 10 Glass film 11 Reflective film 12 Glass film 13 Reflective film 14 Reflective film 15 Glass film 16 Glass substrate 21 Glass film 22 with a reflective film Suction device 23 Application | coating Device 24 Glass laminate 25 Roller 26 Glass film with reflection film 27 Glass laminate 31 Glass laminate 32 Wire saw 33 Glass laminate

Claims (14)

  1. A glass laminate in which glass films having a thickness of 90 μm or less are laminated,
    The Young's modulus of the glass film is 65 GPa or more, the average surface roughness Ra of the surface of the glass film is 100 mm or less,
    A glass film having a reflective film formed on at least one surface is laminated,
    A glass laminate having a reflective film between the glass films.
  2.   The glass laminate according to claim 1, wherein strip-like glass films are laminated.
  3.   The glass laminate according to claim 1, wherein a protective film is further formed on the reflective film formed on the surface of the glass film.
  4.   The glass laminate according to any one of claims 1 to 3, wherein an average surface roughness Ra of the surface of the glass film is 10 mm or less.
  5.   The glass laminate according to any one of claims 1 to 4, wherein the undulation of the glass film is 1 µm or less.
  6.   The glass laminate according to any one of claims 1 to 5, wherein a difference between the maximum thickness and the minimum thickness of the glass film is 20 µm or less.
  7.   The glass laminate according to claim 1, wherein the glass film has an unpolished surface.
  8.   The glass laminate according to any one of claims 1 to 7, wherein a length dimension of the glass film is 500 mm or more.
  9.   The glass laminate according to any one of claims 1 to 8, wherein the glass film is formed by an overflow downdraw method.
  10.   The glass laminate according to any one of claims 1 to 9, wherein an adhesive layer is provided between the glass films, and the thickness of the adhesive layer is 100 µm or less.
  11.   The glass laminate according to claim 1, wherein the reflective film is Al or Ag.
  12. An optical imaging member comprising a pair of glass laminates,
    Each of a pair of glass laminated body is a glass laminated body in any one of Claims 1-11, and a pair of glass laminated body is arrange | positioned so that the surfaces in which the reflecting film was formed may orthogonally cross An optical imaging member characterized by comprising:
  13.   The optical imaging member according to claim 12, wherein a glass substrate is disposed on the outer surface of the pair of glass laminates.
  14.   The optical imaging member according to claim 13, wherein an antireflection film is formed on the outer surface of the glass substrate.
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015131753A (en) * 2013-12-13 2015-07-23 日本電気硝子株式会社 Method for manufacturing glass laminate and glass laminate
DE102015120566A1 (en) 2014-12-01 2016-06-02 Schott Ag Method and device for scribing thin glass and scribed thin glass
JP6400453B2 (en) * 2014-12-05 2018-10-03 有限会社オプトセラミックス Manufacturing method of optical panel for aerial imaging
WO2016132985A1 (en) * 2015-02-18 2016-08-25 コニカミノルタ株式会社 Optical element and method for manufacturing image forming element
JP6574242B2 (en) * 2015-03-18 2019-09-11 コニカミノルタ株式会社 Optical element, micromirror array, and optical element manufacturing method
WO2016190052A1 (en) * 2015-05-25 2016-12-01 コニカミノルタ株式会社 Method for manufacturing optical element and method for manufacturing reflective aerial imaging element
JP6201083B2 (en) * 2015-10-05 2017-09-20 コニカミノルタ株式会社 Optical element manufacturing method and reflective aerial imaging element manufacturing method
JP6202546B2 (en) * 2016-03-16 2017-09-27 治郎 和田 Method for manufacturing optical imaging apparatus
JP6308285B1 (en) * 2016-12-08 2018-04-11 コニカミノルタ株式会社 Method for producing transparent substrate laminate and method for producing aerial image display device

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5345140B2 (en) * 1974-10-14 1978-12-04
JPS5471132A (en) * 1977-11-17 1979-06-07 Teijin Ltd Photo-curable adhesive
JPH0577799A (en) * 1991-09-18 1993-03-30 Nippon Electric Glass Co Ltd Thermal control mirror
JP3415183B2 (en) * 1992-11-27 2003-06-09 オリンパス光学工業株式会社 Manufacturing method of optical element assembly and optical element assembly
JP2505208Y2 (en) * 1993-01-26 1996-07-24 信越ポリマー株式会社 Fine grid anti-glare sheet
JPH10104406A (en) * 1996-09-26 1998-04-24 Sharp Corp Production of light shielding filer and optical display device formed by using the same
JP4006855B2 (en) * 1998-10-30 2007-11-14 エプソントヨコム株式会社 Optical device manufacturing method
JP2002128542A (en) * 2000-10-17 2002-05-09 Nippon Electric Glass Co Ltd Heat-shielding fireproof glass article
JP4298980B2 (en) * 2001-09-05 2009-07-22 日本板硝子株式会社 High transmission glass plate and method of manufacturing high transmission glass plate
JP2003095691A (en) * 2001-09-21 2003-04-03 Nippon Sheet Glass Co Ltd High transmissive glass and method for manufacturing the same
JP2003202405A (en) * 2002-01-08 2003-07-18 Matsushita Electric Ind Co Ltd Optical element with reflection-preventive film and manufacturing method thereof
JP2005017461A (en) * 2003-06-24 2005-01-20 Minolta Co Ltd Forming method of anti-reflection film, and optical element
JP2007137705A (en) * 2005-11-16 2007-06-07 Nippon Sheet Glass Co Ltd Glass composition
JP2008102278A (en) * 2006-10-18 2008-05-01 Shin Etsu Polymer Co Ltd Visual field angle control film for electronic calculator and electronic calculator
US7534734B2 (en) * 2006-11-13 2009-05-19 Corning Incorporated Alkali-free glasses containing iron and tin as fining agents
JP5435394B2 (en) * 2007-06-08 2014-03-05 日本電気硝子株式会社 Tempered glass substrate and manufacturing method thereof
JP2008305711A (en) * 2007-06-08 2008-12-18 Nippon Electric Glass Co Ltd Manufacturing method of glass substrate for plasma display panel and glass substrate for plasma display panel
CN101861544B (en) * 2007-11-22 2013-10-16 夏普株式会社 Liquid crystal display
WO2009131128A1 (en) * 2008-04-22 2009-10-29 Fujishima Tomohiko Optical imaging device and optical imaging method using the same
WO2009136578A1 (en) * 2008-05-09 2009-11-12 パイオニア株式会社 Spatial image display apparatus
JP2009276699A (en) * 2008-05-16 2009-11-26 National Institute Of Information & Communication Technology Dihedral corner reflector array
JP5582446B2 (en) * 2009-07-10 2014-09-03 日本電気硝子株式会社 Film glass manufacturing method and manufacturing apparatus
JP2011081300A (en) * 2009-10-09 2011-04-21 Pioneer Electronic Corp Method for manufacturing reflection type plane-symmetric imaging element
JP5085631B2 (en) * 2009-10-21 2012-11-28 株式会社アスカネット Optical imaging apparatus and optical imaging method using the same
JP2013231744A (en) * 2010-08-20 2013-11-14 Konica Minolta Advanced Layers Inc Film mirror, manufacturing method of the same, and sunlight reflecting mirror using the same
JP2012206460A (en) * 2011-03-30 2012-10-25 Dainippon Printing Co Ltd Method for producing optical laminate
WO2012133403A1 (en) * 2011-03-31 2012-10-04 シャープ株式会社 Reflective imaging element, method of manufacturing reflective imaging element and optical system
JP5938259B2 (en) * 2012-04-18 2016-06-22 有限会社オプトセラミックス Manufacturing method of optical panel for aerial imaging
CN104718468B (en) * 2012-11-08 2018-04-10 亚斯卡奈特股份有限公司 The manufacture method of photocontrol panel

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