WO2019172313A1 - ガラス積層体 - Google Patents

ガラス積層体 Download PDF

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Publication number
WO2019172313A1
WO2019172313A1 PCT/JP2019/008877 JP2019008877W WO2019172313A1 WO 2019172313 A1 WO2019172313 A1 WO 2019172313A1 JP 2019008877 W JP2019008877 W JP 2019008877W WO 2019172313 A1 WO2019172313 A1 WO 2019172313A1
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WO
WIPO (PCT)
Prior art keywords
glass
film
laminate according
glass laminate
shielding film
Prior art date
Application number
PCT/JP2019/008877
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English (en)
French (fr)
Japanese (ja)
Inventor
佐々木　輝幸
Original Assignee
日本板硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Priority to CN201980017186.2A priority Critical patent/CN111819160B/zh
Priority to CN202211572310.1A priority patent/CN115782323A/zh
Publication of WO2019172313A1 publication Critical patent/WO2019172313A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase

Definitions

  • the present invention relates to a glass laminate that is attached to a vehicle.
  • the windshield and side glass installed for vehicles are required to have a function of shielding ultraviolet rays from the viewpoint of preventing sunburn while allowing visible light to pass therethrough.
  • a function of shielding ultraviolet rays from the viewpoint of preventing sunburn while allowing visible light to pass therethrough.
  • an ultraviolet shielding film is laminated on a glass plate to enhance the ultraviolet shielding function.
  • An object of this invention is to provide the glass laminated body for vehicles which has a high ultraviolet-ray shielding function.
  • Item 2 The glass laminate according to Item 1, wherein the glass laminate has a light transmittance of 20% or more at a wavelength of 420 nm.
  • Item 3 When the average value of the transmittance of light having a wavelength of 420 to 800 nm in the glass body is Tavg, In the glass body, the wavelength of light whose transmittance is Tavg * 0.9; In the glass body, the wavelength of light whose transmittance is Tavg * 0.1, Item 3.
  • Item 4 When the average value of the transmittance of light having a wavelength of 420 to 800 nm in the glass laminate is Tavg, In the glass laminate, the wavelength of light whose transmittance is Tavg * 0.9, In the glass laminate, the wavelength of light having a transmittance of Tavg * 0.1, Item 4.
  • the said glass laminated body is a glass laminated body in any one of claim
  • Item 6. The glass laminate according to any one of Items 1 to 5, wherein the glass body has a yellowness YI based on JIS K7373: 2006 of 5 or less.
  • Item 7. The glass laminate according to any one of Items 1 to 6, wherein the glass laminate has a yellowness YI based on JIS K7373: 2006 of 10 or less.
  • Item 8 The glass laminate according to any one of Items 1 to 7, wherein the glass laminate has a transmittance of light having a wavelength of 420 nm of 85% or less.
  • Item 9 The glass laminate according to any one of Items 1 to 8, which is attached to a door of a vehicle as a lift window.
  • Item 10 The glass laminate according to any one of Items 1 to 8, which is used as a windshield.
  • the glass body is A first glass plate; A second glass plate; An intermediate film disposed between the first glass plate and the second glass plate; Item 11.
  • the glass body is A base sheet; An adhesive that is disposed between one of the glass plates and the base sheet, and affixes the base sheet to the glass plate; Further comprising Item 12.
  • Item 13 The glass laminate according to any one of Items 1 to 12, wherein the glass body has a thickness of 2 mm or more.
  • Item 14 The glass laminate according to any one of Items 1 to 13, wherein the amount of trivalent iron oxide contained per unit area of the glass body is 1 to 10 mg / cm 2 in terms of Fe 2 O 3 .
  • Item 15 The glass laminate according to any one of Items 1 to 13, wherein the glass body has a visible light transmittance YA of 70% or more measured using a CIE standard A light source.
  • Item 16 The glass laminate according to any one of Items 1 to 13, wherein the amount of trivalent iron oxide contained per unit area of the glass body is 4 to 15 mg / cm 2 in terms of Fe 2 O 3 .
  • Item 17 The glass laminate according to any one of Items 1 to 13, wherein the glass body has a visible light transmittance YA of 15 to 60% measured using a CIE standard A light source.
  • Item 18 The glass laminate according to any one of Items 1 to 17, wherein at least one of the glass plates contained in the glass body has a surface compressive stress of less than 20 MPa.
  • Item 19 The glass laminate according to any one of Items 1 to 18, wherein at least one of the glass plates contained in the glass body has a surface compressive stress of 80 MPa or more.
  • Item 20 The glass laminate according to any one of Items 1 to 18, wherein all the glass plates included in the glass body have a surface compressive stress of 80 MPa or more.
  • Item 21 In the glass laminate, the surface on which the ultraviolet shielding film is formed is compliant with JIS R3221, and after performing a Taber abrasion test 1000 times with a load of 500 g, the ultraviolet shielding film does not peel off, and Item 21.
  • Item 22 In the glass laminate, Tuv400 after irradiating with ultraviolet rays having a wavelength of 295 to 450 nm and an illuminance of 76 mW / cm 2 from the surface opposite to the surface on which the ultraviolet shielding film is formed, and irradiation with the ultraviolet rays Item 21.
  • the film thickness on the lower side of the vehicle is thicker than the film thickness on the upper side of the vehicle, and the film thickness Item 23.
  • the position where the film thickness is maximum is 10 cm or more away from the periphery of the film thickness, and the film Item 24.
  • Item 25 The glass laminate according to Item 23 or 24, wherein the thickness uniformity of the ultraviolet shielding film is 70% or less.
  • At least one of the glass plates included in the glass body includes a tin component in the first main surface and the second main surface of the glass plate, and a tin component included in the first main surface and the second main surface.
  • Item 26. The glass laminate according to any one of Items 1 to 25, wherein the concentrations of are different.
  • Item 27 In the glass laminate, a mark is formed on the surface of the glass plate exposed to the outside, Item 27.
  • Item 28 The glass laminate according to any one of Items 1 to 27, wherein an end surface of the glass plate included in the glass body is formed in a convex arc shape toward the outside.
  • Item 29 The end surface of the glass plate included in the glass body is formed by connecting three or more flat surfaces, Item 28.
  • Item 30 The glass laminate according to any one of Items 1 to 29, wherein the ultraviolet shielding film further has antifogging performance.
  • Item 31 The glass laminate according to Item 30, wherein the ultraviolet shielding film further has water absorption performance.
  • Item 32 Item 31. The glass laminate according to Item 30, wherein the surface of the ultraviolet shielding film is hydrophilic.
  • Item 33 The glass laminate according to Item 30, wherein the ultraviolet shielding film further has visibility ensuring performance.
  • Item 34 The glass laminate according to Item 33, wherein a surface of the ultraviolet shielding film is water repellent.
  • Item 35 The glass laminate according to any one of Items 1 to 29, further comprising a visibility ensuring film.
  • Item 36 The glass laminate according to Item 35, wherein the visibility ensuring film is disposed on a surface opposite to the glass body side in the ultraviolet shielding film.
  • the glass body is A first glass plate; A second glass plate; An intermediate film disposed between the first glass plate and the second glass plate; With The ultraviolet shielding film is disposed on at least one of the first glass plate and the second glass plate, Item 36.
  • Item 38 The glass laminate according to any one of Items 1 to 37, further comprising a low-reflection film.
  • a high ultraviolet shielding function can be realized.
  • the glass laminate includes a glass body 1 and an ultraviolet shielding film 2 formed over the entire surface.
  • this glass laminated body is used for a windshield (windshield), the raising / lowering glass of a front door, the raising / lowering glass of a rear door, a rear glass, the fixed side glass etc. in the vehicle.
  • high transparency is required for glass such as a windshield and a front door glass for the driver to look outside.
  • glass other than this may be colored because transparency as high as that of the windshield is not required.
  • the glass body and the ultraviolet shielding film will be described in detail.
  • the glass body may be composed of a single glass plate, or may be composed of a laminated glass obtained by bonding two glass plates through an intermediate film.
  • a glass body when referred to as a glass body, for example, when the glass body is composed of a single glass plate, the physical properties of the single glass plate are shown, and the glass body is laminated glass. Indicates physical properties as laminated glass.
  • the front glass is often formed of laminated glass, and the other side glass is often formed of a single glass plate.
  • glass other than the windshield can also be formed of laminated glass.
  • a well-known glass plate can be used for the glass plate which comprises a glass body, and it can form with privacy glass, clear glass, green glass, or UV green glass.
  • the glass plate used for a glass body is demonstrated.
  • the outer glass plate and the inner glass plate may have the same thickness or different thicknesses. Since the outer glass plate mainly needs durability and impact resistance against external obstacles, its thickness is 1.8 mm or more, 1.9 mm or more, 2.0 mm or more, 2.1 mm or more. It is preferable in order of 2 mm or more. Moreover, the upper limit of the thickness of an outer side glass plate is preferable in order of 5.0 mm or less, 4.0 mm or less, 3.1 mm or less, 2.5 mm or less, and 2.4 mm or less. Among them, it is preferably larger than 2.1 mm and 2.5 mm or less, particularly preferably 2.2 mm or more and 2.4 mm or less.
  • the thickness of the inner glass plate is preferably smaller than that of the outer glass plate 11 in order to reduce the weight of the laminated glass 1.
  • the thickness of the inner glass plate 12 is preferably 0.6 mm or more, 0.8 mm or more, 1.0 mm or more, and 1.3 mm or more in this order.
  • the upper limit of the thickness of the inner side glass plate 12 is preferable in order of 1.8 mm or less, 1.6 mm or less, 1.4 mm or less, 1.3 mm or less, and less than 1.1 mm. Among these, for example, 0.6 mm or more and less than 1.1 mm is preferable.
  • the thickness can be 0.6 to 5.0 mm, but the range of the thickness indicated by the outer glass plate and the inner glass plate described above is not limited. It can be adopted as appropriate.
  • composition of the glass plate is not particularly limited, but a soda-lime silicate glass plate having a composition in which the concentration of Fe 2 O 3 is increased and other ultraviolet absorbing components such as TiO 2 and CeO 2 are added as necessary is used. Is preferred. Thereby, ultraviolet shielding performance can be improved.
  • the amount of trivalent iron oxide contained per unit area is converted to Fe 2 O 3 and expressed as 1 ⁇ It can be 10 g / cm 2 .
  • the lower limit is preferably 2 mg, more preferably 3 mg.
  • the upper limit is preferably 8 mg, more preferably 6 mg, and particularly preferably 5 mg.
  • the amount of trivalent iron oxide contained per unit area can be converted to 4 to 15 g / cm 2 in terms of Fe 2 O 3 .
  • the lower limit is preferably 6 mg, more preferably 8 mg.
  • the upper limit is preferably 12 mg, and more preferably 10 mg.
  • the amount of the above trivalent iron oxide is an amount per unit area, and is the same for laminated glass.
  • the glass plate can be formed by a known float method.
  • molten glass is continuously supplied onto a molten metal such as molten tin, and the supplied molten glass is flowed on the molten metal to form a strip.
  • the glass thus formed is referred to as a glass ribbon.
  • the glass ribbon is cooled toward the downstream side, cooled and solidified, and then pulled up from the molten metal.
  • the opposite surface is referred to as the top surface.
  • the bottom surface and the top surface may be unpolished. Since the bottom surface is in contact with the molten metal, when the molten metal is tin, the concentration of tin oxide contained in the bottom surface is higher than the concentration of tin oxide contained in the top surface.
  • the optical properties of the glass body are as follows. (1-3-1) Ultraviolet transmittance
  • the ultraviolet transmittance of the glass body of the present invention is as follows. Tuv400 ⁇ 50% (1)
  • Tuv400 is the ultraviolet transmittance defined in ISO13837: 2008 convention A.
  • the ultraviolet transmittance can be measured with a known spectrophotometer, for example, “UV-3100PC” (manufactured by Shimadzu Corporation).
  • Tuv400 in the above formula (1) is preferably 40% or less, more preferably 30% or less, and particularly preferably 10% or less.
  • the glass body of the present invention has a wavelength W1 where the transmittance of the glass body is Tavg * 0.9 and the transmittance of the glass body is Tavg * 0, where Tavg is the average transmittance for light having a wavelength of 420 to 800 nm.
  • the difference from the wavelength W2 which is 0.1 is preferably 20 to 50 nm.
  • Tavg can be calculated as an arithmetic average of transmittance for each wavelength of 1 nm. This point is the same also in Tavg of the glass laminated body mentioned later.
  • the shortest wavelength is W1.
  • Tavg * 0.1 is 2 or more
  • the longest wavelength is W2.
  • the transmittance of light with a wavelength of 420 to 800 nm is generally high. For example, when it exceeds 500 nm, a certain degree of transmittance is maintained. Therefore, the difference between the wavelength W1 that becomes Tavg * 0.9 and the wavelength W2 that becomes Tavg * 0.1 is small, for example, when entering the visible light region from the ultraviolet region as shown in FIG. This means that the transmittance of the water increases rapidly.
  • this wavelength difference (hereinafter referred to as a sharp cut) is as low as 20 to 50 nm, so that the transmittance in the ultraviolet region is low, and the ultraviolet ray enters a visible light region while providing a sufficient ultraviolet shielding function. Then, since the transmittance increases rapidly, coloring or the like that impedes the visual field in the glass body can be reduced.
  • the visible light transmittance YA measured using a CIE standard A light source is 70% or more. Is preferred.
  • the visible light transmittance YA measured using a CIE standard A light source is 15 to 60%. Is preferred.
  • the transmittance of light having a wavelength of 1500 nm is preferably 35% or less, more preferably 30% or less, and 25% or less. It is particularly preferred.
  • Light having a wavelength of 1500 nm indicates light in the near infrared region, particularly in the near infrared region of solar radiation. If the transmittance of such light is 35% or less as described above, the near-infrared ray of sunlight is appropriately shielded, and when this glass body is used as a window glass of an automobile, the temperature inside the vehicle becomes high. You can relieve it too much.
  • the glass plate of the present invention satisfies the following formula (2) with respect to the yellowness YI defined in JIS K7373: 2006, based on the transmitted light in the CIE standard C light source. Is preferred. Thereby, the yellowness of a glass plate can be reduced and visibility can be improved. YI ⁇ 5 (2)
  • the strength of the glass plate of the present invention is preferably set as follows. For example, it is preferable to use a glass plate having a surface compressive stress of less than 20 MPa as untempered glass that has not been tempered by heat strengthening treatment or chemical strengthening treatment. On the other hand, as the tempered glass that is tempered, it is preferable to use a glass plate having a surface compressive stress of 80 MPa or more. In the laminated glass having a plurality of glass plates, the surface compressive stress of at least one glass plate is preferably 80 MPa or more, but the surface compressive stress of all the glass plates can be 80 MPa or more. Moreover, the surface compressive stress of one glass plate can be less than 20 MPa, and the surface compressive stress of the other glass plate can be 80 MPa or more.
  • Tempered glass generally has an improved ultraviolet shielding function compared to untempered glass. Therefore, in the tempered glass, for example, the ultraviolet shielding function can be lowered by the film by reducing the thickness of the ultraviolet shielding film described later. This contributes to cost reduction. On the other hand, even if it is untempered glass, if an adjustment such as increasing the thickness of the ultraviolet shielding film is performed, the ultraviolet shielding function is improved.
  • the surface of the glass plate of the present invention can be marked with a manufacturer, serial number, product name, standard or the like.
  • the mark can be formed by various methods.
  • the mark can be formed by a rough surface portion formed on the surface of a glass plate or the surface of an ultraviolet shielding film. That is, a rough surface portion having a predetermined shape can be formed by increasing the surface roughness of a part of the surface of the glass plate or the ultraviolet shielding film by shot blasting, wet etching, or the like.
  • the surface roughness Ra of such a rough surface portion can be set to, for example, 1.5 ⁇ m or more.
  • surface roughness Ra is arithmetic mean roughness calculated
  • the mark can be formed with a thin film made of an opaque material.
  • Opaque materials can be colored ceramic colors, conductive pastes, and various commercial products suitable for printing on glass. These can be printed in a thin film on the surface of a glass plate by screen printing, etc. A mark can be formed.
  • Shape of end face of glass plate is not specifically limited, For example, as shown in FIG. 3, it can be set as the circular curved surface 13 from which a cross section becomes convex outside. Such an end face shape is suitable for a single plate.
  • the end surface can be formed of three or more flat surfaces.
  • the end face 13 can be formed.
  • the angles ⁇ and ⁇ formed between the adjacent first side surface 111 and the main end surface 131 and between the adjacent main end surface 131 and the second side surface 121 are obtuse angles.
  • Such a shape of the end face is suitable for a glass plate used for laminated glass.
  • the laminated glass has a resin intermediate film 103 disposed between an outer glass plate 101 and an inner glass plate 102.
  • the material of the intermediate film 103 is a thermoplastic resin, and a polyvinyl acetal-based or ethylene-vinyl acetate copolymer thermoplastic resin is preferably used from the viewpoint of the degree of adhesion to a glass plate when laminated glass is used. it can. Of these, polyvinyl butyral (PVB) thermoplastic resins are preferred.
  • the intermediate film 103 can be obtained by, for example, kneading and molding a thermoplastic resin composition comprising the thermoplastic resin and a known plasticizer. As the intermediate film 103, a commercially available thermoplastic resin film can be used as it is.
  • plasticizer those usually used for interlayer films can be used.
  • the film thickness of the intermediate film 103 is not particularly limited, but is preferably 0.3 to 6.0 mm, more preferably 0.5 to 4.0 mm, and 0.6 to 2.0 mm. Is particularly preferred.
  • the intermediate film 103 can be formed of a plurality of layers.
  • the intermediate film 103 can be configured by three layers in which a soft core layer 1031 is sandwiched between outer layers 1032 that are harder than the soft core layer 1031.
  • it is not limited to this structure, and it is sufficient if it is formed of a plurality of layers having a soft core layer 1031.
  • the intermediate film 103 can be formed of a single layer.
  • the core layer 1031 is softer than the outer layer 1032, but in this respect, the material can be selected based on the Young's modulus. Specifically, it is preferably 1 to 20 MPa, more preferably 1 to 16 MPa at a frequency of 100 Hz and a temperature of 20 degrees. Further, it is preferably 1 to 10 MPa.
  • a measuring method for example, frequency dispersion measurement can be performed with a strain amount of 0.05% using a solid viscoelasticity measuring device DMA-50 manufactured by Metravib.
  • the Young's modulus is a value measured by the above method. However, the measurement when the frequency is 200 Hz or less uses an actual measurement value. When the frequency is higher than 200 Hz, a calculation value based on the actual measurement value is used. The calculated value is based on a master curve calculated by using the WLF method from the actually measured value.
  • the Young's modulus of the outer layer 1032 is not particularly limited as long as it is larger than that of the core layer 1031.
  • the upper limit of the Young's modulus of the outer layer 1032 is not particularly limited, but can be set from the viewpoint of workability, for example. For example, it is empirically known that when it becomes 1750 MPa or more, workability, particularly cutting becomes difficult.
  • the Young's modulus of the outer layer 1032 on the outer glass plate 11 side is preferably larger than the Young's modulus of the outer layer 1032 on the inner glass plate 102 side.
  • the material constituting each of the layers 1031 and 1032 is not particularly limited, but it is necessary that at least the Young's modulus can be in the above range.
  • the outer layer 1032 can be made of polyvinyl butyral resin (PVB). Polyvinyl butyral resin is preferable because it is excellent in adhesiveness and penetration resistance with each glass plate.
  • the core layer 1031 can be made of an ethylene vinyl acetate resin (EVA) or a polyvinyl acetal resin that is softer than the polyvinyl butyral resin that forms the outer layer 1032. By sandwiching the soft core layer 1031 in between, the sound insulation performance can be greatly improved while maintaining the same adhesion and penetration resistance as the single-layer resin intermediate film 103.
  • the hardness of the polyvinyl acetal resin is controlled by (a) the degree of polymerization of the starting polyvinyl alcohol, (b) the degree of acetalization, (c) the type of plasticizer, (d) the addition ratio of the plasticizer, etc. Can do. Therefore, by appropriately adjusting at least one selected from these conditions, a hard polyvinyl butyral resin used for the outer layer 1032 and a soft polyvinyl butyral resin used for the core layer 1031 can be used even if the same polyvinyl butyral resin is used. Can be made separately.
  • the hardness of the polyvinyl acetal resin can also be controlled by the type of aldehyde used for acetalization, coacetalization with a plurality of aldehydes or pure acetalization with a single aldehyde. Although it cannot generally be said, the polyvinyl acetal resin obtained by using an aldehyde having a large number of carbon atoms tends to be softer.
  • the core layer 1032 when the outer layer 1032 is made of polyvinyl butyral resin, the core layer has an aldehyde having 5 or more carbon atoms (for example, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n -Octylaldehyde), a polyvinyl acetal resin obtained by acetalization with polyvinyl alcohol can be used.
  • a predetermined Young's modulus when a predetermined Young's modulus is obtained, it is not limited to the said resin.
  • the total thickness of the intermediate film 103 is the same as the film thickness described above.
  • the thickness of the core layer 1031 is preferably 0.1 to 2.0 mm, and more preferably 0.1 to 0.6 mm. This is because if the thickness is smaller than 0.1 mm, the influence of the soft core layer 1031 is hardly exerted, and if the thickness is larger than 2.0 mm or 0.6 mm, the total thickness increases and the cost is increased.
  • the thickness of the outer layer 1032 is not particularly limited, but is preferably 0.1 to 2.0 mm, and more preferably 0.1 to 1.0 mm.
  • the total thickness of the intermediate film 103 can be made constant, and the thickness of the core layer 1031 can be adjusted therein.
  • the thickness of the core layer 1031 can be measured as follows, for example. First, the cross section of the laminated glass is enlarged and displayed by 175 times using a microscope (for example, VH-5500 manufactured by Keyence Corporation). And the thickness of the core layer 1031 is specified visually, and this is measured. At this time, in order to eliminate visual variation, the number of measurements is set to 5 times, and the average value is set as the thickness of the core layer 1031. For example, an enlarged photograph of a laminated glass can be taken, and the core layer 1031 can be specified in this and the thickness can be measured.
  • the thickness of the intermediate film 103 does not have to be constant over the entire surface, and may be a wedge shape for laminated glass used for a head-up display, for example. In this case, the thickness of the intermediate film 103 is measured at the position where the thickness is smallest, that is, the lowermost side portion of the laminated glass.
  • the manufacturing method of the intermediate film 103 shown in FIG. 6 is not particularly limited, for example, after blending a resin component such as the above-mentioned polyvinyl acetal resin, a plasticizer, and other additives as necessary, and uniformly kneading And a method of extruding each layer at once, and a method of laminating two or more resin films prepared by this method by a press method, a laminating method or the like.
  • the resin film before lamination used in a method of laminating by a press method, a laminating method or the like may have a single layer structure or a multilayer structure.
  • the ultraviolet shielding film is a film containing a component that absorbs ultraviolet rays (ultraviolet absorber).
  • the ultraviolet absorber may be present by being dissolved in the matrix component constituting the film, or the ultraviolet absorber may be present in the form of fine particles dispersed in the matrix component.
  • the matrix component should just hold
  • the method for producing this film is not particularly limited, but a film-forming solution containing an ultraviolet absorber and a matrix component is applied to a glass body and dried or, if necessary, heated and dried to form an ultraviolet shielding film. Can be formed. Details will be described below.
  • each of the three types of components constituting the film forming solution for forming the ultraviolet shielding film will be described, and then a method for preparing the film forming solution will be described below.
  • the silicon compound A is a compound represented by the formula (3). SiX 1 4 (3)
  • X 1 is a hydrolyzable functional group or a halogen atom.
  • the hydrolyzable functional group is a functional group that is hydrolyzed by a hydrolysis catalyst, and is, for example, at least one selected from an alkoxyl group, an acetoxy group, and an alkenyloxy group. All of the exemplified hydrolyzable functional groups are converted into hydroxyl groups by hydrolysis.
  • a preferred hydrolyzable functional group is an alkoxyl group. Examples of the alkoxyl group include an alkoxyl group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group and butoxy group).
  • Halogen atoms are, for example, chlorine and bromine, preferably chlorine.
  • silicon compound A examples include tetraalkoxysilane, specifically, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
  • a compound obtained by at least partially hydrolyzing the silicon compound A or a compound obtained by at least partially hydrolyzing and further polycondensing the silicon compound can be used.
  • a hydrolyzate of silicon compound A is available as a commercial product.
  • Silicon compound B is a compound represented by formula (4).
  • R 1 is an organic group having a reactive functional group
  • R 2 is an organic group having no reactive functional group
  • X 2 is a hydrolyzable functional group or a halogen atom
  • n is an integer from 0 to 2
  • m + n is from 1 to 2.
  • the reactive functional group is at least one selected from, for example, vinyl group, acryloyl group, methacryloyl group, isocyanurate group, ureido group, mercapto group, sulfide group, isocyanate group, epoxy group, and amino group.
  • the epoxy group may be part of a glycidyl group, especially an oxyglycidyl group.
  • the amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
  • Preferred reactive functional groups are epoxy groups and amino groups, especially epoxy groups.
  • the organic group having a reactive functional group may be, for example, an organic group itself which is a reactive functional group (for example, a vinyl group), or an aliphatic hydrocarbon in which at least one hydrogen atom is substituted by a reactive functional group, for example. It may be a group or an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include straight-chain alkyl groups having 1 to 10 carbon atoms and alkyl groups having 3 to 10 carbon atoms. A phenyl group can be illustrated as an aromatic hydrocarbon group.
  • the organic group having no reactive functional group is, for example, an aliphatic or aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group include straight-chain alkyl groups having 1 to 10 carbon atoms and alkyl groups having 3 to 10 carbon atoms.
  • a phenyl group can be illustrated as an aromatic hydrocarbon group.
  • X 2 is a hydrolyzable functional group or a halogen atom, and specific examples of X 2 are the same as the specific examples of X 1 .
  • M may be 1 or 2, preferably n may be 0 or 1, and m + n may be 1 or 2.
  • the silicon compound B may include a silicon compound B1 in which m in the formula (4) is 1 or 2, and n is 0 or 1.
  • Examples of the silicon compound B1 include vinyltriethoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrimethoxysilane, 3-mercaptopropyltri An example is methoxysilane.
  • the silicon compound B1 is a so-called silane coupling agent.
  • the silicon compound B1 preferably has an epoxy group as
  • the silicon compound B may include a silicon compound B2 in which m in Formula (4) is 0 (not including the organic group R 1 having a reactive functional group) and n is 1 or 2.
  • a silicon alkoxide having a phenyl group specifically, phenyltriethoxysilane can be exemplified.
  • UV absorber examples include benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl)].
  • Benzotriazole, etc. benzophenone compounds [2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5, 5′-methylenebis (2-hydroxy-4-methoxybenzophenone) etc.]
  • hydroxyphenyltriazine compound [2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-t- Butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4 6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl)
  • UV absorbers include polymethine compounds, imidazoline compounds, coumarin compounds, naphthalimide compounds, perylene compounds, azo compounds, isoindolinone compounds, quinophthalone compounds and quinoline compounds, thiophene compounds, stilbene compounds, naphthalene compounds and benzimidazole compounds. It may be at least one organic dye selected from Among the ultraviolet absorbers, at least one selected from a benzotriazole compound, a benzophenone compound, a hydroxyphenyltriazine compound, and a cyanoacrylate compound is preferable, and a benzophenone compound is more preferable. Only 1 type may be used for a ultraviolet absorber and it may use 2 or more types together.
  • the ultraviolet absorber preferably has at least one kind selected from an amino group and a hydroxyl group, in particular, a hydroxyl group in the molecule, and particularly preferably has two or more hydroxyl groups in one molecule.
  • the amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group.
  • the ultraviolet absorber may have a benzene skeleton having two or more hydroxyl groups bonded thereto.
  • the ultraviolet absorber does not need to be silylated by reacting with a silicon compound such as silicon compound B1 in advance, and a commercially available product may be used as it is. For this reason, in this embodiment, the ultraviolet absorber which does not contain a silicon atom in a molecule
  • numerator can be used for preparation of a film formation solution as it is. Silylation of the UV absorber is effective for suppressing the bleed-out of the UV absorber, but requires a preliminary process only for that purpose. In the present embodiment, the ultraviolet absorber is usually other components capable of reacting with the ultraviolet absorber or interacting with each other in the film-forming solution, specifically silicon compound A, silicon compound B, organic polymer, etc. Reacts with or interacts with molecules.
  • reaction or intermolecular interaction occurs competitively.
  • examples of the reaction include a reaction in which a covalent bond or an ionic bond is formed.
  • Examples of intermolecular interactions include hydrogen bonds and ⁇ - ⁇ interactions. Therefore, even if the film forming solution contains the silicon compound B1 (silane coupling agent), the total amount of the ultraviolet absorber does not react with the silicon compound B1 or interact with each other, and usually at least A part reacts or interacts with at least one selected from silicon compound A, silicon compound B (excluding silicon compound B1) and organic polymer. This reaction or intermolecular interaction contributes to suppression of bleed-out by fixing the ultraviolet absorber in the film, as in the reaction with the silicon compound B1.
  • organic polymer examples include polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polycaprolactone polyol, and polyvinyl acetal resin. Polyvinyl acetate, polyalkylene glycol resins and the like are known.
  • a preferable organic polymer in the present embodiment is an organic polymer having an epoxy group in the molecule. However, this organic polymer may exist as an organic polymer formed by ring-opening at least a part of the epoxy groups in some cases in the film forming solution or the ultraviolet shielding film.
  • an organic polymer containing a polar group (a carbonyl group, a hydroxyl group, a phenolic hydroxyl group, etc.) capable of hydrogen bonding with a silanol group or a phenolic hydroxyl group
  • a particularly preferable organic polymer is a polyalkylene glycol resin.
  • the polyalkylene glycol-based resin include polyethers that are glycols and derivatives of polyethers, and examples of these polymers include polypropylene glycol and polyethylene glycol dimethacrylate.
  • a polyalkylene glycol resin can effectively suppress the generation of foreign matter in the ultraviolet shielding film, and a film with high wear resistance can be obtained even when the drying temperature after application of the film forming solution is low. Can be obtained.
  • an organic polymer containing an organic group (phenyl group, alkenyl group having a conjugated double bond, etc.) capable of interacting with the aromatic ring of the ultraviolet absorber can be exemplified, and this polymer As an example, bisphenol polyol can be mentioned.
  • the organic polymer is preferably an organic polymer that is soluble in ethanol and / or water.
  • Whether or not it is dissolved in ethanol (water) is determined by whether or not 1 g or more of the organic polymer is dissolved in 100 g of ethanol (water) at 25 ° C. Since the organic polymer is not required to absorb ultraviolet light, the organic polymer does not correspond to a compound that does not correspond to an ultraviolet absorber, specifically, the compounds listed above from benzotriazole compounds to cyanoacrylate compounds and organic dyes. Use a good one.
  • the average number of epoxy groups in the molecule of the organic polymer having an epoxy group may be 2 to 10.
  • organic polymer having an epoxy group examples include polyglycidyl compounds such as polyglycidyl ether compounds, polyglycidyl ester compounds, and polyglycidyl amine compounds.
  • the organic polymer having an epoxy group may be either an aliphatic polyepoxide or an aromatic polyepoxide, but is preferably an aliphatic polyepoxide.
  • Preferred organic polymers having an epoxy group are polyglycidyl ether compounds, particularly aliphatic polyglycidyl ether compounds.
  • the polyglycidyl ether compound is preferably an alcohol glycidyl ether having two or more hydroxyl groups.
  • the alcohol is preferably an aliphatic alcohol, an alicyclic alcohol, or a sugar alcohol.
  • Examples of the glycidyl ether of alcohol having two or more hydroxyl groups include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, Examples include diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. These may use only 1 type and may use 2 or more types together.
  • aliphatic polyols having three or more hydroxyl groups such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. from the viewpoint of wear resistance of the ultraviolet shielding film.
  • Polyglycidyl ether one having an average number of glycidyl groups (epoxy groups) exceeding 2 per molecule is preferred.
  • Organic polymer is a component that contributes to improving the dispersibility of UV absorbers through high affinity with UV absorbers, which are also organic substances, and suppresses bleed-out, improving film flexibility and thickening the film thickness. Even if it is a case, while making it difficult to produce a crack in a film
  • an organic polymer having an epoxy group is a component that contributes to improving the adhesion of a film formed on the surface of the transparent substrate (glass body) having low reactivity.
  • the acid has an acid dissociation constant of less than 1 and a boiling point of 130 ° C. or less, and may be an inorganic acid or an organic acid.
  • the inorganic acid include at least one selected from hydrochloric acid, nitric acid, hydrobromic acid and hydroiodic acid, and hydrochloric acid and nitric acid are preferable. These volatile acids are easier to remove by heating than non-volatile inorganic acids typified by sulfuric acid and phosphoric acid.
  • Examples of the organic acid include trifluoroacetic acid (pKa: 0.23, boiling point: 72.4 ° C.).
  • An organic acid having a low boiling point is easy to remove by heating, like a volatile inorganic acid.
  • an acid that can be easily removed in the drying step is used as the hydrolysis catalyst, whether it is an inorganic acid or an organic acid.
  • the component derived from the hydrolysis catalyst remaining in the membrane can be a factor that impairs the transparency of the membrane after long-term use.
  • pKa ⁇ log ⁇ [H 3 O + ] [A ⁇ ] / [HA] ⁇
  • [H 3 O + ] is the hydrogen ion concentration (mol / L) in the aqueous acid solution
  • [A ⁇ ] is the base concentration (mol / L) in the aqueous acid solution
  • [HA] is in the aqueous HA solution.
  • Concentration (mol / L) When the acid dissociates in multiple stages from the acidic group of HA, pKa means the acid dissociation constant of the first stage.
  • the boiling point of the acid is preferably 100 ° C. or lower, and may be 80 ° C. or lower.
  • the acid is preferably at least one selected from hydrochloric acid, nitric acid and trifluoroacetic acid.
  • the film forming solution may contain an infrared absorber.
  • infrared absorbers include polymethine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, dithiol compounds, immonium compounds, diimonium compounds, aminium compounds, pyrylium compounds, cerium compounds, squarylium compounds, and benzene.
  • Organic infrared absorbers such as counterion conjugates of dithiol metal complex anions and cyanine dye cations; tungsten oxide, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, oxidation Zinc, iron oxide, antimony oxide, lead oxide, bismuth oxide, lanthanum oxide, tungsten oxide, indium tin oxide, antimony tin oxide, fluorine-doped tin oxide, etc.
  • Inorganic infrared absorbing agent and the like.
  • An infrared absorber may be used independently and may use 2 or more types together.
  • the infrared absorber is preferably at least one selected from indium tin oxide, antimony tin oxide, and fluorine-doped tin oxide.
  • the film forming solution may contain inorganic oxide fine particles.
  • the inorganic oxide constituting the inorganic oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica fine particles. is there.
  • Silica fine particles can be introduced into the film-forming solution by adding colloidal silica, for example.
  • the inorganic oxide fine particles are excellent in the action of transmitting the stress applied to the ultraviolet shielding film to the substrate supporting the ultraviolet shielding film, and have a high hardness. Therefore, the addition of inorganic oxide fine particles is advantageous from the viewpoint of improving the wear resistance of the ultraviolet shielding film.
  • an organic solvent it is preferable to add an organic solvent to the film forming solution in order to enhance the solubility of organic substances in the constituent components.
  • the organic solvent a solvent mixed with water in an arbitrary ratio is preferable, and a lower alcohol (methanol, ethanol, propanol) having 1 to 3 carbon atoms is particularly preferable.
  • additives may be added to the film forming solution.
  • examples of the additive include a surfactant having a function of improving the appearance of the ultraviolet shielding film and the dispersibility of the ultraviolet absorber.
  • Leveling agents, antifoaming agents, preservatives and the like may be added as additives.
  • the component CA produced by condensation polymerization of the hydrolyzate of the silicon compound A represented by the formula (3) is SiO 2 .
  • the component CB produced by condensation polymerization of the hydrolyzate of the silicon compound B represented by the formula (4) can be represented by [R 1 m R 2 n SiO (4-mn) / 2 ].
  • the component CB includes a component CB1 generated by condensation polymerization of the hydrolyzate of the silicon compound B1, and a component CB2 generated by condensation polymerization of the hydrolyzate of the silicon compound B2.
  • R 1 , R 2 , m, and n are as described above.
  • the ratio (p / r) of the total mass p of the component CA to the total mass r of the component CA and the component CB is preferably 0.1 or more and less than 0.8, more preferably 0.35 or more and 0.48 or less. It may be 40 or more and 0.48 or less.
  • the ratio (q / r) of the total mass q of the component CB to the total mass r of the component CA and the component CB is preferably more than 0.2 and 0.9 or less, more preferably 0.52 or more and 0.65 or less, It may be 0.52 or more and 0.60 or less.
  • the ratio (c / r) of the mass c of the component CB1 to the total mass r of the component CA and the component CB may be 0 or more and 0.9 or less.
  • the ratio (d / r) of the mass d of the component CB2 to the total mass r of the component CA and the component CB may be 0 or more and 0.4 or less.
  • the ratio (s / r) of the mass s of the organic polymer to the total mass r of the component CA and the component CB (s / r) is preferably 0.001 or more and 1 or less, more preferably 0.001 or more and 0.8 or less. It may be 001 or more and 0.6 or less.
  • the ultraviolet absorber is preferably contained in the film forming solution so that the content in the formed ultraviolet shielding film is 0.5 to 40% by mass, and more preferably 10 to 40% by mass. is there. Moreover, 0.005 or more and 0.7 or less may be sufficient as ratio (e / r) of the mass e of the ultraviolet absorber with respect to the total mass r of component CA and component CB.
  • the preferred content of acid in the film forming solution is 0.001 to 1% by mass, more preferably 0.001 to 0.6% by mass, based on the mass of the film forming solution.
  • the number of moles of water in the film forming solution is preferably 15 times or less, more preferably 4 to 12 times, for example 4 to 10 times the total number of moles of silicon atoms contained in the film forming solution. If the number of moles of water is not increased to the above level, a transparent film can be easily obtained. In addition, if at least the above-mentioned degree is ensured without reducing the number of moles of water, it becomes easy to obtain a denser and higher wear resistant film.
  • the method for preparing the film-forming solution is not particularly limited, but it may be carried out by sequentially supplying each component described above to one container, for example, a mixing tank equipped with a stirring device, in order without limitation, and stirring. .
  • the container only the ultraviolet absorber that has not reacted with either the silicon compound A or the silicon compound B is supplied as the ultraviolet absorber.
  • the entire amount of the ultraviolet absorber is supplied to the container without being subjected to the silylation treatment using the silicon compound A and the silicon compound B.
  • an acid having an acid dissociation constant of less than 1 and a boiling point of 130 ° C. or less is supplied as a hydrolysis catalyst in the container.
  • Film-forming solution 2> A preferred embodiment of the film forming solution based on the sol-gel method will be described.
  • the organic solvent used in the sol-gel method needs to be a solvent that has high compatibility with silicon alkoxide and water and can promote the sol-gel reaction, and a lower alcohol having 1 to 3 carbon atoms is suitable.
  • the silicon alkoxide is not particularly limited, and silicon tetramethoxide, silicon tetraethoxide (TEOS), silicon tetraisopropoxide, or the like may be used.
  • a hydrolyzate of silicon alkoxide may be used as a silicon raw material.
  • Water is expressed by a molar ratio with respect to silicon alkoxide and is preferably 4 times or more, specifically 4 to 40 times, preferably 4 to 35 times.
  • an acid catalyst particularly a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, and paratoluenesulfonic acid. Since the organic substance derived from the acid catalyst may lower the film hardness, an inorganic acid is preferable as the acid catalyst. Hydrochloric acid is the most preferred acid catalyst because it is highly volatile and hardly remains in the membrane.
  • the concentration of the acid catalyst is preferably in the range of 0.001 to 2 mol / kg, expressed by the molar concentration of protons when it is assumed that the protons are completely dissociated from the acid.
  • the solution for forming a film by the sol-gel method containing the above-mentioned components is mixed with a dispersion in which fine particles of an ultraviolet absorber are dispersed, and an organic polymer or the like is further added as necessary.
  • the method for preparing the ultraviolet shielding film forming solution is not limited to this.
  • Components necessary for film formation by the sol-gel method may be sequentially added to the fine particle dispersion, or the film may be formed by a method other than the sol-gel method.
  • a forming solution containing components necessary for the method (for example, polysilazane) may be prepared together with the fine particles of the ultraviolet absorber.
  • UV absorber The ultraviolet absorber is not particularly limited as long as it is solid at room temperature, has a molecular weight of 5000 or less, and can be pulverized so as to have an average particle size of 150 nm or less.
  • Benzotriazole, benzophenone, triazine, polymethine Conventionally known UV absorbers such as those based on imidazole or imidazoline can be used.
  • the molecular weight of the ultraviolet absorber is preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less, and in some cases 1300 or less, further 1200 or less, particularly 900 or less, and particularly 800 or less. However, if the molecular weight of the ultraviolet absorber is too low, it becomes difficult to maintain a solid at room temperature. Therefore, the molecular weight of the ultraviolet absorber is preferably 200 or more, more preferably 300 or more, and even more preferably 500 or more.
  • the ultraviolet absorber preferably does not contain a polymerizable carbon-carbon double bond in the molecule.
  • the polymerizable carbon-carbon double bond include a double bond contained in a polymerizable functional group such as a vinyl group, a vinylene group, or a vinylidene group. It is preferable that the ultraviolet absorber does not contain these functional groups in the molecule.
  • a preferable example of the ultraviolet absorber is an organic compound ⁇ having two or more functional groups represented by the following formula (5), for example, 2 to 8, preferably 2 to 4, in the molecule.
  • a 1 to A 5 each independently represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 20, preferably 5 to 15 carbon atoms, more preferably 7 to 13 carbon atoms. Or a functional group represented by the following formula (6). However, at least one of A 1 to A 5 is a functional group represented by the following formula (6).
  • Organic compound ⁇ is a benzotriazole ultraviolet absorber containing at least two benzotriazole structures (see formula (6)) in the molecule.
  • a benzotriazole structure present in at least two molecules in one molecule contributes to the ultraviolet shielding effect by the organic compound ⁇ , and also contributes to keeping the molecular weight large enough that the organic compound ⁇ is in a solid state at room temperature.
  • the melting point of a compound is not determined only by the molecular weight, but the molecular weight is a factor that greatly affects the melting point.
  • the organic compound ⁇ is a compound that is excellent in the durability of the ultraviolet shielding effect and is suitable for forming an ultraviolet shielding film having a low haze ratio, which is a particularly important characteristic in the case of a glass laminate.
  • the functional group represented by formula (5) is, for example, one of A 1 to A 5 is a hydroxyl group, one is an alkyl group as defined above, and one is a functional group represented by formula (6). There may be two remaining hydrogen atoms.
  • the organic compound ⁇ preferably has two or more functional groups represented by the following formula (7) in the molecule.
  • R 1 is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 5 to 15 carbon atoms, more preferably 7 to 13 carbon atoms.
  • the hydrophobicity of the whole molecule tends to increase as the number of carbon atoms of the alkyl group contained in the organic compound ⁇ increases, it may be present as fine particles in a film prepared from a dispersion liquid containing water as a dispersion medium. It becomes easy. However, when the number of carbon atoms increases too much, the melting point of the organic compound ⁇ tends to decrease due to the influence of steric hindrance or the like.
  • the organic compound ⁇ has a structural unit in which two functional groups represented by the formula (7) are bonded by an alkylene group.
  • the number of carbon atoms constituting the alkylene group is preferably 3 or less, particularly preferably 2 or less.
  • the organic compound ⁇ may be a compound represented by the following formula (8).
  • R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 20, preferably 5 to 15 carbon atoms, more preferably 7 to 13 carbon atoms.
  • Another preferred example of the ultraviolet absorber is an organic compound ⁇ having a structural unit represented by the following formula (8) in the molecule.
  • the organic compound ⁇ is a benzenethiol copper complex derivative.
  • the benzenedithiol copper complex contributes to absorption of light having a wavelength of about 400 nm due to the resonance effect derived from the structure represented by the formula (9).
  • the wavelength absorbed by the resonance effect is shifted when Cu is substituted with another metal atom (for example, when Cu is substituted with Zn or Al, the resonance effect is obtained in a shorter wavelength region).
  • Cu is optimal as the metal atom.
  • the organic compound ⁇ preferably has a structure represented by the following formula (10), more preferably has a structure represented by the formula (11), and may be a compound of the formula (15), for example.
  • L and M are each independently a group represented by any of the following formulas (12), (13), and (14).
  • A is a quaternary ammonium salt.
  • the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetraisopropylammonium salt, tetrabutylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt and trimethylbenzylammonium salt.
  • R 3 and R 4 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.
  • n is an integer from 3 to 5.
  • Bu is a linear or branched butyl group.
  • UV absorber is solid at room temperature.
  • room temperature is used as a term meaning 25 ° C.
  • an ultraviolet absorber that is liquid at room temperature has been used for an ultraviolet shielding film formed from a solution.
  • the ultraviolet absorber is dispersed as a fine liquid.
  • an organic compound that is solid at room temperature is usually dissolved in a solvent and then introduced into the film. This is because the organic compound introduced as a solid into the film formed on the glass plate often impairs the transparency of the glass laminate.
  • the ultraviolet absorber is dispersed as fine particles having an average particle diameter of 150 nm or less in the ultraviolet shielding film.
  • the ultraviolet absorbent is finely crushed to an extent that the average particle size is 150 nm or less and then introduced into the film, the film can be excellent in sustainability of ultraviolet shielding ability without impairing transparency.
  • the ultraviolet absorbent thus introduced into the film preferably retains the crystalline state even in the film. It can be confirmed by X-ray diffraction that the ultraviolet absorber in the film maintains the crystalline state.
  • the time required for the ultraviolet absorber to be pulverized to reach a predetermined average particle size depends on the pulverization conditions such as the type of the pulverizer, the input amount, and the rotation speed. For this reason, in mass production, when the average particle size of the pulverized material sampled by repeatedly interrupting the pulverization with the pulverizer is confirmed in advance, the time until a predetermined average particle size is obtained is determined. Good. In pulverization, a surfactant, a water-soluble resin, or the like may be appropriately added to the ultraviolet absorber to be pulverized.
  • the ultraviolet absorber may be dispersed in the film as fine particles having an average particle size of 150 nm or less, preferably 10 to 150 nm, more preferably 50 to 140 nm, and particularly preferably 70 to 140 nm. Also in the preparation of the fine particle dispersion (fine particle dispersion composition), it is preferable to pulverize the ultraviolet absorber so as to have an average particle diameter in this range. If the average particle size of the fine particles is too large, the transparency of the film is lowered, but if it is too small, the ultraviolet absorbing ability may be deteriorated or the sustainability thereof may be lowered.
  • the “average particle diameter” is a numerical value based on a measured value by a dynamic light scattering method, which is a kind of photon correlation method, including a measured value in an example column to be described later. This is the particle size at which the cumulative frequency is 50% in the volume-based distribution of the size.
  • the “average particle size” can be measured, for example, using “Microtrac Ultra Fine Particle Size Distribution Meter 9340-UPA150” manufactured by Nikkiso Co., Ltd.
  • the ultraviolet absorber is 1 to 80%, more preferably 5 to 60%, especially 5 to 50%, especially 7 to 30%, expressed by mass%, with respect to silicon oxide (SiO 2 equivalent) in the film. It is preferable that it is contained in the range. Considering this, the ultraviolet absorber is also expressed in terms of mass% with respect to the liquid amount of the film forming solution, and is 0.5 to 25%, more preferably 0.5 to 15%. It is preferable to add.
  • Organic polymer contributes to the improvement of the dispersibility of the UV absorber in the film by the interaction with the UV absorber (benzotriazole-based UV absorber). It is a component that suppresses deterioration.
  • an ultraviolet shielding film is formed relatively thick (for example, a thickness exceeding 300 nm or even a thickness of 500 nm or more) by liquid phase film formation such as a sol-gel method, the liquid component contained in the film forming solution is evaporated. Accompanied by this, cracks may occur.
  • the organic polymer is also a component that enables the formation of a thick film while suppressing the occurrence of cracks.
  • the organic polymer is preferably at least one selected from polyether compounds, polyol compounds, polyvinyl pyrrolidones and polyvinyl caprolactams.
  • the organic polymer may be a polyether compound such as a polyether type surfactant, or may be a polyol compound such as polycaprolactone polyol or bisphenol A polyol.
  • the organic polymer may be polyethylene glycol, polypropylene glycol, or the like.
  • the polyether compound means a compound containing two or more ether bonds, and the polyol compound means a polyhydric alcohol containing diol and triol.
  • the polyvinyl pyrrolidone specifically refers to polyvinyl pyrrolidone and its derivatives
  • the polyvinyl caprolactam specifically refers to polyvinyl caprolactam and its derivatives.
  • the organic polymer is expressed in mass% with respect to silicon oxide (in terms of SiO 2 ) in the film, and is 0 to 75%, more preferably 0.05 to 50%, particularly 0.1 to 40%, especially 1 to 30%. %, Sometimes 10% or less, and if necessary, 7% or less. In addition, when there are many ultraviolet absorbers, you may reduce an organic polymer according to the quantity.
  • the type of the silane coupling agent is not particularly limited, but RSiX 3 (R is an organic functional group containing at least one selected from a vinyl group, a glycidoxy group, a methacryl group, an amino group, and a mercapto group. And X is a halogen element or an alkoxyl group).
  • R is an organic functional group containing at least one selected from a vinyl group, a glycidoxy group, a methacryl group, an amino group, and a mercapto group.
  • X is a halogen element or an alkoxyl group.
  • the silane coupling agent contributes to the improvement of the dispersibility of the ultraviolet absorber in the film, and has the effect of enabling the formation of a thick film while suppressing the occurrence of cracks.
  • the silane coupling agent is expressed in mol% with respect to silicon oxide (SiO 2 equivalent) in the film so that it is 0 to 40%, preferably 0.1 to 20%, more preferably 1
  • the ultraviolet shielding film according to the present invention may contain functional components other than the ultraviolet absorber, the organic polymer, and the silane coupling agent.
  • functional components other than the ultraviolet absorber, the organic polymer, and the silane coupling agent.
  • ITO indium tin oxide
  • near infrared absorbers are one of the components that are preferably added to the ultraviolet shielding film.
  • the ITO fine particles may be dispersed in the film as fine particles having an average particle diameter of 200 nm or less, preferably 5 to 150 nm. Similar to the fine particles of the ultraviolet absorber, if the particle size is too large, the transparency of the film is lowered, and if it is too small, the effect of addition cannot be sufficiently obtained. It is preferable to prepare a dispersion liquid of ITO fine particles in advance and add this to the film forming solution.
  • the ultraviolet shielding film contains silicon oxide as an inorganic component.
  • the ultraviolet shielding film may contain an inorganic component other than silicon oxide.
  • inorganic components other than silicon oxide include components derived from the acid catalyst used in the sol-gel method (for example, chlorine, nitrogen, sulfur atoms) in addition to the ITO fine particles.
  • Silicon oxide contained in the ultraviolet shielding film is added to the film forming solution as a silicon-containing compound (silicon compound) such as silicon alkoxide.
  • Silicon oxide in the ultraviolet shielding film is 30% by mass or more of the entire film, preferably 40% by mass or more, more preferably 50% by mass or more (in this case, silicon oxide is the main component of the film). It is preferable to occupy at least mass%.
  • the ultraviolet shielding film preferably has silicon oxide as a main component, and has a form in which fine particles of ultraviolet absorbers and other components are dispersed in a Si—O bond network. A film having such a form is suitable for outdoor use as a window glass or the like.
  • the film forming solution contains an organic substance and an inorganic oxide.
  • the organic substance includes a water absorbent resin, and the inorganic oxide includes silica.
  • the film forming solution contains an ultraviolet absorber and / or an infrared absorber.
  • Water absorbent resin there is no particular limitation as the water absorbent resin, polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, epoxy resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, A polyvinyl acetal resin, polyvinyl acetate, etc. are mentioned. Of these, preferred are hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resin, polyvinyl acetate, epoxy resin and polyurethane resin, and more preferred are polyvinyl acetal resin, epoxy resin and polyurethane resin. Among them, polyvinyl acetal resin is particularly preferable.
  • the polyvinyl acetal resin can be obtained by subjecting polyvinyl alcohol to an acetalization by a condensation reaction of aldehyde with polyvinyl alcohol.
  • the acetalization of polyvinyl alcohol may be carried out using a known method such as a precipitation method using an aqueous medium in the presence of an acid catalyst, or a dissolution method using a solvent such as alcohol.
  • Acetalization can also be carried out in parallel with saponification of polyvinyl acetate.
  • the degree of acetalization is preferably 2 to 40 mol%, more preferably 3 to 30 mol%, particularly 5 to 20 mol%, and in some cases 5 to 15 mol%.
  • the degree of acetalization can be measured based on, for example, 13 C nuclear magnetic resonance spectroscopy.
  • a polyvinyl acetal resin having an acetalization degree in the above range is suitable for forming a film-forming solution having good water absorption and water resistance.
  • the average degree of polymerization of polyvinyl alcohol is preferably 200 to 4500, more preferably 500 to 4500.
  • a high average degree of polymerization is advantageous for the formation of a film-forming solution having good water absorption and water resistance, but if the average degree of polymerization is too high, the viscosity of the solution becomes too high, which may hinder film formation. is there.
  • the saponification degree of polyvinyl alcohol is preferably 75 to 99.8 mol%.
  • aldehyde to be subjected to a condensation reaction with polyvinyl alcohol examples include aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexyl carbaldehyde, octyl carbaldehyde, decyl carbaldehyde.
  • benzaldehyde 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, other alkyl group-substituted benzaldehydes; chlorobenzaldehyde, other halogen atom-substituted benzaldehydes; alkyl such as hydroxy group, alkoxy group, amino group, cyano group
  • aromatic aldehydes such as condensed aromatic aldehydes such as naphthaldehyde and anthraldehyde.
  • An aromatic aldehyde having strong hydrophobicity is advantageous in forming a film-forming solution having a low degree of acetalization and excellent water resistance.
  • the use of an aromatic aldehyde is also advantageous in forming a film having high water absorption while leaving many hydroxyl groups remaining.
  • the polyvinyl acetal resin preferably contains an acetal structure derived from an aromatic aldehyde, particularly benzaldehyde.
  • epoxy resin examples include glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and cyclic aliphatic epoxy resin. Of these, cycloaliphatic epoxy resins are preferred.
  • polyurethane resin examples include a polyurethane resin composed of a polyisocyanate and a polyol.
  • a polyurethane resin composed of a polyisocyanate and a polyol.
  • the polyol an acrylic polyol and a polyoxyalkylene polyol are preferable.
  • the film forming solution contains a water-absorbing resin as a main component.
  • the “main component” means a component having the highest content on a mass basis.
  • the content of the water-absorbing resin based on the weight of the film-forming solution is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 65% by weight or more from the viewpoints of film hardness, water absorption and antifogging properties. And is 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.
  • the inorganic oxide is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce, and Sn, and includes at least an Si oxide (silica).
  • the film-forming solution is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, further preferably 0.2 parts by weight or more, particularly preferably 1 part by weight with respect to 100 parts by weight of the water absorbent resin. Part or more, most preferably 5 parts by weight or more, in some cases 10 parts by weight or more, if necessary, 20 parts by weight or more, preferably 50 parts by weight or less, more preferably 45 parts by weight or less, still more preferably 40 parts by weight.
  • the inorganic oxide is included so that the amount is 35 parts by weight or less, particularly preferably 35 parts by weight or less, most preferably 33 parts by weight or less, and in some cases, 30 parts by weight or less.
  • the inorganic oxide is a component necessary for ensuring the strength of the film-forming solution, particularly the abrasion resistance, but the antifogging property of the film-forming solution decreases when the content thereof increases.
  • the film forming solution may further contain inorganic oxide fine particles as at least a part of the inorganic oxide.
  • the inorganic oxide constituting the inorganic oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica fine particles. is there.
  • Silica fine particles can be introduced into the film-forming solution by adding colloidal silica, for example.
  • the inorganic oxide fine particles are excellent in the action of transmitting the stress applied to the film forming solution to the article supporting the film forming solution, and have high hardness. Therefore, the addition of inorganic oxide fine particles is advantageous from the viewpoint of improving the wear resistance of the film forming solution.
  • inorganic oxide fine particles when added to the film forming solution, fine voids are formed at sites where the fine particles are in contact or close to each other, and water vapor is easily taken into the film from the voids. For this reason, the addition of inorganic oxide fine particles may sometimes have an advantageous effect on improving the antifogging property.
  • the inorganic oxide fine particles can be supplied to the film forming solution by adding the preformed inorganic oxide fine particles to the coating liquid for forming the film forming solution.
  • the average particle size of the inorganic oxide fine particles is preferably 1 to 20 nm, and more preferably 5 to 20 nm.
  • the average particle diameter of the inorganic oxide fine particles is described in the state of primary particles.
  • the average particle size of the inorganic oxide fine particles is determined by measuring the particle sizes of 50 fine particles arbitrarily selected by observation using a scanning electron microscope and adopting the average value. When the content of the inorganic oxide fine particles increases, the water absorption amount of the entire film forming solution decreases, and the film forming solution may become cloudy.
  • the inorganic oxide fine particles are preferably 0 to 50 parts by weight, more preferably 2 to 30 parts by weight, still more preferably 5 to 25 parts by weight, and particularly preferably 10 to 20 parts by weight with respect to 100 parts by weight of the water absorbent resin. It is good to add so that it may become a part.
  • a metal compound having a hydrolyzable group (hydrolyzable metal compound) or a hydrolyzate thereof is added to the coating solution for forming the film-forming solution.
  • a metal compound having a hydrolyzable group (hydrolyzable metal compound) or a hydrolyzate thereof is added to the coating solution for forming the film-forming solution.
  • a silicon compound having a hydrolyzable group represented by the following formula (I) is preferable.
  • the silica contained in the inorganic oxide preferably contains a silicon compound having a hydrolyzable group or silica derived from the hydrolyzate thereof.
  • the silicon compound having a hydrolyzable group represented by the formula (I) may be used alone or in combination of two or more.
  • a silica compound bonded with a siloxane bond, in which an organic metal is directly bonded to a part of the silicon is also included in silica.
  • R in the formula (I) is a hydrocarbon group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted with a reactive functional group.
  • the hydrocarbon group having 1 to 3 carbon atoms includes an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group) and an alkenyl group having 2 to 3 carbon atoms (vinyl group, allyl group). , Propenyl group) and the like.
  • the reactive functional group is preferably at least one selected from an oxyglycidyl group and an amino group.
  • the hydrolyzable metal compound having a reactive functional group can strongly bond a water-absorbing resin that is an organic substance and silica that is an inorganic oxide, and can contribute to an improvement in wear resistance, hardness, and the like of the film-forming solution.
  • X in the formula (I) is a hydrolyzable group or a halogen atom.
  • the hydrolyzable group include at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, and an amino group.
  • the alkoxyl group include an alkoxyl group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group) and the like.
  • an alkoxyl group is preferable, and an alkoxyl group having 1 to 4 carbon atoms is more preferable.
  • An example of the halogen atom is chlorine.
  • M in the formula (I) is an integer of 0 to 2, preferably an integer of 0 to 1.
  • a preferred specific example of the silicon compound having a hydrolyzable group represented by the formula (I) is a silicon alkoxide in which X in the formula (I) is an alkoxyl group.
  • Specific examples of the tetrafunctional silicon alkoxide include tetramethoxysilane and tetraethoxysilane. Silicon alkoxides may be used alone or in combination of two or more, and when two or more types are used in combination, the main component of silicon alkoxide is more preferably tetrafunctional silicon alkoxide.
  • the trifunctional silicon alkoxide having no reactive functional group include methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, and the like.
  • trifunctional silicon alkoxide having a reactive functional group examples include glycidoxyalkyltrialkoxysilane (3-glycidoxypropyltrimethoxysilane, etc.), aminoalkyltrialkoxysilane (3-aminopropyltriethoxysilane, etc.). ) And the like.
  • Silicon alkoxides having reactive functional groups are sometimes referred to as silane coupling agents.
  • Specific examples of the bifunctional silicon alkoxide in which at least one of R has a reactive functional group include glycidoxyalkylalkyldialkoxysilane (3-glycidoxypropylmethyldimethoxysilane and the like), aminoalkylalkyldialkoxysilane [N -2- (aminoethyl) -3-aminopropylmethyldimethoxysilane etc.] and the like.
  • the silicon alkoxide preferably contains a silane coupling agent.
  • light shielding for example, ultraviolet shielding
  • the silane coupling agent makes the light absorber, which is an organic compound, more uniformly dispersed in the water-absorbing resin containing silica.
  • the silicon compound having a hydrolyzable group represented by the formula (I) supplies a component represented by the following formula (II) when the hydrolysis and polycondensation completely proceed.
  • R m SiO (4-m) / 2 (II) R and m in the formula (II) are as described above. After hydrolysis and polycondensation, the compound represented by the formula (II) is actually a siloxane bond in which a silicon atom and an oxygen atom are alternately connected in a film-forming solution and spread three-dimensionally ( Si—O—Si) network structure is formed.
  • silica derived from tetrafunctional silicon alkoxide or trifunctional silicon alkoxide in the film forming solution When the content of silica derived from tetrafunctional silicon alkoxide or trifunctional silicon alkoxide in the film forming solution is increased, the antifogging property of the film forming solution may be lowered. This is partly due to the reduced flexibility of the film-forming solution and the limited swelling and shrinkage of the film that accompanies moisture absorption and release.
  • Silica derived from tetrafunctional silicon alkoxide is preferably added in an amount of 0 to 30 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the water absorbent resin. .
  • Silica derived from trifunctional silicon alkoxide is preferably in the range of 0 to 30 parts by weight, more preferably 0.05 to 15 parts by weight, and still more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the water absorbent resin. Should be added.
  • the ultraviolet absorber and the infrared absorber may be the same as the film forming solutions 1 and 2 described above.
  • the film forming solution may contain a crosslinked structure derived from at least one crosslinking agent selected from an organic boron compound, an organic titanium compound, and an organic zirconium compound.
  • the introduction of a crosslinked structure improves the wear resistance and water resistance of the film forming solution. From another point of view, the introduction of a crosslinked structure facilitates improving the durability of the film-forming solution without degrading the anti-fogging performance.
  • the type of the crosslinking agent is not particularly limited as long as it can crosslink the water-absorbing resin to be used.
  • the organic titanium compound is, for example, at least one selected from titanium alkoxide, titanium chelate compound, and titanium acylate.
  • the titanium alkoxide is, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, or titanium tetraoctoxide.
  • the titanium chelate compound include titanium acetylacetonate, titanium ethylacetoacetate, titanium octylene glycol, titanium triethanolamine, and titanium lactate.
  • the titanium lactate may be an ammonium salt (titanium lactate ammonium).
  • the titanium acylate is, for example, titanium stearate.
  • Preferred organic titanium compounds are titanium chelate compounds, especially titanium lactate.
  • a preferable crosslinking agent is an organic titanium compound, particularly titanium lactate.
  • the additive may be a surfactant, a surface conditioner, a slip property imparting agent, a leveling agent, an antifoaming agent, a preservative, and the like.
  • the film-forming solution is applied using a conventionally known method such as a flow coating method, a dip coating method, a spin coating method, a spray coating method, a roll coating method, a meniscus coating method, or a die coating method. Can do.
  • the relative humidity (RH) of the atmosphere it is preferable to maintain the relative humidity (RH) of the atmosphere at less than 40%, and further 30% or less. If the relative humidity is kept low, the applied film can be prevented from excessively absorbing moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, the water remaining in the membrane matrix may reduce the strength of the membrane.
  • the temperature at which the transparent substrate is dried after applying the film-forming solution is 130 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and may be 180 ° C. or higher in some cases.
  • the drying temperature is preferably 300 ° C. or lower, particularly 250 ° C. or lower, and in some cases 200 ° C. or lower, from the viewpoint of avoiding decomposition of the ultraviolet absorber, the organic polymer and the like.
  • the drying step preferably includes an air drying step and a heat drying step with heating.
  • the air drying step may be carried out by exposing the film forming solution to an atmosphere maintained at a relative humidity of less than 40%, and further 30% or less.
  • the air drying step can be performed at room temperature as a non-heating step.
  • a dehydration reaction involving silanol groups contained in the hydrolyzate of silicon compound A and silicon compound B and hydroxyl groups present on the transparent substrate proceeds, and a matrix composed of silicon atoms and oxygen atoms.
  • the ultraviolet shielding film is fixed on the glass body.
  • the film thickness of the ultraviolet shielding film is not particularly limited, but can be, for example, 0.5 to 10 ⁇ m, and preferably 1 to 5 ⁇ m. When the film thickness of the ultraviolet shielding film exceeds 10 ⁇ m, the glass laminate is yellow, and there is a possibility that cracks may occur in the film. In order to effectively realize the ultraviolet shielding function, the film thickness is preferably uniform, and the uniformity of the film thickness distribution is preferably 70% or less.
  • the film thickness can be adjusted, for example, by applying a film-forming solution and then blowing it toward the glass body with a blower or the like.
  • the film thickness of the ultraviolet shielding film can be set such that, for example, the film thickness on the lower side is larger than that on the upper side in the region excluding the range of 20 mm in width from the periphery of the ultraviolet shielding film. Thereby, especially the ultraviolet-ray irradiated to the lower part side of a glass laminated body can be shielded.
  • Such film thickness distribution can be realized by a flow coating method.
  • the film thickness of the ultraviolet shielding film is, for example, a position where the film thickness is maximum (0.5 to 10 ⁇ m) in the region excluding the range of 20 mm from the periphery of the ultraviolet shielding film from the edge of this region.
  • the position can be 10 cm or more away.
  • the maximum film thickness is preferably 2 to 4 ⁇ m.
  • the transmittance of light having a wavelength of 400 nm is preferably 10% or less, and more preferably 8% or less. Moreover, it is preferable that the transmittance
  • the ultraviolet transmittance of the glass laminate of the present invention is preferably as follows. Tuv400 ⁇ 2.0% (16) Tuv400 is as described above. Further, Tuv400 in the above formula (16) is more preferably 1.0% or less.
  • the transmittance of light having a wavelength of 420 nm is preferably 20% or more, and more preferably 50% or more. This is because the transmittance of ultraviolet rays is lowered as described above, while the transmittance of light in the visible light region is rapidly increased when exceeding the ultraviolet region. That is, it is for reducing the coloring etc. which impede a visual field in a glass plate.
  • the transmittance of light having a wavelength of 420 nm is preferably 85% or less. This is to prevent the human being in the vehicle from being affected and the interior of the vehicle from being deteriorated.
  • the glass laminate of the present invention has a wavelength W1 where the transmittance of the glass laminate is Tavg * 0.9, and the transmittance of the glass plate is Tavg, when the average transmittance for light with a wavelength of 450 to 800 nm is Tavg. * It is preferable that the difference from the wavelength W2 being 0.1 (hereinafter referred to as a sharp cut) is 22 nm or less. This is as described for the glass plate as described above.
  • the transmittance of light having a wavelength of 1500 nm is preferably 35% or less, more preferably 30% or less, and particularly preferably 25% or less.
  • Light having a wavelength of 1500 nm indicates light in the near infrared region, particularly in the near infrared region of solar radiation. If the transmittance of such light is 35% or less as described above, the near-infrared ray of sunlight is appropriately shielded, and when this glass laminate is used as an automobile window glass, the temperature inside the vehicle becomes high. Can alleviate being too much.
  • the glass laminated body of this invention satisfies the following formula
  • the yellowness of the glass body is large, the yellowness of the glass laminate also increases, and there is a risk of feeling psychological discomfort such that a person inside the vehicle is irritated looking at the outside of the vehicle.
  • the blue light cut rate calculated as the effective radiation intensity reduction rate when passing through the glass laminate is the effective radiation intensity related to the blue light interference function of Annex A of JIS T7330: 2000 Is preferably 35% or more.
  • the blue light cut rate here is the ratio of the effective radiant intensity reduced by transmitting the glass laminate to the effective radiant intensity related to retinal damage caused by blue light of sunlight (hereinafter referred to as the effective radiant intensity of sunlight). , Is defined as a value expressed as a percentage. Specifically, it is obtained by the following method.
  • the weight function related to the blue light failure function in Appendix A of JIS T7330: 2000 is used.
  • the sum of wavelengths from 380 to 550 nm is calculated to determine the effective radiation intensity of sunlight.
  • the sum of the products of the spectral transmittance and weight function of the glass laminate at each wavelength in the above wavelength range is calculated, and the effective radiation intensity of the light transmitted through the glass laminate (hereinafter referred to as the effective radiation intensity of the transmitted light).
  • the ratio of the effective radiant intensity of the transmitted light to the effective radiant intensity of sunlight is calculated, and the value is subtracted from 1 and converted into a percentage. The percentage thus calculated was defined as the blue light cut rate of the glass laminate.
  • this blue light cut rate is high, it is possible to prevent glare without glare when looking outside through the glass laminate. In addition, when the yellowness mentioned above is high, a blue light cut rate will also become large.
  • Durability of glass laminate As the durability performance of the glass laminate of the present invention, it is preferable to have the following wear resistance and light resistance (ultraviolet light resistance).
  • the abrasion resistance of the glass laminate of the present invention can be evaluated by an abrasion test based on JIS R3221. That is, when the surface of the ultraviolet shielding film is worn 1000 times with a load of 500 g by a Taber abrasion tester (for example, 5050 ABRA manufactured by TABER INDUSTRIES), the ultraviolet shielding film does not peel from the glass body, and this
  • the haze ratio after the abrasion test is preferably 5% or less.
  • HZ-1S manufactured by Suga Test Instruments Co., Ltd. can be used.
  • Light resistance (UV resistance)> Light resistance (ultraviolet light resistance) can be evaluated by the following test. That is, using an ultraviolet irradiation device (EYE SUPER UV TESTER SUV-W13) manufactured by Iwasaki Electric Co., Ltd., applying the conditions of wavelength 295 to 450 nm, illuminance 76 mW / cm 2 , black panel temperature 83 ° C., humidity 50% RH, 100 The surface of the glass laminate on which the ultraviolet shielding film was not formed was irradiated with ultraviolet rays for a time. And it is preferable that the difference of Tuv400 of the glass laminated body before and behind irradiation is 2% or less.
  • the ultraviolet shielding function of the entire glass laminate can be enhanced by providing both the glass body and the ultraviolet shielding film with an ultraviolet shielding function.
  • the Tuv400 of the glass body is 50% or less
  • the light transmittance at a wavelength of 400 nm in the entire glass laminate is 10% or less
  • the Tuv400 is 2.0% or less. Therefore, it is possible to reliably shield ultraviolet rays near the upper limit of the ultraviolet region.
  • the ultraviolet-ray shielding film is formed by apply
  • an ultraviolet shielding film is formed by applying a film-forming solution to a base sheet.
  • an adhesive can be apply
  • the above-described film forming solution is applied to a transparent resin sheet material such as polyethylene or polyethylene terephthalate to form an ultraviolet shielding film.
  • a transparent resin sheet material such as polyethylene or polyethylene terephthalate
  • this sheet material is affixed on the surface of a glass body with an acrylic adhesive and a silicone type adhesive agent, for example. Also by this, the glass laminated body of this invention can be formed.
  • the ultraviolet shielding film does not have to be applied to the entire surface of the glass body, and can be applied to a necessary part.
  • a portion where the ultraviolet shielding film is not formed can be provided in at least one of the portions along the upper side and the side side. This is because, for example, this portion is stored in a glass run or the like.
  • the ultraviolet shielding film can also have antifogging performance. Thereby, an anti-fogging performance can be provided together with an ultraviolet shielding function. Therefore, dew condensation etc. can be prevented even under a situation where the window glass such as rainy weather is likely to be clouded, and a view through the window glass can be secured.
  • Such anti-fogging performance can be realized by providing the UV shielding film with water absorption performance. Thereby, water vapor and moisture can be absorbed.
  • a water-absorbing resin can be contained in the ultraviolet shielding film.
  • the water absorbent resin polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, epoxy resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, A polyvinyl acetal resin, polyvinyl acetate, etc. are mentioned.
  • hydroxyalkyl cellulose preferred are hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resin, polyvinyl acetate, epoxy resin and polyurethane resin, and more preferred are polyvinyl acetal resin, epoxy resin and polyurethane resin. Among them, polyvinyl acetal resin is particularly preferable.
  • the content of the water-absorbing resin based on the weight of the ultraviolet shielding film is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 65% by weight or more from the viewpoints of film hardness, water absorption and antifogging properties. And is 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.
  • the surface of the ultraviolet shielding film can be made hydrophilic by hydrophilic treatment. Thereby, it is possible to prevent water generated by condensation on the surface of the ultraviolet shielding film from becoming a continuous film covering the surface of the film and hindering the visibility.
  • the visibility ensuring performance means that the haze ratio of the glass laminate is low in a state where water droplets are generated on the film surface due to condensation. In other words, even when condensation occurs, the cloudiness is small. In this case, if the water droplet generated by condensation is large, the cloudiness is small and the haze ratio is small. On the other hand, if the water droplet is large, the haze ratio increases.
  • the surface of the film having such visibility ensuring performance is made hydrophobic. Therefore, since the area which a glass body is covered with the water droplet by the water produced by condensing on the film
  • the ultraviolet shielding film further contains a water repellent group.
  • Preferred water-repellent groups are linear or cyclic alkyl groups having 3 to 30 carbon atoms, and linear or cyclic alkyl groups having 1 to 30 carbon atoms in which part of hydrogen atoms are substituted with fluorine, particularly preferably carbon.
  • a water-repellent group and a hydrolyzable functional group or a compound having a halogen atom are contained in the film-forming solution, and the liquid is applied to a glass body (or a base sheet), whereby the water-repellent group is added to the ultraviolet film.
  • a glass body or a base sheet
  • the water-repellent group is added to the ultraviolet film.
  • Another means for imparting visibility ensuring performance to the glass laminate is, for example, to further form a visibility ensuring film on the ultraviolet shielding film.
  • membrane can also be laminated
  • a visibility ensuring film can be formed on either glass plate on the side opposite to the surface on which the ultraviolet shielding film is laminated.
  • the visibility ensuring film includes a water repellent group and a metal oxide component.
  • membrane may further contain the other functional component as needed, for example, may further contain resin.
  • the resin imparts flexibility to the film and contributes to improvement of hydrophobic uniformity. However, if the content of the resin is too high, the strength of the film may be reduced. Therefore, the visibility ensuring film may not contain any resin in some cases.
  • the visibility ensuring film preferably does not contain a resin when it is formed on the surface of a glass plate that can slide with other members as the window glass is opened and closed. A typical window glass that slides with another member is a vehicle door glass.
  • the water repellent group makes the surface of the visibility ensuring film hydrophobic, and makes the surface hard to condense water vapor.
  • the water-repellent group contributes to ensuring the straightness of incident light even if water droplets are formed on the surface of the visibility ensuring film, depending on the type.
  • a water-repellent group suitable for ensuring straightness of light is a linear alkyl group having 3 to 9, preferably 4 to 8, particularly 5 to 8, especially 5 to 7 carbon atoms.
  • the area where water drops formed by condensation of the same amount of water vapor on the surface of the film cover the film tends to be smaller as the contact angle of water on the surface increases.
  • the smaller the area covered by water droplets the smaller the extent to which light incident on the film is scattered.
  • the visibility ensuring film in which the contact angle of water is increased due to the presence of the water repellent group is less likely to form water droplets on the surface, and the area covered by the water droplets is relatively small even when the water droplets are formed. This is advantageous in maintaining the straightness of transmitted light.
  • the straightness of transmitted light has an influence on the uniformity of hydrophobicity as well as the hydrophobicity indicated by the contact angle of water. This is because, on the surface where the hydrophobicity of the film surface is not uniform and hydrophilic spots are scattered, water droplets are formed starting from water vapor adsorbed on the hydrophilic spots. Therefore, it is preferable that the water-repellent group is oriented on the film surface so that the film surface is uniformly hydrophobic.
  • a water repellent group suitable for existing on the film surface in a highly oriented state arranged in the same direction is a linear alkyl group having a certain number of carbon atoms. However, a long straight-chain alkyl group having too many carbon atoms is difficult to achieve high orientation because the straight-chain alkyl group is easily bent in the middle.
  • a perfluoroalkyl group is used, stronger hydrophobicity can be realized.
  • the perfluoroalkyl group is a rigid functional group whose crystallinity is remarkably increased particularly when the number of carbon atoms is large, it tends to exist in a polycrystalline orientation on the film surface. For this reason, a locally low hydrophobic portion tends to occur on the film surface. From the viewpoint of ensuring hydrophobic uniformity, a linear alkyl group having the above-described number of carbon atoms is more suitable than a perfluoroalkyl group.
  • a metal compound having a water repellent group water repellent group-containing metal compound
  • a metal compound having a water repellent group and a hydrolyzable functional group or a halogen atom water repellent group-containing hydrolyzable metal compound
  • the water repellent group may be derived from a water repellent group-containing hydrolyzable metal compound.
  • the water repellent group-containing hydrolyzable metal compound is preferably a water repellent group-containing hydrolyzable silicon compound represented by the following formula (I).
  • R is a water repellent group, specifically a linear alkyl group having 3 to 9 carbon atoms
  • Y is a hydrolyzable functional group or a halogen atom
  • m is an integer of 1 to 3.
  • the hydrolyzable functional group is, for example, at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, and an amino group, preferably an alkoxy group, particularly an alkoxy group having 1 to 4 carbon atoms.
  • An alkenyloxy group is, for example, an isopropenoxy group.
  • the halogen atom is preferably chlorine.
  • the functional groups exemplified here can also be used as “hydrolyzable functional groups” described below.
  • m is preferably 1 or 2.
  • the compound represented by formula (I) supplies the component represented by the following formula (II) when hydrolysis and polycondensation have completely proceeded.
  • R and m are as described above.
  • the compound represented by the formula (II) actually forms a network structure in which silicon atoms are bonded to each other through oxygen atoms in the visibility ensuring film.
  • the compound represented by the formula (I) is hydrolyzed or partially hydrolyzed, and further, at least partly polycondensed to alternately connect silicon atoms and oxygen atoms, and three-dimensionally.
  • a network structure of spreading siloxane bonds Si—O—Si
  • a water repellent group R is connected to silicon atoms included in the network structure.
  • the water repellent group R is fixed to the network structure of the siloxane bond through the bond R—Si. This structure is advantageous in uniformly dispersing the water repellent group R in the film.
  • the network structure may contain a silica component supplied from a silicon compound (for example, tetraalkoxysilane, silane coupling agent) other than the water repellent group-containing hydrolyzable silicon compound represented by the formula (I).
  • a silica component supplied from a silicon compound for example, tetraalkoxysilane, silane coupling agent
  • a hydrolyzable functional group or a halogen atom-containing silicon compound water repellent group-free hydrolyzable silicon compound
  • a network structure of siloxane bonds including silicon atoms bonded to water repellent groups and silicon atoms not bonded to water repellent groups can be formed. With such a structure, it becomes easy to adjust the water repellent group content and the metal oxide component content in the visibility ensuring film independently of each other.
  • the water repellent group is added to such an extent that the contact angle of water on the surface of the visibility ensuring film is 85 degrees or more, preferably 90 degrees or more, more preferably 95 degrees or more.
  • the contact angle of water a value measured by dropping a 4 mg water droplet on the surface of the membrane is adopted.
  • the upper limit of the contact angle of water is not particularly limited, but is, for example, 105 degrees or less, and further 103 degrees or less. It is preferable that the water repellent group is uniformly contained in the visibility ensuring film so that the contact angle of water is in the above range in all regions of the surface of the visibility ensuring film.
  • membrane is 1 mass part or more with respect to 100 mass parts of metal oxide components, Preferably it is 3 mass parts or more, More preferably, it is in the range of 4 mass parts or more, and 50 mass parts or less, It is preferable to include a water-repellent group so that it is preferably within a range of 30 parts by mass or less, more preferably 20 parts by mass or less, and in some cases 15 parts by mass or less.
  • the visibility ensuring film contains a metal oxide component.
  • the metal oxide component is, for example, an oxide component of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and preferably an Si oxide component (silica component) ).
  • the metal oxide component may be a hydrolyzable metal compound or a metal oxide component derived from the hydrolyzate added to the coating liquid for forming the visibility ensuring film.
  • the hydrolyzable metal compound has a) a metal compound having a water repellent group and a hydrolyzable functional group or a halogen atom (water repellent group-containing hydrolyzable metal compound), and b) a water repellent group. It is at least one selected from a metal compound having a hydrolyzable functional group or a halogen atom (a water-repellent group-free hydrolyzable metal compound).
  • the metal oxide component derived from a) and / or b) is an oxide of metal atoms constituting the hydrolyzable metal compound.
  • the metal oxide component includes a metal oxide component derived from the metal oxide fine particles added to the coating solution for forming the visibility ensuring film, and a hydrolyzable metal compound or a metal oxide component added to the coating solution. And a metal oxide component derived from the hydrolyzate.
  • the hydrolyzable metal compound is at least one selected from a) and b) above.
  • the b), that is, the hydrolyzable metal compound having no water repellent group may contain at least one selected from tetraalkoxysilane and a silane coupling agent.
  • the metal oxide fine particles and the above b) will be described except for the above-described a).
  • the visibility ensuring film may further include metal oxide fine particles as at least a part of the metal oxide component.
  • the metal oxide constituting the metal oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica fine particles. is there.
  • Silica fine particles can be introduced into the film, for example, by adding colloidal silica.
  • the metal oxide fine particles have an excellent effect of transmitting the stress applied to the visibility ensuring film to the transparent article (glass laminate) that supports the film, and have high hardness. Therefore, the addition of metal oxide fine particles is advantageous from the viewpoint of improving the wear resistance and scratch resistance of the visibility ensuring film.
  • the metal oxide fine particles can be supplied to the visibility ensuring film by adding the metal oxide fine particles formed in advance to the coating liquid for forming the visibility ensuring film.
  • the metal oxide fine particles can cause a hydrophilic spot on the surface of the film, it is desirable that the metal oxide fine particles should not be added to the film unless there are circumstances to improve the wear resistance and the like. That is, it is preferable to use the visibility ensuring film in a form that does not include metal oxide fine particles unless there is a particular situation where the wear resistance or the like should be emphasized.
  • the preferable average particle diameter of the metal oxide fine particles is 1 to 20 nm, particularly 5 to 20 nm.
  • the average particle diameter of the metal oxide fine particles is described in the state of primary particles.
  • the average particle diameter of the metal oxide fine particles is determined by measuring the particle diameters of 50 fine particles arbitrarily selected by observation using a scanning electron microscope and adopting the average value. If the content of the metal oxide fine particles is excessive, the film may become cloudy.
  • membrane may contain the metal oxide component derived from the hydrolysable metal compound (water repellent group non-containing hydrolyzable compound) which does not have a water repellent group.
  • a preferred hydrolyzable metal compound containing no water repellent group is a hydrolyzable silicon compound having no water repellent group.
  • the hydrolyzable silicon compound having no water repellent group is, for example, at least one silicon compound selected from silicon alkoxide, chlorosilane, acetoxysilane, alkenyloxysilane and aminosilane (however, having no water repellent group), Silicon alkoxide having no water repellent group is preferred.
  • An example of alkenyloxysilane is isopropenoxysilane.
  • the hydrolyzable silicon compound having no water repellent group may be a compound represented by the following formula (III).
  • SiY 4 (III) As described above, Y is a hydrolyzable functional group, and is preferably at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • the water repellent group-free hydrolyzable metal compound is hydrolyzed or partially hydrolyzed, and further, at least a part thereof is polycondensed to supply a metal oxide component in which a metal atom and an oxygen atom are bonded.
  • This component firmly bonds the metal oxide fine particles and the resin, and can contribute to improvement of the wear resistance, hardness, water resistance, etc. of the visibility ensuring film.
  • a preferred example of the hydrolyzable silicon compound having no water repellent group is tetraalkoxysilane, more specifically, tetraalkoxysilane having an alkoxy group having 1 to 4 carbon atoms.
  • Tetraalkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, and tetra-tert- It is at least one selected from butoxysilane.
  • the hydrophobicity of the visibility ensuring film may be lowered.
  • Resin is an optional component in the visibility ensuring film, but when added, in order to prevent the wear resistance of the film from deteriorating, it exceeds 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the metal oxide component. It is preferable to add in the range.
  • a preferable blending amount of the resin is, for example, 1 part by mass or more, further 5 parts by mass or more, particularly 10 parts by mass or more, 40 parts by mass or less, further 35 parts by mass or less, particularly 30 parts by mass with respect to 100 parts by mass of the metal oxide component. It is below mass parts. Addition of a large amount of resin is desirable to avoid a hydrophilic spot formed on the surface of the film.
  • the kind of resin is not specifically limited, In order to prevent formation of a hydrophilic spot, it is preferable to avoid resin with high water absorption.
  • the degree of butyralization degree of acetalization
  • the degree of butyralization is preferably 50 mol% or more, particularly 55 mol% or more, and more preferably 60 mol% or more.
  • the upper limit of the degree of butyralization is not particularly limited, but may be 85 mol% or less.
  • Additives may be glycols, surfactants, leveling agents, ultraviolet absorbers, colorants, antifoaming agents, preservatives, and the like.
  • the thickness of the visibility ensuring film is preferably 3 to 70 nm, preferably 5 to 50 nm, more preferably 7 to 45 m, and particularly 10 to 40 nm.
  • the visibility ensuring film can be formed by applying a coating liquid on a glass laminate such as a transparent substrate and drying the applied coating liquid.
  • the drying of the working solution may be accompanied by heating.
  • Conventionally known materials and methods may be used as the solvent used for preparing the coating liquid and the coating method.
  • the relative humidity of the atmosphere it is preferable to maintain the relative humidity of the atmosphere at less than 40%, more preferably 30% or less. Keeping the relative humidity low can prevent the film from absorbing excessive moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, the water remaining in the membrane matrix may reduce the strength of the membrane.
  • the drying process of the coating liquid includes an air drying process and a heating drying process with heating.
  • the air drying step is preferably performed by exposing the coating liquid to an atmosphere in which the relative humidity is kept below 40%, and further 30% or less.
  • the air drying process can be performed as a non-heating process, in other words, at room temperature.
  • Appropriate heating temperature in the heating and drying step is 300 ° C. or less, for example, 100 to 200 ° C., and the heating time is 1 minute to 1 hour.
  • the glass laminate can further include a low reflection film.
  • the low reflection film can be formed on the ultraviolet shielding film, or can be formed on the surface of the glass body opposite to the surface on which the ultraviolet shielding film is formed.
  • a low reflection film can be formed on the surface of either glass plate opposite to the surface on which the ultraviolet shielding film is formed. Specific examples of the low reflection film are as follows. In the following, an example in which a low-reflection film is formed mainly on a glass body has been described, but the case where it is formed on an ultraviolet shielding film is substantially the same.
  • the low reflection film contains silica fine particles and a binder in a weight ratio of 60:40 to 95: 5, respectively.
  • the low reflection film comprises (1) raw material fine particles comprising at least one of non-aggregated silica fine particles having an average particle size of 40 to 1000 nm and chain-aggregated silica fine particles having an average primary particle size of 10 to 100 nm,
  • a coating solution prepared by mixing a decomposable metal compound, (3) water, and (4) a solvent, and hydrolyzing the hydrolyzable metal compound in the presence of the raw material fine particles is used as a glass body or ultraviolet light. It is formed by covering a shielding film and heat-treating it.
  • the silica fine particles used here may be made by any manufacturing method, such as silica fine particles synthesized by reacting silicon alkoxide with a basic catalyst such as ammonia by a sol-gel method, or colloidal silica made from sodium silicate. Examples thereof include fumed silica synthesized in the gas phase.
  • the structure of the low reflection film obtained varies greatly depending on the particle diameter of the silica fine particles. If the particle size of the silica particles is too small, the size of the pores generated between the particles in the low reflection film will be reduced, increasing the capillary force, making it difficult to remove the attached dirt, and removing moisture and organic substances in the air. The reflectance gradually increases with time because it gradually enters the holes.
  • the upper limit of the amount of the binder used for bonding between the silica particles and between the silica particles and the glass body is set as described later, if the particle size of the silica particles is too small, the surface area of the particles is relatively large. As a result, the amount of the binder that reacts with the surface is insufficient, and as a result, the adhesion of the film is weakened.
  • the silica fine particle diameter primary particle diameter
  • the roughness value of the film surface to be formed or the internal porosity of the film the film volume in the space where the binder is not buried in the space between the silica fine particles
  • the ratio of the relative refractive index becomes smaller and the apparent refractive index increases.
  • the average primary particle size of silica fine particles is desirably 40 nm or more in order to lower the value so as to be close to a square root value of about 1.5) (about 1.22). More preferably, it is 50 nm or more.
  • the particle size of the silica fine particles is too large, light scattering becomes violent and adhesion to the glass body becomes weak.
  • the average particle size of silica fine particles is preferably 500 nm or less, preferably 300 nm. The following is more preferable.
  • the most preferable average particle diameter of the silica fine particles is 50 to 200 nm, and more preferably 70 to 160 nm.
  • the average particle size of the silica fine particles as the raw material fine particles is actually primary particles (aggregated to form chain-like secondary particles) in a planar field of view with a transmission electron microscope of 10,000 to 50,000 times.
  • the sphericity of the silica fine particles is represented by an average of 100 ratios of the major axis length and minor axis length of each fine particle.
  • the sphericity of the silica fine particles is 1.0 to 1.2, it is preferable because a low reflective film with an increased degree of fine particle filling is formed and the mechanical strength of the film is increased. A more preferable sphericity is 1.0 to 1.1. Further, when silica fine particles having a uniform particle diameter are used, voids between the fine particles can be increased, so that the apparent refractive index of the film is lowered and the reflectance can be lowered. Accordingly, the standard deviation of the particle size representing the particle size distribution of the silica fine particles is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, still more preferably 1.0 to 1.1. is there.
  • Non-aggregated silica fine particles having an average particle size of 40 to 1000 nm include commercially available products such as “Snowtex OL”, “Snowtex YL”, “Snowtex ZL” manufactured by Nissan Chemical Industries, and “Seahoster KE-W10” manufactured by Nippon Shokubai. “Seahoster KE-W20”, “Seahoster KE-W30”, “Seahoster KE-W50”, “Seahoster KE-E70”, “Seahoster KE-E90”, etc. are preferable.
  • As the silica fine particles a silica fine particle dispersion liquid dispersed in a solvent is preferable because it is easy to handle.
  • dispersion medium examples include water, alcohols, cellosolves, and glycols, and silica fine particle dispersions dispersed in these dispersion media are commercially available. Further, silica fine particle powder may be used by dispersing in these dispersion media.
  • the average particle size of the individual fine particles (primary fine particles) constituting the aggregated fine particles is defined as the average primary particle size.
  • the film becomes bulky because each fine particle is fixed while maintaining its aggregated state when the film is formed.
  • the value of the roughness on the surface of the film to be formed and the internal porosity of the film are larger than in the case of non-aggregated silica fine particles having the same average particle size as the average primary particle size of the chain aggregated fine particles. .
  • the chain aggregated silica fine particles may have an average primary particle diameter of less than 40 nm, and chain aggregated silica fine particles having an average primary particle diameter d of 10 to 100 nm are used.
  • the chain-aggregated silica fine particles preferably have an average length (L) of 60 to 500 nm and an average length ratio (L / d) to an average primary particle size of 3 to 20.
  • Examples of the chain aggregated silica fine particles include “Snowtex OUP” and “Snowtex UP” manufactured by Nissan Chemical Co., Ltd.
  • Preparation of a coating solution for forming a low reflection film is performed by hydrolyzing a metal compound that can be hydrolyzed in the presence of silica fine particles, and the mechanical strength of the resulting film is significantly improved.
  • the metal compound is hydrolyzed in the presence of silica fine particles
  • the condensation reaction between the product generated by hydrolysis and the silanol present on the surface of the fine particles occurs almost simultaneously with the hydrolysis, and therefore (1)
  • the reactivity of the surface of the fine particles is improved by the condensation reaction with the binder component.
  • the binder adheres to the fine silica particles and the glass body. It is effectively used to improve performance.
  • the binder component when the metal compound is hydrolyzed in the absence of fine particles, the binder component is polymerized by a condensation reaction between the hydrolysis products.
  • a coating liquid is prepared by mixing the polymerized binder component and silica fine particles, (1) since the condensation reaction between the binder component and the silica fine particles hardly occurs, the reactivity of the fine particle surface is poor. And (2) The surface of silica fine particles is hardly coated with a binder. Therefore, if the adhesiveness between the glass and the silica fine particles is to be increased as in the former case, a larger amount of binder component is required.
  • the binder used here is made of, for example, a metal oxide, and at least one metal oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and tantalum oxide is preferably used. .
  • the weight ratio of the silica fine particles and the binder forming the low reflection film is in the range of 60:40 to 95: 5.
  • the amount of the binder is larger than this range, the fine particles are embedded in the binder, and the roughness value by the fine particles or the porosity in the film is reduced, so that the antireflection effect is reduced.
  • the amount of the binder is less than this, the adhesion between the fine particles and the glass body and between the fine particles is lowered, and the mechanical strength of the film is weakened.
  • the weight ratio of the silica fine particles to the binder is more preferably 65:35 to 85:15.
  • the binder is preferably coated on the entire surface of the silica fine particles, and the coating thickness is preferably 1 to 100 nm and 2 to 9% of the average particle diameter of the silica fine particles.
  • metal alkoxides of Si, Al, Ti, Zr, and Ta are preferable from the viewpoint of film strength and chemical stability.
  • metal alkoxides silicon tetraalkoxide, aluminum trialkoxide, titanium tetraalkoxide and zirconium tetraalkoxide, particularly methoxide, ethoxide, propoxide and butoxide are preferably used.
  • the refractive index of the binder component affects the reflectivity, so that a silicon alkoxide having a low refractive index, particularly silicon tetraalkoxide or an oligomer thereof is most preferable.
  • the binder component may be a mixture of a plurality of these metal alkoxides.
  • the metal alkoxide there is no limitation as long as the reaction product of M (OH) n is obtained by hydrolysis. Examples thereof include metal halides and metal compounds having an isocyanate group, acyloxy group, aminoxy group, and the like. .
  • R 2 is, for example, an alkyl group, and n is an integer of 1 to 3) can also be used as a binder raw material.
  • R 1 n M (OR 2 ) 4-n an organic residue remains in the gel film after coating.
  • the base becomes a nanometer-sized micropore, and the small pore size increases the capillary force, making it difficult to remove attached dirt, and dirt and water enter the micropore and cause the reflectance to change over time. Since problems arise and the film strength becomes weak, it is preferable not to use a large amount of the compound represented by R 1 n M (OR 2 ) 4-n .
  • the total amount of binder in terms of metal oxide To 50% by weight.
  • the haze ratio of the glass laminate coated with the low reflection film is a total of the haze ratio of the glass body and the haze ratio of the low reflection film, but as the glass body in the present invention, the haze ratio is as small as possible, for example, A glass body having a haze ratio of 0.1% or less can be used. Therefore, the haze ratio of the glass laminate of the present invention is substantially equal to the haze ratio of the low reflective film.
  • the haze ratio of the low reflection film is preferably adjusted to an optimum range that varies depending on the application. For example, a window for automobiles preferably has a low haze ratio from the viewpoint of safety, and the haze ratio of the low reflection glass laminate is 1% or less, more preferably 0.5% or less.
  • the reflectance of the film is such that the silica fine particles (hereinafter sometimes simply referred to as fine particles) whose surface is coated with a binder have a shape that covers almost the entire surface of the glass body. Best to reduce.
  • fine particles having exactly the same particle diameter are closely packed and spread on a glass body, the occupation area viewed from the top of the fine particles is theoretically about 90%.
  • the occupied area is preferably 50% or more, more preferably 70% or more, in order to obtain low reflection performance. If the occupied area is less than 50%, the glass body surface is exposed, and reflection due to the difference in refractive index between the glass and air is strong, so that the reflection cannot be reduced.
  • the structure may be a low reflection film in which fine particles are arranged in a single layer on the upper surface of the glass, or may have a structure in which fine particles are stacked in multiple stages. Whether it is a single layer or a multi-layered structure, pores corresponding to the particle diameter are formed in the gap between the glass body and the particles or in the gaps between the particles, and these holes reduce the apparent refractive index. It becomes effective for. Observe the film with an electron microscope from directly above the film, and observe even a small amount of fine particles that are arranged in a plane on the outermost surface of the film and a gap between the fine particles on the outermost surface.
  • the total number of fine particles that can be produced is 30 to 3000 particles in a square area of 1 ⁇ m ⁇ 1 ⁇ m when non-aggregated silica fine particles having an average particle diameter of 40 to 500 nm are used as raw material fine particles. It is preferable to have an average particle size.
  • the total number is more preferably 100 or more and 1000 or less.
  • the total number of fine particles is 10 to 50,000 in a square area of 10 ⁇ m ⁇ 10 ⁇ m. It preferably has an average particle size of 100 to 1000 nm.
  • the total number is more preferably 20 or more and 25000 or less.
  • the fine particle density depends on the size of the fine particles, and the number decreases as the particle diameter increases, and the number increases as the particle diameter decreases.
  • a structure in which fine particles are densely present and in contact with each other through a binder and bonded is more desirable than a case where fine particles are supported alone on a glass plate.
  • the average particle diameter of the fine particles is Dnm
  • the number of fine particles observed with an electron microscope from directly above a 10 ⁇ m ⁇ 10 ⁇ m square film is preferably 5,000,000 / D 2 to 10,000,000 / D 2 .
  • the average thickness of the low reflection film of the present invention is defined below.
  • the length of 10cm (substantially 2 ⁇ m) of the electron micrograph is taken arbitrarily, and 12 points are selected in order from the largest convex part of the film, and the glass bodies of the ten convex parts from the third to the twelfth are counted.
  • the average value from the surface is defined as the average thickness. If the size of the fine particles used is large or the fine particles are sparsely present and 12 convex portions cannot be selected, the magnification of the electron microscope can be sequentially reduced from 50,000 times to select the 12 convex portions.
  • the average thickness is obtained by the above method.
  • a film having an average thickness in the range of 90 nm to 180 nm most reduces the reflectance in the visible light region.
  • the value of the physical thickness d defined by the optical thickness (n ⁇ d) is smaller than the average thickness, and the physical thickness d corresponding to the average thickness of 90 to 180 nm is 80 to 140 nm. This is because the interference condition of the reflected light between the glass / film interface and the film / air interface is satisfied. This interference condition is established even when the thickness is 2n-1 times (n is a natural number) as described above. Therefore, the reflectance is reduced even when the thickness is 3 times or more, but the film strength is lowered, which is not preferable.
  • the average thickness of the low reflection film is 90 nm to 350 nm. It is preferable. This corresponds to a physical thickness d of 80 nm to 300 nm.
  • the mounting angle (inclination angle from the vertical plane) is around 60 degrees, so that it is necessary to design a film according to the usage method.
  • the surface reflectivity (excluding back reflection) of soda lime glass with a refractive index of 1.52 is 4.2% at an incident angle of 12 degrees, but an incident angle of 60 degrees, which is a windshield attached to an automobile
  • the surface reflectance in the angle corresponding to the incident angle of the incident light from the horizontal direction reaches 9% or more.
  • a low-reflection film composed of fine particles and a binder can be approximated as a single-layer film having an average refractive index including pores, but interference between reflected light at the glass-low reflection film interface and reflected light at the low-reflection film-air interface.
  • Low reflection performance is realized by shifting the optical path difference between the reflected lights by a half wavelength using the action.
  • this optical path difference moves in a direction that decreases, so it is necessary to increase the optical thickness (nd) of the low reflection film as compared with the normal incidence reflection. .
  • the optical thickness In order to reduce the reflectivity at 60 ° incidence, it is preferable to design the optical thickness to about 140 nm to 250 nm.
  • the surface reflectance at an incident angle of 60 degrees largely depends on the apparent refractive index and optical thickness of the low reflective film, but is 6% or less, preferably 5% or less, more preferably 4% or less.
  • the coating liquid for the low reflection film is hydrolyzed by mixing silica fine particles, a hydrolyzable metal compound, a catalyst for hydrolysis, water and a solvent.
  • the reaction can be performed by stirring for 1 to 24 hours at room temperature, or by stirring for 10 to 50 minutes at a temperature higher than room temperature, for example, 40 ° C. to 80 ° C.
  • the obtained coating solution may then be diluted with a suitable solvent according to the coating method.
  • an acid catalyst is most effective, and examples thereof include mineral acids such as hydrochloric acid and nitric acid, and acetic acid.
  • the polycondensation reaction rate is lower than the hydrolysis reaction rate of a hydrolyzable metal compound such as a metal alkoxide, and a large amount of hydrolysis reaction product M (OH) n is generated. Since it acts effectively as a binder, it is preferable.
  • the condensation polymerization reaction rate is higher than the hydrolysis reaction rate, so the metal alkoxide becomes a fine-particle reaction product, or is used for particle size growth of silica particles that are originally present, As a result, the action of the metal alkoxide as a binder is reduced.
  • the catalyst content is preferably 0.001 to 4 in terms of molar ratio to the metal compound serving as the binder.
  • the amount of water required for hydrolysis of the metal compound is preferably 0.1 to 100 in terms of molar ratio with respect to the metal compound. If the amount of water added is less than 0.1 in terms of molar ratio, the hydrolysis of the metal compound is not sufficiently promoted, and if it is more than 100 in terms of molar ratio, the stability of the liquid tends to decrease.
  • chloro group containing compound when using the said chloro group containing compound as said metal compound, addition of a catalyst is not necessarily required.
  • the chloro group-containing compound can be hydrolyzed without a catalyst. However, there is no problem even if an acid is additionally added.
  • the solvent may be basically anything as long as it substantially dissolves the metal compound, but alcohols such as methanol, ethanol, propanol and butanol, cellosolves such as ethyl cellosolve, butyl cellosolve and propyl cellosolves, ethylene glycol, propylene Glycols such as glycol and hexylene glycol are most preferred. If the concentration of the metal compound dissolved in the solvent is too high, the amount of silica fine particles to be dispersed is also related, but sufficient voids cannot be formed between the fine particles in the film. The concentration is preferably 1 to 20% by weight.
  • the ratio of the amount of the silica fine particles and the amount of the above metal compound (converted into the metal oxides SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , Ta 2 O 5 , respectively) in the coating liquid is the weight ratio. 60:40 to 95: 5 is preferable, and 65:35 to 85:15 is more preferable.
  • the preferable raw material compounding ratio of the coating liquid in the present invention is as shown in Table 1 below.
  • the coating liquid By applying the coating liquid to a glass body (or UV shielding film, the same applies hereinafter) and heating, the dehydration condensation reaction of the metal compound hydrolyzate and the vaporization / combustion of volatile components are carried out on the glass substrate. A low reflection film is formed.
  • the coating method is not particularly limited as long as a known technique is used, but a method using a spin coater, roll coater, spray coater, curtain coater or the like, a dip-up method (dip coating method), a flow coating method ( And various printing methods such as screen printing, gravure printing, and curved surface printing are used.
  • a high boiling point solvent for example, printing methods such as flexographic printing and gravure printing, glycols are effective solvents, and the reason is not clear. Therefore, it is a convenient solvent for producing a low reflection film having a low content.
  • the weight ratio of glycol contained in the coating liquid is preferably 5% or more and 80% or less.
  • Cleaning and surface modification methods include degreasing and cleaning with organic solvents such as alcohol, acetone and hexane, cleaning with alkali and acid, polishing the surface with an abrasive, ultrasonic cleaning, ultraviolet irradiation treatment, ultraviolet ozone treatment, Examples include plasma treatment.
  • the heat treatment after coating is an effective method for increasing the adhesion between the silica fine particle and binder film and the glass body.
  • the treatment temperature is 200 ° C. or higher, preferably 400 ° C. or higher, more preferably 600 ° C. or higher and 1800 ° C. or lower as a maximum temperature.
  • the solvent component of the coating solution evaporates, and the gelation of the film proceeds and adhesive strength is generated.
  • the organic components remaining in the film are almost completely lost by combustion.
  • 600 ° C. the condensation reaction of the remaining unreacted silanol groups and the hydrolyzate of the hydrolyzate of the metal compound is almost completed, resulting in densification of the film and further improving the film strength.
  • the heating time is preferably 5 seconds to 5 hours, more preferably 30 seconds to 1 hour.
  • the glass laminates according to Examples 1 to 11 and the glass laminate according to the comparative example were prepared as shown in Table 1 below. More specifically, as described below, for Comparative Examples and Examples 1 to 11, a film-forming solution for an ultraviolet absorber was prepared and applied to each glass body to form an ultraviolet shielding film.
  • UV absorber 2 ', 4,4'-Tetrahydroxyxybenzophenone BASF, UVINUL 3050 6.500 parts by mass, 17.622 parts by mass of tetraethoxysilane (manufactured by Tama Chemical Industry) 13.312 parts by mass of 3-glycidoxypropyl polymethoxylane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass of ITO fine particle dispersion (Mitsubishi Materials Electronics Chemicals, Ltd.) containing 40% by mass of fine particles of indium tin oxide, 0.218 parts by mass of polypropylene glycol (Kishida Chemical, PPG700) Concentrated nitric acid (manufactured by Futaba Chemical, concentration 60 mass%) 0.025 parts by mass, 42.028 parts by mass of ethanol as solvent and 28.125 parts by mass of water (however, ethanol and water include the dispersion medium of fine particle dispersion and water contained
  • a normal transparent float plate glass made by Nippon Sheet Glass, thickness 3.1 mm
  • the film forming solution is flowed on this glass plate in an environment of 20 ° C. and 30% RH.
  • the coating method was applied. After drying for 5 minutes in the same environment, the glass plate coated with the film-forming solution was dried at a temperature of 180 ° C. to produce a glass laminate having an ultraviolet shielding film.
  • Example 1 A film forming solution was obtained in the same manner as in Comparative Example 1 except that the amount of the same UV absorber as in Comparative Example was 6.000 parts by mass.
  • a glass laminate having an ultraviolet shielding film was prepared in the same manner as in the comparative example except that UV cut green glass (manufactured by Nippon Sheet Glass, thickness 3.4 mm) was used instead of the transparent float glass plate of the comparative example.
  • UV cut green glass manufactured by Nippon Sheet Glass, thickness 3.4 mm
  • Example 2 A film-forming solution was obtained in the same manner as in the comparative example except that the same ultraviolet absorber as in comparative example 1 was used at 7.00 parts by mass.
  • a laminated glass plate (commercially available interlayer film for laminated glass (Solucia Japan Co., Ltd., Saflex, thickness 0.76 mm), 2.1 mm thick transparent float plate glass ( A glass laminate having an ultraviolet shielding film was prepared in the same manner as in the comparative example, except that a laminated glass plate sandwiched between Nippon Sheet Glass) was used.
  • Example 3 The same film forming solution as the comparative example was obtained.
  • a glass laminate having an ultraviolet shielding film was prepared in the same manner as in the comparative example, except that a dark-colored float glass plate (Legart 50 made by Nippon Sheet Glass with a thickness of 3.4 mm) was used instead of the transparent float glass plate of the comparative example.
  • a dark-colored float glass plate Legart 50 made by Nippon Sheet Glass with a thickness of 3.4 mm
  • R1 and R2 both contain 1,1,3,3-tetramethylbutyl group benzotriazole-based UV absorber (manufactured by Ciba Specialty Chemicals, TINUVIN360) as a dispersoid and disperse water
  • a dispersion liquid solid content concentration 10% by weight, average particle size 110 nm
  • the said benzotriazole type ultraviolet absorber used what was pulverized by mixing with a zirconia bead beforehand using a paint conditioner so that it might become the said average particle diameter.
  • a glass laminate having an ultraviolet shielding film was prepared in the same manner as in the comparative example, except that a dark float glass sheet (Galaxsee, manufactured by Nippon Sheet Glass with a thickness of 3.1 mm) was used instead of the transparent float glass sheet of the comparative example.
  • a dark float glass sheet (Galaxsee, manufactured by Nippon Sheet Glass with a thickness of 3.1 mm) was used instead of the transparent float glass sheet of the comparative example.
  • Example 5 A film forming solution was obtained in the same manner as in Example 4 except that the ultraviolet absorbent dispersion in Example 4 was changed to 30.0 parts by mass. And the glass laminated body which has an ultraviolet-ray shielding film was produced like Example 4 except having used the dark-colored float glass plate (Legart 20 made from Japanese plate glass of thickness 3.1mm) different from Example 4.
  • FIG. 5 A film forming solution was obtained in the same manner as in Example 4 except that the ultraviolet absorbent dispersion in Example 4 was changed to 30.0 parts by mass.
  • the glass laminated body which has an ultraviolet-ray shielding film was produced like Example 4 except having used the dark-colored float glass plate (Legart 20 made from Japanese plate glass of thickness 3.1mm) different from Example 4.
  • Example 6 25.0 parts by mass of the ultraviolet absorbent dispersion of Example 4 31.2 parts by mass of tetraethoxysilane, 3.54 parts by mass of 3-glycidoxypropyl-trimethoxylane, 5 parts by mass of the ITO fine particle dispersion of the comparative example, Nippon Lubrizol Solsperse 41000 (polyether phosphate ester polymer 0.55 parts by weight Concentrated hydrochloric acid 0.071 part by weight Example 4 ethanol 17.4 parts by weight and water 29.7 parts by weight (however, ethanol and water are the dispersion medium of the fine particle dispersion) (Including water contained in concentrated hydrochloric acid) Were mixed and stirred to obtain an ultraviolet shielding film forming solution.
  • a glass laminate having an ultraviolet shielding film was produced in the same manner as in Comparative Example 1 except that UV-cut green plate glass (manufactured by Nippon Sheet Glass, thickness 3.1 mm) was used instead of the transparent float plate glass of Comparative Example.
  • Example 7 As a UV absorber, a commercially available antioxidant (benzenethiol copper complex derivative; (bis (4-morpholinosulfonyl-1,2dithioferrate) copper) having the structural formula in which Bu is an n-butyl group in formula (15) Tetra-n-butylammonium); EST-5) manufactured by Sumitomo Seika Co., Ltd. as a dispersoid and a dispersion using water as a dispersion medium (the copper complex content is 10% by weight and the average particle size is 135 nm) are used in Example 4.
  • a commercially available antioxidant (benzenethiol copper complex derivative; (bis (4-morpholinosulfonyl-1,2dithioferrate) copper) having the structural formula in which Bu is an n-butyl group in formula (15) Tetra-n-butylammonium); EST-5) manufactured by Sumitomo Seika Co., Ltd. as a dispersoid and
  • a glass laminate having an ultraviolet shielding film was prepared in the same manner as in the comparative example except that green plate glass (manufactured by Nippon Sheet Glass, thickness 3.1 mm) was used instead of the transparent float plate glass of the comparative example.
  • Example 8 1.0 part by weight of the same UV absorber as in the comparative example 0.69 part by weight of tetraethoxysilane S-LEC KX-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) , Acetalization degree 9mol%) 62.5 parts by mass Nitric acid 0.05 parts by mass As a solvent, 18.62 parts by mass of alcohol and 17.63 parts by mass of water were mixed and stirred to obtain an ultraviolet shielding film forming solution.
  • a glass laminate having an ultraviolet shielding film was produced in the same manner as in the comparative example except that the same UV cut green plate glass as in Example 6 was used instead of the transparent float glass in the comparative example.
  • Example 9 30.0 parts by mass of the same UV absorber as in Example 4 1.04 parts by mass of tetraethoxysilane n-hexyltrimethoxysilane (HTMS, 0.37 parts by mass of “KBM-3063” manufactured by Shin-Etsu Silicone, S-LEC KX-5 manufactured by Shin-Etsu Chemical Co., Ltd. (polyvinyl acetal resin containing 8% by weight solids, including acetal degree derived from benzaldehyde, acetalization degree of 9 mol%) 62.5 parts by mass Nitric acid 0.05 parts by mass As a solvent, 10.82 parts by mass of alcohol and 10.22 parts by mass of water were mixed and stirred to obtain an ultraviolet shielding film forming solution.
  • HTMS tetraethoxysilane n-hexyltrimethoxysilane
  • KBM-3063 manufactured by Shin-Etsu Silicone
  • S-LEC KX-5 manufactured by Shin-Etsu Chemical Co.
  • Example 4 a glass having an ultraviolet shielding film in the same manner as the comparative example except that the same dark color float plate glass as in Example 4 (Galaxsee made by Nippon Sheet Glass with a thickness of 3.1 mm) was used. A laminate was produced.
  • Example 10 A film forming solution was obtained in the same manner as in Example 8, except that the ultraviolet absorbent dispersion of Example 7 was changed to 20.0 parts by mass. And the glass laminated body which has an ultraviolet-ray shielding film was produced like the comparative example except having used the same laminated glass plate as Example 2 instead of the transparent float plate glass of a comparative example.
  • Example 11 was obtained by further forming a visibility ensuring film on Example 1. Specifically, it was produced as follows. n-hexyltrimethoxysilane (HTMS, 0.03 mass% “KBM-3063” manufactured by Shin-Etsu Silicone Co., Ltd.), tetraethoxysilane (TEOS, “KBM-04” manufactured by Shin-Etsu Silicone Co., Ltd.) 0.3 mass%, purified water 0. A coating solution for forming a film for ensuring visibility, which was 15% by mass, 0.2% by mass of hydrochloric acid as an acid catalyst, and the balance being an alcohol solvent (“Solmix AP-7” manufactured by Nippon Alcohol Industry Co., Ltd.) was prepared.
  • HTMS n-hexyltrimethoxysilane
  • TEOS tetraethoxysilane
  • KBM-04 tetraethoxysilane
  • a coating solution for forming a film for ensuring visibility which was 15% by mass, 0.2% by mass
  • Example 11 the above coating solution was applied on the ultraviolet shielding film of Example 1 by the flow coating method in an environment of room temperature 20 ° C. and relative humidity 30%. After drying for 10 minutes in the same environment, a heat treatment was performed at 120 ° C. for 20 minutes to produce Example 11.
  • FIG. 7 shows the light transmittance for each wavelength of each glass body, and representative examples are extracted from the glass bodies used in the comparative examples and Examples 1 to 11.
  • FIG. 8 shows the light transmittance for each wavelength of Examples 1, 2, 4, 6 to 8. 7 and 8 show only a part of the examples and comparative examples, but all the evaluation results are shown in Tables 3 and 4.
  • the float glass used in the glass body of the comparative example has a higher light transmittance in the wavelength region of 300 to 400 nm than the other glass bodies, and the Tuv 400 of the glass body becomes very high. Yes. Thereby, it is thought that Tuv400 of a glass laminated body is also high. For example, as shown in FIG. 8, the light transmittance in the wavelength region of 300 to 350 nm is almost 0 in the embodiment, whereas the comparative example is high. In other examples, a glass body whose Tuv400 is not so low is used, but the Tuv400 of the glass laminate is 2.0% or less due to the ultraviolet shielding film.
  • the Tuv400 of the glass laminate is 2.0% or less
  • the light transmittance at a wavelength of 420 nm is 20% or more, and in particular, for Examples 2 and 10, 70% or more. It has become. That is, in the embodiment of the present invention, the transmission of light near the upper limit of the ultraviolet region is sufficiently suppressed, while visible light having a wavelength of about 400 nm or more is sufficiently transmitted and has high visibility. It can be said that.
  • the glass laminates of Examples 8 to 11 were allowed to stand for 1 hour in an environment with a room temperature of 20 ° C. and a relative humidity of 30%. Using a constant temperature water bath, the water temperature was set to 35 ° C. so that Examples 8 to 11 were exposed to water vapor, and the time until clouding was observed on the ultraviolet shielding film was set and evaluated according to the following criteria: did. A: It took 50 seconds or more until cloudiness was recognized, and sufficient water absorption was recognized. B: It took longer than 30 seconds until clouding was recognized, but clouding was confirmed in less than 50 seconds, and some water absorption was recognized. C: Cloudiness was confirmed in 30 seconds or less, and water absorption was insufficient.
  • CA-A contact angle meter
  • the contact angle was 90 ° or more, it was judged that there was water repellency, and when it was 60 ° or less, it was judged that there was hydrophilicity.
  • A The haze ratio is 15% or less, and has sufficient visibility ensuring performance.
  • B The haze ratio is more than 15% and not more than 35%, and has a certain degree of visibility ensuring performance.
  • C The haze ratio is more than 35%, and the visibility ensuring performance is insufficient.
  • the straightness of light evaluated as described above represents the visibility ensuring property.
  • the comparative example had low anti-fogging properties and clouding occurred in a short time. Therefore, visibility was poor.
  • Examples 8 to 10 all had high antifogging properties, and it took time until cloudiness was observed.
  • Example 11 has low anti-fogging properties, it showed high water repellency from the viewpoint of the contact angle, so that visibility was high.
  • Examples 8 and 10 had high anti-fogging properties, they showed hydrophilicity in terms of contact angle, and the visibility was low.
  • Example 9 showed water repellency and high visibility.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
PCT/JP2019/008877 2018-03-06 2019-03-06 ガラス積層体 WO2019172313A1 (ja)

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