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WO2018105669A1 - Pare-brise - Google Patents

Pare-brise Download PDF

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Publication number
WO2018105669A1
WO2018105669A1 PCT/JP2017/043884 JP2017043884W WO2018105669A1 WO 2018105669 A1 WO2018105669 A1 WO 2018105669A1 JP 2017043884 W JP2017043884 W JP 2017043884W WO 2018105669 A1 WO2018105669 A1 WO 2018105669A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
glass plate
information acquisition
antifogging
film
Prior art date
Application number
PCT/JP2017/043884
Other languages
English (en)
Japanese (ja)
Inventor
大家　和晃
大介 辻
橘高　重雄
拓光 坂本
寺西　豊幸
神谷　和孝
山本　透
河津　光宏
瑞穂 小用
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
Priority claimed from JP2017138635A external-priority patent/JP6909660B2/ja
Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Publication of WO2018105669A1 publication Critical patent/WO2018105669A1/fr

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Classifications

    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10009—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 of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—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 of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10009—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 of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/1011—Properties of the bulk of a glass sheet having predetermined tint or excitation purity
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • B32B17/10348—Specific parts of the laminated safety glass or glazing being colored or tinted comprising an obscuration band
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
    • B32B17/1044—Invariable transmission
    • B32B17/10449—Wavelength selective transmission
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/1055—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 of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—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 of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/1055—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 of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—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 of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
    • B60R11/04—Mounting of cameras operative during drive; Arrangement of controls thereof relative to the vehicle
    • 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
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R11/00—Arrangements for holding or mounting articles, not otherwise provided for
    • B60R2011/0001—Arrangements for holding or mounting articles, not otherwise provided for characterised by position
    • B60R2011/0003—Arrangements for holding or mounting articles, not otherwise provided for characterised by position inside the vehicle
    • B60R2011/0026—Windows, e.g. windscreen
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions

Definitions

  • the present invention relates to a windshield for automobiles.
  • some windshields for automobiles are provided with a shielding layer for blocking the field of view from the outside of the vehicle.
  • This shielding layer is provided along the peripheral edge of the windshield so that the adhesive for attaching the windshield to the automobile cannot be seen from the outside of the vehicle.
  • an in-vehicle system in which an information acquisition device such as a camera is installed in the vehicle in order to acquire information outside the vehicle has been proposed.
  • an information acquisition device such as a camera
  • this in-vehicle system for example, by analyzing a captured image of a subject acquired by a camera, an oncoming vehicle, a preceding vehicle, a pedestrian, a traffic sign, a lane boundary line, etc. are recognized, and the driver is notified of the danger.
  • Various driving assistance can be provided.
  • an information acquisition device such as a camera of this in-vehicle system may be installed at a position where the above-described shielding layer is included in the information acquisition range, such as the vicinity of a support portion of the rearview mirror.
  • the shielding layer may hinder the acquisition of information by the information acquisition device.
  • Patent Documents 1 and 2 propose providing a transmission window in a part of the shielding layer. For example, by replacing a part of the intermediate film with a material with a high visible light transmittance, or by providing a region that is not laminated with ceramic, information on a region with a high visible light transmittance is obtained in a part of the shielding layer. Form as a region. Thereby, the information acquisition apparatus installed in the vehicle can acquire information outside the vehicle through the information acquisition region without being obstructed by the shielding layer.
  • the windshield having an information acquisition area has the following problems. That is, strong light may enter the vehicle from the information acquisition area due to reflection from surrounding objects (such as an automobile) and other external environments. In this case, acquisition of information by the information acquisition device may be hindered by the strong light. For example, when a camera is installed in the vehicle as an information acquisition device, if strong light enters the vehicle from the information acquisition region, whiteout occurs, and the camera may not be able to correctly capture the situation outside the vehicle. As described above, in the conventional windshield, when strong light is incident on the inside of the vehicle from the information acquisition area, the information acquisition apparatus may not be able to acquire information correctly through the information acquisition area. I found a point.
  • strong light may be required. If weak light is incident on such an information acquisition device, there is a possibility that the situation outside the vehicle cannot be photographed correctly.
  • the present invention has been made in view of such a situation, and an object of the present invention is to provide a windshield in which acquisition of information by an information acquisition device is hardly hindered even when strong light or weak light is incident. Is to provide.
  • Item 1 A windshield of an automobile in which an information acquisition device that acquires information from outside the vehicle by performing light irradiation and / or light reception can be arranged, An information acquisition area through which the light passes facing the information acquisition apparatus, and a glass plate having a visual field area where a driver driving the automobile confirms traffic conditions during driving,
  • the windshield configured to have a light transmittance of the information acquisition region different from a light transmittance of the visual field region.
  • the information acquisition device is not particularly limited as long as it is a device that can acquire information from outside the vehicle by irradiating and / or receiving light.
  • the information acquisition device may be various types of photographing devices such as a stereo camera.
  • the visual field area is an area to be noted when the driver who has arrived at the driver's seat performs driving, and can be set as appropriate according to the embodiment.
  • the test area A defined in the appendix “Test Area for Optical Properties and Light Resistance of Safety Glass” of JIS R3212 (1998, “Safety Glass Test Method for Automobiles”) is adopted as the visual field area. May be.
  • Item 2 The windshield according to item 1, wherein the information acquisition region is configured to have a light transmittance lower than a light transmittance of the visual field region.
  • Item 3 provided in a region of the glass plate other than the visual field region, further comprising a shielding layer that shields the visual field from the outside of the vehicle, Item 3.
  • the light incident from the area around the information acquisition area can be blocked by the shielding layer. Therefore, even if strong light is incident, it is possible to prevent the acquisition of information by the information acquisition apparatus from being hindered.
  • Item 4 The light transmittance in the visible region of the information acquisition region is 70% or less, Item 4.
  • light in the visible region refers to light having a wavelength in the range of, for example, 380 nm to 780 nm.
  • the upper limit of the visible region wavelength may be set at 760 nm to 830 nm, and the lower limit of the visible region wavelength may be set at 360 nm to 400 nm.
  • Item 5 The haze ratio of the visual field region is 0.6% or less, Item 5.
  • the haze ratio (cloudiness) can be calculated by “diffuse transmittance Td / total light transmittance Tt ⁇ 100”.
  • Item 6 The windshield according to any one of Items 1 to 5, wherein the information acquisition region is configured to have a light transmittance in an infrared region lower than a light transmittance in the infrared region in the visual field region. .
  • the light in the infrared region refers to all electromagnetic waves having a wavelength longer than that of red light having an upper limit of visible light and shorter than that of millimeter wavelengths, for example, light having a wavelength in a range of about 0.7 ⁇ m to 1000 ⁇ m. .
  • the glass plate includes an outer glass plate disposed outside the vehicle, an inner glass plate disposed inside the vehicle, and an intermediate film disposed between the outer glass plate and the inner glass plate,
  • the outer glass plate, the intermediate film, and the inner glass plate are configured to have substantially the same light transmittance in the information acquisition region and the visual field region,
  • a film material configured to reduce the light transmittance to either surface of the outer glass plate and the inner glass plate in the information acquisition region, the information acquisition region is Item 7.
  • the windshield according to any one of Items 1 to 6, wherein the windshield is configured to have a light transmittance lower than a light transmittance of the visual field region.
  • Item 8 The surface of the glass plate in the information acquisition region includes a base material layer and an antifogging layer having an antifogging property and laminated on one surface of the base material layer.
  • the film is stuck, By adding fine particles having an average particle size of 1 nm to 500 nm to the antifogging layer, the information acquisition region has a light transmittance lower than the light transmittance of the visual field region.
  • Item 8 The windshield according to any one of Items 1 to 7, which is configured.
  • the information acquisition region is prevented from being fogged by the anti-fogging layer having anti-fogging properties, and the fine particles added to the anti-fogging layer are arranged inside the vehicle even when strong light is incident from the outside of the vehicle. It is possible to prevent light from reaching the information acquisition device while maintaining a strong light amount. Therefore, according to the said structure, the windshield which has an information acquisition area
  • Item 9 The windshield according to Item 8, wherein the fine particles are silica fine particles.
  • Item 10 The windshield according to Item 8 or 9, wherein the base material layer is composed of a polarizing film.
  • Item 11 The surface of the glass plate in the information acquisition region includes a base material layer and an antifogging layer having an antifogging property and laminated on one surface of the base material layer.
  • the film is placed, Item 8.
  • a low reflection film is arranged on the vehicle interior side of the glass plate in the information acquisition region.
  • Item 12 At least on the surface of the glass plate in the information acquisition area, Item 2.
  • Item 13 On the surface of the glass plate in the visual field region, Item 13. The windshield according to Item 12, wherein the low reflection film is not disposed.
  • Item 14 The windshield according to Item 12 or 13, wherein an adhesive layer and a base material layer are sequentially disposed between the surface of the glass plate and the low-reflection film.
  • the low-reflection film includes a main body portion, a surface portion disposed on the main body portion and facing the vehicle interior; With Item 15.
  • Item 16 The windshield according to item 15, wherein the surface portion is uneven.
  • Item 17 The windshield according to item 15 or 16, wherein the surface portion contains silica fine particles.
  • Item 18 The windshield according to any one of Items 12 to 14, wherein a refractive index of the low reflection film is smaller than a refractive index of the glass plate and larger than a refractive index of air.
  • Item 19 The windshield according to Item 18, wherein the low-reflection film has a porous structure.
  • Item 20 The windshield according to Item 18 or 19, further comprising an antifogging layer disposed between the glass plate and the low reflection film.
  • Item 21 The windshield according to any one of Items 18 to 20, wherein the low-reflection film contains hollow fine particles.
  • Item 22 The windshield according to Item 18, wherein the low reflective film contains fine particles having a refractive index lower than that of the glass plate.
  • the low reflection film is composed of a plurality of layers lower than the refractive index of the glass plate, Item 15.
  • the low reflective film is composed of a plurality of layers, The plurality of layers include a first layer laminated from the glass plate side, and at least one second layer, Item 15.
  • Item 25 The windshield according to Item 24, wherein the first layer is formed of a transparent conductive film.
  • Item 26 The windshield according to Item 24 or 25, further comprising an antifogging layer disposed between the glass plate and the low reflection film.
  • Item 27 On the surface of the glass plate in the information acquisition area, A base material layer disposed on the glass plate; At least one antifogging layer having antifogging properties and laminated on one side of the base material layer; Are arranged in this order, anti-fogging film is arranged, The refractive index of the base material layer is larger than the refractive index of the glass plate, Item 2.
  • Item 28 On the surface of the glass plate in the information acquisition area, A base material layer disposed on the glass plate; At least one antifogging layer having antifogging properties and laminated on one side of the base material layer; An anti-fogging film is disposed, Item 2.
  • Item 29 The windshield according to Item 27, wherein the base material has a refractive index of 1.6 or more.
  • Item 30 The windshield according to any one of Items 27 to 29, wherein the antifogging layer has a refractive index of 1.45 or less.
  • Item 31 On the surface of the glass plate in the information acquisition area, A base material layer disposed on the glass plate; At least one antifogging layer having antifogging properties and laminated on one side of the base material layer; An anti-fogging film is disposed, Item 2.
  • Item 32 On the surface of the glass plate in the information acquisition area, A base material layer disposed on the glass plate; At least one antifogging layer having antifogging properties and laminated on one side of the base material layer; An anti-fogging film is disposed, Item 2.
  • the windshield according to the present invention is An automotive windshield in which an information acquisition device that acquires information from outside the vehicle by irradiating and / or receiving light can be arranged, A low reflection film is provided on the surface of the glass plate in the information acquisition area.
  • the low reflection film includes a main body portion disposed on the glass plate side and a surface portion disposed on the main body portion, and a refractive index of the surface portion is determined by a refraction of the main body portion. It can be smaller than the refractive index and larger than the refractive index of air.
  • irregularities can be formed on the surface portion.
  • silica fine particles can be contained in the surface portion.
  • the refractive index of the low reflection film can be smaller than the refractive index of the glass plate and larger than the refractive index of air.
  • the low reflection film may have a porous structure.
  • the windshield may further include an anti-fogging layer disposed between the glass plate and the low reflection film.
  • the low-reflection film may contain hollow fine particles.
  • the low reflective film may contain fine particles having a refractive index lower than that of the glass plate.
  • the low-reflection film can be composed of a plurality of layers that are lower than the refractive index of the glass plate, and the refractive index of the plurality of layers decreases as the distance from the glass plate increases. Can be configured.
  • the low-reflection film includes a plurality of layers, and the plurality of layers includes a first layer stacked from the glass plate side and at least one second layer.
  • the refractive index of the first layer may be larger than the refractive index of the glass plate, and the refractive index of the second layer may be smaller than the refractive index of the glass plate.
  • the first layer can be formed of a transparent conductive film.
  • the windshield may further include an anti-fogging layer disposed between the glass plate and the low reflection film.
  • the present invention it is possible to provide a windshield in which acquisition of information by the information acquisition device is hardly hindered even when strong light is incident.
  • FIG. 1 It is a front view which illustrates typically the windshield which concerns on embodiment. It is sectional drawing which illustrates typically the windshield which concerns on embodiment. It is the elements on larger scale which illustrate typically the information acquisition area vicinity of the windshield which concerns on embodiment. It is a fragmentary sectional view which illustrates typically the information acquisition field vicinity of the windshield concerning an embodiment.
  • the state which the water droplet adhered to the anti-fogging layer is illustrated.
  • the state which the water droplet adhered to the anti-fogging layer is illustrated.
  • the state of the vehicle exterior side of the bracket which concerns on embodiment is illustrated typically.
  • the state inside the car of the bracket concerning an embodiment is illustrated typically
  • the cover which concerns on embodiment is illustrated typically.
  • the manufacturing process of the glass plate which concerns on embodiment is illustrated typically.
  • the windshield which concerns on another form is illustrated typically.
  • the windshield which concerns on another form is illustrated typically.
  • the windshield which concerns on another form is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically.
  • a part of windshield concerning other forms is illustrated typically. It is a photograph of the section of the glass plate concerning an example.
  • this embodiment will be described with reference to the drawings.
  • this embodiment described below is only an illustration of the present invention in all respects. It goes without saying that various improvements and modifications can be made without departing from the scope of the present invention. That is, in implementing the present invention, a specific configuration according to the embodiment may be adopted as appropriate. In the following description, for convenience of description, the description will be made with reference to the direction in the drawing.
  • FIGS. 1 and 2 are a front view and a cross-sectional view schematically illustrating an example of the windshield 100 according to the present embodiment.
  • the windshield 100 includes a glass plate 1 and a shielding layer 2 that is made of dark ceramic and shields the field of view from the outside of the vehicle. Yes.
  • the shielding layer 2 is provided along the peripheral edge of the glass plate 1, and has an annular peripheral edge 21 and a protrusion 22 that protrudes inward in the surface direction from the center of the upper edge of the peripheral edge 21.
  • the projecting portion 22 is provided with an opening 23 in which ceramic is not laminated, and a frame-like bracket 6 is fixed around the opening 23.
  • a cover 7 for attaching an information acquisition device for acquiring information from outside the vehicle by irradiating and / or receiving light can be attached to the bracket 6.
  • the windshield 100 is comprised so that an information acquisition apparatus can be arrange
  • a camera 8 (photographing device) is attached in the vehicle.
  • the information acquisition region 3 through which light passes is set at a position facing the camera 8 in the opening 23. That is, the camera 8 captures the situation outside the vehicle via the information acquisition area 3.
  • a visual field region 5 is provided in a range different from the information acquisition region 3.
  • the visual field area 5 is an area for confirming the traffic situation when the driver driving the vehicle to which the windshield 100 is attached, and corresponds to the front of the driver when the windshield is divided into left and right. It is.
  • the glass plate 1 is set on the inner side in the surface direction of the shielding layer 2.
  • the antifogging film 4 is affixed on the surface inside the vehicle of the glass plate 1 in the information acquisition area 3 as an example of the film material comprised so that the light transmittance may be reduced. Yes.
  • the information acquisition region 3 is configured to have a light transmittance lower than the light transmittance of the visual field region 5.
  • the information acquisition region 3 emits the strong light. Can be cut. Therefore, in this embodiment, it is possible to prevent the light from reaching the camera 8 disposed inside the vehicle with a strong light amount, so that even if strong light is incident from the outside of the vehicle, the image is captured by the camera 8. Is difficult to be inhibited, that is, it is difficult to cause whiteout.
  • each component will be described.
  • the glass plate 1 As illustrated in FIG. 2, the glass plate 1 according to this embodiment includes a glass plate 1, an outer glass plate 11 disposed on the vehicle outer side, an inner glass plate 12 disposed on the vehicle inner side, and an outer glass plate. 11 and an intermediate film 13 disposed between the inner glass plate 12 and the inner glass plate 12.
  • the intermediate film 13 joins the inner surface of the outer glass plate 11 and the outer surface of the inner glass plate 12.
  • the glass plate 1 is comprised as what is called a laminated glass.
  • the outer surface of the outer glass plate 11 is referred to as “first surface”
  • the inner surface of the outer glass plate 11 is referred to as “second surface”
  • the outer surface of the inner glass plate 12 is referred to as “third surface”.
  • the surface on the vehicle inner side of the inner glass plate 12 is also referred to as “fourth surface”.
  • Both glass plates (11, 12) are substantially identical to each other and are formed in a trapezoidal shape in plan view. Both glass plates (11, 12) may be curved in a perpendicular direction or flat. In this embodiment, each glass plate (11, 12) has a curved shape such that the vehicle outer surface is convex and the vehicle inner surface is concave.
  • each glass plate (11, 12) may be heat ray absorbing glass, clear glass, green glass, UV green glass, or the like.
  • each glass plate (11, 12) is comprised so that the visible light transmittance according to the safety standard of the country where a motor vehicle is used is implement
  • each glass plate (11, 12) is configured so that the light transmittance in the visible region (380 nm to 780 nm) is 70% or more as defined by JIS R 3211.
  • the transmittance can be measured by a spectroscopic method specified in JIS Z 8722, as defined in JIS R 3212 (3.11 Visible Light Transmittance Test).
  • each glass plate (11, 12) is comprised so that a haze rate may be 0.6% or less.
  • This haze rate (cloudiness) can be calculated based on the calculation of “diffuse transmittance Td / total light transmittance Tt ⁇ 100” as described above. That is, the haze ratio can be obtained by measuring the diffuse transmittance and the total light transmittance with a commercially available haze meter, spectrophotometer, or the like.
  • the light transmittance and the haze ratio of both glass plates (11, 12) do not need to match.
  • a desired solar radiation absorptivity may be secured by the outer glass plate 11, and the visible light transmittance may be adjusted by the inner glass plate 12 so as to satisfy safety standards.
  • an example of a composition of a clear glass and an example of a heat ray absorption glass composition are shown as an example of the composition of the glass which can comprise each glass plate (11, 12).
  • the composition of the heat-absorbing glass is, for example, based on the clear glass composition, the ratio of total iron oxide (T-Fe2O3) converted to Fe2O3 is 0.4 to 1.3% by mass, and the ratio of CeO2 is 0 to 2
  • the composition can be such that the ratio of TiO2 is 0 to 0.5 mass%, and the glass skeleton components (mainly SiO2 and Al2O3) are reduced by the increments of T-Fe2O3, CeO2 and TiO2.
  • the thickness of the glass plate 1 according to the present embodiment is not particularly limited, but from the viewpoint of weight reduction, the total thickness of both glass plates (11, 12) is preferably 2.0 mm to 6.0 mm, More preferably, the thickness is 3.0 mm to 5.0 mm, and particularly preferably 3.5 mm to 4.5 mm. Thus, what is necessary is just to make the total thickness of both glass plates (11, 12) small for weight reduction.
  • each glass plate (11, 12) is not specifically limited,
  • the thickness of each glass plate (11, 12) can be determined as follows. That is, the outer glass plate 11 is mainly required to have durability and impact resistance against impacts of flying objects such as pebbles. On the other hand, as the thickness of the outer glass plate 11 is increased, the weight increases, which is not preferable. From this viewpoint, the thickness of the outer glass plate 11 is preferably 1.6 mm to 2.5 mm, and more preferably 1.8 mm to 2.1 mm. Which thickness is adopted can be appropriately determined according to the embodiment.
  • the thickness of the inner glass plate 12 can be made equal to the thickness of the outer glass plate 11.
  • the thickness can be made smaller than that of the outer glass plate 11 in order to reduce the weight of the glass plate 1.
  • the thickness of the inner glass plate 12 is preferably 0.4 mm to 2.5 mm, and more preferably 0.6 mm to 2.0 mm. Which thickness is used for the inner glass plate 12 can be determined as appropriate according to the embodiment.
  • the intermediate film 13 is a film that is sandwiched between both glass plates (11, 12) and joins both glass plates (11, 12).
  • the intermediate film 13 can be appropriately configured according to the embodiment.
  • the intermediate film 13 can be configured by a three-layer structure in which a soft core layer is sandwiched between a pair of outer layers harder than this. By configuring the intermediate film 13 with a plurality of layers of a soft layer and a hard layer in this way, the breakage resistance performance and sound insulation performance of the glass plate 1 can be enhanced.
  • the material of the intermediate film 13 is not particularly limited and may be appropriately selected according to the embodiment.
  • polyvinyl butyral resin PVB
  • This polyvinyl butyral resin (PVB) is preferable as a material for the outer layer because it is excellent in adhesiveness and penetration resistance with the outer glass plate 11 and the inner glass plate 12, respectively.
  • EVA ethylene vinyl acetate resin
  • a polyvinyl acetal resin softer than the polyvinyl butyral resin used for the outer layer can be used.
  • the hardness of the polyvinyl acetal resin is (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 be controlled. Therefore, a hard polyvinyl acetal resin used for the outer layer and a soft polyvinyl acetal resin used for the core layer may be produced by appropriately adjusting at least one of the conditions (a) to (d).
  • the hardness of the polyvinyl acetal resin can be controlled by the type of aldehyde used for acetalization, coacetalization with a plurality of types 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 has an aldehyde having 5 or more carbon atoms (for example, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n- Octyl aldehyde) can be used as a polyvinyl acetal resin obtained by acetalization with polyvinyl alcohol.
  • an aldehyde having 5 or more carbon atoms for example, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n- Octyl aldehyde
  • the total thickness of the intermediate film 13 can be appropriately set according to the embodiment.
  • the total thickness of the intermediate film 13 can be 0.3 to 6.0 mm, preferably 0.5 to 4.0 mm, and more preferably 0.6 to 2.0 mm.
  • the thickness of the core layer is preferably 0.1 to 2.0 mm, and preferably 0.1 to 0 mm. More preferably, it is 6 mm.
  • the thickness of each outer layer is preferably larger than the thickness of the core layer. Specifically, it is preferably 0.1 to 2.0 mm, and more preferably 0.1 to 1.0 mm. preferable.
  • the method for producing such an interlayer film 13 is not particularly limited.
  • a resin component such as the above-described polyvinyl acetal resin, a plasticizer, and other additives as necessary, and uniformly kneading
  • examples thereof include a method of extruding each layer at once, and a method of laminating two or more resin films produced 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 intermediate film 13 can be formed of a single layer in addition to the above-described plural layers.
  • the intermediate film 13 is configured so that the light transmittance in the visible region (380 nm to 780 nm) is 70% or more by appropriately adopting the above materials and manufacturing processes. Further, the intermediate film 13 is configured so that the haze ratio is 0.6% or less.
  • FIG. 3 is a partially enlarged view schematically illustrating the vicinity of the information acquisition region 3 of the windshield 100 according to the present embodiment.
  • the shielding layer 2 is provided in a region other than the visual field region 5 on the fourth surface of the glass plate 1, that is, the inner surface of the inner glass plate 12.
  • the shielding layer 2 has a substantially rectangular shape that protrudes inward in the surface direction from the annular peripheral portion 21 stacked along the peripheral portion of the fourth surface of the glass plate 1 and the upper side portion center of the peripheral portion 21. And a protrusion 22.
  • the visual field region 5 is set on the inner side in the surface direction of the peripheral edge 21. That is, the shielding layer 2 is provided so as to surround the visual field region 5.
  • the protrusion 22 is provided with an opening 23 arranged corresponding to the information acquisition region 3.
  • the shape of the opening 23 may be appropriately selected according to the embodiment.
  • the opening 23 is formed in a substantially trapezoidal shape.
  • the planar dimension of the opening 23 is set to be larger than the planar dimension of the information acquisition region 3. Thereby, the information acquisition region 3 is disposed so as to be surrounded by the shielding layer 2.
  • the shielding layer 2 is formed by laminating ceramics. As will be described later, a bracket for attaching the cover of the camera 8 is adhered to the protrusion 22 formed on the inner surface of the inner glass plate 12 with an adhesive. At this time, for example, if a urethane / silicon adhesive is used, the adhesive may be deteriorated by ultraviolet rays or the like. Therefore, the thickness of the shielding layer 2 is preferably 20 ⁇ m to 100 ⁇ m, for example, from the viewpoint of ensuring light shielding properties and preventing deterioration of the adhesive.
  • the material of the shielding layer 2 may be appropriately selected according to the embodiment as long as the field of view from the outside of the vehicle can be shielded.
  • the shielding layer 2 can be formed of a dark ceramic such as black, brown, gray, and dark blue.
  • the shielding layer 2 can be formed of a ceramic having the composition shown in Table 1 below.
  • the composition of the ceramic forming the shielding layer 2 is not limited to the following Table 1, and may be appropriately selected according to the embodiment.
  • each part of the shielding layer 2 may be appropriately set according to the embodiment.
  • the width of the portion along the upper edge and the lower edge of the glass plate 1 in the peripheral portion 21 may be set in a range of 20 mm to 100 mm, and the width of the portion along the left edge and the right edge of the glass plate 1 is It may be set in the range of 15 mm to 70 mm.
  • the protrusion 22 may be set in a range of 200 mm (vertical) ⁇ 100 mm (horizontal) to 400 mm (vertical) ⁇ 200 mm (horizontal).
  • the plane size of the information acquisition area 3 is determined by the information acquisition device (camera 8) installed in the vehicle.
  • the planar dimension of the opening 23 may be set as appropriate so as to be larger than the planar dimension of the information acquisition region 3.
  • the opening 23 may be set as a trapezoidal region having an upper side of 85 mm, a lower side of 95 mm, and a height of 65 mm in plan view.
  • FIG. 4 is a partial cross-sectional view schematically illustrating the vicinity of the information acquisition region 3 including the antifogging film 4.
  • the antifogging film 4 is formed in a rectangular cross-section, and includes a sheet-like base material layer 42, and an antifogging layer 43 laminated on one surface of the base material layer 42.
  • the antifogging film 4 is attached to the inner surface (fourth surface) of the information acquisition region 3 via an adhesive layer 41.
  • each layer will be described.
  • the antifogging layer 43 is a layer that is disposed as the outermost layer of the antifogging film 4 and exhibits an antifogging function.
  • the antifogging layer 43 according to the present embodiment scatters light so that the light transmittance of the information acquisition region 3 to which the antifogging film 4 is attached is lower than the light transmittance of the visual field region 5.
  • Fine particles 44 are added.
  • the type of the anti-fogging layer 43 is not particularly limited as long as the fine particles 44 can be added and has anti-fogging properties, and known ones can be used.
  • the antifogging layer includes a hydrophilic type in which water generated from water vapor is formed on the surface as a water film, a water absorbing type that absorbs water vapor, and a water repellent type that repels water droplets generated from water vapor. Any type can be used for the antifogging layer 43.
  • the antifogging layer 43 can be configured as follows, for example. That is, the anti-fogging layer 43 includes a water repellent group and a metal oxide component, and preferably can further include a water absorbent resin.
  • the metal oxide component includes metal oxide fine particles as the fine particles 44.
  • the anti-fogging layer 43 may further contain other functional components as necessary.
  • the type of water-absorbing resin is not limited as long as it can absorb and retain water.
  • the water repellent group can be supplied to the antifogging layer 43 from a metal compound having a water repellent group (water repellent group-containing metal compound).
  • the metal oxide component can be supplied to the antifogging layer 43 from the metal oxide fine particles, a water repellent group-containing metal compound, and other metal compounds.
  • each component will be described.
  • the anti-fogging layer 43 can contain at least one polymer selected from the group consisting of urethane resin, epoxy resin, acrylic resin, polyvinyl acetal resin, and polyvinyl alcohol resin as a water-absorbing resin.
  • the urethane resin include a polyurethane resin composed of a polyisocyanate and a polyol.
  • the polyol an acrylic polyol and a polyoxyalkylene polyol are preferable.
  • the epoxy resins include glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, and cyclic aliphatic epoxy resins.
  • a preferred epoxy resin is a cycloaliphatic epoxy resin.
  • a polyvinyl acetal resin hereinafter simply referred to as “polyacetal” which is a preferred water-absorbing resin will be described.
  • Polyvinyl acetal can be obtained by subjecting polyvinyl alcohol to an acetal 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, 13C nuclear magnetic resonance spectroscopy.
  • Polyvinyl acetal having an acetalization degree in the above range is suitable for forming an antifogging layer 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 an antifogging layer 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 and the formation of the antifogging layer is hindered.
  • the saponification degree of polyvinyl alcohol is preferably 75 to 99.8 mol%.
  • aldehyde to be subjected to the 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.
  • Aromatic aldehydes having strong hydrophobicity are advantageous in forming an antifogging layer having a low degree of acetalization and excellent water resistance.
  • the use of an aromatic aldehyde is also advantageous for forming an antifogging layer having high water absorption while remaining a large amount of hydroxyl groups.
  • the polyvinyl acetal preferably contains an acetal structure derived from an aromatic aldehyde, particularly benzaldehyde.
  • the content of the water-absorbing resin (polymer) in the anti-fogging layer 43 is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more from the viewpoints of hardness, water absorption and anti-fogging properties. 99 mass% or less, more preferably 95 mass% or less, and particularly preferably 92 mass% or less.
  • the water-repellent group facilitates the balance between the strength and anti-fogging property of the anti-fogging layer, and ensures the straightness of incident light even if water droplets are formed by making the surface of the anti-fogging layer water-repellent. To contribute. In order to sufficiently obtain the effect of the water repellent group, it is preferable to use a water repellent group having high water repellency.
  • the antifogging layer 43 includes (1) a linear or cyclic alkyl group having 3 to 30 carbon atoms, and (2) a linear or cyclic group having 1 to 30 carbon atoms in which at least a part of hydrogen atoms are substituted with fluorine atoms. It may contain at least one water repellent group selected from cyclic alkyl groups (hereinafter sometimes referred to as “fluorine-substituted alkyl groups”).
  • the chain or cyclic alkyl group is preferably a chain alkyl group.
  • the chain alkyl group may be a branched alkyl group, but is preferably a linear alkyl group.
  • An alkyl group having more than 30 carbon atoms may cause the antifogging layer to become cloudy.
  • the carbon number of the chain alkyl group is preferably 20 or less, for example, 1 to 8, and for example, 4 to 16, preferably 4 to 8.
  • alkyl groups are linear alkyl groups having 4 to 8 carbon atoms, such as n-pentyl, n-hexyl, n-heptyl, and n-octyl.
  • the fluorine-substituted alkyl group may be a group in which only part of the hydrogen atoms of the chain or cyclic alkyl group is substituted with fluorine atoms, and all of the hydrogen atoms of the chain or cyclic alkyl group. May be a group substituted with a fluorine atom, for example, a linear perfluoroalkyl group.
  • the fluorine-substituted alkyl group has high water repellency, a sufficient effect can be obtained by adding a small amount. However, if the content of the fluorine-substituted alkyl group is excessive, it may be separated from other components in the coating solution for forming the antifogging layer.
  • a metal compound having a water repellent group (water repellent group-containing metal compound), particularly a metal compound having a water repellent group and a hydrolyzable functional group or a halogen atom.
  • water repellent group-containing hydrolyzable metal compound or a hydrolyzate thereof may be added to a coating solution for forming an antifogging layer.
  • 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).
  • RmSiY4-m (I)
  • R is a water repellent group, that is, a linear or cyclic alkyl group having 1 to 30 carbon atoms in which at least part of hydrogen atoms may be substituted with fluorine atoms
  • Y is a hydrolyzable functional group.
  • a group or a halogen atom, and 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 to 2.
  • the compound represented by the formula (I) supplies a component represented by the following formula (II) when hydrolysis and polycondensation are completely advanced.
  • R and m are as described above.
  • the compound represented by formula (II) actually forms a network structure in which the silicon atoms are bonded to each other via oxygen atoms in the antifogging layer.
  • 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 antifogging layer.
  • 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 silicon compound for example, tetraalkoxysilane, silane coupling agent
  • the water-repellent group improves the anti-fogging performance by improving the water vapor permeability on the surface of the anti-fogging layer containing the water-absorbing resin. Since the two functions of water absorption and water repellency are contradictory to each other, the water-absorbing material and the water-repellent material have heretofore been allocated to different layers, but the water-repellent group contained in the anti-fogging layer is The uneven distribution of water in the vicinity of the surface of the cloudy layer is eliminated, the time until condensation is extended, and the antifogging property of the antifogging layer is improved. The effect will be described below.
  • the water vapor that has entered the anti-fogging layer containing the water-absorbing resin is hydrogen-bonded with a hydroxyl group of the water-absorbing resin or the like, and is retained in the form of bound water. As the amount increases, the water vapor becomes retained in the form of bound water, through the form of semi-bound water, and finally in the form of free water retained in the voids in the antifogging layer.
  • the water repellent group prevents the formation of hydrogen bonds and facilitates the dissociation of the formed hydrogen bonds. If the content of the water-absorbing resin is the same, there is no difference in the number of hydroxyl groups capable of hydrogen bonding in the antifogging layer, but the water repellent group reduces the rate of hydrogen bond formation.
  • the antifogging layer containing a water repellent group moisture is finally held in the antifogging layer in any of the above forms, but until the bottom, It can diffuse up to steam. Moreover, the water once retained also dissociates relatively easily and easily moves to the bottom of the antifogging layer in the state of water vapor. As a result, the distribution of moisture retention in the thickness direction of the antifogging layer is relatively uniform from the vicinity of the surface to the bottom of the antifogging layer.
  • a water-repellent group is introduced into the anti-fogging layer using a water-repellent group-containing hydrolyzable silicon compound (see formula (I))
  • a strong siloxane bond (Si—O—Si) network structure is formed.
  • the formation of this network structure is advantageous not only from the viewpoint of wear resistance but also from the viewpoint of improving hardness, water resistance and the like.
  • the water repellent group may be added to such an extent that the contact angle of water on the surface of the antifogging layer is 70 degrees or more, preferably 80 degrees or more, more preferably 90 degrees or more.
  • As the water contact angle a value measured by dropping 4 mg of water droplets on the surface of the anti-fogging layer is adopted.
  • the upper limit of the contact angle of water is not particularly limited, but is, for example, 150 degrees or less, 120 degrees or less, and 105 degrees or less. It is preferable that the water repellent group is uniformly contained in the antifogging layer so that the water contact angle is in the above range in all regions of the surface of the antifogging layer.
  • FIGS. 5A and 5B show a state in which water droplets (430, 431) having different contact angles are attached to the antifogging layer 43.
  • FIG. 5A and FIG. 5B show the area where water drops (430, 431) formed by condensation of the same amount of water vapor on the surface of the antifogging layer 43 cover the antifogging layer 43 is the contact of water on the surface. The larger the angle, the smaller the tendency. Further, the smaller the area covered by the water droplets (430, 431), the smaller the ratio of the area where the light incident on the antifogging layer 43 is scattered. Therefore, the anti-fogging layer 43 whose water contact angle is increased due to the presence of the water repellent group is advantageous in maintaining the straightness of transmitted light in a state where water droplets are formed on the surface thereof.
  • the anti-fogging layer 43 preferably contains a water-repellent group so that the contact angle of water is in the above-mentioned preferable range.
  • the anti-fogging layer 43 is 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the water-absorbing resin.
  • a water repellent group is included so that it is within a range of 10 parts by mass or less, preferably 5 parts by mass or less.
  • 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 anti-fogging layer 43 is 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 100 parts by mass of the water-absorbing resin.
  • the metal oxide component is included so that it is 30 parts by mass or less, particularly preferably 20 parts by mass or less, and in some cases 18 parts by mass or less.
  • the metal oxide component is a component necessary for ensuring the strength of the antifogging layer, particularly the scratch resistance, but if the content is excessive, the antifogging property of the antifogging layer is lowered.
  • the metal oxide component may be a hydrolyzable metal compound or a metal oxide component derived from the hydrolyzate added to the coating solution for forming the antifogging layer.
  • 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 metal oxide fine particles added to the coating liquid for forming the antifogging layer, a hydrolyzable metal compound added to the coating liquid, 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 antifogging layer 43 includes metal oxide fine particles as at least a part of the metal oxide component.
  • the metal oxide particles correspond to the fine particles 44 that scatter light.
  • 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 ITO (Indium Tin Oxid) fine particles and zirconia fine particles.
  • Silica fine particles can be introduced into the anti-fogging layer by adding, for example, colloidal silica.
  • the metal oxide particles as the fine particles 44 By adding the metal oxide particles as the fine particles 44 to the anti-fogging layer 43, the light transmittance of the information acquisition region 3 to which the anti-fogging film 4 is attached can be lowered and the haze rate can be raised. . Furthermore, since such fine particles are present alone or aggregated and exist in the vicinity of the surface of the anti-fogging layer, irregularities are produced on the surface of the anti-fogging layer 43, so that light is reflected on the surface of the anti-fogging layer 43. Can be suppressed. As a result, the reflection in the vehicle on the camera 8 is reduced, and the camera 8 can acquire a clear image with less noise.
  • the metal oxide fine particles are excellent in the action of transmitting the stress applied to the antifogging layer to the transparent article that supports the antifogging layer, and have a 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 antifogging layer. Furthermore, when metal oxide fine particles are added to the anti-fogging layer, 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 anti-fogging layer from these voids.
  • metal oxide fine particles may advantageously work to improve antifogging properties.
  • the metal oxide fine particles can be supplied to the antifogging layer by adding the metal oxide fine particles formed in advance to the coating liquid for forming the antifogging layer.
  • the preferable average particle diameter of the metal oxide fine particles is 1 nm to 500 nm, particularly 5 nm to 200 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.
  • the metal oxide fine particles are 0.01 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the water absorbent resin. Particularly preferably, it is added in an amount of 5 to 25 parts by mass, and in some cases 10 to 20 parts by mass.
  • the antifogging layer 43 may include a metal oxide component derived from a hydrolyzable metal compound having no water repellent group (water repellent group-free hydrolyzable compound).
  • 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).
  • 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 joins the metal oxide fine particles and the water-absorbent resin, and can contribute to improvement of the wear resistance, hardness, water resistance, etc. of the antifogging layer.
  • the antifogging layer contains a water-absorbing resin
  • the metal oxide component derived from the hydrolyzable metal compound having no water-repellent group is 0 to 40 parts by weight, preferably 0.
  • the amount may be in the range of 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, particularly preferably 3 to 10 parts by mass, and in some cases 4 to 12 parts by mass.
  • 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 antifogging property of the antifogging layer may be lowered.
  • the softness of the antifogging layer is reduced, and the swelling and shrinkage of the antifogging layer accompanying the absorption and release of moisture is limited.
  • the metal oxide component derived from tetraalkoxysilane is 0 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 parts per 100 parts by weight of the water-absorbing resin. It may be added in a range of ⁇ 10 parts by mass.
  • silane coupling agents are silicon compounds having different reactive functional groups. A part of the reactive functional group is preferably a hydrolyzable functional group.
  • the silane coupling agent is, for example, a silicon compound having an epoxy group and / or an amino group and a hydrolyzable functional group.
  • preferable silane coupling agents include glycidyloxyalkyltrialkoxysilane and aminoalkyltrialkoxysilane. In these silane coupling agents, the number of carbon atoms of the alkylene group directly bonded to the silicon atom is preferably 1 to 3.
  • the glycidyloxyalkyl group and the aminoalkyl group include a functional group (epoxy group or amino group) that exhibits hydrophilicity, the glycidyloxyalkyl group and the aminoalkyl group are not water-repellent as a whole although they include an alkylene group.
  • the silane coupling agent strongly binds the water-absorbing resin that is an organic component and metal oxide fine particles that are an inorganic component, and can contribute to the improvement of wear resistance, hardness, water resistance, and the like of the antifogging layer.
  • the content of the metal oxide (silica) component derived from the silane coupling agent is excessive, the antifogging property of the antifogging layer is lowered, and in some cases, the antifogging layer becomes cloudy.
  • the metal oxide component derived from the silane coupling agent is 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the water-absorbing resin. Preferably, it is added in the range of 0.1 to 2 parts by mass.
  • the antifogging layer 43 may include a crosslinked structure derived from a crosslinking agent, preferably at least one crosslinking agent selected from an organic boron compound, an organic titanium compound, and an organic zirconium compound.
  • a crosslinked structure improves the abrasion resistance, scratch resistance and water resistance of the antifogging layer. From another point of view, the introduction of the crosslinked structure facilitates improving the durability of the antifogging layer without deteriorating the antifogging performance.
  • the antifogging layer When a crosslinked structure derived from a crosslinking agent is introduced into the antifogging layer in which the metal oxide component is a silica component, the antifogging layer has a metal atom other than silicon as a metal atom, preferably boron, titanium or zirconium, May be contained.
  • 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, particularly titanium lactate.
  • the anti-fogging layer 43 may contain other additives.
  • the additive include glycols such as glycerin and ethylene glycol having a function of improving antifogging properties.
  • Additives may be surfactants, leveling agents, ultraviolet absorbers, colorants, antifoaming agents, preservatives, and the like.
  • an antifogging film suitable for sticking to the information acquisition region 3 can be provided.
  • the additive include BYK-323, BYK-333, BYK-342, BYK-377, BYK-3455 by BYK, KP-109, KP-110, KP-112, KP-341 from Shin-Etsu Chemical.
  • Momentive's TSF4440, TSF4452, and TSF4450 can be used.
  • the antifogging layer 43 includes the following. That is, the antifogging layer 43 preferably contains 0.1 to 60 parts by mass of the metal oxide component and 0.05 to 10 parts by mass of the water-repellent group with respect to 100 parts by mass of the water absorbent resin. At this time, metal oxide fine particles (fine particles 44) such as silica fine particles (colloidal silica) and ITO fine particles are used as at least a part of the metal oxide component.
  • the water repellent group is a chain alkyl group having 1 to 8 carbon atoms, and the water repellent group is directly bonded to the metal atom constituting the metal oxide component, and the metal atom may be silicon.
  • the hydrolyzable metal compound may be at least one selected from a hydrolyzable metal compound having a water repellent group and a hydrolyzable metal compound having no water repellent group.
  • the hydrolyzable metal compound having no water repellent group may contain at least one selected from tetraalkoxysilane and silane coupling agents.
  • anti-fogging layer 43 examples include, for example, a polyvinyl acetal resin-containing solution (“S-REC KX-5” manufactured by Sekisui Chemical Co., Ltd., solid content 8 mass%, acetalization degree 9 mol%, acetal structure derived from benzaldehyde.
  • S-REC KX-5 polyvinyl acetal resin-containing solution manufactured by Sekisui Chemical Co., Ltd., solid content 8 mass%, acetalization degree 9 mol%, acetal structure derived from benzaldehyde.
  • silica fine particle dispersion (“Snowtex ST-O-40” manufactured by Nissan Chemical Industries, solid content 40% by mass, average particle size (temporary particle size) 20-25 nm) 2.50 mass %, N-hexyltrimethoxysilane (HTMS, “KBM-3063” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.526% by mass, 3-glycidoxypropyltrimethoxylane (GPTMS, “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.198 parts by mass, tetraethoxysilane (TEOS, “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.) 2.774% by mass, alcohol Solvent (“Solmix AP-7” manufactured by Nippon Alcohol Industry) 5.607% by mass, 0.875% by mass purified water, 0.01% by mass hydrochloric acid as an acid catalyst, leveling agent (“KP-341 manufactured by Shin-Etsu Chemical
  • the type of the anti-fogging layer 43 may not be limited to a water absorption type, and may be appropriately selected according to the embodiment. As described above, the type of the anti-fogging layer 43 may be, for example, a hydrophilic type or a water repellent type. Further, when the anti-fogging layer 43 is constituted by a type other than the water absorption type, metal oxide fine particles such as silica fine particles and ITO fine particles are added to the anti-fogging layer 43 as fine particles 44 as in the case of the water absorption type. Good.
  • the base material layer 42 is a layer that serves as a base of the antifogging film 4 and holds the antifogging layer 43 and the adhesive layer 41 on each surface side.
  • the adhesive layer 41 is a layer for adhering the antifogging film 4 to an object.
  • the material of the adhesive layer 41 may be appropriately selected according to the embodiment as long as the antifogging film 4 can be attached to the inner surface of the information acquisition region 3 and is transparent.
  • the material of the adhesive layer 41 may be an acrylic or silicon adhesive.
  • the material of the base material layer 42 may be appropriately selected according to the embodiment as long as it is a transparent material.
  • the material of the base material layer 42 may be a transparent resin sheet such as polyethylene or polyethylene terephthalate.
  • the antifogging film 4 is attached to the fourth surface which is the surface of the glass plate 1 on the vehicle interior side. Since the 4th surface which sticks this anti-fogging film 4 is located in the inside of a car, it is easy to be put in a warm environment. However, if heat is easily dissipated from the surface (fourth surface) on which the antifogging film 4 is adhered to the other surface (first surface) side, the vicinity of the antifogging film 4 is likely to be cooled.
  • the anti-fogging layer 43 is constituted by the water absorption type as described above, when the temperature around the anti-fogging film 4 is lowered, the anti-fogging property of the anti-fogging layer 43 is lowered. Therefore, if the vicinity of the antifogging film 4 is easily cooled, the antifogging property of the antifogging layer 43 may not be sufficiently exhibited. Therefore, the base material layer 42 is preferably made of a material having a thermal conductivity of 5 ⁇ 10 ⁇ 4 cal / cm ⁇ sec ⁇ ° C. or less.
  • Examples of materials that satisfy such conditions include Cosmo Shine A4300 (manufactured by Toyobo Co., Ltd.) and Lumirror (Toray Industries, Inc.). Thereby, it is possible to prevent heat from being radiated from the surface side where the antifogging film 4 is adhered to the other surface side, and to suppress the deterioration of the antifogging function of the antifogging film 4.
  • the base material layer 42 can be formed of various materials.
  • the base material layer 42 can be composed of a polarizing film.
  • a polarizing film for example, light reflected from a wet road surface, a facing building, or a car in front can be attenuated by the polarizing film, so that light from the foreground to be acquired by the camera 8 can be obtained. Since the unnecessary reflected light can be attenuated while only obtaining the image, the forward field of view of the camera 8 can be easily seen without depending on the changing conditions outside the vehicle.
  • the reflected light from a wet road surface that is visible in the front is strongly polarized in the horizontal (horizontal) direction of the electric field vibration.
  • the reflected light can be almost eliminated.
  • the light from the foreground includes randomly polarized light. Since the horizontally polarized light is attenuated by passing through the polarizing film, approximately 50% of the light incident on the camera 8 can be attenuated. .
  • region 3 can also be reduced by making a base material into a polarizing film.
  • the polarizing film used for the anti-fogging film 4 according to the present embodiment is not particularly limited.
  • SEG1425DU, TEG1456DU manufactured by Nitto Denko Corporation, WGF manufactured by Asahi Kasei Co., Ltd., THC-125U manufactured by Polatechno Co., Ltd., etc. are used. be able to.
  • a polarizing plate can be provided in the camera 8.
  • the polarizing plate on the camera 8 side can be rotated, the amount of light that is actively received is adjusted by the difference in the direction of the polarizing film of the base material layer 42 and the angle of the deflecting plate on the camera 8 side. Can respond to changing conditions outside the vehicle.
  • the camera since the camera is energized, there is an advantage that it is easy to provide such a rotation mechanism.
  • the base material layer 42 can also be formed of a heat reflecting film.
  • heat from the outside of the vehicle can be reflected by the antifogging film 4, so that it is possible to prevent the heat from outside the vehicle from reaching the camera 8 and causing the camera 8 to reach a high temperature. This can prevent the camera 8 from malfunctioning.
  • a heat reflection film For example, 3M scotch tent window film (NANO80S, NANO90S etc.) by 3M Japan Co., Ltd., Teijin Frontier Co., Ltd.
  • heat can also be reflected by using a heat
  • fever reflection film for example, XIR film manufactured by EASTMAN can be used.
  • the base material layer 42 can be formed of a blue light cut film.
  • a camera for visible light can be used as the camera 8 used in the present embodiment, but such a camera 8 uses visible light having a wavelength of about ⁇ 100 nm with a peak at about 550 nm, but the blue light cut When a film is used, blue light having a peak wavelength of 450 nm can be cut. Since blue light has a wavelength range different from that of visible light, there is no problem even if light from which blue light is cut enters the camera 8. That is, the blue light is cut, so that transmission of light not used by the camera 8 can be suppressed, and the total amount of light received by the camera can be effectively reduced without reducing the sensitivity of the camera. it can.
  • the light transmittance in the information acquisition region 3 can be reduced.
  • a blue cut film for example, a blue light cut liquid crystal protective film (EF-FLBL series, etc.) manufactured by Elecom Co., Ltd., Venus Guard Coat Lapis RUV manufactured by HOYA Co., Ltd. can be used.
  • the antifogging film 4 can be produced by forming the antifogging layer 43 on one surface of the base material layer 42 and applying an adhesive on the other surface to form the adhesive layer 41.
  • the antifogging layer 43 is formed by applying a coating liquid (liquid agent) for forming the antifogging layer 43 onto the base material layer 42, drying the applied coating liquid, and further increasing the temperature of the antifogging layer 43 as necessary. It can be performed by performing a wet treatment or the like. 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 carried out by exposing the coating liquid to an atmosphere maintained at a relative humidity of less than 40%, more preferably 30% or less.
  • the air drying process can be performed as a non-heating process, in other words, at room temperature.
  • the temperature applied in the heat drying process should not be excessively high.
  • An appropriate heating temperature in this case is 300 ° C. or less, for example, 100 to 200 ° C., and the heating time is 1 minute to 1 hour.
  • a high-temperature and high-humidity treatment step may be appropriately performed.
  • the high-temperature and high-humidity treatment step can be carried out, for example, by holding in an atmosphere of 50 to 100 ° C. and a relative humidity of 60 to 95% for 5 minutes to 1 hour.
  • the high temperature and high humidity treatment step may be performed after the coating step and the drying step, or may be performed after the coating step and the air drying step and before the heat drying step.
  • a heat treatment step may be further performed after the high temperature and high humidity treatment step. This additional heat treatment step can be performed, for example, by holding in an atmosphere of 80 to 180 ° C. for 5 minutes to 1 hour.
  • the antifogging layer 43 formed from the coating solution may be washed and / or wiped with a poultice as necessary. Specifically, it can be carried out by exposing the surface of the anti-fogging layer 43 to a water flow or wiping with a cloth soaked with water.
  • the water used in these is suitably pure water. It is better to avoid using solutions containing detergents for cleaning. By this step, dust, dirt, etc. adhering to the surface of the anti-fogging layer 43 can be removed, and a clean coating surface can be obtained.
  • the thickness of each layer may be appropriately set according to the embodiment.
  • the thickness of the adhesive layer 41 may be set in the range of several ⁇ m to several hundred ⁇ m.
  • the thickness of the base material layer 42 may be set in the range of 20 ⁇ m to 150 ⁇ m.
  • the thickness of the antifogging layer 43 may be set in the range of 1 ⁇ m to 20 ⁇ m.
  • the shape and plane dimension of the anti-fogging film 4 are demonstrated.
  • the antifogging film 4 is formed in a rectangular shape in plan view, and each of the four corners is rounded.
  • the antifogging film 4 is not easily peeled off from the inner surface of the information acquisition area 3.
  • at least one of the four corners may be sharp. With the sharp corners, the antifogging film 4 can be easily peeled off.
  • planar dimension of the antifogging film 4 is larger than the planar dimension of the information acquisition region 3 and smaller than the planar dimension of the opening 23 of the shielding layer 2.
  • the planar dimension of the anti-fogging film 4 may be set to be smaller than the planar dimension of the opening 23 by 2 mm each in the vertical direction and the horizontal direction, for example.
  • the information acquisition area 3 and the visual field area 5 will be described.
  • the dark ceramic constituting the shielding layer 2 is not laminated. Therefore, the light transmittance of the visual field region 5 is determined based on the light transmittance of each glass plate (11, 12) and the intermediate film 13.
  • the information acquisition region 3 arranged in the opening 23 is the same as the visual field region 5 in that the dark ceramic constituting the shielding layer 2 is not laminated. It differs from the visual field region 5 in that the antifogging film 4 to be included is adhered. Therefore, the light transmittance of the information acquisition region 3 is determined based on the light transmittance of the antifogging film 4 in addition to the glass plates (11, 12) and the intermediate film 13.
  • the glass plates (11, 12) and the intermediate film 13 according to the present embodiment have substantially the same light so that there is no difference in light transmittance between the information acquisition region 3 and the visual field region 5. It may be configured to have a transmittance. Even if each glass plate (11, 12) and the intermediate film 13 are configured to have substantially the same light transmittance, information is acquired on the antifogging film 4 configured to decrease the light transmittance. By sticking to the region 3, the information acquisition region 3 is configured to have a light transmittance lower than the light transmittance of the visual field region 5.
  • the light transmittance of the visual field region 5 is increased. Is also configured to have a low light transmittance.
  • the light transmittance of the visible region (380 nm to 780 nm) is set to 70% or more by appropriately adjusting the light transmittance of each glass plate (11, 12) and the intermediate film 13. May be configured.
  • the light transmittance in the visible region is 25% or more and 70% or less by appropriately adjusting the amount of the fine particles 44 added to the antifogging layer 43 of the antifogging film 4. You may be comprised so that it may become.
  • the haze ratio of the information acquisition area 3 becomes larger than the haze ratio of the visual field area 5.
  • the visual field region 5 may be configured such that the haze ratio is 0.6% or less by appropriately adjusting the haze ratio of each glass plate (11, 12) and the intermediate film 13.
  • the information acquisition area 3 adjusts the amount of the fine particles 44 added to the antifogging layer 43 of the antifogging film 4 as appropriate so that the haze ratio is 0.6% or more and 20% or less. It may be configured.
  • ITO fine particles can be added to the anti-fogging layer 43 as the fine particles 44.
  • the ITO fine particles can absorb light in the infrared region (800 nm or more). Therefore, when ITO fine particles are added as the fine particles 44, the information acquisition region 3 is configured to have a light transmittance in the infrared region lower than the light transmittance in the infrared region in the visual field region 5.
  • the visual field region 5 is configured such that the light transmittance of the infrared region is 15% or more and 60% or less by appropriately adjusting the light transmittance of each glass plate (11, 12) and the intermediate film 13. May be.
  • the average transmittance at a wavelength of 1000 to 2000 nm is 30% by appropriately adjusting the amount of ITO fine particles (fine particles 44) added to the anti-fogging layer 43 of the anti-fogging film 4.
  • You may be comprised so that it may become the following.
  • the camera 8 is an example of an information acquisition device arranged in the vehicle.
  • the camera 8 includes an image sensor such as a CCD (Charge Coupled Device) and a CMOS (Complementary MOS) and a lens system, and is configured to be able to photograph a situation outside the vehicle through the information acquisition region 3.
  • the image acquired by the camera 8 is sent to an image processing device (not shown).
  • the image acquisition device analyzes the type of the subject based on the image acquired by the camera 8.
  • the type of subject can be estimated by a known image analysis method such as pattern recognition.
  • the image processing apparatus is configured as a computer having a storage unit, a control unit, an input / output unit, and the like so that it can perform such image analysis and present the result to a user (driver).
  • Such an image processing apparatus may be a general-purpose apparatus such as a PC (Personal Computer) or a tablet terminal in addition to an apparatus designed exclusively for a service to be provided.
  • FIG. 6A schematically illustrates the state of the bracket 6 according to this embodiment on the vehicle exterior side.
  • FIG. 6B schematically illustrates the state of the inside of the bracket 6 according to this embodiment.
  • FIG. 7 schematically illustrates the cover 7 according to this embodiment.
  • the bracket 6 is formed in a rectangular frame shape having a mounting opening 61 in which a cover 7 that holds the camera 8 is disposed.
  • the bracket 6 includes a rectangular main body 62 that surrounds the mounting opening 61, and support portions 63 that are disposed on both sides of the main body 62 and fix the cover 7.
  • the bracket 6 is disposed around the opening 23 of the shielding layer 2.
  • the main body 62 has a flat surface, and an adhesive 64 and a double-sided tape 65 are attached to the flat surface.
  • the main body 62 is bonded to the shielding layer 2 (projecting portion 22) or the glass plate 1 by the adhesive 64 and the double-sided tape 65. Thereby, the bracket 6 is fixed so as to be shielded entirely or at least partially by the shielding layer 2 (projection 22).
  • the types of the adhesive 64 and the double-sided tape 65 are not particularly limited, and may be appropriately selected according to the embodiment.
  • an adhesive such as a urethane resin adhesive or an epoxy resin adhesive can be used as the adhesive 64.
  • a known double-sided tape can be used for the double-sided tape 65.
  • positioning of the adhesive agent 64 and the double-sided tape 65 which are shown by FIG. 6A is an example, and does not need to be limited to this example.
  • the bracket 6 is fixed around the opening 23 of the shielding layer 2 by the adhesive 64 and the double-sided tape 65.
  • a cover 7 that holds the camera 8 is attached to the bracket 6 from the vehicle interior after a harness (not shown) or the like is attached. Thereby, the camera 8 is accommodated in a space surrounded by the bracket 6, the cover 7, and the glass plate 1.
  • the cover 7 is formed in a rectangular shape, is supported by the support portion 63 of the bracket 6, and is disposed so as to close the attachment opening 61.
  • a recess 71 is formed on the surface facing the glass plate 1 through the mounting opening 61.
  • the recess 71 is inclined so that the upper end is deepest and becomes shallower toward the lower end, and the lens 73 of the camera 8 is disposed on the wall 72 at the upper end.
  • the lens 73 is appropriately aligned so as to correspond to the information acquisition region 3 (opening 23).
  • the camera 8 can acquire information outside the vehicle through the information acquisition region 3 (opening 23) while being supported by the bracket 6 and the cover 7. It becomes like this.
  • a light shielding member such as an adhesive 64 and a double-sided tape 65 so as to surround the recess 71.
  • the bracket 6 and the cover 7 can be appropriately manufactured by a known processing method.
  • FIG. 8 schematically illustrates a manufacturing process of the glass plate 1 according to the present embodiment.
  • the manufacturing method of the windshield 100 demonstrated below is only an example, and each step may be changed as much as possible. Further, in the manufacturing process described below, steps can be omitted, replaced, and added as appropriate according to the embodiment.
  • the glass plate 1 including the shielding layer 2 is manufactured by the manufacturing line illustrated in FIG.
  • the production line illustrated in FIG. 8 includes a ring-shaped mold 200, a transport table 201 that transports the mold 200, a heating furnace 202, and a slow cooling furnace 203.
  • a flat laminated glass 10 is formed by stacking the outer glass plate 11 and the inner glass plate 12 up and down so that the second surface and the third surface face each other. Then, the formed flat laminated glass 10 is placed on the mold 200.
  • the forming mold 200 is disposed on the transfer table 201, and the transfer table 201 sequentially passes through the heating furnace 202 and the slow cooling furnace 203 in a state where the glass 10 is placed on the forming mold 200.
  • both glass plates (11, 12) are bent downward on the inner side of the peripheral edge by their own weight, and are formed into curved surfaces.
  • both glass plates (11, 12) are carried into the slow cooling furnace 203 from the heating furnace 202 and subjected to a slow cooling process, and then carried out of the slow cooling furnace 203 to be cooled.
  • both glass plates (11, 12) are shape
  • both glass plates (11, 12) and intermediate film 13 are inserted
  • stacked these is produced.
  • This laminate is put in a rubber bag and pre-adhered at about 70 to 110 ° C. while sucking under reduced pressure.
  • the pre-adhesion method may be appropriately selected according to the embodiment.
  • the laminated body that has been pre-adhered is subjected to main bonding by an autoclave at, for example, 8 to 15 atm and 100 to 150 ° C.
  • the main bonding can be performed under the conditions of 14 atm and 135 ° C.
  • an antifogging film 4 is prepared. Then, the prepared antifogging film 4 is pressed against the inner surface of the information acquisition area 3. For example, the antifogging film 4 is pressed against the inner surface of the information acquisition region 3 manually or automatically using an instrument such as a squeegee. Thereby, the anti-fogging film 4 can be stuck on the vehicle inner surface of the information acquisition area 3.
  • a bracket 6 for attaching the cover 7 is prepared. Then, the prepared bracket 6 is arranged around the opening 23 of the shielding layer 2 and fixed by the adhesive 64 and the double-sided tape 65 so as to be at least partially shielded by the shielding layer 2. Further, a cover 7 that holds the camera 8 is attached to the bracket 6. Thereby, the windshield 100 to which the camera 8 is attached and the antifogging film 4 is attached to the information acquisition region 3 can be manufactured.
  • the information acquisition region 3 is configured to transmit light less than the visual field region 5.
  • the light transmittance of the visual field region 5 is set to 70% or more, whereas the light transmittance of the information acquisition region 3 is set to 70% or less.
  • the haze ratio of the visual field area 5 is set to 0.6% or less, whereas the haze ratio of the information acquisition area 3 is set to 0.6% or more.
  • the shielding layer 2 (protrusion 22) is provided around the information acquisition region 3, and the camera 8 is housed in a space closed by the glass plate 1, the bracket 6, and the cover 7. . Therefore, the shielding layer 2, the bracket 6, and the cover 7 can block the incidence of light from the area around the information acquisition area 3. Therefore, according to the present embodiment, even when strong light is incident from the outside of the vehicle, it is possible to further prevent the camera 8 from taking a picture of the situation outside the vehicle.
  • the light transmittance in the infrared region in the information acquisition region 3 is made lower than the light transmittance in the infrared region in the visual field region 5. Can do. Therefore, by blocking the light in the infrared region by the information acquisition region 3, it is possible to prevent the light in the infrared region from reaching the camera 8 with a strong light amount. Therefore, according to this embodiment, it can suppress that the camera 8 periphery is warmed by the light of an infrared region, and, thereby, can prevent that the camera 8 becomes high temperature and breaks down.
  • an infrared light blocking effect has the following advantages. That is, when the anti-glare effect and the infrared light blocking effect are realized by separate films, a plurality of films are attached to the information acquisition region 3. Thereby, the total thickness of the film stuck on the information acquisition area
  • the antifogging film 4 comprised so that the light transmittance may be reduced by adding the microparticles
  • the transmittance is set lower than the light transmittance of the visual field region 5. That is, each glass plate (11, 12) and the intermediate film 13 may have substantially the same light transmittance in the information acquisition region 3 and the visual field region 5, for example, the information acquisition region 3 It is not necessary to perform special processing that reduces the light transmittance in the portion. Therefore, according to this embodiment, it is possible to make the information acquisition region 3 less likely to transmit light than the visual field region 5 by a simple process of sticking the antifogging film 4. Therefore, it is possible to realize the windshield 100 that is difficult to prevent photographing by the camera 8 even when strong light is incident at a low cost.
  • the light transmittance of the information acquisition region 3 is made lower than the light transmittance of the visual field region 5 by adding the fine particles 44 to the antifogging layer 43. Therefore, according to the present embodiment, even if strong light is incident from the outside of the vehicle by the fine particles 44 added to the antifogging layer 43 while preventing the information acquisition region 3 from being fogged by the antifogging function of the antifogging layer 43. It is possible to make it difficult for the photographing by the camera 8 to be hindered. Therefore, it is possible to realize the windshield 100 having the information acquisition area 3 suitable for photographing with the camera 8.
  • the glass plate 1 of the windshield 100 is configured as a laminated glass in which an outer glass plate 11 and an inner glass plate 12 are bonded to each other via an intermediate film 13.
  • the type of the glass plate 1 may not be limited to such an example, and may be appropriately selected according to the embodiment.
  • the glass plate 1 may be one sheet, for example.
  • the glass plate 1 is formed in the substantially trapezoid shape.
  • the shape of the glass plate 1 may not be limited to such an example, and may be appropriately selected according to the embodiment.
  • the glass plate 1 is formed in a curved shape by self-weight bending.
  • the method for forming the glass plate 1 may not be limited to such an example, and may be appropriately selected according to the embodiment.
  • the glass plate 1 may be formed in a curved shape by known press molding.
  • the camera 8 is used as the information acquisition device.
  • the information acquisition device is not limited to such an example as long as it can acquire information from outside the vehicle by performing light irradiation and / or light reception, and may be appropriately selected according to the embodiment. May be selected.
  • the number of information acquisition devices installed in the vehicle is not limited to one, and may be appropriately selected according to the embodiment.
  • the information acquisition device may be, for example, a stereo camera that can specify the position of the subject by stereoscopic viewing.
  • the bracket 6 is formed in frame shape, and the cover 7 is formed in the rectangular shape so that attachment to this bracket 6 is possible.
  • the shape of the bracket 6 and the cover 7 is not limited to such an example as long as it can be fixed to the shielding layer 2 while supporting the information acquisition device, and is appropriately selected according to the embodiment. It's okay.
  • the bracket 6 may be provided with a plurality of openings so as to correspond to a plurality of information acquisition devices.
  • a plurality of sets of brackets 6 and covers 7 are prepared, and the prepared plurality of sets of brackets 6 and covers 7 may be attached to the glass plate 1. .
  • the information acquisition region 3 may be disposed adjacent to the shielding layer 2 instead of being surrounded by the shielding layer 2.
  • FIG. 9 illustrates a windshield 100B according to this modification.
  • the protrusion 22 and the opening 23 are omitted in the shielding layer 2B, and the information acquisition region 3 is slightly below the center of the upper end side of the shielding layer 2B (peripheral portion 21). Is arranged.
  • the information acquisition area 3 may be arranged so that at least one side is adjacent to the shielding layer 2.
  • the information acquisition region 3 is provided in a range different from the visual field region 5. However, the information acquisition area 3 may fall within the driver's visual field range.
  • FIG. 10 illustrates a windshield 100B to which a stereo camera 83 including two cameras (831, 832) can be attached.
  • the shielding layer 2C has a protruding portion 22C that is slightly long in the left-right direction.
  • the projection 22C is provided with an opening 23C corresponding to the position of each camera (831, 832) of the stereo camera 83.
  • the information acquisition area 3C is appropriately set in each opening 23C.
  • the antifogging film 4 may be attached separately to the two information acquisition regions 3 ⁇ / b> C.
  • the planar dimension of the anti-fogging film 4 is smaller than the planar dimension of the opening part 23 of the shielding layer 2.
  • the planar dimension of the anti-fogging film 4 may not be limited to such an example, and may be larger than the planar dimension of the opening 23.
  • the fine particles 44 are added to the antifogging layer 43.
  • the fine particles 44 may be added to the base material layer 42.
  • the anti-fogging film 4 may be configured not to add the fine particles 44 but to reduce the light transmittance by other processing.
  • ITO fine particles can be used as the fine particles 44 to impart an infrared light blocking effect to the anti-fogging layer 43.
  • the form which provides this infrared light blocking effect is not limited to such an example, and may be configured as follows. That is, an anti-glare effect may be imparted to one of the base material layer 42 and the anti-fogging layer 43 and an infrared light shielding effect may be imparted to the other.
  • the light transmittance of the information acquisition area 3 is made into the light of the visual field area
  • the transmittance is lower.
  • the method of making the light transmittance of the information acquisition region 3 lower than the light transmittance of the visual field region 5 may not be limited to such an example, and may be appropriately selected according to the embodiment. .
  • the light transmittance of the information acquisition region 3 can be reduced to that of the visual field region 5. It may be lower than the light transmittance.
  • a film material in which the antifogging layer 43 of the antifogging film 4 is omitted and the fine particles 44 are added to the base material layer 42 can be exemplified. That is, by attaching a film material including a base material layer to which fine particles for scattering light are added and an adhesive layer laminated on one surface of the base material layer to the information acquisition region 3, The transmittance may be lower than the light transmittance of the visual field region 5.
  • the light transmittance of the information acquisition region 3 can be made lower than the light transmittance of the visual field region 5 without depending on the film material.
  • FIG. 11 illustrates a windshield 100D according to this modification.
  • the intermediate film 13D is configured to have different light transmittances in the portion 131 corresponding to the information acquisition region 3D and other portions.
  • the portion 131 is configured to have a lower light transmittance than the other portions.
  • Such an intermediate film 13D prepares a sheet material having a low light transmittance and a sheet material having a high light transmittance, cuts both sheets corresponding to the range of the portion 131, and replaces the cut portions. Thus, it can be manufactured.
  • the light transmittance of the information acquisition region can be made lower than the light transmittance of the visual field region.
  • the above-described antifogging film can be disposed in the information acquisition region 3 together with the low reflection film. Accordingly, it is possible to suppress the reflection of light from the inside of the vehicle toward the camera side, and it is possible to make the light transmittance from the outside of the vehicle in the information acquisition region 3 lower than the light transmittance of the visual field region 5.
  • the refractive index of the glass plate is about 1.52 and the refractive index of air is 1, the material having a refractive index between them can be mainly disposed in the information acquisition region 3 as a low reflection film.
  • the refractive index of the low reflection film is between 1 and 1.52, the wavefront of the reflected light W1 on the surface of the low reflection film and the reflected light on the surface of the glass plate as shown in FIG.
  • the wavefront of W2 cancels out, and the amount of light transmitted from the air layer to the glass plate increases. As a result, the reflected light to the camera side can be reduced.
  • the film thickness of the low reflective film is ⁇ (wavelength of visible light) / 4 ⁇ (odd number), and the refractive index of the low reflective film is about 1.23 (1/2 of the refractive index of glass). If so, the reflected light from the low reflection film can be substantially eliminated. However, since this is ideal, it is possible to reduce reflection by adopting a material and film thickness that are close to such a mechanism.
  • the refractive index of the low reflection film can be calculated by the following method, for example.
  • Step 1 Black paint is applied to the surface opposite to the low-reflection film, that is, the surface of the glass plate outside the vehicle, and preparation is made so that the reflection of light on this surface does not affect the amount of reflection.
  • Step 2 Using a spectrophotometer (for example, UV-3100PC, manufactured by Shimadzu Corporation), measure the reflectance of light in the wavelength range of 550 to 600 nm at an angle at which the incident angle of the incident light from the inside of the vehicle can be regarded as almost vertical incidence Then, the average reflectance R is obtained.
  • the low reflection film has a porous structure. That is, since the air gap is formed over almost the entire low reflection film, the refractive index can be reduced.
  • a low reflection film can be formed by a film containing silica fine particles and a binder.
  • silica gel or chain silica fine particles voids are generated in the layer, and thereby the refractive index of the film can be lowered as compared with the case without voids.
  • moisture content can be absorbed into a space
  • the silica fine particles may include chain silica fine particles in which a plurality of silica fine particles are aggregated in a chain shape.
  • the length of the chain silica fine particles is, for example, 60 to 300 nm.
  • the average particle diameter of the silica fine particles constituting the chain silica fine particles is, for example, 10 to 200 nm.
  • the refractive index of the low reflection film having chain silica fine particles is not limited, but can be lowered to, for example, 1.25 to 1.40.
  • the average particle diameter can be determined by the average value of the particle diameters of 50 particles observed using a scanning electron microscope and, if necessary, a transmission electron microscope.
  • the binder plays a role in bonding the silica fine particles to each other and the silica fine particles and the glass plate.
  • the binder preferably contains silicon oxide as a main component, that is, a component of 50% by mass or more. If necessary, an oxide other than silicon oxide such as aluminum oxide, titanium oxide, or zirconium oxide may be added.
  • the binder can be introduced into the film using, for example, a hydrolyzable metal compound, specifically, a metal alkoxide as a raw material.
  • the ratio of the silica fine particles to the binder in the low reflection film is, for example, 60:40 to 95: 5, preferably 65:35 to 85:15 on a mass basis.
  • the thickness of the low reflection film is, for example, 40 to 1000 nm, preferably 110 to 180 nm.
  • the low reflection film can be formed, for example, from a raw material liquid in which silica fine particles, a hydrolyzable metal compound, a hydrolysis catalyst, water, and an organic solvent are mixed.
  • An acid is suitable as the hydrolysis catalyst
  • a lower alcohol is suitable as the organic solvent.
  • the ratio of each component constituting the raw material liquid is, for example, 150 to 1900 parts by mass of silica fine particles, 50 to 10000 parts by mass of water, 0.01 to 200 parts by mass of hydrolysis catalyst with respect to 100 parts by mass of the hydrolyzable metal compound,
  • the organic solvent is 1,000 to 500,000 parts by mass.
  • the raw material liquid is applied to the surface on which the low reflection film is to be formed and heated.
  • the heating temperature is preferably 200 ° C. or higher, particularly 400 ° C. or higher, and may be 1000 ° C. or lower.
  • the heating time is, for example, 30 seconds to 1 hour.
  • a low reflection film is formed on the glass plate.
  • the low-reflection film is provided in the information acquisition region 3 and is operated. Since this is not an area that is directly viewed by a person, even if such a situation occurs, there is no particular problem.
  • hollow fine particles can be mixed to form voids.
  • Such hollow fine particles can be formed by silica fine particles, for example. That is, hollow silica fine particles can be used.
  • the diameter of such hollow fine particles can be set to, for example, 50 to 60 nm.
  • fine particles mainly composed of MgF 2 fine particles can be contained.
  • the phrase that the fine particles contain MgF 2 fine particles as a main component means that, for example, the content of the MgF 2 fine particles in the fine particles is 95% by mass or more.
  • fine particles may preferably include MgF 2 particles less than 98 wt%, may be composed of only MgF 2 particles.
  • fine particles other than MgF 2 fine particles may be further contained, and various fine particles can be contained according to a required function.
  • TiO 2 fine particles can be included for imparting photocatalytic performance, ZnO fine particles for imparting an ultraviolet cut function, and SnO 2 fine particles for imparting an antistatic function.
  • the MgF 2 fine particles preferably have an average particle size of 10 to 30 nm. According to the MgF 2 fine particles having such an average particle diameter, a highly transparent coating can be formed.
  • the “average particle size” of the fine particles means a particle size (D50) corresponding to 50% of volume accumulation in the particle size distribution measured by the laser diffraction particle size distribution measurement method.
  • the binder included in the low reflection film includes, for example, an inorganic oxide as a main component.
  • the binder containing an inorganic oxide as a main component means that the content of the inorganic oxide in the binder is 80% by mass or more.
  • the binder preferably contains 90% by mass or more of an inorganic oxide, and may be composed of only an inorganic oxide.
  • the binder may further contain an organic component. Further, the binder may be amorphous or crystalline.
  • the inorganic oxide contained in the binder may be an oxide of at least one metal selected from the group consisting of Si, Al, Zr, Ti, Sn, and Fe.
  • the inorganic oxide may be made of Si oxide, Si oxide and Al oxide, or Al oxide.
  • the binder is made of an oxide of Si, a coating having a low reflectance and a high transmittance can be obtained.
  • the binder is made of an oxide of Al, a coating having a high refractive index but a low reflectance can be obtained.
  • the wear resistance of the coating is improved when the binder is composed of Si oxide and Al oxide.
  • the inorganic oxide contained in the binder is composed of Si oxide and Al oxide, the Si oxide content is converted to SiO 2 , and the Al oxide content is converted to Al 2 O 3 .
  • the mass ratio (SiO 2 : Al 2 O 3 ) between SiO 2 and Al 2 O 3 in the inorganic oxide contained in the binder is preferably 99.5: 0.5 to 97: 3, for example.
  • the mass ratio of fine particles to binder can be, for example, 95: 5 to 35:65.
  • an anti-fogging film can be disposed on the glass plate together with such a low reflection film.
  • an antifogging film 4 can be disposed between the glass plate 1 and the low reflection layer 9.
  • the antifogging film 4 includes the base material 42 and the antifogging layer 43 disposed thereon, and the base material 42 is attached to the glass plate 1 by the adhesive layer 41. Since the low reflection film 9 has a porous structure, moisture from the air layer can pass through the low reflection film 9 having a gap and move to the antifogging film 4. Therefore, by providing such a low reflection film 9, it is possible to achieve both a low reflection function and an antifogging function.
  • the haze ratio may increase.
  • the low reflection film 9 is provided in the information acquisition area 3 and is not an area that is directly viewed by the driver. Even if such a situation occurs, there is no particular problem.
  • the low reflection film 9 faces the information acquisition device side, and has an uneven surface.
  • the refractive index can be reduced, and as a result, the reflection of light from the camera side can be suppressed and the transmittance of the information acquisition region can be improved. More specifically, since the surface of the low reflection film is in a state where air and the low reflection film are mixed due to the unevenness, the apparent refractive index is reduced.
  • Such a low reflection film is not particularly limited as long as it is formed of a material capable of suppressing reflection of light in the visible light range.
  • silica fine particles for example, colloidal silica
  • a binder are used.
  • the silica fine particles are exposed on the surface, thereby forming irregularities.
  • the thickness of the portion where the irregularities are formed can be set to, for example, 50 to 500 nm.
  • the amount of the binder it is possible to adjust the amount of silica fine particles exposed from the surface, and as a result, it is possible to adjust the film thickness of the portion where the irregularities are formed.
  • the film thickness of the portion where the unevenness is formed in order to reduce the apparent refractive index, it is preferable that the film thickness of the portion where the unevenness is formed be smaller than the wavelength of light, and the film thickness may be adjusted in consideration of that. .
  • the portion where the irregularities are formed constitutes the surface portion of the present invention, and the portion other than the irregularities constitutes the main body portion of the present invention.
  • the average particle diameter of the silica fine particles is, for example, 10 to 200 nm, but the unevenness depth varies depending on the size of the silica fine particles.
  • the average particle diameter of the silica fine particles is small, as shown in FIG. 16, the above-described unevenness with a depth of 50 to 500 nm is formed by laminating a large number of silica fine particles.
  • the low-reflection film is provided in the information acquisition region 3 and is operated. Since this is not an area that is directly viewed by a person, even if such a situation occurs, there is no particular problem.
  • the low reflection film according to the third aspect is composed of a plurality of layers.
  • the refractive index of the plurality of layers is between 1 and 1.52, and the layer closer to the glass plate has a higher refractive index.
  • the low reflection film 9 is composed of two layers.
  • a layer close to the glass plate is referred to as a first layer 91
  • a far layer is referred to as a second layer 92.
  • the refractive index of the first layer 91 is n1 and the refractive index of the second layer 92 is n2, 1 (air layer) ⁇ n1 ⁇ n2 ⁇ 1.52 (glass plate) is satisfied.
  • the refractive index gradually decreases as going from the glass plate 1 to the air layer. Therefore, since the refractive index does not change abruptly between the glass plate 1 and the air layer, but gradually changes, the amount of light reflected from the glass plate 1 to the information acquisition device can be reduced.
  • the number of layers constituting the low reflection film 9 is not particularly limited, and may be three or more layers in which the refractive index gradually decreases from the glass plate side to the air layer side.
  • the material which comprises each layer is not specifically limited, What is necessary is just a material which shows the above refractive indexes.
  • the low reflection film 9 according to the fourth aspect is also composed of a plurality of layers.
  • the refractive index of the first layer closest to the glass plate 1 is larger than the refractive index of the glass plate 1, and the refractive index of the layer between the first layer and the air layer is smaller than that of the first layer.
  • it has the 1st layer 901 which is a layer near the glass plate 1, and the 2nd layer 902 which is a distant layer.
  • the refractive index of the first layer 901 is m1 and the refractive index of the second layer 902 is m2, 1 (air layer) ⁇ m2 ⁇ 1.52 (glass plate) ⁇ m1 is satisfied. Even with such a layer configuration, the amount of light reflected from the glass plate 1 to the air layer can be reduced.
  • the material which comprises each layer is not specifically limited, As the 1st layer 901, transparent conductive films, such as ITO, can be used, for example. Further, the refractive index can be increased by containing titanium oxide (TiO 2 ) or tin oxide (SnO 2 ). The refractive index of such a transparent conductive film is about 1.6 to 1.8.
  • the second layer 902 can be a layer containing the above-described silica fine particles, and the refractive index thereof is 1.25 to 1.40.
  • the number of layers constituting the low reflection film 9 is not particularly limited.
  • the second layer 902 having a refractive index smaller than that of the first layer 901 can be composed of a plurality of layers.
  • the plurality of second layers 902 are preferably configured such that the refractive index gradually decreases from the glass plate side to the air layer side.
  • the low reflection film 9 is formed directly on the glass plate by applying a liquid.
  • the low reflection film 9 is formed on the base material like an antifogging film, for example. It is also possible to form a low reflection film on which the reflection film 9 is formed, and attach this to the glass plate 1 with an adhesive layer. Further, a primer layer may be provided between the base material and the low reflection film 9 to increase the formation strength. In this case, the same material as the antifogging film can be used for the substrate and the adhesive layer.
  • the information acquisition region 3 is preferably a narrow region so as not to affect the visual field region.
  • the low reflection film is disposed in the information acquisition region 3, the low reflection film is applied to such a narrow region. It may not be easy. Therefore, when the low reflection film as described above is used, it is only necessary to apply the adhesive layer to the information acquisition area 3 after forming it to an appropriate size, so that the operation is simplified.
  • the low reflection film reduces the reflection of light from the inside of the vehicle and suppresses the reflection of the camera, but this improves the light transmittance in the windshield.
  • the light transmittance is improved, strong light is incident on the information acquisition device through the information acquisition region 3, which may cause a problem.
  • the information acquisition device is a camera, low reflection at the information acquisition region 3 is required to prevent reflection, so that even if the light transmittance is improved as a result, low If reflection is realized, it can withstand practical use.
  • the upper limit of the transmittance is extremely large.
  • the transmittance is extremely large.
  • the windshield can be easily touched by the driver, durability is required. For example, it is a problem to place a low-reflection film with irregularities on the surface of such a windshield. is there.
  • a low-reflection film having a porous structure has a large haze ratio and is not suitable for the visual field region 3.
  • the cost increases because it is necessary to arrange the low-reflection films by a method such as sputtering. Therefore, it is preferable to arrange the low reflection film only in the information acquisition region 3.
  • a low reflection film can be disposed as long as it is an end away from the driver's visual field.
  • the antifogging film can have a low reflection function.
  • the refractive index of the base material layer 42 is made higher than that of the glass plate 1
  • the refractive index of 43 can be made lower than that of the base material 42.
  • the refractive index of the antifogging layer 43 is preferably lower than that of the glass plate 1.
  • the refractive index of the base material layer 42 is, for example, preferably 1.6 or more, more preferably 1.8 or more, and particularly preferably 2.0 or more.
  • the As such a substrate for example, “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd. or Lumirror (manufactured by Toray Industries, Inc.) can be used.
  • the refractive index of the anti-fogging layer 43 is preferably 1.45 or less, and more preferably 1.40 or less. it can.
  • an antifogging layer for example, a hollow fine particle can be contained.
  • irregularities can be formed on the surface of the anti-fogging layer 43.
  • the antifogging layer 43 can be formed of a plurality of layers. For example, as shown in FIG. 19, two antifogging layers, that is, a first antifogging layer 431 and a second antifogging layer 432 can be laminated on the base material layer 42 in this order. In this case, adjustment is performed such that the refractive index n1 of the first antifogging layer 431 is larger than the refractive index of the glass plate, and the refractive index n2 of the second antifogging layer 432 is smaller than the refractive index of the base material layer 42. be able to.
  • the refractive index n1 of the first antifogging layer 431 is made larger than the refractive index of the glass plate, or the refractive index n2 of the second antifogging layer 432 is made smaller than the refractive index of the base layer 42, Either adjustment can be made.
  • the first antifogging layer 431 contains tantalum pentoxide (TaO 5 ) or fine metal particles (for example, zirconia, titania, niobium oxide sol).
  • the second anti-fogging layer 432 contains silica fine particles or hollow fine particles. Alternatively, the surface of the second antifogging layer 432 is made uneven.
  • the reflectance can be reduced by including a light-absorbing substance in the anti-fogging layer 43.
  • a light-absorbing substance for example, Au and Ag fine particles, a dye, and a pigment can be used.
  • the light-absorbing substance for example, Au and Ag fine particles, a dye, and a pigment can be used.
  • the glass plate used was a normal soda lime silicate composition manufactured by Nippon Sheet Glass Co., Ltd., with a thickness of 3.2 mm and a size of 200 ⁇ 300 mm.
  • This glass plate was immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), cleaned using an ultrasonic cleaner, and washed with deionized water. Then, it was made to dry at normal temperature and it was set as the glass plate used by an Example and a comparative example.
  • alkaline solution alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.
  • silica fine particle dispersion Quarton PL-7, substantially spherical primary particles having an average particle size of 125 nm, solid content concentration 23% by weight, manufactured by Fuso Chemical Industries, Ltd.
  • the ratio of the mass of silica fine particles converted to SiO 2 to the mass of silicon oxide components contained in the binder converted to SiO 2 is 70:30, and the solid content concentration converted to SiO 2 is 10 wt%. It is.
  • the solid content concentration obtained by converting silicon oxide (derived from silica fine particles and tetraalkoxysilane) into SiO 2 is 7.0 wt%.
  • a coating liquid A1 was applied to the main surface of the glass plate on which the transparent conductive film was not applied, using a roll coater. At this time, the film thickness of the coating solution was adjusted to 1 to 5 ⁇ m. Next, the coating liquid applied to the glass plate was dried and cured with hot air.
  • This hot air drying uses a belt-conveying hot air drying device, the hot air set temperature is set to 300 ° C., the distance between the hot air discharge nozzle and the glass plate is set to 5 mm, and the conveying speed is set to 0.5 m / min. This was performed by reciprocating four times and passing under the nozzle four times.
  • the time during which the glass plate coated with the coating solution was in contact with hot air was 140 seconds, and the maximum temperature reached on the glass surface coated with the coating solution of the glass plate was 199 ° C.
  • the glass plate after drying and curing was allowed to cool to room temperature, and the glass plate was coated.
  • the reflectance of the glass plate which concerns on the said Example and comparative example was measured.
  • the reflectance curve (reflection spectrum) of the main surface of each glass plate was measured using a spectrophotometer (Shimadzu Corporation, UV-3100). The measurement was performed in accordance with JIS K5602 by making light incident from the normal direction and introducing directly reflected light having a reflection angle of 8 ° into the integrating sphere. The average reflectance was measured at a wavelength of 380 nm to 1200 nm.
  • the difference in average reflectance between the example and the comparative example was 2.98%.
  • the apparent refractive index is 1.29 when the above-described formula (1) is used.
  • the refractive index of the comparative example was 1.54. Therefore, it turned out that the refractive index which concerns on an Example is reducing significantly rather than the comparative example.

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Abstract

Selon un aspect, la présente invention concerne un pare-brise qui est un pare-brise pour un véhicule qui peut être pourvu d'un dispositif d'acquisition d'informations pour acquérir des informations provenant de l'extérieur d'un véhicule par irradiation et/ou réception de lumière. Ce pare-brise comprend une plaque de verre qui comporte une région d'acquisition d'informations qui fait face au dispositif d'acquisition d'informations et permet à la lumière de passer à travers celle-ci, et une région de visualisation qui permet au conducteur conduisant le véhicule de confirmer des conditions de trafic pendant la conduite, la région d'acquisition d'informations étant conçue pour avoir un facteur de transmission optique inférieur à celui de la région de visualisation.
PCT/JP2017/043884 2016-12-07 2017-12-06 Pare-brise WO2018105669A1 (fr)

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CN110228236A (zh) * 2019-04-25 2019-09-13 福耀玻璃工业集团股份有限公司 一种车辆用夹层玻璃
WO2020054286A1 (fr) * 2018-09-10 2020-03-19 Ａｇｃ株式会社 Verre et verre feuilleté
CN112521002A (zh) * 2021-01-15 2021-03-19 谭美艳 一种高耐碱蚀型玻璃纤维材料的制备方法
CN112533883A (zh) * 2018-08-09 2021-03-19 Ａｇｃ株式会社 玻璃、夹层玻璃
WO2021075359A1 (fr) * 2019-10-17 2021-04-22 日本板硝子株式会社 Corps en verre
CN112811829A (zh) * 2020-04-30 2021-05-18 法国圣戈班玻璃公司 防雾玻璃、车辆以及制造防雾玻璃的方法

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