WO2017183701A1 - Vitre de véhicule - Google Patents

Vitre de véhicule Download PDF

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Publication number
WO2017183701A1
WO2017183701A1 PCT/JP2017/015944 JP2017015944W WO2017183701A1 WO 2017183701 A1 WO2017183701 A1 WO 2017183701A1 JP 2017015944 W JP2017015944 W JP 2017015944W WO 2017183701 A1 WO2017183701 A1 WO 2017183701A1
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WO
WIPO (PCT)
Prior art keywords
vehicle
film
glass plate
glass
visibility ensuring
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/015944
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English (en)
Japanese (ja)
Inventor
神谷　和孝
大家　和晃
寺西　豊幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2018513217A priority Critical patent/JP6899382B2/ja
Publication of WO2017183701A1 publication Critical patent/WO2017183701A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/20—Accessories, e.g. wind deflectors, blinds
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins

Definitions

  • the present invention relates to a window glass for a vehicle in which even if water droplets are formed on the surface due to condensation of water vapor, it is difficult to visually recognize the outside of the vehicle from the inside of the vehicle.
  • Patent Document 1 discloses a laminated glass having a transparent conductive film therein as a window glass having an energization type defroster.
  • the defroster is effective as a defogging means when fogging occurs, but requires energy and time to remove the mist. In spite of such problems, as far as the present inventors know, it is not practical to alleviate the reduction in visibility after fogging by improving the surface of the vehicle window glass itself. There are no examples of reports.
  • an object of the present invention is to provide a vehicle window glass in which visibility from the inside of the vehicle is hardly hindered even when water droplets are formed on the surface due to condensation of water vapor.
  • the present invention Comprising a glass plate, and a visibility ensuring film formed on the inner surface of the glass plate,
  • the visibility ensuring film includes a water repellent group and a metal oxide component,
  • the water repellent group provides a vehicle window glass, which is a linear alkyl group having 3 to 9 carbon atoms, which is directly bonded to a metal atom constituting the metal oxide component.
  • the window glass for a vehicle according to the present invention is suitable for preventing a decrease in visibility from the inside of the vehicle to the outside even if fogging occurs due to condensation of water vapor on the inner surface of the vehicle.
  • the linear alkyl group having 3 to 9 carbon atoms directly bonded to the metal atom constituting the metal oxide component of the film is suitable for providing a uniform hydrophobic surface, that is, a hydrophobic surface with few hydrophilic spots, It is suitable for suppressing the degree of scattering of light transmitted through the vehicle window glass in a state where water vapor is condensed on the surface of the vehicle window glass.
  • metal oxide component is intended to include a component composed of only metal atoms and oxygen atoms bonded to each other, as well as a portion in which metal atoms and oxygen atoms are directly bonded. Therefore, for example, the portion represented by MO in the component represented by the formula RMO (R: water repellent group, M: metal atom) constitutes a metal oxide component. Further, the term “metal” in the terms “metal oxide component”, “metal atom”, “metal compound” and the like is used in a sense including boron (B) and silicon (Si) according to common usage.
  • the glass plate may be, for example, a float plate glass that is most commonly used in the fields of vehicles, buildings, and industries.
  • the glass plate need not be colored, but may be colored green, bronze or the like. Moreover, you may process or process into tempered glass, a laminated glass, a multilayer glass, etc.
  • the shape of the main surface may be either a flat surface or a curved surface.
  • the plate thickness is not particularly limited, but is preferably 1 to 5 mm.
  • a ceramic shielding layer may be formed on the periphery of the vehicle window glass in order to improve the design of the vehicle.
  • the ceramic shielding layer also plays a role of preventing deterioration of the resin material such as an adhesive and a foam material for joining the window glass to the vehicle body due to ultraviolet rays.
  • the ceramic shielding layer is formed by applying a ceramic paste and baking it.
  • the visibility ensuring film is formed on the surface of the glass plate.
  • the surface on which the visibility ensuring film is formed is a surface that faces the inside of the vehicle when installed on a vehicle window. This surface is typically a concave surface of a bent glass sheet.
  • membrane is formed in the concave surface of the glass plate which has a convex surface arrange
  • the visibility ensuring film may be a multilayer film, but is preferably a single layer film.
  • the visibility ensuring film is preferably formed directly on the surface of the glass plate.
  • the visibility ensuring film contains a water repellent group and a metal oxide component.
  • membrane may further contain the other functional component as needed, for example, may further contain resin.
  • the resin imparts flexibility to the film and contributes to improvement of hydrophobic uniformity. However, if the content of the resin is too high, the strength of the film may be reduced. Therefore, the visibility ensuring film may not contain any resin in some cases.
  • the visibility ensuring film preferably does not contain a resin when it is formed on the surface of a glass plate that can slide with other members as the window glass is opened and closed. A typical window glass that slides with another member is a vehicle door glass.
  • the water repellent group makes the surface of the visibility ensuring film hydrophobic, and makes the surface hard to condense water vapor.
  • the water-repellent group contributes to ensuring the straightness of incident light even if water droplets are formed on the surface of the visibility ensuring film, depending on the type.
  • a water-repellent group suitable for ensuring straightness of light is a linear alkyl group having 3 to 9, preferably 4 to 8, particularly 5 to 8, especially 5 to 7 carbon atoms.
  • the area where the water droplets 160 and 161 formed by condensing the same amount of water vapor on the surface of the film 16 cover the film 16 becomes smaller as the contact angle of water on the surface increases. Has a tendency.
  • the visibility ensuring film in which the contact angle of water is increased due to the presence of the water repellent group is less likely to form water droplets on the surface, and the area covered by the water droplets is relatively small even when the water droplets are formed. This is advantageous in maintaining the straightness of transmitted light.
  • the straightness of transmitted light has an influence on the uniformity of hydrophobicity as well as the hydrophobicity indicated by the contact angle of water. This is because, on the surface where the hydrophobicity of the surface of the film 16 is not uniform and hydrophilic spots are scattered, water droplets are formed starting from water vapor adsorbed on the hydrophilic spots. Therefore, it is preferable that the water-repellent group is oriented on the film surface so that the surface of the film 16 becomes uniform hydrophobic.
  • a water repellent group suitable for existing on the film surface in a highly oriented state arranged in the same direction is a linear alkyl group having a certain number of carbon atoms. However, a long straight-chain alkyl group having too many carbon atoms is difficult to achieve high orientation because the straight-chain alkyl group is easily bent in the middle.
  • a perfluoroalkyl group is used, stronger hydrophobicity can be realized.
  • the perfluoroalkyl group is a rigid functional group whose crystallinity is remarkably increased particularly when the number of carbon atoms is large, it tends to exist in a polycrystalline orientation on the film surface. For this reason, a locally low hydrophobic portion tends to occur on the film surface. From the viewpoint of ensuring hydrophobic uniformity, a linear alkyl group having the above-described number of carbon atoms is more suitable than a perfluoroalkyl group.
  • a metal compound having a water repellent group water repellent group-containing metal compound
  • a metal compound having a water repellent group and a hydrolyzable functional group or a halogen atom water repellent group-containing hydrolyzable metal compound
  • the water repellent group may be derived from a water repellent group-containing hydrolyzable metal compound.
  • the water repellent group-containing hydrolyzable metal compound is preferably a water repellent group-containing hydrolyzable silicon compound represented by the following formula (I).
  • R is a water repellent group, specifically a linear alkyl group having 3 to 9 carbon atoms
  • Y is a hydrolyzable functional group or a halogen atom
  • m is an integer of 1 to 3.
  • the hydrolyzable functional group is, for example, at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, and an amino group, preferably an alkoxy group, particularly an alkoxy group having 1 to 4 carbon atoms.
  • An alkenyloxy group is, for example, an isopropenoxy group.
  • the halogen atom is preferably chlorine.
  • the functional groups exemplified here can also be used as “hydrolyzable functional groups” described below.
  • m is preferably 1 or 2.
  • the compound represented by formula (I) supplies the component represented by the following formula (II) when hydrolysis and polycondensation have completely proceeded.
  • R and m are as described above.
  • the compound represented by the formula (II) actually forms a network structure in which silicon atoms are bonded to each other through oxygen atoms in the visibility ensuring film.
  • the compound represented by the formula (I) is hydrolyzed or partially hydrolyzed, and further, at least partly polycondensed to alternately connect silicon atoms and oxygen atoms, and three-dimensionally.
  • a network structure of spreading siloxane bonds Si—O—Si
  • a water repellent group R is connected to silicon atoms included in the network structure.
  • the water repellent group R is fixed to the network structure of the siloxane bond through the bond R—Si. This structure is advantageous in uniformly dispersing the water repellent group R in the film.
  • the network structure may contain a silica component supplied from a silicon compound (for example, tetraalkoxysilane, silane coupling agent) other than the water repellent group-containing hydrolyzable silicon compound represented by the formula (I).
  • a silica component supplied from a silicon compound for example, tetraalkoxysilane, silane coupling agent
  • a hydrolyzable functional group or a halogen atom-containing silicon compound water repellent group-free hydrolyzable silicon compound
  • a network structure of siloxane bonds including silicon atoms bonded to water repellent groups and silicon atoms not bonded to water repellent groups can be formed. With such a structure, it becomes easy to adjust the water repellent group content and the metal oxide component content in the visibility ensuring film independently of each other.
  • the water repellent group is added to such an extent that the contact angle of water on the surface of the visibility ensuring film is 85 degrees or more, preferably 90 degrees or more, more preferably 95 degrees or more.
  • the contact angle of water a value measured by dropping a 4 mg water droplet on the surface of the membrane is adopted.
  • the upper limit of the contact angle of water is not particularly limited, but is, for example, 105 degrees or less, and further 103 degrees or less. It is preferable that the water repellent group is uniformly contained in the visibility ensuring film so that the contact angle of water is in the above range in all regions of the surface of the visibility ensuring film.
  • membrane is 1 mass part or more with respect to 100 mass parts of metal oxide components, Preferably it is 3 mass parts or more, More preferably, it is in the range of 4 mass parts or more, and 50 mass parts or less, It is preferable to include a water-repellent group so that it is preferably within a range of 30 parts by mass or less, more preferably 20 parts by mass or less, and in some cases 15 parts by mass or less.
  • the visibility ensuring film contains a metal oxide component.
  • the metal oxide component is, for example, an oxide component of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and preferably an Si oxide component (silica component) ).
  • the metal oxide component may be a hydrolyzable metal compound or a metal oxide component derived from the hydrolyzate added to the coating liquid for forming the visibility ensuring film.
  • the hydrolyzable metal compound has a) a metal compound having a water repellent group and a hydrolyzable functional group or a halogen atom (water repellent group-containing hydrolyzable metal compound), and b) a water repellent group. It is at least one selected from a metal compound having a hydrolyzable functional group or a halogen atom (a water-repellent group-free hydrolyzable metal compound).
  • the metal oxide component derived from a) and / or b) is an oxide of metal atoms constituting the hydrolyzable metal compound.
  • the metal oxide component includes a metal oxide component derived from the metal oxide fine particles added to the coating solution for forming the visibility ensuring film, and a hydrolyzable metal compound or a metal oxide component added to the coating solution. And a metal oxide component derived from the hydrolyzate.
  • the hydrolyzable metal compound is at least one selected from a) and b) above.
  • the b), that is, the hydrolyzable metal compound having no water repellent group may contain at least one selected from tetraalkoxysilane and a silane coupling agent.
  • the metal oxide fine particles and the above b) will be described except for the above-described a).
  • the visibility ensuring film may further include metal oxide fine particles as at least a part of the metal oxide component.
  • the metal oxide constituting the metal oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica fine particles. is there.
  • Silica fine particles can be introduced into the film, for example, by adding colloidal silica.
  • the metal oxide fine particles are excellent in the action of transmitting the stress applied to the visibility ensuring film to the transparent article supporting the film, 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 visibility ensuring film.
  • the metal oxide fine particles can be supplied to the visibility ensuring film by adding the metal oxide fine particles formed in advance to the coating liquid for forming the visibility ensuring film.
  • the metal oxide fine particles can cause a hydrophilic spot on the surface of the film, it is desirable that the metal oxide fine particles should not be added to the film unless there are circumstances to improve the wear resistance and the like. That is, it is preferable to use the visibility ensuring film in a form that does not include metal oxide fine particles unless there is a particular situation where the wear resistance or the like should be emphasized.
  • the preferable average particle diameter of the metal oxide fine particles is 1 to 20 nm, particularly 5 to 20 nm.
  • the average particle diameter of the metal oxide fine particles is described in the state of primary particles.
  • the average particle diameter of the metal oxide fine particles is determined by measuring the particle diameters of 50 fine particles arbitrarily selected by observation using a scanning electron microscope and adopting the average value. If the content of the metal oxide fine particles is excessive, the film may become cloudy.
  • membrane may contain the metal oxide component derived from the hydrolysable metal compound (water repellent group non-containing hydrolyzable compound) which does not have a water repellent group.
  • a preferred hydrolyzable metal compound containing no water repellent group is a hydrolyzable silicon compound having no water repellent group.
  • the hydrolyzable silicon compound having no water repellent group is, for example, at least one silicon compound selected from silicon alkoxide, chlorosilane, acetoxysilane, alkenyloxysilane and aminosilane (however, having no water repellent group), Silicon alkoxide having no water repellent group is preferred.
  • An example of alkenyloxysilane is isopropenoxysilane.
  • the hydrolyzable silicon compound having no water repellent group may be a compound represented by the following formula (III).
  • SiY 4 (III) As described above, Y is a hydrolyzable functional group, and is preferably at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • the water repellent group-free hydrolyzable metal compound is hydrolyzed or partially hydrolyzed, and further, at least a part thereof is polycondensed to supply a metal oxide component in which a metal atom and an oxygen atom are bonded.
  • This component firmly bonds the metal oxide fine particles and the resin, and can contribute to improvement of the wear resistance, hardness, water resistance, etc. of the visibility ensuring film.
  • a preferred example of the hydrolyzable silicon compound having no water repellent group is tetraalkoxysilane, more specifically, tetraalkoxysilane having an alkoxy group having 1 to 4 carbon atoms.
  • Tetraalkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, and tetra-tert- It is at least one selected from butoxysilane.
  • the hydrophobicity of the visibility ensuring film may be lowered.
  • Resin is an optional component in the visibility ensuring film, but when added, in order to prevent the wear resistance of the film from deteriorating, it exceeds 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the metal oxide component. It is preferable to add in the range.
  • a preferable blending amount of the resin is, for example, 1 part by mass or more, further 5 parts by mass or more, particularly 10 parts by mass or more, 40 parts by mass or less, further 35 parts by mass or less, particularly 30 parts by mass with respect to 100 parts by mass of the metal oxide component. It is below mass parts. Addition of a large amount of resin is desirable to avoid a hydrophilic spot formed on the surface of the film.
  • the kind of resin is not specifically limited, In order to prevent formation of a hydrophilic spot, it is preferable to avoid resin with high water absorption.
  • the degree of butyralization degree of acetalization
  • the degree of butyralization is preferably 50 mol% or more, particularly 55 mol% or more, and more preferably 60 mol% or more.
  • the upper limit of the degree of butyralization is not particularly limited, but may be 85 mol% or less.
  • Additives may be glycols, surfactants, leveling agents, ultraviolet absorbers, colorants, antifoaming agents, preservatives, and the like.
  • the thickness of the visibility ensuring film is preferably 3 to 70 nm, preferably 5 to 50 nm, more preferably 7 to 45 m, and particularly 10 to 40 nm.
  • the visibility ensuring film can be formed by applying a coating liquid on a transparent article such as a transparent substrate and drying the applied coating liquid.
  • the drying of the working solution may be accompanied by heating.
  • Conventionally known materials and methods may be used as the solvent used for preparing the coating liquid and the coating method.
  • the relative humidity of the atmosphere it is preferable to maintain the relative humidity of the atmosphere at less than 40%, more preferably 30% or less. Keeping the relative humidity low can prevent the film from absorbing excessive moisture from the atmosphere. If a large amount of moisture is absorbed from the atmosphere, the water remaining in the membrane matrix may reduce the strength of the membrane.
  • the drying process of the coating liquid includes an air drying process and a heating drying process with heating.
  • the air drying step is preferably performed by exposing the coating liquid to an atmosphere in which the relative humidity is kept below 40%, and further 30% or less.
  • the air drying process can be performed as a non-heating process, in other words, at room temperature.
  • Appropriate heating temperature in the heating and drying step is 300 ° C. or less, for example, 100 to 200 ° C., and the heating time is 1 minute to 1 hour.
  • the vehicle window glass provided with the visibility ensuring film may be used for a fixed window such as a windshield, and is used for an openable window represented by a door glass. Also good.
  • the glass plate can be used in a form connected to a glass moving device (a glass lifting device in the case of door glass).
  • a glass moving device a glass lifting device in the case of door glass.
  • the working solution is applied to the inner surface of a glass plate bent into a door glass shape using, for example, a nozzle flow coater provided with a robot arm and a discharge unit.
  • the coating apparatus called a nozzle flow coater includes a robot arm 7 that moves while holding the glass plate 10 and an injection unit 8 that injects the coating liquid G.
  • the glass plate 10 is held by the robot arm 7 so that a portion held by the robot arm 7 is inclined by an angle d with respect to the vertical direction.
  • the angle d is preferably ⁇ 3 ° to + 30 ° when the angle at which the vehicle interior main surface 17 faces upward is indicated as positive (+) and the angle at which the vehicle interior main surface 17 faces downward is negative ( ⁇ ).
  • the injection unit 8 includes a nozzle 82 and a base 81 that supports the nozzle 82.
  • the coating liquid G supplied by the tube 84 is injected from the nozzle 82 toward the glass plate 10.
  • the robot arm 7 can hold the glass plate 10 with a suction cup at the tip and move the glass plate 10 relative to the nozzle 82.
  • the coating liquid G can be applied to a predetermined region on the vehicle inner main surface 17.
  • the illustrated glass plate 10 is installed in a door window on the right front side in the traveling direction of a passenger car or the like. As shown in FIG. 4, the left side is shorter than the right side when viewed from the inside of the vehicle.
  • the inner main surface 17 is concave. The locus of the position where the coating liquid G is in contact with the glass plate is shown in FIG.
  • the injection of the coating liquid G from the nozzle 82 starts from the application start area Ra on the main surface 17 in FIG. 4 and controls the robot arm 7 to move the glass plate 10 downward (arrow U in FIG. 3). Let At this time, the coating liquid G is ejected inward in the surface direction to the extent that the injected coating liquid G does not reach the right end 13. Thereby, the right edge line L2 which is the right edge part of the area
  • the application position of the coating liquid G moves from the application start area Ra in FIG. 4 in the direction of the arrow S101 and reaches the area Rb, and then the application position moves from the area Rb along the arrow S102 and reaches the area Rc. Then, the glass plate 10 is moved. At this time, the coating liquid G is applied with a gap from the upper end portion 11. The applied coating solution G flows down and reaches the lower end 12. Thereby, the upper edge line L1 of the coating liquid G appears on the lower side in the surface direction from the upper end portion 11 of the glass plate 10, and the coating liquid G is also applied to a region where the lower coating liquid G is not directly injected from the upper edge line L1.
  • the liquid G can be spread.
  • the glass plate 10 When the application position of the coating liquid G reaches the region Rc, the glass plate 10 is moved so that the application position moves from the region Rc along the arrow S103 and reaches the region Rd. At this time, the injected coating liquid G is injected inward in the surface direction to the extent that the injected coating liquid G does not reach the left end 14. Thereby, the left side edge line L3 which is the left side edge part of the area
  • the coating liquid G reaches the left end 14 in FIG. 4 or other main surface (the vehicle outer main surface 18 (see FIG. 8) which is the back surface of the main surface 17 on which the visibility ensuring film 16 is formed). Can be surely prevented from going around.
  • the visibility ensuring film 16 is formed on a part of the main surface 17 as shown in FIG. 6, but between the upper edge line L1 and the upper end portion 11, the right side A region (film non-formation region) 15 in which the visibility ensuring film 16 is not formed is left between the edge line L2 and the right end 13 and between the left edge line L3 and the left end 14.
  • a door glass installed in a front door window of a passenger car or the like is attached to a window frame so that the window glass can be moved up and down to open and close the window.
  • a glass run (sometimes called weatherstrip, molding, etc.) is provided as a member to fill the gap between the window frame and the window glass, and when the window is completely closed, the upper end of the window glass Not only the side end but also the glass run is sandwiched.
  • FIG. 7 when the window glass is raised and lowered, the upper end portion and the peripheral portion of the side end portion of the glass plate slide with the glass run.
  • the glass 7 has an opening 25 surrounded by a frame 2, specifically, an upper frame 21, a lower frame 22, a rear frame 23, and a front frame 24.
  • the glass run 6 includes an upper frame run 61 in the upper frame 21, a lower frame run 62 in the lower frame 22, a rear frame run 63 in the rear frame 23, and a front frame run 64 in the front frame 24.
  • the glass plate 10 moves up and down between the height H1 and the height H2 by the glass lifting device 3 to which the lower end is connected.
  • the window glass When the window glass is raised and lowered and the opening and closing operation of the window is repeated, the vicinity of the upper end portion and the vicinity of the side end portion of the window glass slide repeatedly on the glass run.
  • a film is also applied to the sliding area, the film is damaged by sliding and the surface roughness is increased.
  • the scratches on the coating near the top edge noticeably deteriorate the appearance, and the appearance near the side edge deteriorates and the coefficient of friction with the glass run increases due to the size of the surface roughness. Occasionally, abnormal noise such as chatter noise may occur. In addition, the glass run tends to deteriorate.
  • the film non-formation region 15 in the periphery of the window glass may be set so as to include at least a part of the region in contact with the glass run 6, preferably all of the region in contact with the glass run 6. .
  • the visibility ensuring film 16 formed on the main surface 17 by sliding is less likely to be scratched, and thus the above-described problems can be suppressed.
  • the glass plate is at least part of it from the window frame of the window when lowered by the glass lifting device to open the window from a state where it is installed on the window so that the vehicle window is closed.
  • membrane is formed in the vehicle inner surface of a glass plate so that it may not contact
  • the visibility ensuring film is preferably formed so as to recede from the upper end so as not to contact the glass run 61. More preferably, the visibility ensuring film is formed so as to substantially cover a region where the outside of the vehicle can be seen through from the inside of the vehicle when the vehicle window is closed so that the vehicle window is closed.
  • substantially covering means covering 90% or more, more preferably 95% or more. It is also preferable for the glass plate used for the fixed window that the visibility ensuring film substantially covers the region.
  • a vehicle window glass as a windshield is provided with a region where a visibility ensuring film is not formed, and a sticker that is required to be attached is attached to this region, or for this region to be attached.
  • An indication indicating the presence may be added to the glass plate. According to this embodiment, it is possible to avoid damage to the film during the replacement work.
  • Example 1 0.03% by mass of n-hexyltrimethoxysilane (HTMS, Shin-Etsu Silicone “KBM-3063”), tetraethoxysilane (TEOS, Shin-Etsu Silicone “KBE-04”) 0.3% by mass, purified water 0
  • a coating solution for forming a visibility-enhancing film was prepared in which 15% by mass, 0.2% by mass of hydrochloric acid as an acid catalyst, and the remainder was an alcohol solvent (“SOLMIX AP-7” manufactured by Nippon Alcohol Industry)
  • the coating solution was applied by a flow coating method on a washed float plate glass (soda lime silicate glass, thickness 3.1 mm, size 100 ⁇ 100 mm) in an environment of room temperature 20 ° C. and relative humidity 30%. After drying for 10 minutes under the same environment, a heat treatment was performed at 120 ° C. for 20 minutes to prepare a sample.
  • a washed float plate glass sida lime silicate glass, thickness 3.1 mm, size 100 ⁇ 100 mm
  • Example 2 Except that 0.025% by mass of polyvinyl butyral resin (“S-REC BM-2” manufactured by Sekisui Chemical Co., Ltd., medium polymerization type, butyralization degree 65 mol%) was further added in the same manner as in Example 1, A sample was made.
  • S-REC BM-2 polyvinyl butyral resin manufactured by Sekisui Chemical Co., Ltd., medium polymerization type, butyralization degree 65 mol%
  • Example 3 A sample was produced in the same manner as in Example 2 except that the amount of n-hexyltrimethoxysilane was 0.01% by mass.
  • Example 4 Except that 0.035% by mass of n-hexyltrimethoxysilane, 0.7% by mass of tetraethoxysilane, 10% by mass of purified water, and 2% by mass of hydrochloric acid, the same as in Example 1, A sample was made.
  • Example 1 Comparative Example 1 In the same manner as in Example 1 except that the same amount of methyltrimethoxysilane (MTES, “KBE-13” manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 0.03% by mass of n-hexyltrimethoxysilane. A sample was made.
  • MTES methyltrimethoxysilane
  • Comparative Example 2 In the same manner as in Example 1, except that the same amount of decyltrimethoxysilane (DTMS, “KBM-3103C” manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of 0.03% by mass of n-hexyltrimethoxysilane. A sample was made.
  • DTMS decyltrimethoxysilane
  • Example 4 A sample was prepared in the same manner as in Example 1 except that the same amount of FAS (tridecafluorooctyltrimethoxysilane, manufactured by GELEST) was used instead of 0.03% by mass of n-hexyltrimethoxysilane. Produced.
  • the FAS used is indicated by CF 3 (CF 2 ) 5 (CH 2 ) 2 Si (OCH 3 ) 3 .
  • Table 1 shows the components of the visibility ensuring film and the evaluation results of the samples.
  • the mass part of the silica component which is a metal oxide component is set to 100, and the mass part of each component is shown.
  • the value of the haze ratio for the exposed glass surface on which the visibility ensuring film was not formed was 38.3%.
  • Comparative Example 4 using FAS a surface having a large contact angle was obtained with respect to 4 mg of water droplets. On this surface, a large number of fine water droplets were formed in the above-described evaluation (4).
  • the haze rate which is a measure showing a decrease in straightness, greatly increased.
  • a surface with non-uniform hydrophobicity is not suitable for ensuring visibility when water droplets are formed even if the contact angle of water is large.
  • the addition of the resin can be a factor for improving the straightness of light by the oriented water-repellent group. However, if priority should be given to ensuring the hardness of the film, it is better to avoid the addition of organic resin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Selon l'invention, afin d'empêcher une gêne de la visibilité d'un véhicule extérieur depuis un intérieur de véhicule même si des gouttelettes se forment sur une surface en raison de la condensation de vapeur, une vitre de véhicule comprend : une plaque de verre (10) ; et un film assurant la visibilité (16) qui est formé sur une surface sur le côté intérieur de véhicule, le film assurant la visibilité contenant un groupe hydrofuge et un constituant d'oxyde métallique. Le groupe hydrofuge est un groupe alkyle à chaîne linéaire qui est directement lié à un atome de métal constituant le constituant d'oxyde métallique et comportant de 3 à 9 atomes de carbone. La plaque de verre (10) est dotée d'une partie extrémité supérieure (11) dans laquelle au moins une partie de cette dernière est retirée d'un cadre de vitre du véhicule lorsqu'elle est déplacée vers le haut et vers le bas dans la vitre de véhicule, et le film assurant la visibilité (16) peut être formé sur une surface côté intérieur de véhicule (17) de la plaque de verre de façon à ne pas entrer en contact avec la partie extrémité supérieure (11).
PCT/JP2017/015944 2016-04-22 2017-04-20 Vitre de véhicule Ceased WO2017183701A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US20190212475A1 (en) * 2017-12-26 2019-07-11 Tsinghua University Hydrophobic window, house and vehicle using the same
JPWO2022050362A1 (fr) * 2020-09-04 2022-03-10
JP2023068303A (ja) * 2021-11-02 2023-05-17 Ａｇｃ株式会社 車両用サイドガラス
JP2025026962A (ja) * 2019-12-27 2025-02-26 日本板硝子株式会社 透明積層体

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Publication number Priority date Publication date Assignee Title
WO2021132696A1 (fr) 2019-12-27 2021-07-01 日本板硝子株式会社 Stratifié transparent

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JP2003113371A (ja) * 2001-10-05 2003-04-18 Toyo Riken Kk 撥水処理剤組成物
JP2011256060A (ja) * 2010-06-07 2011-12-22 Asahi Glass Co Ltd 被膜付き自動車用窓ガラスの製造方法
JP2013213181A (ja) * 2011-09-14 2013-10-17 National Institute Of Advanced Industrial Science & Technology 有機−無機透明ハイブリッド皮膜とその製造方法
WO2015186360A1 (fr) * 2014-06-05 2015-12-10 日本板硝子株式会社 Article transparent avec film anti-buée

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JPWO2008072707A1 (ja) * 2006-12-15 2010-04-02 旭硝子株式会社 撥水性表面を有する物品
JP6007664B2 (ja) * 2012-08-14 2016-10-12 旭硝子株式会社 窓ガラスおよびその製造方法

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JP2003113371A (ja) * 2001-10-05 2003-04-18 Toyo Riken Kk 撥水処理剤組成物
JP2011256060A (ja) * 2010-06-07 2011-12-22 Asahi Glass Co Ltd 被膜付き自動車用窓ガラスの製造方法
JP2013213181A (ja) * 2011-09-14 2013-10-17 National Institute Of Advanced Industrial Science & Technology 有機−無機透明ハイブリッド皮膜とその製造方法
WO2015186360A1 (fr) * 2014-06-05 2015-12-10 日本板硝子株式会社 Article transparent avec film anti-buée

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190212475A1 (en) * 2017-12-26 2019-07-11 Tsinghua University Hydrophobic window, house and vehicle using the same
US10732326B2 (en) * 2017-12-26 2020-08-04 Tsinghua University Hydrophobic window, house and vehicle using the same
JP2025026962A (ja) * 2019-12-27 2025-02-26 日本板硝子株式会社 透明積層体
JPWO2022050362A1 (fr) * 2020-09-04 2022-03-10
WO2022050362A1 (fr) * 2020-09-04 2022-03-10 Ａｇｃ株式会社 Procédé de production d'une plaque de verre avec cadre en résine pour fenêtre de véhicule et dispositif de production de plaque de verre avec cadre en résine pour fenêtre de véhicule
CN116507473A (zh) * 2020-09-04 2023-07-28 Ａｇｃ株式会社 车窗用带树脂框体玻璃板的制造方法和车窗用带树脂框体玻璃板的制造装置
US12358193B2 (en) 2020-09-04 2025-07-15 AGC Inc. Method for producing glass plate with resin frame for vehicle window and device for producing glass plate with resin frame for vehicle window
JP2023068303A (ja) * 2021-11-02 2023-05-17 Ａｇｃ株式会社 車両用サイドガラス
JP7800055B2 (ja) 2021-11-02 2026-01-16 Ａｇｃ株式会社 車両用サイドガラス

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