WO2019073983A1 - 乗り物用窓ガラス、及び警告表示方法 - Google Patents
乗り物用窓ガラス、及び警告表示方法 Download PDFInfo
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- WO2019073983A1 WO2019073983A1 PCT/JP2018/037626 JP2018037626W WO2019073983A1 WO 2019073983 A1 WO2019073983 A1 WO 2019073983A1 JP 2018037626 W JP2018037626 W JP 2018037626W WO 2019073983 A1 WO2019073983 A1 WO 2019073983A1
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- Prior art keywords
- light
- window glass
- glass
- vehicle window
- vehicle
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Images
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- G02B6/0013—Means for improving the coupling-in of light from the light source into the light guide
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- H01L33/50—Wavelength conversion elements
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Definitions
- the present invention relates to a window glass for a vehicle such as a car and a warning display method using the window glass for a vehicle.
- the warning display on the conventional indicator or the side mirror may be difficult for the driver to check, and the warning may be overlooked.
- the warning even when the warning is displayed on the windshield by the head up display, it is necessary to display the warning without obstructing the driver's view, so it is difficult to check the warning as in the case of the conventional indicator. There is.
- the head-up display has a problem that the device size is large, and the interior space of the car is narrowed.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to facilitate warning display by a driver without narrowing the indoor space or obstructing visibility in a vehicle such as a car. Providing a vehicle glazing that can be identified.
- the present inventors have found that the above-mentioned problems can be solved by enabling visible light to be emitted from the end of the vehicle window glass by the incidence of excitation light, and complete the present invention described below.
- the That is, the present invention provides the following [1] to [14].
- [1] A vehicle window glass for emitting visible light by being incident upon excitation light emitted from a light source, the vehicle window glass emitting light at an end of the vehicle window glass by irradiation of the excitation light .
- the vehicle window glass according to the above [1] wherein the vehicle window glass includes a transparent plate.
- a fluorescent material that has a multilayer structure in which the window glass for vehicles has a laminate of at least one transparent plate and a resin film, and the resin film emits visible light when the resin and the excitation light are incident A vehicle window glass according to the above [2], including [4] The vehicle window glass according to any one of the above [1] to [3], wherein the vehicle window glass is any of a windshield and a side glass of a car. [5] The vehicle window glass according to any one of the above [1] to [4], which causes the end to emit light when it is detected that at least one of a person and an object approaches a vehicle. [6] The vehicle window glass according to the above [5], wherein the method of emitting light is changed according to the detected content.
- the vehicle window glass has a multilayer structure in which at least one transparent plate and a resin film are laminated, The warning display method according to the above [8] or [9], wherein the resin film contains a resin and a fluorescent material that emits visible light upon incidence of excitation light.
- the warning display method according to any one of the above [8] to [10] wherein the vehicle window glass is any of a windshield and a side glass of a car.
- the warning display method according to any one of [8] to [11] above which causes the end to emit light when it is detected that at least one of a person and an object approaches a vehicle.
- the warning display method according to [12] wherein the method of emitting light is changed according to the detected content.
- the warning display method according to [13] wherein at least one of the light emission intensity, the light emission area, and the light emission position is changed according to the distance to the approaching object.
- the present invention provides a vehicle window glass in which a driver can easily confirm a warning display without narrowing the indoor space or obstructing the view in a vehicle such as a car.
- the indoor space of the motor vehicle provided with the window glass for vehicles which concerns on the 1st Embodiment of this invention is shown.
- 1st Embodiment it is a schematic diagram which shows the arrangement position of the light source provided in the circumference
- the indoor space of the motor vehicle provided with the window glass for vehicles which concerns on the 3rd Embodiment of this invention is shown.
- the indoor space of the motor vehicle provided with the window glass for vehicles which concerns on the 4th Embodiment of this invention is shown. It is a schematic diagram which shows the whole view of the light emission system in the 5th Embodiment of this invention.
- FIG. 1 shows an indoor space of a vehicle provided with a vehicle window glass according to a first embodiment of the present invention.
- a vehicle window glass according to the first embodiment is a windshield 10 of a car.
- the windshield 10 is supported on four sides by support members provided on the pillars 21 and 22 on both sides, a bonnet (not shown), and a roof 23.
- the windshield 10 can emit visible light upon incidence of excitation light by containing a fluorescent material or the like as described in detail below.
- FIG. 1 shows an indoor space of a vehicle provided with a vehicle window glass according to a first embodiment of the present invention.
- a vehicle window glass according to the first embodiment is a windshield 10 of a car.
- the windshield 10 is supported on four sides by support members provided on the pillars 21 and 22 on both sides, a bonnet (not shown), and a roof 23.
- the windshield 10 can emit visible light upon incidence of excitation light by containing a fluorescent material or the like as described in detail below.
- FIG. 1 shows an indoor space of
- the end 10E of the windshield 10 is caused to emit light by the incidence of excitation light.
- a warning is issued to call attention to an occupant such as a driver of the own vehicle.
- the windshield 10 is provided with a light source 11 around its periphery.
- the light source 11 emits excitation light, and a laser light source, an LED light source, a xenon lamp, or the like is used.
- the excitation light emitted from the light source 11 may be any light as long as the front glass 10 can emit visible light by being incident on the front glass 10.
- the maximum emission wavelength of the light emitted by the light source 11 is not particularly limited, but is preferably 420 nm or less, more preferably 410 nm or less, and still more preferably 408 nm or less. Moreover, 300 nm or more is preferable, 350 nm or more is more preferable, and 380 nm or more is more preferable.
- a light source 11 provided around the windshield 10 causes excitation light to enter the windshield 10 from the outer peripheral surface 10X side of the windshield 10.
- a plurality of light sources 11 are provided, and are provided, for example, in the inside of the bonnet and the inside of the pillars 21 and 22.
- the plurality of light sources 11 are arranged such that excitation light is made to enter from the outer peripheral surface 10X side outside the light emitting end 10E of the windshield 10.
- the plurality of light sources 11 are arranged such that excitation light is incident from the outer peripheral surface 10 X side of the lower right portion and the lower left portion of the windshield 10.
- FIG. 3 is a schematic perspective view showing the windshield in the present embodiment in more detail.
- the windshield 10 includes, for example, two transparent plates 10A and 10B and an intermediate film 10C disposed therebetween, and the transparent plates 10A and 10B are adhered by the intermediate film 10C. It is a laminated glass.
- the intermediate film 10C may be made of a resin film (light emitting layer) containing a fluorescent material, or may be a resin film comprising two or more resin films, wherein at least one resin film contains a fluorescent material ( It may be a light emitting layer).
- the front glass 10 is not limited to such a configuration, and may have any configuration as long as at least one layer emits light, as described in detail below.
- the light source 11 may be provided so that the emission end 11A faces the outer peripheral surface 10X of the windshield 10.
- the emission end 11A of the light source 11 may be disposed to face or contact the light emitting layer (in FIG. 3, the intermediate film 10C) of the windshield 10 in order to enhance the luminous efficiency of the windshield 10. preferable.
- the optical axis of the light source 11 is generally parallel to the surface direction of the windshield 10, it may be appropriately inclined with respect to the surface direction. By inclining the optical axis, the excitation light from the light source 11 does not easily enter the inside, so it becomes easy to make only the end 10E emit light.
- the plurality of light sources 11 are, for example, LED chips, and in the outer peripheral surface 10X or in the vicinity of the outer peripheral surface 10X. , And may be disposed between the transparent plates 10A and 10B.
- the light source 11 may be attached to the transparent plates 10A and 10B, for example, or may be embedded in the resin film 11C.
- a diffusion lens or the like may be provided at the emission end 11A of the light source 11, and the excitation light from the light source 11 may be diffused and then be incident on the windshield 10.
- the excitation light emitted from the light source 11 enters the inside of the windshield 10 while attenuating the amount of light by being incident from the outer peripheral surface 10X side. Therefore, by adjusting the light amount to such an extent that it does not enter the center of the vehicle glass 12, as shown in FIG. 1, it is possible to cause the warning to be emitted and displayed only at the end 10E of the windshield 10.
- the edge of the windshield means a region having a length of 30% or less with respect to the glass dimension from the edge of the windshield (vehicle window glass). If it exceeds 30%, the light emission may interfere with the driver's view. Moreover, in order not to obstruct a driver
- an edge means the outermost part of the exposed part of the glass surface by the side of the inside of a vehicle (vehicle interior) of a windshield (window glass for vehicles).
- the glass size refers to the average of the maximum length in the horizontal direction and the maximum length in the vertical direction on the glass surface of the vehicle window glass exposed inside the vehicle.
- the glass size is the same as the size of the opening closed to the window glass in the vehicle inside, and the edge is the opening Means the edge.
- the light emitting portion of the windshield 10 means the brightness of the vehicle glass 12 measured at a distance of 35 cm vertically from the light emitting surface with a color luminance meter ("CS-150" manufactured by Konica Minolta) When it does, it means the part where brightness becomes 100 cd / m 2 or more, therefore, in this specification, the part which emits a little light by irradiation of excitation light is not treated as the part which emits light.
- FIG. 4 illustrates a light emitting system provided in a car in the present embodiment.
- the light emitting system 30 includes a control unit 15 and a detection unit 16 in addition to the windshield 10 and the light source 11 described above.
- the control means 15 controls the entire light emitting system 30, and is constituted by a CPU or the like provided in a car, but is not particularly limited.
- the detection means 16 is a means for grasping the situation outside the vehicle, and when an approaching object approaches, detects the distance, direction, etc. with the approaching object.
- the detection unit 16 is a human sensor provided in a car, a stereo camera, an objective sensor, or the like.
- the human sensor is a sensor that detects that a person approaches the car.
- the objective sensor is a sensor that detects that the moving object approaches the car.
- the stereo camera captures an image of the outside of the vehicle and detects that a person, an object, or the like has approached the vehicle by image analysis.
- the detection information is sent to the control means 15.
- the detection information includes information such as the direction of the approaching object and the distance between the approaching object and the vehicle.
- the control means 15 controls the light source 11 based on the detection information. Specifically, when it is detected that the distance of the approaching object is within the specified value, the light source 11 is turned on, the excitation light is made incident on the windshield 10, and the end 10E of the windshield 10 is made to emit light. The light emission of the end 10E of the windshield 10 is recognized by the driver as a warning display.
- the light emitting position of the windshield 10 may be changed according to the direction of the approaching object or the like. Specifically, when the approaching object is approaching from the right side of the vehicle, as shown in FIG. 1, the end 10E on the right side of the windshield 10, more specifically, the end 10E on the lower right is emitted You should do it. On the other hand, when the approaching object is approaching from the left side of the vehicle, the left end 10E of the windshield 10, more specifically, the lower left end 10E may emit light. As described above, in the present embodiment, by causing the end 10E in the same direction as the approaching object to emit light, the driver can instantly recognize the direction of the approaching object, and it becomes easy to avoid the collision with the approaching object. .
- the method of emitting light when it is detected that the approaching object approaches the automobile, the method of emitting light can be changed according to the contents such as the detected distance and direction.
- the light emission intensity, the light emission area, and the light emission position may be changed according to the distance to the approaching object.
- the intensity of the excitation light emitted from the light source 11 is increased, or the number of the light sources 11 emitting the excitation light is increased.
- At least one of the light emission intensity of 10E and the light emission area may be increased.
- the light emission area may be extended to the center side.
- the part that emits light it is also possible to move the part that emits light to the center side as the distance to the approaching object approaches.
- the light emitting part spreads to the center side, and moving to the center side makes it easy for the light emitting part to enter the driver's field of vision, making it possible for the driver to visually recognize that the danger is high. .
- the light emission intensity at a position near the center is relatively high.
- the emission intensity at a position away from the center may be relatively low.
- the present embodiment by emitting the end of the windshield by emitting the excitation light, it is possible to emit and display a warning that can be easily confirmed by the driver without obstructing the driver's view. It is possible.
- the light emission is performed using a window glass, it is possible to perform a warning display without almost narrowing the indoor space inside the car.
- the driver can easily visually recognize the content of the warning and the like.
- FIG. 5 is a schematic perspective view showing a vehicle window glass according to a second embodiment of the present invention. Hereinafter, only differences from the first embodiment will be described with respect to the second embodiment.
- the vehicle is further provided with a light guide 24.
- the light guy 24 is arranged to extend along the outer peripheral surface 10 ⁇ / b> X of the windshield 10.
- the light guide 24 is provided such that the emitting end 11A of the light source 11 is opposed to the end 24A, and the excitation light emitted from the light source 11 is incident from the end 24A.
- the light source 11 is provided inside the bonnet and inside the pillars 21 and 22 as in the first embodiment.
- the light guide 24 may be any one as long as it can emit excitation light incident from the end 24 A from the side surface 24 X of the light guide 24.
- a side light emitting optical fiber may be used.
- an optical fiber having a core and a clad, in which a light scatterer or the like is dispersed, may be mentioned.
- the light emitted from the side surface 24X of the ride guide 24 is incident on the inside of the windshield 10 from the outer peripheral surface 10X of the windshield 10.
- the windshield 10 emits visible light by the incident excitation light.
- membrane which absorbs or reflects excitation light may be formed.
- a film containing an ultraviolet absorber may be formed.
- the light guide 24 faces or contacts the light emitting layer of the windshield 10 (the intermediate film 10C in FIG. 5) as shown in FIG. 5 in order to increase the incident efficiency of excitation light to the windshield 10. You should do it. Furthermore, in the case where the intermediate film 10C provided between the two transparent plates 10A and 10B has a resin film consisting of a light emitting layer, the light guide 24 has two sheets in the vicinity of the outer peripheral surface 10X or the outer peripheral surface 10X. It may be disposed between the transparent plates 10A and 10B. In this case, the light guide 24 may be disposed, for example, so as to be embedded inside the intermediate film 10C.
- the arrangement position of the light guide 24 may be determined according to the position of the light emission of the windshield. That is, as shown in FIG. 1, when the lower right end 10E and the lower left end 10E emit light, the light guide 24 is disposed along the outer peripheral surface 10X of the lower right and lower left of the windshield 10 respectively. You should do it.
- at least one light guide 24 may be provided, a plurality of light guides 24 may be provided, and each of the light guides 24 may be disposed on the outer circumferential surface 10X at different positions in the circumferential direction of the windshield 10.
- the end portion of the windshield to emit light and display a warning, without almost narrowing the indoor space inside the vehicle Become.
- the method of emitting light is changed according to the contents of the detected distance, direction, etc. be able to. For example, by appropriately changing at least one of the light emission intensity, the light emission area, and the light emission position according to the distance, the direction, and the like of the approaching object, the driver can easily visually recognize the content of the warning.
- FIG. 6 is a schematic view showing a third embodiment of the present invention.
- the light emitting vehicle window glass is the windshield 10, but in the third embodiment, it is the windshield 10 and the front side glass 12. That is, in the present embodiment, similarly to the windshield 10 described above, the light source 11 or the light guide 24 is provided around the front side glass 12, and the end 12E of the front side glass 12 can also emit light.
- the end 12E of the front side glass 12 to emit light may be an end on the front side as shown in FIG. 6, but may be an end of the lower end or an upper end. Good. Also, a combination of two or more of these may be used.
- the light emission pattern of the warning display can be made more rich in variation.
- the end 12E of the front side glass 12 is made to emit light
- the end 10E of the windshield 10 or both ends of the windshield 10 and the front side glass 12 It suffices to emit light from the portions 10E and 12E. More specifically, for example, when an approaching object approaches from the right side, only the end 12E of the right front side glass 12 emits light while the distance is long, while the approaching object approaches the front when the distance is close.
- Both the right end 10E of the glass 10 or the right end 10E of the windshield 10 and the end 12E of the right front side glass 12 may emit light.
- the left end 10E of the front glass 10, the end 12E of the left front side glass 12, and the like may be made to emit light.
- the end 12E of the front side glass 12 when the approaching object is present in the rear or side, the end 12E of the front side glass 12 is made to emit light while the approaching object is present in the front, the windshield 10
- the end 10E of the light source may emit light.
- the right end 10E of the windshield 10 and the end 12E of the front side glass 12 on the right may be made to emit light.
- the left end 10E of the front glass 10, the end 12E of the left front side glass 12, etc. be made to emit light.
- the method of emitting light when it is detected that an approaching object approaches the car, the method of emitting light can be changed according to the content such as the detected distance and direction. For example, at least one of the light emission intensity, the light emission area, and the light emission position of the windshield 10 and the front side glass 12 may be appropriately changed according to the distance of the approaching object.
- either the light source or the light guide may be disposed around the front side glass 12, and excitation light may be made incident from the outer peripheral surface side of the front side glass 12, for example.
- FIG. 7 is a schematic view showing a fourth embodiment of the present invention.
- the delta window glass 13 in addition to the windshield 10 and the front side glass 12, the delta window glass 13 is also capable of emitting light.
- the delta window glass 13 is a window which is further to the front of the front side glass 12 on the side of the vehicle, and is generally a glass window which is not opened or closed.
- a light source or a light guide is provided around the delta window glass 13 as well.
- the delta window glass 13 emits light when excitation light is incident from the outer peripheral surface side thereof.
- the delta window glass 13 is generally a small window, and the driver can not alert the driver sufficiently even if only the end is illuminated, it is added to the end of the delta window glass 13 as well as the end. A portion other than the end may also emit light, or the entire portion may emit light.
- the delta window glass 13 can also emit light, so that the light emission pattern of the warning display can be made more rich in variations.
- the end 12E of the front side glass 12 emits light
- the delta window glass 13 or the end 12E of the front side glass 12 and the delta window glass 13 emit light.
- the distance is relatively short, at least one of the end 10E of the windshield 10 or the end 10E of the windshield 10 and the end 12E of the front side glass or the delta window glass 13 may be emitted.
- the end 12E of the front side glass 12 is made to emit light
- the delta window 13 is made to emit light
- the end 10E of the windshield 10 may be made to emit light.
- the lower right end 10E of the windshield 10 the end 12E of the right front side glass 12, and the delta window 13 on the right side may be made to emit light. The same is true when the approaching object is on the left side.
- the method of emitting light when it is detected that an approaching object approaches the automobile, the method of emitting light can be changed according to the contents such as the detected distance and direction. For example, at least one of the light emission intensity, the light emission area, and the light emission position of the windshield 10, the delta window glass 13, and the front side glass 12 may be changed according to the distance of the approaching object.
- the vehicle window glass such as the windshield has a mode in which the excitation light is made incident from the outer peripheral surface side to emit light, but in the present embodiment, the windshield etc.
- the vehicle window glass is made to emit light by excitation light that is incident from the surface inside the vehicle.
- a light source unit 31 provided with a MEMS (Micro Electro Mechanical Systems) mirror 33 is used.
- the light source unit 31 is not particularly limited as long as the excitation light can be irradiated to the window glass for each vehicle inside the vehicle.
- the windshield 10 when it emits light, it may be provided on the dashboard or on the front side of the roof.
- the front side glass 12 or the delta window glass is made to emit light, for example, it may be provided on the inner surface of the door body of the front side door.
- the MEMS mirror 33 is swingable, for example, about two axes, and irradiates the inner surface of the vehicle glass (the surface 10Y of the windshield 10 in FIG. 8) while scanning the light from the light source 11 .
- the excitation light from the light source 11 is emitted to the vehicle window glass as scanning light by being irradiated to the vehicle window glass through the MEMS mirror 33 whose drive is controlled.
- the MEMS mirror 33 by controlling the MEMS mirror 33 appropriately, it is possible to cause a desired portion of the vehicle glass to emit light. Therefore, also in the present embodiment, it is possible to cause the windshield 10 and the end portions 10E and 12E of the front side glass 12 to emit light as in the above-described embodiments.
- the MEMS mirror is generally small, use of the MEMS mirror makes it possible to cause the end of the window glass to emit light without almost narrowing the indoor space inside the vehicle.
- a light source unit in this embodiment things other than the light source unit which has a MEMS mirror 33 may be used as long as excitation light can be irradiated from the surface of the window glass for vehicles.
- scanning light other than the light source unit having the MEMS mirror 33 may be irradiated. Since the light source unit for emitting the scanning light is generally small in size, it can emit light and display the window glass without occupying a large space inside the automobile, similarly to the light source unit having the MEMS mirror.
- the light source unit may be a light source unit capable of irradiating the window glass for a vehicle with excitation light as beam light.
- the beam light illuminates all of the light emitting parts of the window glass at the same timing, and there is no occurrence of a scanning deviation as in the case of using a scanning light.
- a light source unit which has a MEMS mirror the light source unit using a DMD (Digital Micromirror Device) system using DLP (Digital Light Processing), LCOS (Liquid crystal on silicon), etc. is mentioned.
- DMD Digital Micromirror Device
- DLP Digital Light Processing
- LCOS Liquid crystal on silicon
- one or more of the window glass of an automobile is It is not limited to the above configuration as long as it emits light.
- the end of the rear glass may emit light, or the end of any one of the side glasses may emit light.
- the side glass is configured to emit light at the end 12E of the front side glass 12.
- the end of the rear side glass may be configured to emit light.
- the window glass for vehicle shows an aspect in which excitation light is incident from the outer peripheral surface side to emit light
- excitation light from the inner surface of the vehicle
- the front glass may emit light when excitation light is incident from the surface inside the vehicle and the side glass may emit light when excitation light is incident from the outer peripheral surface side of the glass.
- the vehicle glass is used for window glass for automobiles, but may be used for window glass of other vehicles.
- examples of such vehicles include railway vehicles such as trains, trains and trains, heavy vehicles for civil engineering such as forklifts and shovels, and various vehicles such as carts and amusement park vehicles.
- vehicles ships, airplanes, etc. may be used.
- the glass for vehicles of the present invention it is preferable to use as a window glass that comes into the driver's view during driving.
- the vehicle window glass used in the present invention may consist of a single layer or may have a multilayer structure having two or more layers.
- at least one layer of the vehicle window glass is a transparent plate.
- the transparent plate is made of either inorganic glass or organic glass.
- Organic glass is also referred to as so-called resin glass.
- the number of transparent plates may be one, or two or more.
- the transparent plate may be a light emitting layer that contains a fluorescent material and emits light when the excitation light is incident, but the layer other than the transparent plate contains a fluorescent material and the light emitting layer
- the window glass for vehicles preferably has a multilayer structure in which at least one transparent plate and a resin film are laminated, and in this multilayer structure, the resin film contains a resin and a fluorescent material.
- the light emitting layer is more preferable.
- the light emitting layer is not limited to the above-described resin film or transparent plate, and may be a fluorescent material film formed by vacuum evaporation, sputtering or the like of a fluorescent material.
- the fluorescent material film may be formed, for example, on at least one surface of the transparent plate.
- the fluorescent material emits visible light upon incidence of excitation light, and more specifically absorbs the excitation light emitted from the light source and emits visible light having a longer wavelength than the excitation light. is there. Further, the fluorescent material may be a material that emits so-called phosphorescence by being irradiated with excitation light. Specific examples of the fluorescent material include, for example, a lanthanoid complex having a ligand containing a halogen atom because it can exhibit high light emission. Among the lanthanoid complexes, the lanthanoid complex having a ligand containing a halogen atom emits light at high emission intensity upon irradiation with light.
- lanthanoid complex having a ligand including a halogen atom a lanthanoid complex having a monodentate ligand including a halogen atom, a lanthanoid complex having a bidentate ligand including a halogen atom, a tridentate including a halogen atom
- Halogens such as lanthanide complexes having a ligand, lanthanoid complexes having a tetradentate ligand containing a halogen atom, lanthanoids complexes having a pentadentate ligand containing a halogen atom, lanthanoid complexes having a hexadentate ligand containing a halogen atom
- Lanthanide complexes having multidentate ligands containing atoms are included.
- a lanthanoid complex having a bidentate ligand including a halogen atom or a lanthanoid complex having a tridentate ligand including a halogen atom emits high visible light when irradiated with light having a wavelength of 300 to 410 nm. It is possible to emit light at an intensity.
- the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom is also excellent in heat resistance.
- the window glass for vehicles is often used in a high temperature environment by being irradiated with infrared rays of sunlight, and therefore, a lanthanoid complex having a bidentate ligand containing the above-mentioned halogen atom or a tridentate arrangement containing a halogen atom Deterioration of the fluorescent material can be prevented by using a lanthanoid complex having an orientation.
- lanthanoids include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
- the lanthanoid is preferably neodymium, europium or terbium, more preferably europium or terbium, and still more preferably europium, since higher emission intensity can be obtained.
- the ligand which has a structure represented by following General formula (1) As a bidentate ligand containing the said halogen atom, the ligand which has a structure represented by following General formula (1), the ligand which has a structure represented by following General formula (2), etc. are mentioned, for example It can be mentioned.
- R 1 and R 3 represents an organic group, at least one of R 1 and R 3 is an organic group containing a halogen atom, R 2 is the number 1 or more linear carbon Represents an organic group.
- R 1 and R 3 are preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, It is particularly preferable that it is a hydrocarbon group having 1 to 3 carbon atoms.
- part of hydrogen atoms may be substituted with atoms other than hydrogen atoms and functional groups.
- hydrocarbon group having 1 to 3 carbon atoms a methyl group, an ethyl group, a propyl group in which a hydrogen atom is not substituted, or a methyl group, an ethyl group, a propyl group in which a part of hydrogen atoms is substituted by a halogen atom Groups and the like.
- a halogen atom of a methyl group an ethyl group or a propyl group in which a part of hydrogen atoms is substituted by a halogen atom
- a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be used.
- the above-mentioned hydrocarbon group having 1 to 3 carbon atoms is preferably a methyl group, an ethyl group or a propyl group in which a part of hydrogen atoms are substituted by a halogen atom, since light emission is performed with high emission intensity. More preferably, it is a fluoromethyl group.
- R 2 is preferably an alkylene group having 1 or more carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group having 1 carbon atoms. In the alkylene group having one or more carbon atoms, a part of hydrogen atoms may be substituted with atoms other than hydrogen atoms and functional groups.
- the lanthanoid complex having a ligand containing a halogen atom may have at least one ligand containing a halogen atom, and may have a ligand not containing a halogen atom.
- a ligand identical to the general formula (1) except that the halogen atom is not contained structures represented by the following general formulas (2) to (8) And the like.
- some or all of the hydrogen atoms are -COOR, -SO 3 , -NO 2 , -OH, an alkyl group, -NH It may be substituted by 2 or the like.
- two N may be anywhere in the bipyridine skeleton.
- two N may be anywhere in the bipyridine skeleton. Among them, it is preferable that there are two N's at 1,10 positions.
- two N may be anywhere in the bipyridine skeleton. Among them, it is preferable that there are two N's at 1,10 positions.
- three N's may be anywhere in the terpyridine skeleton.
- central R 4 represents a linear organic group having 1 or more carbon atoms.
- two R 5 represent a linear organic group having one or more carbon atoms.
- n represents an integer of 1 or 2.
- the lanthanoid complex having a bidentate ligand containing a halogen atom is, for example, tris (trifluoroacetylacetone) phenanthroline europium (Eu (TFA) 3 phen), tris (trifluoroacetylacetone) diphenylphenanthroline europium (Eu (TFA) 3 dpphen), tris (hexafluoroacetylacetone) diphenylphenanthroline europium, tris (hexafluoroacetylacetone) bis (triphenylphosphine) europium, tris (trifluoroacetylacetone) 2,2'-bipyridine europium, tris (hexafluoroacetylacetone) 2,2 '-Bipyridine europium, tris (5,5,6,6,7,7,7,7-heptafluoro-2,4-pentanedionate) 2 2'-bipyridine europium (
- a halogen atom of the lanthanoid complex having a ligand containing a halogen atom a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be used.
- a fluorine atom is preferred because the structure of the ligand is stabilized.
- lanthanoid complexes having a bidentate ligand containing a halogen atom or the lanthanoid complexes having a tridentate ligand containing a halogen atom particularly from the viewpoint of excellent initial light emission property, a diazonium compound having an acetylacetone skeleton containing a halogen atom Preference is given to lanthanoid complexes having a ligand.
- the lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing a halogen atom is, for example, Eu (TFA) 3 phen, Eu (TFA) 3 dpphen, Eu (HFA) 3 phen, [Eu (FPD) 3 ].
- Eu (TFA) 3 phen Eu (TFA) 3 dpphen, Eu (HFA) 3 phen, [Eu (FPD) 3 ].
- bpy, [Eu (TFA) 3 ] tmphen, [Eu (FPD) 3 ] phen etc. may be mentioned.
- the structure of a lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing these halogen atoms is shown.
- Lanthanide complex having a bidentate ligand having acetylacetone skeleton containing the halogen atom Additional e.g., Tb (TFA) 3 phen, Tb (TFA) 3 dpphen, Tb (HFA) 3 phen, [Tb (FPD ] 3 ] bpy, [Tb (TFA) 3 ] tmphen, [Tb (FPD) 3 ] phen etc. may be mentioned.
- the lanthanoid complex having a ligand containing a halogen atom is preferably in the form of particles. By being in the form of particles, it becomes easier to finely disperse the lanthanoid complex having a ligand containing a halogen atom in the light emitting layer.
- the preferred lower limit of the average particle diameter of the lanthanoid complex is 0.01 ⁇ m
- the preferred upper limit is 10 ⁇ m
- the more preferred lower limit is 0.03 ⁇ m
- more preferred The upper limit is 1 ⁇ m.
- the fluorescent material which has a terephthalic-acid-ester structure can also be used.
- the fluorescent material having a terephthalic acid ester structure emits light when irradiated with light.
- Examples of the fluorescent material having a terephthalic acid ester structure include a compound having a structure represented by the following general formula (9) and a compound having a structure represented by the following general formula (10). These may be used alone or two or more may be used.
- R 6 represents an organic group, and x is 1, 2, 3 or 4. It is preferable that x be 1 or 2, and it is more preferable to have a hydroxyl group at the 2- or 5-position of the benzene ring, since the visible light transmittance of the window glass for vehicles is further increased, and the 2-position of the benzene ring It is more preferable to have a hydroxyl group at the 5- and 5-positions.
- the organic group of R 6 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, It is particularly preferable that it is a hydrocarbon group having 1 to 3 carbon atoms.
- the fluorescent material which has the said terephthalic-acid-ester structure as the carbon number of the said hydrocarbon group is 10 or less can be disperse
- the hydrocarbon group is preferably an alkyl group.
- Examples of the compound having a structure represented by the above general formula (9) include diethyl-2,5-dihydroxy terephthalate and dimethyl-2,5-dihydroxy terephthalate.
- the compound having a structure represented by the above general formula (9) is preferably diethyl-2,5-dihydroxy terephthalate ("diethyl 2,5-dihydroxyterephthalate" manufactured by Aldrich).
- R 7 represents an organic group
- R 8 and R 9 each represent a hydrogen atom or an organic group
- y is 1, 2, 3 or 4.
- the organic group of R 7 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, still more preferably a hydrocarbon group having 1 to 5 carbon atoms, It is particularly preferable that it is a hydrocarbon group having 1 to 3 carbon atoms.
- the fluorescent material which has the said terephthalic-acid-ester structure as the carbon number of the said hydrocarbon group is below the said upper limit can be easily disperse
- the hydrocarbon group is preferably an alkyl group.
- NR 8 R 9 is an amino group.
- R 8 and R 9 are preferably hydrogen atoms.
- the hydrogen atoms of the benzene ring of the compound having a structure represented by the general formula (10) one hydrogen atom may be the above amino group, and two hydrogen atoms may be the above amino group. And three hydrogen atoms may be the above amino group, and four hydrogen atoms may be the above amino group.
- diethyl-2,5-diamino terephthalate eg, manufactured by Aldrich
- a resin film to be a light emitting layer be provided in the window glass for vehicles, as described above. Further, it is preferable that the vehicle window glass has a laminated glass structure in which an intermediate film is provided between two transparent plates, and the two transparent plates are bonded via the intermediate film. In the laminated glass structure, it is preferable that the intermediate film be formed of a resin film of one layer, and the resin film be a light emitting layer. Further, two or more resin films may be provided on the intermediate film, and at least one resin film of the plurality of resin films may be a light emitting layer.
- the resin film to be the light emitting layer does not necessarily have to form the intermediate film, and for example, in the laminated glass structure, even if it is provided on the surface opposite to the surface on the intermediate film side of any one transparent plate. Good. Moreover, when the transparent plate provided in the window glass for vehicles is one, you may be provided in any one surface of the transparent plate of the single layer.
- the sheet-like member having the light emitting layer is an adhesive It may be adhered to the surface of a single layer glass or laminated glass structure via an adhesive or the like. Thereby, a light emitting layer can be provided in the window glass for vehicles by bonding a sheet-like member by so-called post-pasting to the existing window glass.
- the resin film to be the light emitting layer contains a resin and a fluorescent material, and usually, the fluorescent material is dispersed in the resin.
- the fluorescent material may be dispersed throughout the light emitting layer.
- a resin used in the resin film a thermoplastic resin is preferable.
- the resin film can easily function as an adhesive layer, and as described above, when forming an intermediate film, it becomes easy to adhere to a transparent plate or the like.
- the content of the fluorescent material is preferably 0.001 parts by mass or more, more preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin. Is more preferred.
- the thickness of the resin film is not particularly limited, and is, for example, 0.1 to 2 mm, preferably 0.2 to 1 mm. When the thickness of the resin film is in this range, it is possible to secure sufficient light emission luminance without impairing the transparency of the vehicle window glass.
- the thickness of the intermediate film is not particularly limited, and is, for example, 0.1 to 3 mm, preferably 0.2 to 2 mm.
- thermoplastic resin As described above, as the resin used for the resin film, a thermoplastic resin is preferable.
- the thermoplastic resin used for the resin film is not particularly limited, and examples thereof include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ionomer resin, polyurethane resin, and thermoplastic elastomer.
- the use of these resins makes it easy to ensure the adhesiveness of the resin film to the transparent plate, and is particularly suitable when the resin film is used to form an intermediate film.
- the thermoplastic resin in the resin film may be used singly or in combination of two or more.
- polyvinyl acetal resin is particularly preferable in that it exhibits excellent adhesiveness to inorganic glass when the resin film contains a plasticizer.
- the resin film may further contain a plasticizer.
- a plasticizer in the resin film, the resin film becomes flexible, and as a result, the vehicle window glass becomes flexible.
- the transparent plate in particular, the transparent plate is an inorganic glass, it is also possible to increase the adhesion to the transparent plate.
- the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. .
- organic ester plasticizers are preferable, and triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferable.
- the content of the plasticizer is not particularly limited, but a preferable lower limit is 30 parts by mass and a preferable upper limit is 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the content of the plasticizer is 30 parts by mass or more, the vehicle window glass becomes appropriately flexible and the handling property and the like become good. In addition, when the content of the plasticizer is 70 parts by mass or less, separation of the plasticizer from the resin film is prevented.
- the more preferable lower limit of the content of the plasticizer is 35 parts by mass, and the more preferable upper limit is 63 parts by mass.
- the resin film of the present invention contains a thermoplastic resin
- the thermoplastic resin or the thermoplastic resin and the plasticizer are the main components
- the total amount of the thermoplastic resin and the plasticizer is the resin film
- the total amount is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.
- the resin film may contain additives such as an antioxidant, an adhesion regulator, an ultraviolet absorber, an infrared absorber, and an antistatic agent, as necessary.
- additives such as an antioxidant, an adhesion regulator, an ultraviolet absorber, an infrared absorber, and an antistatic agent, as necessary.
- Transparent plate Any transparent plate can be used without particular limitation as long as it can be used for vehicle window glass, and inorganic glass and organic glass can be used.
- the inorganic glass include, but are not limited to, clear glass, float plate glass, polished plate glass, template glass, reticulated plate glass, lined plate glass, green glass and the like.
- organic glass what is generally called resin glass is used, and although it is not particularly limited, transparent organic glass composed of resins such as polycarbonate, acrylic resin, acrylic copolymer resin, polyester and the like can be mentioned.
- the plurality of transparent plates may be made of the same material as each other, or may be made of different materials.
- one may be inorganic glass and the other may be organic glass.
- all of the plurality of transparent plates be inorganic glass or all organic glass.
- the thickness of each transparent plate is not particularly limited, and is, for example, about 0.1 to 15 mm, preferably 0.5 to 5 mm.
- the thickness of each transparent plate may be the same as or different from each other.
- the transparent plate may be a light emitting layer that emits visible light.
- the transparent plate is a light emitting layer, the transparent plate itself contains a fluorescent material.
- the fluorescent material may be dispersed in an inorganic material constituting the inorganic glass of the transparent plate or in an organic material (resin) constituting the organic glass.
- the fluorescent material may be dispersed throughout the transparent plate.
- the content of the fluorescent material is 0.001 parts by mass or more with respect to 100 parts by mass of the inorganic material constituting the inorganic glass or 100 parts by mass of the resin constituting the organic glass Is preferable, 0.05 parts by mass or more is more preferable, and 0.1 parts by mass or more is more preferable.
- content of a fluorescent material more than these lower limits, it becomes possible for the window glass for vehicles to light-emit enough.
- 10 mass parts or less are preferable, as for content of the said fluorescent material, 3 mass parts or less are more preferable, and 1.5 mass parts or less are more preferable.
- the vehicle window glass may have the laminated glass structure as described above, or the transparent plate may be a single layer . In the case of having a laminated glass structure, at least one transparent plate may be a light emitting layer.
- the window glass for vehicles may transmit visible light or may not transmit visible light, but preferably transmits visible light.
- Transmission of visible light means, for example, a visible light transmittance of 30% or more, preferably 50% or more.
- the visible light transmittance is from the viewpoint of enhancing the transparency of the vehicle window glass and from the viewpoint of securing the safety of the vehicle. 70% or more is preferable, 75% or more is more preferable, and 80% or more is more preferable.
- the upper limit of the visible light transmittance is not particularly limited, and is preferably as high as possible. However, for practical use, it is preferably 99% or less, and more preferably 95% or less.
- the visible light transmittance means the average value of the visible light transmittance at 400 to 780 nm, and can be measured, for example, by an ultraviolet visible infrared spectrophotometer (manufactured by Hitachi High-Tech, UH4150) in accordance with JIS R 3212. .
- the window glass for vehicles emits visible light when the excitation light from the light source is incident. Visible light is generally light having a wavelength of 400 to 780 nm. Also, the vehicle window glass may emit light such as blue, green and red, or light of two or more colors may be mixed to emit white light and the like. In the case where light of two or more colors is mixed, for example, two or more light emitting layers may be provided, and each layer may be mixed by irradiating different lights, but two types of light emitting layers may be used. The above fluorescent materials may be contained. The vehicle glazing preferably emits red light to alert the driver of the vehicle.
- the vehicle window glass preferably emits light having a maximum emission wavelength of 590 to 780 nm, more preferably 600 to 750 nm, and still more preferably 620 to 700 nm.
- a lanthanoid complex having a ligand containing a halogen atom may be used as a fluorescent material, and europium may be used as a lanthanoid.
- the window glass for vehicles may be provided with the reflective film which reflects visible light or excitation light.
- the reflective film is preferably provided on the vehicle outer side (that is, the vehicle outer side) than the light emitting layer.
- the reflective film may reflect visible light or may reflect excitation light.
- a known film such as a metal film or a visible light reflective film may be used. Since the visible light etc. which light-emitted by the light emitting layer etc. are reflected by a reflecting film by providing a reflecting film, it becomes possible to make the light emission intensity of the window glass for vehicles higher.
- a reflective film is provided when the window glass for vehicles is a side glass or a rear glass from a viewpoint which does not prevent a driver
- Front glass (window glass for vehicles) 10A, 10B Transparent plate 10C Intermediate film 10E Edge 10X Outer peripheral surface 11 Light source 11A Output end 12 Front side glass (window glass for vehicles) 12E edge 13 delta window glass (window glass for vehicles) 15 Control Means 16 Detection Means 21, 22 Pillars 23 Roof 24 Light Guide 24A End 24X Side
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Abstract
Description
すなわち、本発明は、以下の[1]~[14]を提供する。
[1]光源から照射された励起光が入射されることによって可視光を放射する乗り物用窓ガラスであって、前記励起光の照射により前記乗り物用窓ガラスの端部を発光させる乗り物用窓ガラス。
[2]前記乗り物用窓ガラスが、透明板を含む上記[1]に記載の乗り物用窓ガラス。
[3]前記乗り物用窓ガラスが、少なくとも1枚の透明板と樹脂膜が積層されてなる多層構造を有し、前記樹脂膜が、樹脂と、励起光の入射によって可視光を放射する蛍光材料とを含む上記[2]に記載の乗り物用窓ガラス。
[4]前記乗り物用窓ガラスが、自動車のフロントガラス及びサイドガラスのいずれかである上記[1]~[3]のいずれか1項に記載の乗り物用窓ガラス。
[5]人及び物の少なくともいずれかが乗り物に近づいたと検知されると、前記端部を発光させる上記[1]~[4]のいずれか1項に記載の乗り物用窓ガラス。
[6]前記検知される内容に応じて、発光のさせ方を変更させる、上記[5]に記載の乗り物用窓ガラス。
[7]接近物との距離に応じて、発光の強度、発光面積、及び発光位置の少なくとも1つを変更させる、上記[6]に記載の乗り物用窓ガラス。
[8]光源から照射された励起光を入射することによって可視光を放射する乗り物用窓ガラスを利用した警告表示方法であって、前記励起光の照射により前記乗り物用窓ガラスの端部を発光させ、乗員に注意喚起する警告表示方法。
[9]前記乗り物用窓ガラスが、透明板を含む上記[8]に記載の警告表示方法。
[10]前記乗り物用窓ガラスが、少なくとも1枚の透明板と樹脂膜が積層されてなる多層構造を有し、
前記樹脂膜が、樹脂と、励起光の入射によって可視光を放射する蛍光材料とを含む上記[8]又は[9]に記載の警告表示方法。
[11]前記乗り物用窓ガラスが、自動車のフロントガラス及びサイドガラスのいずれかである上記[8]~[10]のいずれか1項に記載の警告表示方法。
[12]人及び物の少なくともいずれかが乗り物に近づいたと検知されると、前記端部を発光させる上記[8]~[11]のいずれか1項に記載の警告表示方法。
[13]前記検知される内容に応じて、発光のさせ方を変更させる、上記[12]に記載の警告表示方法。
[14]接近物との距離に応じて、発光の強度、発光面積、及び発光位置の少なくとも1つを変更させる、上記[13]に記載の警告表示方法。
図1は、本発明の第1の実施形態に係る乗り物用窓ガラスを備えた自動車の室内空間を示す。第1の実施形態に係る乗り物用窓ガラスは、自動車のフロントガラス10である。フロントガラス10は、図1に示すように、両側のピラー21、22、ボンネット(図示せず)、及びルーフ23に設けられた支持部材により四方が支持されている。フロントガラス10は、下記で詳述するように、蛍光材料などを含有することで、励起光の入射によって可視光を放射することができる。
本実施形態では、図1に示すように、励起光の入射により、フロントガラス10の端部10Eを発光させるものである。端部10Eを発光させることで、後述するように車外の状況に応じて、自車の運転手などの乗員に注意喚起する警告を発することになる。
光源11が照射する光の最大発光波長は、特に限定されないが、420nm以下が好ましく、410nm以下がより好ましく、408nm以下がさらに好ましい。また、300nm以上が好ましく、350nm以上がより好ましく、380nm以上がさらに好ましい。
光源11が照射する光の最大発光波長を上記下限値以上及び上限値以下とすることで、フロントガラス10が、光源11からの励起光により効率よく可視光を発光することが可能である。
さらに、光源11の光軸は、通常、フロントガラス10の面方向に対して平行であるが、面方向に対して適宜傾斜させてもよい。光軸を傾けることで、光源11からの励起光は、内部に進入しにくくなるので端部10Eのみを発光させやすくなる。
図4は、本実施形態において自動車に設けられる発光システムを説明する。本実施形態において、発光システム30は、上記したフロントガラス10、光源11に加えて、制御手段15及び検知手段16を備える。制御手段15は、発光システム30の全体を制御するものであり、自動車に設けられるCPUなどにより構成されるが、特に限定されない。
検知手段16は、具体的には、自動車に設けられた人感センサ、ステレオカメラ、対物センサなどである。人感センサは、自動車に人が近づいたことを検知するセンサである。対物センサは、自動車に移動体が近づいたことを検知するセンサである。さらに、ステレオカメラは、車外を撮影して画像解析により、人、物体などが自動車に近づいたことを検知する。
なお、ライトガイド24の側面24Xにおいて、フロントガラス10に対向していない部分は、励起光を放射する必要がないので、励起光を吸収又は反射する皮膜が形成されていてもよい。具体的には、紫外線吸収剤を含有する皮膜などが形成されていてもよい。
また、ライトガイド24は、少なくとも1本設けられればよいが、複数本設けられて、それぞれがフロントガラス10の周方向における異なる位置の外周面10Xに配置されることで、第1の実施形態と同様に、発光位置や発光面積を変更したり、発光位置ごとに発光強度を変更したりすることも可能になる。
すなわち、本実施形態では、上記したフロントガラス10と同様に、フロントサイドガラス12の周囲に光源11又はライトガイド24が設けられ、フロントサイドガラス12の端部12Eも発光可能なものとする。ここで、発光させるフロントサイドガラス12の端部12Eは、図6に示すように前方側の端部であってもよいが、下端部の端部であってもよいし、上端部であってもよい。また、これらの2箇所以上の組み合わせでもよい。
より具体的には、例えば接近物が右側から近づいた場合、距離が遠い間は、右側のフロントサイドガラス12の端部12Eのみを発光させる一方で、接近物の距離が近づいた場合には、フロントガラス10の右側の端部10E、又はフロントガラス10の右側の端部10E及び右側のフロントサイドガラス12の端部12Eの両方を発光させるとよい。接近物が左側から近づいた場合も同様に、フロンガラス10の左側の端部10E、左側のフロントサイドガラス12の端部12Eなどを発光させるとよい。
さらには、第1の実施形態と同様に、接近物が自動車に近づいたと検知されると、その検知される距離、方向等の内容に応じて、発光のさせ方を変更させることができる。例えば、接近物の距離に応じてフロントガラス10、及びフロントサイドガラス12の発光の強度、発光面積、及び発光位置の少なくとも一つを適宜変更してもよい。
例えば、距離が相対的に遠いときにはフロントサイドガラス12の端部12Eを発光させるともに、距離が中位であるときにはデルタウィンドウガラス13、又はフロントサイドガラス12の端部12E及びデルタウィンドウガラス13を発光させるとよい。そして、距離が相対的に近いときにはフロントガラス10の端部10E、又はフロントガラス10の端部10E及びフロントサイドガラスの端部12E若しくはデルタウィンドウガラス13の少なくとも一方を発光させればよい。
また、光源ユニットとしては、励起光を乗り物用窓ガラスにビーム光として照射することが可能な光源ユニットであってもよい。ビーム光は、窓ガラスの発光される部分の全てを同じタイミングで照射するものであり、走査光を使用する場合のように走査ずれなどが生じることがない。
なお、MEMSミラーを有する光源ユニット以外のものとしては、DLP(Digital Light Processing)を用いたDMD(Digital Micromirror Device)方式やLCOS(Liquid crystal on silicon)などを利用した光源ユニットが挙げられる。
さらに、上記第1~第4の実施形態において、乗り物用窓ガラスは、外周面側から励起光が入射されて発光する態様を示すとともに、第5の実施形態では、車内側の表面から励起光が入射されて発光する態様を示したが、これらは組み合わせて使用してもよい。例えば、フロントガラスは、車内側の表面から励起光が入射されて発光する一方、サイドガラスは、ガラスの外周面側から励起光が入射されて発光してもよい。
次に、本発明に使用される乗り物用窓ガラスの構造についてより詳細に説明する。本発明で使用する乗り物用窓ガラスは、1層単体からなってもよいし、2以上の層を有する多層構造であってもよい。また、乗り物用窓ガラスは、少なくとも1層が透明板であることが好ましい。透明板は、無機ガラス、及び有機ガラスのいずれかからなるものである。有機ガラスは、いわゆる樹脂ガラスともいわれるものである。多層構造の乗り物用窓ガラスにおいては、透明板は1枚でもよいし、2枚以上であってもよい。また、乗り物用窓ガラスは、透明板が、蛍光材料を含有し、励起光が入射されることで発光する発光層となってよいが、透明板以外の層が蛍光材料を含有して発光層となってもよい。
また、乗り物用窓ガラスにおいては、少なくとも1枚の透明板と樹脂膜が積層されてなる多層構造を有することが好ましく、この多層構造においては、樹脂膜が、樹脂と、蛍光材料とを含有し、発光層となることがより好ましい。
また、発光層は、上記した樹脂膜や、透明板に限定されず、蛍光材料を真空蒸着、スパッタリングなどすることで形成される蛍光材料皮膜であってもよい。蛍光材料皮膜は、例えば、透明板の少なくとも一方の表面上に形成されるとよい。
蛍光材料は、励起光の入射によって可視光を放射するものであり、より具体的には上記光源から出射される励起光を吸収して、励起光より長波長である可視光を発光するものである。また、蛍光材料は、励起光が照射されることでいわゆるリン光を発する材料であってもよい。
上記蛍光材料としては、具体的には例えば、高い発光性を発揮できることから、ハロゲン原子を含む配位子を有するランタノイド錯体が挙げられる。ランタノイド錯体のなかでも、ハロゲン原子を含む配位子を有するランタノイド錯体は光線を照射することにより高い発光強度で発光する。上記ハロゲン原子を含む配位子を有するランタノイド錯体としては、ハロゲン原子を含む単座配位子を有するランタノイド錯体や、ハロゲン原子を含む二座配位子を有するランタノイド錯体、ハロゲン原子を含む三座配位子を有するランタノイド錯体、ハロゲン原子を含む四座配位子を有するランタノイド錯体、ハロゲン原子を含む五座配位子を有するランタノイド錯体、ハロゲン原子を含む六座配位子を有するランタノイド錯体等のハロゲン原子を含む多座配位子を有するランタノイド錯体が挙げられる。
しかも、上記ハロゲン原子を含む二座配位子を有するランタノイド錯体又はハロゲン原子を含む三座配位子を有するランタノイド錯体は、耐熱性にも優れる。乗り物用窓ガラスは太陽光の赤外線が照射されることにより、高温環境下で使用されることが多いため、上記ハロゲン原子を含む二座配位子を有するランタノイド錯体又はハロゲン原子を含む三座配位子を有するランタノイド錯体を用いることにより、蛍光材料の劣化が防止できる。
上記R2は、炭素数1以上のアルキレン基であることが好ましく、炭素数1~5のアルキレン基であることがより好ましく、炭素数1のメチレン基であることが最も好ましい。上記炭素数1以上のアルキレン基は水素原子の一部が、水素原子以外の原子及び官能基と置換されていても良い。
なお、上記式(2)において、2つのNはビピリジン骨格のどこにあってもよい。例えば、ビピリジン骨格の2,2’位、3,3’位、4,4’位、2,3’位、2,4’位、3,4’位に2つのNがあることが挙げられる。なかでも、2,2’位に2つのNがあることが好ましい。
上記ハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体は、例えば、Eu(TFA)3phen、Eu(TFA)3dpphen、Eu(HFA)3phen、[Eu(FPD)3]bpy、[Eu(TFA)3]tmphen、[Eu(FPD)3]phen等が挙げられる。これらのハロゲン原子を含むアセチルアセトン骨格を有する二座配位子を有するランタノイド錯体の構造を示す。
上記ハロゲン原子を含む配位子を有するランタノイド錯体が粒子状である場合、ランタノイド錯体の平均粒子径の好ましい下限は0.01μm、好ましい上限は10μmであり、より好ましい下限は0.03μm、より好ましい上限は1μmである。
上記テレフタル酸エステル構造を有する蛍光材料は、例えば、下記一般式(9)で表される構造を有する化合物や下記一般式(10)で表される構造を有する化合物が挙げられる。これらは単独で用いてもよく、2種以上を用いてもよい。
乗り物用窓ガラスの可視光線透過率がより一層高くなることから、xは1又は2であることが好ましく、ベンゼン環の2位又は5位に水酸基を有することがより好ましく、ベンゼン環の2位及び5位に水酸基を有することが更に好ましい。
上記R6の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。上記炭化水素基の炭素数が10以下であると、上記テレフタル酸エステル構造を有する蛍光材料を発光層に容易に分散させることができる。上記炭化水素基はアルキル基であることが好ましい。
上記R7の有機基は炭化水素基であることが好ましく、炭素数が1~10の炭化水素基であることがより好ましく、炭素数が1~5の炭化水素基であることが更に好ましく、炭素数が1~3の炭化水素基であることが特に好ましい。上記炭化水素基の炭素数が上記上限以下であると、上記テレフタル酸エステル構造を有する蛍光材料を発光層中に容易に分散させることができる。上記炭化水素基はアルキル基であることが好ましい。
上記一般式(10)中、NR8R9はアミノ基である。R8及びR9は、水素原子であることが好ましい。上記一般式(10)で表される構造を有する化合物のベンゼン環の水素原子のうち、一つの水素原子が上記アミノ基であってもよく、二つの水素原子が上記アミノ基であってもよく、三つの水素原子が上記アミノ基であってもよく、四つの水素原子が上記アミノ基であってもよい。
上記一般式(10)で表される構造を有する化合物として、ジエチル-2,5-ジアミノテレフタレート(例えば、Aldrich社製)が好ましい。
乗り物用窓ガラスにおいては、上記したように、発光層となる樹脂膜が設けられることが好ましい。また、乗り物用窓ガラスは、2枚の透明板の間に、中間膜が設けられ、その中間膜を介して2枚の透明板が接着された合わせガラス構造を有することが好ましい。
合わせガラス構造において、中間膜は、1層の樹脂膜からなり、その樹脂膜が発光層となることが好ましい。また、中間膜には、2層以上の樹脂膜が設けられ、複数の樹脂膜のうち、少なくとも1層の樹脂膜が発光層となってもよい。
合わせガラス構造の上記反対側の面や、単層の透明板のいずれか一方の面に、発光層となる樹脂膜が設けられる場合、発光層(樹脂膜)を有するシート状部材が、接着剤、粘着剤などを介して単層ガラスや合わせガラス構造の表面に接着されてもよい。これにより、既存の窓ガラスにいわゆる後貼りによりシート状部材を貼り合せることで、乗り物用窓ガラスに発光層を設けることができる。
樹脂膜に蛍光材料を含有させる場合、蛍光材料の含有量は、樹脂100質量部に対して、0.001質量部以上が好ましく、0.05質量部以上がより好ましく、0.1質量部以上がさらに好ましい。蛍光材料の含有量をこれら下限値以上とすることで、乗り物用窓ガラスが十分に発光することが可能になる。また、上記蛍光材料の含有量は、10質量部以下が好ましく、3質量部以下がより好ましく、1.5質量部以下がさらに好ましい。これら上限値以下とすることで、乗り物用窓ガラスの透明性を確保しやすくなる。
また、中間膜の厚さは、特に限定されないが、例えば、0.1~3mm、好ましくは0.2~2mmである。
樹脂膜において熱可塑性樹脂は、1種単独で使用してもよいし、2種以上を併用してもよい。また、これらの中では、樹脂膜に可塑剤を含有させた場合に、無機ガラスに対して優れた接着性を発揮する点から、ポリビニルアセタール樹脂が特に好適である。
可塑剤としては、例えば、一塩基性有機酸エステル及び多塩基性有機酸エステル等の有機エステル可塑剤、並びに有機リン酸可塑剤及び有機亜リン酸可塑剤などのリン酸可塑剤等が挙げられる。なかでも、有機エステル可塑剤が好ましく、特にトリエチレングリコール-ジ-2-エチルヘキサノエート(3GO)が好適である。
可塑剤の含有量は、特に限定されないが、熱可塑性樹脂100質量部に対して、好ましい下限は30質量部であり、好ましい上限は70質量部である。可塑剤の含有量を30質量部以上とすると、乗り物用窓ガラスが適度に柔軟になり、取り扱い性等が良好になる。また、可塑剤の含有量を70質量部以下とすると、樹脂膜から可塑剤が分離することが防止される。可塑剤の含有量のより好ましい下限は35質量部、より好ましい上限は63質量部である。
また、本発明の樹脂膜は、熱可塑性樹脂を含有する場合、熱可塑性樹脂、又は熱可塑性樹脂及び可塑剤が主成分となるものであり、熱可塑性樹脂及び可塑剤の合計量が、樹脂膜全量基準で、通常70質量%以上、好ましくは80質量%以上、さらに好ましくは90質量%以上である。
透明板としては、乗り物用窓ガラスに使用できるものであれば特に限定なく使用でき、無機ガラス、有機ガラスが使用できる。無機ガラスとしては、特に限定されないが、クリアガラス、フロート板ガラス、磨き板ガラス、型板ガラス、網入り板ガラス、線入り板ガラス、グリーンガラス等が挙げられる。
また、有機ガラスとしては、一般的に樹脂ガラスと呼ばれるものが使用され、特に限定されないが、ポリカーボネート、アクリル樹脂、アクリル共重合体樹脂、ポリエステルなどの樹脂から構成される透明有機ガラスが挙げられる。
また、各透明板の厚さは、特に限定されないが、例えば、0.1~15mm程度、好ましくは0.5~5mmである。乗り物用窓ガラスが複数の透明板を有する場合、各透明板の厚さは、互いに同一であってもよいし、異なっていてもよい。
透明板が、蛍光材料を含有し発光層となる場合、乗り物用窓ガラスは、上記したような合わせガラス構造を有していてもよいし、透明板が単層からなるものであってもよい。合わせガラス構造を有する場合には、少なくとも1枚の透明板が発光層となるとよい。
乗り物用窓ガラスが、例えば自動車のフロントガラスやフロントサイドガラスに使用される場合には、可視光線透過率は、乗り物用窓ガラスの透明性を高める観点、及び自動車の安全性を確保する観点から、70%以上が好ましく、75%以上がより好ましく、80%以上がさらに好ましい。また、可視光線透過率は、その上限は特に限定されず、高ければ高いほどよいが、実用的には99%以下が好ましく、95%以下がより好ましい。なお、可視光線透過率とは、400~780nmにおける可視光線透過率の平均値を意味し、例えばJISR3212に準拠した、紫外可視赤外分光光度計(日立ハイテク社製、 UH4150)により測定可能である。
乗り物用窓ガラスは、自車の運転手に注意を喚起するために、赤色光を放射することが好ましい。具体的には、乗り物用窓ガラスは、好ましくは最大発光波長が590~780nm、より好ましくは最大発光波長が600~750nm、さらに好ましくは620~700nmの光を放射するとよい。なお、赤色光を放射するためには、蛍光材料として、例えば、ハロゲン原子を含む配位子を有するランタノイド錯体を使用し、かつランタノイドとしてユーロピウムを使用すればよい。
なお、反射膜は、運転手の視界を妨げない観点から、乗り物用窓ガラスが、サイドガラス又はリアガラスであるときに設けられることが好ましい。
10A、10B 透明板
10C 中間膜
10E 端部
10X 外周面
11 光源
11A 出射端
12 フロントサイドガラス(乗り物用窓ガラス)
12E 端部
13 デルタウィンドウガラス(乗り物用窓ガラス)
15 制御手段
16 検知手段
21、22 ピラー
23 ルーフ
24 ライトガイド
24A 端部
24X 側面
Claims (14)
- 光源から照射された励起光が入射されることによって可視光を放射する乗り物用窓ガラスであって、前記励起光の照射により前記乗り物用窓ガラスの端部を発光させる乗り物用窓ガラス。
- 前記乗り物用窓ガラスが、透明板を含む請求項1に記載の乗り物用窓ガラス。
- 前記乗り物用窓ガラスが、少なくとも1枚の透明板と樹脂膜が積層されてなる多層構造を有し、
前記樹脂膜が、樹脂と、励起光の入射によって可視光を放射する蛍光材料とを含む請求項2に記載の乗り物用窓ガラス。 - 前記乗り物用窓ガラスが、自動車のフロントガラス及びサイドガラスのいずれかである請求項1~3のいずれか1項に記載の乗り物用窓ガラス。
- 人及び物の少なくともいずれかが乗り物に近づいたと検知されると、前記端部を発光させる請求項1~4のいずれか1項に記載の乗り物用窓ガラス。
- 前記検知される内容に応じて、発光のさせ方を変更させる、請求項5に記載の乗り物用窓ガラス。
- 接近物との距離に応じて、発光の強度、発光面積、及び発光位置の少なくとも1つを変更させる、請求項6に記載の乗り物用窓ガラス。
- 光源から照射された励起光を入射することによって可視光を放射する乗り物用窓ガラスを利用した警告表示方法であって、前記励起光の照射により前記乗り物用窓ガラスの端部を発光させ、乗員に注意喚起する警告表示方法。
- 前記乗り物用窓ガラスが、透明板を含む請求項8に記載の警告表示方法。
- 前記乗り物用窓ガラスが、少なくとも1枚の透明板と樹脂膜が積層されてなる多層構造を有し、
前記樹脂膜が、樹脂と、励起光の入射によって可視光を放射する蛍光材料とを含む請求項8又は9に記載の警告表示方法。 - 前記乗り物用窓ガラスが、自動車のフロントガラス及びサイドガラスのいずれかである請求項8~10のいずれか1項に記載の警告表示方法。
- 人及び物の少なくともいずれかが乗り物に近づいたと検知されると、前記端部を発光させる請求項8~11のいずれか1項に記載の警告表示方法。
- 前記検知される内容に応じて、発光のさせ方を変更させる、請求項12に記載の警告表示方法。
- 接近物との距離に応じて、発光の強度、発光面積、及び発光位置の少なくとも1つを変更させる、請求項13に記載の警告表示方法。
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EP18865883.5A EP3696003A4 (en) | 2017-10-10 | 2018-10-09 | VEHICLE PASSENGER WINDOW GLASS AND WARNING DISPLAY PROCESS |
CN201880065313.1A CN111183055A (zh) | 2017-10-10 | 2018-10-09 | 交通工具用窗玻璃及警告显示方法 |
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