JP6625727B2 - Windshield - Google Patents

Description

  The present invention relates to a windshield in which an information acquisition device for acquiring information from outside a vehicle by irradiating and / or receiving light can be arranged, a method for manufacturing the windshield, and an antifogging laminate used for the windshield.

  In recent years, the safety performance of automobiles has been dramatically improved. As one of them, in order to avoid collision with the vehicle in front, the distance to the vehicle in front and the speed of the vehicle in front are sensed. A safety system in which the brake operates is proposed. Such a system measures the distance to a vehicle in front using a laser radar or a camera. A laser radar or a camera is generally arranged inside a windshield, and performs measurement by irradiating light such as infrared rays forward (for example, Patent Document 1).

JP 2006-96331 A

  As described above, the measuring devices such as the laser radar and the camera are arranged on the inner surface side of the glass plate constituting the windshield, and irradiate and receive light through the glass plate. However, on cold days or cold days, the glass plate may become cloudy. However, when the glass plate is fogged, there is a possibility that the light cannot be accurately irradiated from the measuring device or the light cannot be received. As a result, the distance between vehicles and the like may not be accurately calculated.

  Such a problem is not limited to the inter-vehicle distance measuring device, but may be a problem that may occur in any information acquisition device that acquires information from outside the vehicle by receiving light such as a rain sensor, a light sensor, and an optical beacon.

  As a method for solving this problem, it is conceivable to use a glass plate having an antifogging film at least on a portion on the inner surface side of the glass plate where light irradiation or light reception is performed. In this case, the antifogging film may be directly coated on the glass plate, but the process is complicated and expensive, and it is extremely difficult to perform the coating process after the glass plate is mounted on the vehicle.

  Therefore, a transparent and flexible base film has an anti-fog layer on one main surface and an anti-fog sheet having a transparent adhesive layer on the other main surface is prepared in advance, and a predetermined anti-fog sheet of the glass plate is provided. It is conceivable to attach the anti-fog sheet to a portion with an adhesive layer.

  However, in general, the flexible base film is often an organic polymer material, and such a material is inferior in light resistance to a glass plate or an anti-fog layer, and when mounted on a vehicle, it is exposed to outdoor light transmitted through the glass plate. May become cloudy. Then, when the base film becomes cloudy, there is a possibility that the measurement device may not be able to accurately irradiate light or receive light, as in the case where the glass is clouded. As a result, the distance between vehicles and the like may not be accurately calculated.

  The present invention has been made in order to solve the above-mentioned problem, and a light shield and / or a light receiving device are provided in a windshield to which an information acquisition device that performs light irradiation and / or light receiving via a glass plate can be attached. It is an object of the present invention to provide a windshield, a method for manufacturing the same, and an antifogging laminate used for the windshield, which can be performed accurately and can process information accurately.

  The windshield according to the present invention is a windshield in which an information acquisition device that acquires information from outside the vehicle by irradiating and / or receiving light can be arranged, and Tuv380 ≦ 0.5% and Tuv400 <3. .5% laminated glass, and an anti-fog sheet disposed on the inner surface of the laminated glass, wherein the laminated glass includes an inner glass plate, an outer glass plate, and the inner glass plate and an outer glass plate. An interlayer film disposed between the glass sheet and the laminated glass, wherein the laminated glass has at least one information acquisition area through which the light passes while facing the information acquisition apparatus, and the anti-fog sheet Has an adhesive layer, a base film, and an anti-fog layer laminated in this order, and is fixed to at least a part of the information acquisition region of the laminated glass by the adhesive layer.

  In the windshield, the laminated glass may be configured to satisfy Tuv400 ≦ 2.5%.

  In each of the windshields, the laminated glass may further include an ultraviolet shielding layer disposed on at least one of an inner surface of the outer glass plate and an inner surface of the inner glass plate.

  In each of the windshields, the intermediate film of the laminated glass may have an ultraviolet shielding function.

  In each of the windshields, at least one of the outer glass plate and the inner glass plate can be made of an ultraviolet absorbing glass.

  In each of the windshields, a mask layer that blocks a field of view from outside the vehicle is laminated on the laminated glass, and the information acquisition region can be configured by an opening formed in the mask layer.

  In each of the windshields, the anti-fog sheet can be formed smaller than the opening.

  In each of the windshields, the anti-fog sheet may be formed to have a size exceeding a peripheral edge of the opening and covering a part of the mask layer.

  In each of the windshields, the anti-fog layer may be formed such that a layer thickness in a lower half of the base film is larger than a layer thickness in an upper half of the base film.

  In each of the windshields, the anti-fog sheet can be disposed so as to cover at least a lower half of the information acquisition area.

  In each of the above windshields, the angle at which the laminated glass is attached to the vehicle body can be 45 degrees or more.

  ADVANTAGE OF THE INVENTION According to this invention, in a windshield to which an information acquisition device that irradiates and / or receives light via a glass plate can be attached, light irradiation and / or light reception can be accurately performed, and information processing can be performed. Can be done accurately.

It is a top view showing one embodiment of a windshield concerning the present invention. It is sectional drawing of FIG. It is sectional drawing of a laminated glass. It is a schematic plan view which shows the measurement position of the thickness of a laminated glass. It is an example of an image used for measurement of an intermediate film. FIG. 2 is a block diagram of a vehicle-mounted system arranged in the windshield of FIG. 1. It is sectional drawing of an anti-fog sheet. FIG. 2 is a schematic view illustrating an example of a manufacturing process of the windshield of FIG. 1. It is explanatory drawing of the attachment angle of a laminated glass. It is a top view of a roller apparatus. It is a top view showing other examples of a windshield concerning the present invention. It is a figure which shows the surface property after ultraviolet irradiation which concerns on Example 12 and a comparative example.

  First, the configuration of the windshield according to the present embodiment will be described with reference to FIGS. 1 is a plan view of the windshield, and FIG. 2 is a sectional view of FIG. For convenience of description, the up-down direction in FIG. 1 is referred to as “up / down”, “vertical”, and “vertical”, and the left-right direction in FIG. 1 is referred to as “left / right”. FIG. 1 illustrates the windshield viewed from the inside of the vehicle. That is, the back side of the paper of FIG. 1 is the outside of the vehicle, and the front side of the paper of FIG.

  The windshield includes a substantially rectangular laminated glass 10 and is installed on the vehicle body in an inclined state. A mask layer 110 for blocking the field of view from outside the vehicle is provided on an inner surface 130 of the laminated glass 10 facing the inside of the vehicle, and the photographing device 2 is arranged so as to be invisible from outside the vehicle by the mask layer 110. ing. However, the photographing device 2 is a camera for photographing a situation outside the vehicle. For this reason, the mask layer 110 is provided with a photographing window 113 at a position corresponding to the photographing device 2, and through this photographing window 113, the photographing device 2 arranged in the car can take information such as photographing outside the vehicle by photographing. Can be obtained. Further, an anti-fog sheet 7 is attached to the photographing window 113.

  An information processing device 3 is connected to the imaging device 2, and information such as a captured image acquired by the imaging device 2 is processed by the information processing device 3. The photographing device 2 and the information processing device 3 constitute an in-vehicle system 5, and the in-vehicle system 5 can provide various information to a passenger according to the processing of the information processing device 3. Hereinafter, each component will be described.

<1. Laminated glass>
FIG. 3 is a sectional view of the laminated glass. As shown in FIG. 1, the laminated glass 10 includes an outer glass plate 11 and an inner glass plate 12, and an interlayer 13 made of resin is disposed between the glass plates 11 and 12. Hereinafter, these configurations will be described.

<1-1. Glass plate>
First, the outer glass plate 11 and the inner glass plate 12 will be described. As the outer glass plate 11 and the inner glass plate 12, known glass plates can be used, and they can also be formed of heat ray absorbing glass, general clear glass or green glass, or UV green glass. However, these glass plates 11 and 12 need to realize visible light transmittance in accordance with safety standards of the country where the automobile is used. For example, the required solar absorptance can be secured by the outer glass plate 11 and the visible light transmittance can be adjusted by the inner glass plate 12 so as to satisfy the safety standard. Hereinafter, examples of clear glass, green glass, heat ray absorbing glass, ultraviolet ray absorbing glass, and soda-lime glass are shown.

(Clear glass)
SiO ₂ : 70 to 73% by mass
Al ₂ O ₃ : 0.6 to 2.4 mass%
CaO: 7 to 12% by mass
MgO: 1.0 to 4.5 mass%
R ₂ O: 13 to 15% by mass (R is an alkali metal)
Fe total iron oxide in terms of _{2 O 3 (T-Fe 2} O 3): 0.08~0.14 wt%

(Green glass)
SiO ₂ : 70 to 73% by mass
Al ₂ O ₃ : 0.6 to 2.4 mass%
CaO: 7 to 12% by mass
MgO: 1.0 to 4.5 mass%
R ₂ O: 13 to 15% by mass (R is an alkali metal)
Fe total iron oxide in terms of _{2 O 3 (T-Fe 2} O 3): 0.4~0.6 wt%

(Heat absorbing glass)
SiO ₂ : 70 to 73% by mass
Al ₂ O ₃ : 0.6 to 2.4 mass%
CaO: 7 to 12% by mass
MgO: 1.0 to 4.5 mass%
R ₂ O: 13 to 15% by mass (R is an alkali metal)
Fe total iron oxide in terms of _{2 O 3 (T-Fe 2} O 3): 0.5~1.1 wt%

(UV absorbing glass)
SiO ₂ : 70 to 73% by mass
Al ₂ O ₃ : 0.6 to 2.4 mass%
CaO: 7 to 12% by mass
MgO: 1.0 to 4.5 mass%
R ₂ O: 13 to 15% by mass (R is an alkali metal)
Fe total iron oxide in terms of _{2 O 3 (T-Fe 2} O 3): 0.7~1.3 wt%
CeO ₂ : 0 to 2% by mass
TiO ₂ : 0 to 0.5% by mass

(Soda-lime glass)
SiO ₂ : 65 to 80% by mass
Al ₂ O ₃ : 0 to 5% by mass
CaO: 5 to 15% by mass
MgO: 2% by mass or more NaO: 10 to 18% by mass
K ₂ O: 0 to 5 wt%
MgO + CaO: 5 to 15% by mass
Na ₂ O + K ₂ O: 10 to 20% by mass
SO ₃ : 0.05 to 0.3% by mass
B ₂ O ₃ : 0 to 5% by mass
Fe total iron oxide in terms of _{2 O 3 (T-Fe 2} O 3): 0.02~0.03 wt%

  Although the thickness of the laminated glass according to the present embodiment is not particularly limited, the total thickness of the outer glass plate 11 and the inner glass plate 12 can be, for example, 2.1 to 6 mm, from the viewpoint of weight reduction. , The total thickness is preferably from 2.4 to 3.8 mm, more preferably from 2.6 to 3.4 mm, particularly preferably from 2.7 to 3.2 mm. As described above, in order to reduce the weight, it is necessary to reduce the total thickness of the outer glass plate 11 and the inner glass plate 12, and the thickness of each glass plate is not particularly limited, For example, the thickness of the outer glass plate 11 and the inner glass plate 12 can be determined as follows.

  The outer glass plate 11 mainly requires durability and impact resistance against external obstacles. For example, when this laminated glass is used as a windshield of an automobile, the outer glass plate 11 has an impact resistance to flying objects such as pebbles. is necessary. On the other hand, as the thickness increases, the weight increases, which is not preferable. In this respect, the thickness of the outer glass plate 11 is preferably 1.8 to 2.3 mm, and more preferably 1.9 to 2.1 mm. Which thickness is adopted can be determined according to the use of the glass.

  The thickness of the inner glass plate 12 can be made equal to that of the outer glass plate 11, but for example, the thickness can be made smaller than that of the outer glass plate 11 in order to reduce the weight of the laminated glass. Specifically, in consideration of the strength of glass, it is preferably 0.6 to 2.0 mm, more preferably 0.8 to 1.6 mm, and particularly preferably 1.0 to 1.4 mm. preferable. Furthermore, it is preferable that it is 0.8 to 1.3 mm. Which thickness is adopted for the inner glass plate 12 can be determined according to the use of the glass.

  Here, an example of a method of measuring the thickness when the glass plate (laminated glass) 1 is curved will be described. First, as shown in FIG. 4, the measurement positions are two upper and lower positions on a center line S extending vertically in the center of the glass plate in the left-right direction. The measuring instrument is not particularly limited, but for example, a thickness gauge such as SM-112 manufactured by Teclock Corporation can be used. At the time of measurement, the glass plate is placed so that the curved surface of the glass plate rests on a flat surface, and the thickness is measured by holding the end of the glass plate with the thickness gauge. Note that even when the glass plate is flat, measurement can be performed in the same manner as when the glass plate is curved.

<1-2. Interlayer>
The intermediate film 13 is formed of at least one layer. As an example, as shown in FIG. 3, the intermediate film 13 can be formed of three layers in which a soft core layer 131 is sandwiched by a harder outer layer 132. However, the present invention is not limited to this configuration, and may be formed of a plurality of layers having the core layer 131 and at least one outer layer 132 disposed on the outer glass plate 11 side. For example, two layers of the intermediate film 13 including the core layer 131 and one outer layer 132 disposed on the outer glass plate 11 side, or two or more even outer layers 132 on both sides of the core layer 131, respectively. The intermediate film 13 may be an arranged intermediate film 13 or an intermediate film 13 having an odd outer layer 132 on one side and an even outer layer 132 on the other side with the core layer 131 interposed therebetween. When only one outer layer 132 is provided, the outer layer 132 is provided on the outer glass plate 11 side as described above, but this is to improve the resistance to breakage against external force from outside the vehicle or outdoors. In addition, when the number of the outer layers 132 is large, the sound insulation performance also increases.

  As long as the core layer 131 is softer than the outer layer 132, its hardness is not particularly limited. The material constituting each of the layers 131 and 132 is not particularly limited. For example, the material can be selected based on the Young's modulus. Specifically, at a frequency of 100 Hz and a temperature of 20 degrees, the pressure is preferably 1 to 20 MPa, more preferably 1 to 18 MPa, and particularly preferably 1 to 14 MPa. With such a range, it is possible to prevent the STL from lowering in a low frequency range of approximately 3500 Hz or less. On the other hand, as described later, the Young's modulus of the outer layer 132 is preferably large for improving sound insulation performance in a high frequency range, and is 560 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more at a frequency of 100 Hz and a temperature of 20 degrees. It can be 750 MPa or more, 880 MPa or more, or 1300 MPa or more. On the other hand, the upper limit of the Young's modulus of the outer layer 132 is not particularly limited, but can be set, for example, from the viewpoint of workability. For example, it is empirically known that when the pressure is 1750 MPa or more, workability, particularly cutting becomes difficult.

  As a specific material, the outer layer 132 can be made of, for example, polyvinyl butyral resin (PVB). Polyvinyl butyral resin is preferable because it has excellent adhesion to glass plates and penetration resistance. On the other hand, the core layer 131 can be made of, for example, an ethylene vinyl acetate resin (EVA) or a polyvinyl acetal resin softer than the polyvinyl butyral resin constituting the outer layer. By sandwiching the soft core layer therebetween, the sound insulation performance can be greatly improved while maintaining the same adhesiveness and penetration resistance as a single-layer resin interlayer.

  Generally, the hardness of the polyvinyl acetal resin is controlled by (a) the degree of polymerization of the starting polyvinyl alcohol, (b) the degree of acetalization, (c) the type of plasticizer, and (d) the proportion of the plasticizer added. Can be. Therefore, by appropriately adjusting at least one selected from these conditions, even with the same polyvinyl butyral resin, a hard polyvinyl butyral resin used for the outer layer 132 and a soft polyvinyl butyral resin used for the core layer 131 It is possible to make differently. Furthermore, the hardness of the polyvinyl acetal resin can also be controlled by the type of aldehyde used for acetalization, the co-acetalization with a plurality of types of aldehydes, or the pure acetalization with a single type of aldehyde. Although it cannot be said unconditionally, the polyvinyl acetal resin obtained by using an aldehyde having a large number of carbon atoms tends to be softer. Therefore, for example, when the outer layer 132 is made of a polyvinyl butyral resin, the core layer 131 has an aldehyde having 5 or more carbon atoms (for example, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n-octyl aldehyde) with polyvinyl alcohol. In addition, when a predetermined Young's modulus is obtained, it is not limited to the above resin and the like.

  Further, the total thickness of the intermediate film 13 is not particularly limited, but is preferably 0.3 to 6.0 mm, more preferably 0.5 to 4.0 mm, and more preferably 0.6 to 2.0 mm. It is particularly preferred that there is. Further, the thickness of the core layer 131 is preferably from 0.1 to 2.0 mm, and more preferably from 0.1 to 0.6 mm. On the other hand, the thickness of each outer layer 132 is preferably 0.1 to 2.0 mm, and more preferably 0.1 to 1.0 mm. In addition, the total thickness of the intermediate film 13 may be kept constant, and the thickness of the core layer 131 may be adjusted.

  The thickness of the core layer 131 and the outer layer 132 can be measured, for example, as follows. First, the cross section of the laminated glass is magnified and displayed 175 times by a microscope (for example, VH-5500 manufactured by Keyence Corporation). Then, the thicknesses of the core layer 131 and the outer layer 132 are visually identified and measured. At this time, in order to eliminate visual variations, the number of measurements is set to five, and the average value is defined as the thickness of the core layer 131 and the outer layer 132. For example, an enlarged photograph of the laminated glass as shown in FIG. 7 is taken, and the core layer and the outer layer 132 are specified and the thickness is measured.

  Note that the thickness of the core layer 131 and the outer layer 132 of the intermediate film 13 does not need to be constant over the entire surface, and may be, for example, a wedge shape for a laminated glass used in a head-up display. In this case, the thickness of the core layer 131 and the outer layer 132 of the intermediate film 13 is measured at the point where the thickness is the smallest, that is, at the lowermost side of the laminated glass. When the intermediate film 13 has a wedge shape, the outer glass plate and the inner glass plate are not arranged in parallel, but such an arrangement is also included in the glass plate in the present invention. That is, in the present invention, for example, the arrangement of the outer glass plate and the inner glass plate when the intermediate film 13 using the core layer 131 or the outer layer 132 whose thickness is increased at a change rate of 3 mm or less per 1 m is included. .

  The method for producing the intermediate film 13 is not particularly limited. For example, a resin component such as the polyvinyl acetal resin described above, a plasticizer, and other additives as necessary are blended and uniformly kneaded. And a method of laminating two or more resin films formed by this method by a pressing method, a laminating method, or the like. The resin film before lamination used in a method of laminating by a pressing method, a lamination method, or the like may have a single-layer structure or a multilayer structure. Further, the intermediate film 13 may be formed of a single layer other than the above-described plurality of layers.

<1-3. Optical properties of glass plate>
As described above, since the windshield according to the present embodiment captures the outside of the vehicle using the information acquisition device, it is necessary that the windshield has a visible light transmittance enough to capture the situation outside the vehicle. Therefore, it is configured such that the visible light transmittance is 70% or more. In addition, this transmittance | permeability can be measured by the spectrometry method prescribed | regulated to JISZ8722 as prescribed by JISR3212 (3.11 visible light transmittance test).

The ultraviolet transmittance as a laminated glass is as follows.
Tuv380 ≦ 0.5% and Tuv400 <3.5% (1)
Here, Tuv380 is an ultraviolet transmittance specified in ISO9050: 1990, and Tuv400 is an ultraviolet transmittance specified in ISO13837: 2008 convention A. The ultraviolet transmittance can be measured by any known spectrophotometer, for example, “UV-3100PC” (manufactured by Shimadzu Corporation). Further, Tuv400 in the above formula (1) is preferably at most 2.5%, more preferably at most 2.0%, particularly preferably at most 1.0%.

  In the present embodiment, the following method can be used to impart such an ultraviolet transmittance to the laminated glass. In addition, the following (1) to (3) can be appropriately combined. Further, the laminated glass of the present invention includes the following configurations (1) to (3).

(1) A laminated glass is formed of green glass, heat ray absorbing glass, or ultraviolet ray absorbing glass. The laminated glass using these satisfies the above formula (1), as described later.

(2) A film having an ultraviolet shielding property is provided on at least one of the inner surface of the outer glass plate of the laminated glass and the interior surface of the inner glass plate and the anti-fog sheet. Examples of the film having ultraviolet shielding properties include an organic-inorganic composite film containing an ultraviolet absorbent and a light-resistant film.

  The organic-inorganic composite film may be, for example, a film containing a hydrolysis-condensation product of a tetrafunctional silicon alkoxide, a hydrolysis-condensation product of a trifunctional silicon alkoxide, an ultraviolet absorber that is an organic substance, and an organic polymer. it can.

  The light-resistant film is, for example, a polyester film and may be a film containing an ultraviolet absorber in an amount of 0.05 to 30% by mass.

(3) To impart ultraviolet absorption performance to the intermediate film. For example, an intermediate film having a long-wavelength ultraviolet absorption function can be used. Specifically, it is possible to use an intermediate film containing an ultraviolet absorber (for example, one containing more than usual) or an intermediate film containing a specific light absorber.

  As the light absorber, for example, those having an anthraquinone structure having a thiophenyl group can be employed. Thereby, the ultraviolet light transmittance can be reduced without lowering the visible light transmittance. The light absorber having such an anthraquinone structure may have at least one or more thiophenyl groups, and preferably has two or more thiophenyl groups. In addition, the lower limit of the content of the light absorber having an anthraquinone structure with respect to the intermediate film is, for example, 0.003 parts by weight, and the upper limit is, for example, 0.007 parts by weight with respect to 100 parts by weight of the thermoplastic resin. it can. The laminated glass in which an interlayer containing such a light absorbing agent is, for example, about 0.0035 parts by weight is sandwiched between clear glasses can have a Tuv 380 of about 0% and a Tuv 400 of about 2.8%. However, in such a laminated glass, when, for example, green glass, heat ray absorbing glass, or ultraviolet ray absorbing glass is used instead of the clear glass, the ultraviolet ray transmittance can be further reduced.

<2. Mask layer>
Next, the mask layer 110 will be described. As illustrated in FIGS. 1 and 2, in the present embodiment, the mask layer 110 is laminated on the inner surface (the inner surface of the inner glass plate 12) 130 of the laminated glass 10 on the vehicle interior, and is provided on the periphery of the laminated glass 10. It is formed along. Specifically, as illustrated in FIG. 1, the mask layer 110 according to the present embodiment includes a peripheral region 111 along the peripheral portion of the laminated glass 10 and a rectangular shape projecting downward from the upper side of the laminated glass 10. Protruding region 112. The peripheral region 111 shields light from entering from the peripheral portion of the windshield 1. On the other hand, the protruding region 112 makes the photographing device 2 arranged inside the vehicle invisible from outside the vehicle.

  However, if the mask layer 110 blocks the photographing range of the photographing device 2, the photographing device 2 cannot photograph a situation outside the vehicle. Therefore, in the present embodiment, a rectangular information acquisition area (opening) 113 is provided at a position corresponding to the imaging device 2 in the projecting region 112 of the mask layer 110 so that the imaging device 2 can be out of the vehicle. Has been. That is, the imaging window 113 is provided independently of the non-shielding region 120 inside the mask layer 110 in the plane direction. The photographing window 113 is a region where the material of the mask layer 110 is not laminated, and the outside of the vehicle can be photographed by the laminated glass having the above-described visible light transmittance.

  The mask layer 110 may be laminated on the inner surface of the outer glass plate 11 and the outer surface of the inner glass plate 12, for example, in addition to being laminated on the inner surface of the inner glass plate 12, as described above. Further, it can be laminated at two places on the inner surface of the outer glass plate 11 and the inner surface of the inner glass plate 12.

  Next, the material of the mask layer 110 will be described. The material of the mask layer 110 may be appropriately selected according to the embodiment as long as it can shield the field of view from outside the vehicle. For example, black, brown, gray, dark blue or other dark ceramics may be used. Is also good.

  When a black ceramic is selected as the material of the mask layer 110, for example, a black ceramic is laminated on the peripheral portion on the inner surface 130 of the inner glass plate 12 by screen printing or the like, and the ceramic laminated with the inner glass plate 12 is heated. I do. Thereby, the mask layer 110 can be formed on the peripheral portion of the inner glass plate 12. When printing black ceramic, an area is provided in which black ceramic is not partially printed. Thereby, the imaging window 113 can be formed. Note that various materials can be used for the ceramic used for the mask layer 110. For example, a ceramic having a composition shown in Table 1 below can be used for the mask layer 110.

* 1, main components: copper oxide, chromium oxide, iron oxide, and manganese oxide * 2, main components: bismuth borosilicate, zinc borosilicate

<3. In-vehicle system>
Next, an in-vehicle system 5 including the photographing device 2 and the image processing device 3 will be described with reference to FIG. FIG. 6 illustrates the configuration of the vehicle-mounted system 5. As illustrated in FIG. 6, an in-vehicle system 5 according to the present embodiment includes the above-described imaging device 2 and an image processing device 3 connected to the imaging device 2.

  The image processing device 3 is a device that processes a photographed image acquired by the photographing device 2. The image processing apparatus 3 has, for example, general hardware such as a storage unit 31, a control unit 32, and an input / output unit 33 connected by a bus as a hardware configuration. However, the hardware configuration of the image processing device 3 does not have to be limited to such an example, and the specific hardware configuration of the image processing device 3 may be appropriately added or omitted according to the embodiment according to the embodiment. And additions are possible.

  The storage unit 31 stores various data and programs used in the processing executed by the control unit 32 (not shown). The storage unit 31 may be realized by, for example, a hard disk or a recording medium such as a USB memory. The various data and programs stored in the storage unit 31 may be acquired from a recording medium such as a CD (Compact Disc) or a DVD (Digital Versatile Disc). Further, the storage unit 31 may be called an auxiliary storage device.

  As described above, the laminated glass 10 is arranged in an inclined posture with respect to the vertical direction and is curved. Then, the photographing device 2 photographs a situation outside the vehicle through the laminated glass 10. Therefore, the image captured by the image capturing device 2 is deformed according to the posture, shape, refractive index, optical defect, and the like of the laminated glass 10. In addition, an aberration unique to the camera lens of the photographing device 2 is also added. Therefore, the storage unit 31 may store correction data for correcting an image deformed by the aberration of the laminated glass 10 and the camera lens.

  The control unit 32 includes one or more processors such as a microprocessor or a CPU (Central Processing Unit), and peripheral circuits (ROM (Read Only Memory), RAM (Random Access Memory), and interface circuit) used for processing of the processor. Etc.). The ROM, the RAM, and the like may be called a main storage device in the sense that they are arranged in an address space handled by the processor in the control unit 32. The control unit 32 functions as the image processing unit 321 by executing various data and programs stored in the storage unit 31.

  The image processing unit 321 processes a captured image acquired by the imaging device 2. The processing of the captured image can be appropriately selected according to the embodiment. For example, the image processing unit 321 may recognize a subject appearing in the captured image by analyzing the captured image by pattern matching or the like. In the present embodiment, since the image capturing device 2 captures an image of the situation in front of the vehicle, the image processing unit 321 further determines whether or not a living thing such as a human is captured in front of the vehicle based on the subject recognition. Is also good. When a person is in front of the vehicle, the image processing unit 321 may output a warning message by a predetermined method. In addition, for example, the image processing unit 321 may perform predetermined processing on a captured image. Then, the image processing unit 321 may output the processed captured image to a display device (not shown) such as a display connected to the image processing device 3.

  The input / output unit 33 is one or a plurality of interfaces for transmitting and receiving data to and from a device existing outside the image processing device 3. The input / output unit 33 is, for example, an interface for connecting to a user interface, or an interface such as a USB (Universal Serial Bus). In the present embodiment, the image processing device 3 is connected to the photographing device 2 via the input / output unit 33, and acquires a photographed image photographed by the photographing device 2.

  As the image processing device 3, a general-purpose device such as a PC (Personal Computer) or a tablet terminal may be used in addition to a device designed exclusively for a provided service.

  The information acquisition device is attached to a bracket (not shown), and the bracket is attached to a mask layer. Therefore, in this state, the attachment of the information acquisition device to the bracket and the attachment of the bracket to the mask layer are adjusted so that the optical axis of the camera of the information acquisition device passes through the information acquisition region. A cover (not shown) is attached to the bracket so as to cover the photographing device 2. Therefore, the photographing device 2 is disposed in a space surrounded by the laminated glass 10, the bracket, and the cover, so that the photographing device 2 cannot be seen from the inside of the vehicle, and only a part of the photographing device 2 can be seen from the outside of the vehicle through the photographing window 113. Not to be. The photographing device 2 and the above-mentioned input / output unit 33 are connected by a cable (not shown), which is pulled out of the cover and connected to the image processing device 3 disposed at a predetermined position in the vehicle. .

<4. Anti-fog sheet>
Next, the anti-fog sheet will be described. As described above, the anti-fog sheet is attached to the information acquisition area, and as shown in FIG. 7, an adhesive layer 71, a base film 72, and an anti-fog layer 73 are laminated in this order. It is.
Until fixed to the information acquisition area, the adhesive layer 71 is provided with a peelable first protective sheet 74, and the antifogging layer 73 is also provided with a peelable second protective sheet 75. Constitutes an anti-fog laminate.
Further, the anti-fog sheet 7 is formed in a shape corresponding to the imaging window 113, but can be formed in a shape slightly smaller than the imaging window 113, for example. Alternatively, it can be formed to be larger than the imaging window 113 and to cover a part of the mask layer 110 beyond the imaging window 113. Hereinafter, each layer will be described.

<4-1. Anti-fog layer>
The anti-fog layer is not particularly limited as long as it has the anti-fog effect of the laminated glass plate 10, and a known anti-fog layer can be used. Generally, the anti-fog layer is formed of a hydrophilic type that forms on the surface water generated from water vapor as a water film, a water-absorbing type that absorbs water vapor, a water-repellent water-absorbing type in which water droplets hardly condense on the surface, and a water-repellent type that repels water droplets generated from water vapor. Although there is a water-repellent type that is watered, any type of anti-fog layer is applicable. Hereinafter, an example of a water-repellent / water-absorbing type anti-fog layer will be described as an example.

[Organic-inorganic composite anti-fog layer]
The organic-inorganic composite anti-fog layer is a single layer film formed on the surface of the substrate film or a multilayer film laminated. The organic-inorganic composite anti-fog layer contains at least a water absorbent resin, a water repellent group, and a metal oxide component. The anti-fogging film may further include other functional components as necessary. The water-absorbing resin is not particularly limited as long as it can absorb and hold water. The water-repellent group can be supplied to the anti-fogging film from a metal compound having a water-repellent group (a metal compound having a water-repellent group). The metal oxide component can be supplied to the anti-fogging film from a water-repellent group-containing metal compound, other metal compounds, metal oxide fine particles and the like. Hereinafter, each component will be described.

(Water absorbent resin)
There is no particular limitation on the water-absorbing resin, polyethylene glycol, polyether resin, polyurethane resin, starch resin, cellulose resin, acrylic resin, epoxy resin, polyester polyol, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, Examples include polyvinyl acetal resin and polyvinyl acetate. Of these, preferred are hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal resin, polyvinyl acetate, epoxy resin and polyurethane resin, and more preferred are polyvinyl acetal resin, epoxy resin and polyurethane resin. Yes, particularly preferred are polyvinyl acetal resins.

The polyvinyl acetal resin can be obtained by subjecting polyvinyl alcohol to an aldehyde condensation reaction to form an acetal. Acetalization of polyvinyl alcohol may be performed by a known method such as a precipitation method using an aqueous medium in the presence of an acid catalyst or a dissolution method using a solvent such as alcohol. Acetalization can also be performed in parallel with saponification of polyvinyl acetate. The degree of acetalization is preferably 2 to 40 mol%, more preferably 3 to 30 mol%, particularly preferably 5 to 20 mol%, and in some cases 5 to 15 mol%. The degree of acetalization can be measured based on, for example, ¹³ C nuclear magnetic resonance spectroscopy. A polyvinyl acetal resin having a degree of acetalization within the above range is suitable for forming an organic-inorganic composite antifog layer having good water absorption and water resistance.

  The average degree of polymerization of polyvinyl alcohol is preferably from 200 to 4,500, and more preferably from 500 to 4,500. A high average degree of polymerization is advantageous for forming an organic-inorganic composite anti-fog layer having good water absorption and water resistance, but if the average degree of polymerization is too high, the viscosity of the solution becomes too high and hinders film formation. May come. The saponification degree of polyvinyl alcohol is preferably from 75 to 99.8 mol%.

  Examples of the aldehyde to be subjected to a condensation reaction with polyvinyl alcohol include aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexylcarbaldehyde, octylcarbaldehyde, and decylcarbaldehyde. Also, benzaldehyde; 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, and other alkyl-substituted benzaldehydes; chlorobenzaldehyde, other halogen-substituted benzaldehydes; alkyls such as hydroxy, alkoxy, amino, and cyano groups A substituted benzaldehyde in which a hydrogen atom is substituted by a functional group other than a group; and aromatic aldehydes such as condensed aromatic ring aldehydes such as naphthaldehyde and anthralaldehyde. An aromatic aldehyde having strong hydrophobicity is advantageous in forming an organic-inorganic composite antifog layer having a low degree of acetalization and excellent water resistance. Use of the aromatic aldehyde is advantageous in forming a film having high water absorption while leaving a large amount of hydroxyl groups. The polyvinyl acetal resin preferably contains an acetal structure derived from an aromatic aldehyde, particularly benzaldehyde.

  Examples of the epoxy resin include a glycidyl ether-based epoxy resin, a glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, and a cycloaliphatic epoxy resin. Of these, cycloaliphatic epoxy resins are preferred.

  Examples of the polyurethane resin include a polyurethane resin composed of a polyisocyanate and a polyol. As the polyol, an acrylic polyol and a polyoxyalkylene polyol are preferable.

  The organic-inorganic composite anti-fog layer contains a water absorbent resin as a main component. In the present invention, the “main component” means a component having the highest content on a mass basis. The content of the water-absorbent resin based on the weight of the organic-inorganic composite antifogging layer is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 65% by weight, from the viewpoint of film hardness, water absorption and antifogging property. It is at least 95% by weight, more preferably at most 90% by weight, particularly preferably at most 85% by weight.

(Water-repellent group)
In order to sufficiently obtain the above-described effects of the water-repellent group, it is preferable to use a water-repellent group having high water repellency. Preferred water-repellent groups are (1) a chain or cyclic alkyl group having 3 to 30 carbon atoms, and (2) a chain or cyclic alkyl group having 1 to 30 carbon atoms in which at least a part of a hydrogen atom is substituted by a fluorine atom. It is at least one selected from an alkyl group (hereinafter sometimes referred to as a “fluorine-substituted alkyl group”).

  Regarding (1) and (2), the chain or cyclic alkyl group is preferably a chain alkyl group. The chain alkyl group may be a branched alkyl group, but is preferably a linear alkyl group. An alkyl group having more than 30 carbon atoms may make the antifogging film cloudy. In light of balance between the anti-fogging property, strength, and appearance of the film, the alkyl group preferably has 20 or less carbon atoms, and more preferably 6 to 14 carbon atoms. Particularly preferred alkyl groups are straight-chain alkyl groups having 6 to 14 carbon atoms, particularly 6 to 12 carbon atoms, such as n-hexyl group (6 carbon atoms), n-decyl group (10 carbon atoms), and n-dodecyl group ( Carbon number 12). Regarding (2), the fluorine-substituted alkyl group may be a group in which only a part of the hydrogen atoms of a chain or cyclic alkyl group is substituted with a fluorine atom, and all of the hydrogen atoms of the chain or cyclic alkyl group may be substituted. May be substituted by a fluorine atom, for example, a linear perfluoroalkyl group. Since a fluorine-substituted alkyl group has high water repellency, a sufficient effect can be obtained by adding a small amount. However, if the content of the fluorine-substituted alkyl group is too large, it may be separated from other components in a coating solution for forming a film.

(Hydrolysable metal compound having a water-repellent group)
In order to incorporate a water-repellent group into the anti-fog film, a metal compound having a water-repellent group (a metal compound containing a water-repellent group), particularly a metal compound having a water-repellent group and a hydrolyzable functional group or a halogen atom ( The water-repellent group-containing hydrolyzable metal compound) or a hydrolyzate thereof may be added to a coating solution for forming a film. In other words, the water-repellent group may be derived from a water-repellent group-containing hydrolyzable metal compound. As the water-repellent group-containing hydrolyzable metal compound, a water-repellent group-containing hydrolyzable silicon compound represented by the following formula (I) is preferable.
RmSiY4-m (I)

  Here, R is a water-repellent group, that is, a chain or cyclic alkyl group having 1 to 30 carbon atoms in which at least a part of hydrogen atoms may be substituted by a fluorine atom, and Y is a hydrolyzable functional group. 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, and is 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. Note that the functional groups exemplified here can also be used as “hydrolyzable functional groups” described below. m is preferably 1 to 2.

The compound represented by the formula (I) supplies a component represented by the following formula (II) when hydrolysis and polycondensation have completely progressed.
RmSiO (4-m) / 2 (II)

  Here, R and m are as described above. After hydrolysis and polycondensation, the compound represented by the formula (II) actually forms a network structure in which silicon atoms are bonded to each other via oxygen atoms in the antifogging film.

  As described above, the compound represented by the formula (I) is hydrolyzed or partially hydrolyzed, and further at least partially polycondensed, so that silicon atoms and oxygen atoms are connected alternately and three-dimensionally. A network structure of expanding siloxane bonds (Si-O-Si) is formed. Water-repellent groups R are connected to silicon atoms included in this network structure. In other words, the water-repellent group R is fixed to the siloxane bond network structure via the bond R-Si. This structure is advantageous in uniformly dispersing the water-repellent groups R in the film. The network structure may include a silica component supplied from a silicon compound (eg, tetraalkoxysilane, silane coupling agent) other than the water-repellent group-containing hydrolyzable silicon compound represented by the formula (I). To form a silicon compound having a water-repellent group and having a hydrolyzable functional group or a halogen atom (a water-repellent group-free hydrolyzable silicon compound) together with a water-repellent group-containing hydrolyzable silicon compound to form an antifogging film. When it is blended with the coating liquid, a siloxane-bonded network structure containing silicon atoms bonded to the water-repellent group and silicon atoms not bonded to the water-repellent group can be formed. With such a structure, the content of the water-repellent group and the content of the metal oxide component in the anti-fog film can be easily adjusted independently of each other.

  The water-repellent group has an effect of improving the anti-fogging performance by improving the permeability of water vapor on the surface of the anti-fogging film containing the water absorbing resin. Since the two functions of water absorption and water repellency are opposite to each other, the water-absorbing material and the water-repellent material have conventionally been distributed to different layers, but the water-repellent groups are located near the surface of the antifogging layer. Eliminates the uneven distribution of water to prolong the time until dew condensation, and improves the antifogging property of the antifogging film having a single-layer structure. Hereinafter, the effect will be described.

  The water vapor that has entered the anti-fogging film containing the water-absorbing resin forms a hydrogen bond with a hydroxyl group of the water-absorbing resin or the like, and is held in the form of bound water. As the amount increases, water vapor becomes retained in the form of bound water, through the form of semi-bound water, and eventually in the form of free water retained in voids in the anti-fog membrane. In the anti-fog film, the water-repellent groups prevent the formation of hydrogen bonds and facilitate the dissociation of the formed hydrogen bonds. If the content of the water-absorbing resin is the same, there is no difference in the number of hydroxyl groups capable of hydrogen bonding in the film, but the water-repellent group reduces the rate of hydrogen bond formation. Therefore, in the anti-fogging film containing a water-repellent group, moisture is eventually retained in the film in any one of the above-mentioned forms, but before being retained, water vapor remains at the bottom of the film until it is retained. Can spread. Further, the water once held is also relatively easily dissociated, and easily moves to the bottom of the film in a state of water vapor. As a result, the distribution of the retained amount of moisture in the thickness direction of the film becomes relatively uniform from the vicinity of the surface to the bottom of the film. That is, since water supplied to the film surface can be absorbed by effectively utilizing the entire thickness direction of the anti-fogging film, water droplets hardly condense on the surface, and the anti-fogging property is enhanced. Furthermore, since the water droplets hardly condense on the surface, the antifogging film that has absorbed moisture has a feature that it is difficult to freeze even at a low temperature. Therefore, when this anti-fog film is fixed to the information acquisition area, the field of view of the information acquisition area can be secured in a wide temperature range.

  On the other hand, in a conventional anti-fogging film containing no water-repellent group, the water vapor that has entered the film is very easily retained in the form of bound water, semi-bound water or free water. Therefore, the invading water vapor tends to be retained near the surface of the film. As a result, the moisture in the film is extremely high near the surface and decreases rapidly as it goes to the bottom of the film. In other words, although water can still be absorbed at the bottom of the film, it is saturated with moisture near the surface of the film and condenses as water droplets, so that the antifogging property is limited.

  When a water-repellent group is introduced into the antifogging film using a water-repellent group-containing hydrolyzable silicon compound (see formula (I)), a strong siloxane bond (Si—O—Si) network structure is formed. The formation of this network structure is advantageous from the viewpoint of improving not only wear resistance but also hardness, water resistance and the like.

  The water-repellent group may be added to such an extent that the contact angle of water on the surface of the anti-fogging film becomes 70 degrees or more, preferably 80 degrees or more, more preferably 90 degrees or more. As the contact angle of water, a value measured by dropping a water droplet of 4 mg on the surface of the film is adopted. In particular, when a methyl group or an ethyl group having slightly weak water repellency is used as the water repellent group, it is preferable to mix the water repellent group in such an amount that the contact angle of water is within the above range in the antifogging film. Although the upper limit of the contact angle of the water droplet is not particularly limited, it is, for example, 150 degrees or less, for example, 120 degrees or less, and further 100 degrees or less. It is preferable that the water-repellent group is uniformly contained in the anti-fogging film so that the contact angle of the water droplet is in the above range in all regions on the surface of the anti-fogging film.

  The antifogging film is contained in an amount of 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the water-absorbing resin. It is preferable to include a water-repellent group so as to be in a range of not more than 5 parts by mass, preferably not more than 5 parts by mass.

(Inorganic oxide)
The inorganic oxide is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce, and Sn, and includes at least an oxide of silica (silica). The organic-inorganic composite anti-fog layer is preferably at least 0.01 part by weight, more preferably at least 0.1 part by weight, still more preferably at least 0.2 part by weight, particularly preferably at least 100 parts by weight, based on 100 parts by weight of the water absorbent resin. Is at least 1 part by weight, most preferably at least 5 parts by weight, in some cases at least 10 parts by weight, if necessary at least 20 parts by weight, preferably at most 50 parts by weight, more preferably at most 45 parts by weight, even more preferably It is preferable that the inorganic oxide is contained so as to be 40 parts by weight or less, particularly preferably 35 parts by weight or less, most preferably 33 parts by weight or less, and in some cases 30 parts by weight or less. Inorganic oxide is a component necessary to ensure the strength of the organic-inorganic composite anti-fog layer, especially the abrasion resistance, but when its content increases, the anti-fogging property of the organic-inorganic composite anti-fog layer decreases. .

(Inorganic oxide fine particles)
The organic-inorganic composite anti-fog layer may further include inorganic oxide fine particles as at least a part of the inorganic oxide. The inorganic oxide constituting the inorganic oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and preferably silica fine particles. is there. Silica fine particles can be introduced into the organic-inorganic composite antifogging layer by adding, for example, colloidal silica. The inorganic oxide fine particles have an excellent effect of transmitting the stress applied to the organic-inorganic composite anti-fog layer to an article supporting the organic-inorganic composite anti-fog layer, and have high hardness. Therefore, the addition of the inorganic oxide fine particles is advantageous from the viewpoint of improving the wear resistance of the organic-inorganic composite antifog layer. Further, when inorganic oxide fine particles are added to the organic-inorganic composite anti-fog layer, fine voids are formed in the portions where the fine particles are in contact with or in close proximity, and water vapor is easily taken into the film from these voids. For this reason, the addition of the inorganic oxide fine particles may advantageously act to improve the anti-fogging property. The inorganic oxide fine particles can be supplied to the organic-inorganic composite anti-fog layer by adding inorganic oxide fine particles formed in advance to a coating liquid for forming the organic-inorganic composite anti-fog layer.

  If the average particle size of the inorganic oxide fine particles is too large, the organic-inorganic composite antifogging layer may become cloudy. If the average particle size is too small, it becomes difficult to aggregate and uniformly disperse. In this respect, the average particle diameter of the inorganic oxide fine particles is preferably 1 to 20 nm, more preferably 5 to 20 nm. Here, the average particle diameter of the inorganic oxide fine particles is described in the state of primary particles. The average particle size of the inorganic oxide fine particles is determined by measuring the particle sizes of 50 fine particles arbitrarily selected by observation using a scanning electron microscope, and employing the average value. When the content of the inorganic oxide fine particles increases, the water absorption of the entire organic-inorganic composite anti-fog layer decreases, and the organic-inorganic composite anti-fog layer may become cloudy. The inorganic oxide fine particles are preferably 0 to 50 parts by weight, more preferably 2 to 30 parts by weight, still more preferably 5 to 25 parts by weight, particularly preferably 10 to 20 parts by weight with respect to 100 parts by weight of the water-absorbent resin. Parts.

(Hydrolysable metal compound without water-repellent group)
The anti-fog film may include a metal oxide component derived from a hydrolyzable metal compound having no water-repellent group (hydrolyzable compound not containing a water-repellent group). Preferred hydrolyzable metal compounds not containing a water-repellent group are hydrolyzable silicon compounds 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 (but not having a water-repellent group), Silicon alkoxides having no water-repellent groups are preferred. In addition, as alkenyloxysilane, isopropenoxysilane can be exemplified.

The hydrolyzable silicon compound having no water-repellent group may be a compound represented by the following formula (III).
SiY4 (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 hydrolyzable metal compound containing no water-repellent group is hydrolyzed or partially hydrolyzed, and at least a part thereof is polycondensed to supply a metal oxide component in which a metal atom and an oxygen atom are bonded. This component firmly joins the metal oxide fine particles and the water-absorbing resin, and can contribute to the improvement of the abrasion resistance, hardness, water resistance and the like of the antifogging film. The metal oxide component derived from the hydrolyzable metal compound having no water-repellent group is 0 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the water-absorbent resin. 20 parts by mass, particularly preferably 3 to 10 parts by mass, and in some cases, 4 to 12 parts by mass.

  A preferred example of the hydrolyzable silicon compound having no water-repellent group is tetraalkoxysilane, more specifically, a 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.

  If the content of the metal oxide (silica) component derived from tetraalkoxysilane is too large, the antifogging property of the antifogging film may be reduced. One reason is that the flexibility of the anti-fogging film is reduced, and the swelling and shrinking of the film due to the absorption and release of water are limited. The metal oxide component derived from tetraalkoxysilane may be added in an amount of 0 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass based on 100 parts by mass of the water-absorbing resin.

  Another preferred example of the hydrolyzable silicon compound having no water-repellent group is a silane coupling agent. The silane coupling agent is a silicon compound having different reactive functional groups. It is preferable that a part of the reactive functional group is a hydrolyzable functional group. The silane coupling agent is, for example, a silicon compound having an epoxy group and / or an amino group and a hydrolyzable functional group. Preferred silane coupling agents include glycidyloxyalkyl trialkoxysilane and aminoalkyl trialkoxysilane. In these silane coupling agents, the alkylene group directly bonded to the silicon atom preferably has 1 to 3 carbon atoms. Since the glycidyloxyalkyl group and the aminoalkyl group contain a functional group (epoxy group, amino group) showing hydrophilicity, they contain an alkylene group but are not water-repellent as a whole.

  The silane coupling agent firmly bonds the water-absorbing resin as an organic component and the metal oxide fine particles and the like as an inorganic component, and can contribute to improvement of abrasion resistance, hardness, water resistance and the like of the anti-fog film. However, when the content of the metal oxide (silica) component derived from the silane coupling agent is excessive, the anti-fogging property of the anti-fogging film decreases, and in some cases, the anti-fogging film becomes cloudy. The metal oxide component derived from the silane coupling agent is in the range of 0 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the water-absorbing resin. It is good to add in.

(Crosslinked structure)
The antifogging film may include a crosslinked structure derived from a crosslinking agent, preferably at least one crosslinking agent selected from an organic boron compound, an organic titanium compound, and an organic zirconium compound. The introduction of the crosslinked structure improves the abrasion resistance, scratch resistance, and water resistance of the antifogging film. Stated another way, the introduction of a crosslinked structure facilitates improving the durability of the antifogging film without deteriorating its antifogging performance.

  When a cross-linking structure derived from a cross-linking agent is introduced into the anti-fog film in which the metal oxide component is a silica component, the anti-fog film is a metal atom other than silicon together with silicon as a metal atom, preferably boron, titanium or zirconium, May be contained.

  The type of the crosslinking agent is not particularly limited as long as it can crosslink the water-absorbing resin used. Here, an example is given only of the organic titanium compound. The organic titanium compound is, for example, at least one selected from a titanium alkoxide, a titanium chelate compound and a titanium acylate. The titanium alkoxide is, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraoctoxide. Examples of the titanium chelate compound include titanium acetylacetonate, titanium ethyl acetoacetate, titanium octylene glycol, titanium triethanolamine, and titanium lactate. The titanium lactate may be an ammonium salt (titanium lactate ammonium). The titanium acylate is, for example, titanium stearate. Preferred organic titanium compounds are titanium chelate compounds, especially titanium lactate.

  When the water absorbent resin is polyvinyl acetal, a preferable crosslinking agent is an organic titanium compound, particularly titanium lactate.

(Other optional components)
Other additives may be blended in the anti-fogging film. Examples of the additives include glycols such as glycerin and ethylene glycol having a function of improving the anti-fogging property. Additives may be surfactants, leveling agents, UV absorbers, colorants, defoamers, preservatives, and the like.

  When the ultraviolet absorber or the infrared absorber is an organic substance, it is particularly preferable that the silicon alkoxide contains a silane coupling agent. This is because the light shielding property (for example, ultraviolet shielding property) by the ultraviolet absorber or the infrared absorber is improved. The reason that the silane coupling agent improves the light shielding property of the organic-inorganic composite anti-fog layer is that the addition of the silane coupling agent causes the light absorber, which is an organic compound, to be more uniformly dispersed in the water-absorbing resin containing silica. It is thought to be in.

  As the ultraviolet absorber, for example, a benzotriazole compound [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) Benzotriazole and the like], benzophenone compounds [2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5, 5′-methylenebis (2-hydroxy-4-methoxybenzophenone)], a hydroxyphenyltriazine compound [2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-t-) Butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxy) ) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-t-butylphenyl) -s- Organic compounds such as triazine and the like and cyanoacrylate compounds [ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate and the like]. The ultraviolet absorbers may be used alone or in combination of two or more. The ultraviolet absorber may be at least one organic dye selected from a polymethine compound, an imidazoline compound, a coumarin compound, a naphthalimide compound, a perylene compound, an azo compound, an isoindolinone compound, a quinophthalone compound, and a quinoline compound. . Among the ultraviolet absorbers, preferred are organic ultraviolet absorbers, and more preferred are at least one selected from benzotriazole compounds, benzophenone compounds, hydroxyphenyltriazine compounds and cyanoacrylate compounds, and further preferred. Is a benzophenone compound. The benzophenone compound is preferable because it has good solubility in an alcohol-based solvent contained in a coating liquid for forming an organic-inorganic composite antifog layer and is uniformly dispersed in a polyvinyl acetal resin. The ultraviolet absorber preferably has a hydroxyl group, and more preferably has two or more hydroxyl groups bonded to one benzene skeleton of the ultraviolet absorber. The ultraviolet absorber is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 1.0 to 40 parts by weight, and still more preferably 2 to 35 parts by weight, based on 100 parts by weight of the water absorbent resin.

  As the infrared absorber, for example, polymethine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, naphthoquinone compounds, anthraquinone compounds, dithiol compounds, immonium compounds, diimonium compounds, aminium compounds, pyrylium compounds, cerium compounds, squarylium compounds, benzene Organic infrared absorbers such as counter ion conjugates of dithiol metal complex anions and cyanine dye cations; tungsten oxide, tin oxide, indium oxide, magnesium oxide, titanium oxide, chromium oxide, zirconium oxide, nickel oxide, aluminum oxide, oxide Inorganic infrared absorbers such as zinc, iron oxide, ammonium oxide, lead oxide, bismuth oxide, lanthanum oxide, tungsten oxide, indium tin oxide and antimony tin oxide Etc. The. The infrared absorbers may be used alone or in combination of two or more. Preferred among the infrared absorbers are inorganic infrared absorbers, and more preferred are indium tin oxide and / or antimony tin oxide. Indium tin oxide and / or antimony tin oxide are preferable because they have good stability in a coating solution for forming an organic-inorganic composite antifog layer and are uniformly dispersed in a polyvinyl acetal resin. The infrared absorber is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 1.0 to 40 parts by weight, and still more preferably 2 to 35 parts by weight, based on 100 parts by weight of the water-absorbing resin.

(Hydrophilic type)
The above-described anti-fog layer is a water-absorbing type containing a water-absorbing resin as a main component, but a hydrophilic type can also be adopted. The hydrophilic type is mainly composed of a hydrophilic resin, and a known type, for example, an antifogging layer described in JP-A-2011-213555 can be used. Specifically, it is as follows.

  Preferably, a plurality of closed holes are formed inside the anti-fog layer. Further, the antifogging layer is mainly composed of silicon oxide, and has a double-chain anionic interface having two carbon chains each having 6 or more carbon atoms at a position branched from the hydrophilic group. The silicon oxide preferably contains an activator and a polyol compound, and the silicon oxide preferably contains silicon oxide fine particles and a silicon oxide component generated by a hydrolysis reaction and a polycondensation reaction of a silicon alkoxide. The “closed hole” is a hole that is not opened on the film surface. The “main component” means the component with the largest content, as usual, and specifically refers to the component that accounts for 50% by mass or more. The “polyol compound” is a polyhydric alcohol such as a diol and a triol.

  Further, such a hydrophilic type anti-fog layer is formed by applying a solution for forming an anti-fog layer containing silicon alkoxide and silicon oxide fine particles to form a coating film, and drying the coated film to form an anti-fog layer. By doing so, it can be obtained. The solution for forming the anti-fog layer is at least 1) a double-chain anionic surfactant, 2) a polyol compound, 3) fine particles of silicon oxide (fine silica particles), and 4) at least a part thereof is a silicon tetraalkoxide. It can be prepared by mixing silicon alkoxide, 5) water, 6) organic solvent, and 7) hydrolysis catalyst. However, the hydrophilic type antifogging layer is not limited to this.

[Thickness]
The thickness of the organic-inorganic composite anti-fog layer may be appropriately adjusted according to the required anti-fog characteristics and the like. The thickness of the organic-inorganic composite anti-fog layer is preferably 1 to 20 μm, more preferably 2 to 15 μm, and still more preferably 3 to 10 μm.

  The above-described anti-fog layer is an example, and an ultraviolet absorber or an infrared absorber is not essential. In addition, other known antifogging layers can be used. For example, various antifogging layers such as those described in JP-A-2014-14802 and JP-A-2001-146585 can be used.

<4-2. Base Film>
The base film 72 is formed of a transparent resin film, and can be formed of, for example, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, or an acrylic resin.

  Further, since the base film 72 is a film that supports the anti-fog layer 73, a certain degree of rigidity is required. However, if the thickness is too large, the haze ratio tends to increase. Therefore, the thickness of the base film 72 is preferably, for example, 30 to 200 μm.

<4-3. Adhesive layer>
The adhesive layer 71 may be any as long as it can fix the base film 72 to the inner glass plate 12 with sufficient strength, as described later. Specifically, it is possible to use an adhesive layer of a resin or the like which is obtained by copolymerizing acrylic, rubber, and methacrylic and acrylic monomers having tackiness at room temperature and setting a desired glass transition temperature. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, stearyl acrylate, and 2-ethylhexyl acrylate. Examples of the methacrylic monomer include ethyl methacrylate, butyl methacrylate, and methacrylic acid. Isobutyl and stearyl methacrylate can be applied. In the case of applying heat lamination or the like, an organic material that softens at the lamination temperature may be used. For example, in the case of a resin obtained by copolymerizing a methacrylic and acrylic monomer, the glass transition temperature can be adjusted by changing the mixing ratio of each monomer.

<4-4. Protective sheet>
The first protective sheet 74 protects the adhesive layer 71 until it is fixed to the information acquisition area of the laminated glass, and is formed of, for example, a resin sheet coated with a release agent such as silicone. ing. Similarly, the second protective sheet 75 is for protecting the anti-fog layer 73 until it is fixed to the information acquisition area of the laminated glass, and is formed of a resin sheet coated with a release agent. Have been. In each case, a known general release sheet can be adopted.

<4-5. Manufacturing method of anti-fog sheet>
Next, a method for manufacturing the anti-fog sheet 7 will be described. First, the antifogging layer 73 is formed on one surface of the base film 72. The above-mentioned organic-inorganic composite anti-fog layer is formed by applying a coating liquid for forming the organic-inorganic composite anti-fog layer on an article such as a transparent substrate and drying the applied coating liquid. Can be. Known materials and methods may be used for the solvent used for preparing the coating liquid and the method of applying the coating liquid.

  At this time, it is preferable to maintain the relative humidity of the atmosphere at less than 40%, and more preferably at 30% or less. When the relative humidity is kept low, it is possible to prevent the organic-inorganic composite antifog layer from excessively absorbing moisture from the atmosphere. When a large amount of water is absorbed from the atmosphere, water remaining in the matrix of the organic-inorganic composite anti-fog layer may reduce the strength of the film.

  The drying step of the coating liquid preferably includes an air drying step and a heating drying step involving heating. The air drying step may be performed by exposing the coating liquid to an atmosphere in which the relative humidity is kept at less than 40%, and more preferably at 30% or less. The air drying step can be performed as a non-heating step, in other words, at room temperature. When the coating liquid contains a hydrolyzable silicon compound, in the heating and drying step, a dehydration reaction involving a silanol group contained in the hydrolyzate of the silicon compound and a hydroxyl group present on the article proceeds, and silicon A matrix structure (a network of Si—O bonds) composed of atoms and oxygen atoms develops. The air drying step can be performed, for example, for about 10 minutes.

  In order to avoid decomposition of organic substances such as a water-absorbing resin, the temperature applied in the heating and drying step is preferably not excessively high. A suitable heating temperature in this case is 300 ° C. or less, for example, 100 to 200 ° C. Specifically, three steps can be performed. For example, baking at a temperature of about 120 ° C. for about 5 minutes, drying at a temperature of about 80 ° C. and a humidity of 90% for about 2 hours, and then baking at a temperature of about 120 ° C. for about 30 minutes. Thus, the formation of the anti-fog layer 73 is completed. Then, in order to protect the anti-fog layer 73, a second protective sheet 75 is attached on the anti-fog layer 73.

  Next, after applying the adhesive layer 71 to the other surface of the base film 72, the first protective sheet 74 is attached. Thus, an antifogging laminate is completed. The antifogging laminate is cut into a required size as described above, and is then attached to the imaging window 113 as described later.

<5. Manufacturing method of windshield>
Next, an example of a method for manufacturing a windshield will be described. First, a glass sheet production line will be described.

  As shown in FIG. 8, in this production line, a heating furnace 901 and a molding device 902 are arranged in this order from upstream to downstream. A roller conveyor 903 is arranged from the heating furnace 901 to the forming apparatus 902 and a downstream side thereof, and the outer glass plate 11 and the inner glass plate 12 to be processed are conveyed by the roller conveyor 903. . These glass plates 11 and 12 are formed in a flat plate shape before being carried into the heating furnace 901. For example, the above-described mask layer 110 is formed on the inner surface (the inner surface of the vehicle) of the inner glass plate 12. After being stacked, it is carried into the heating furnace 901. Note that, as described above, the mask layer 110 can be laminated on a portion other than the inner surface of the inner glass plate 12.

  Although various configurations are possible for the heating furnace 901, for example, an electric heating furnace can be used. The heating furnace 901 includes a square tubular furnace body whose upstream and downstream ends are open, and a roller conveyor 903 is disposed inside the heating furnace 901 from upstream to downstream. Heaters (not shown) are respectively disposed on the upper surface, the lower surface, and a pair of side surfaces of the inner wall surface of the furnace main body, and a temperature at which the glass plates 11 and 12 passing through the heating furnace 901 can be formed, for example, a glass temperature. Heat to near the softening point.

  The forming device 902 is configured to press the glass plates 11 and 12 with the upper die 921 and the lower die 922 to form them into a predetermined shape. The upper mold 921 has a curved shape that is convex downward so as to cover the entire upper surfaces of the glass plates 11 and 12, and is configured to be vertically movable. The lower mold 922 is formed in a frame shape corresponding to the periphery of the glass plates 11 and 12, and the upper surface thereof has a curved surface shape corresponding to the upper mold 921. With this configuration, the glass plates 11 and 12 are press-formed between the upper die 921 and the lower die 922 to be formed into a final curved surface shape. A roller conveyor 903 is arranged in the frame of the lower mold 922, and the roller conveyor 903 is vertically movable so as to pass through the frame of the lower mold 922. Although not shown, a cooling device (not shown) is disposed downstream of the forming device 902 to cool the formed glass sheet.

  The roller conveyor 903 as described above is a known one, and a plurality of rollers 931 rotatably supported at both ends are arranged at predetermined intervals. There are various methods for driving each roller 931. For example, a sprocket may be attached to an end of each roller 931 and a chain may be wound around each sprocket for driving. Then, by adjusting the rotation speed of each roller 931, the conveyance speed of the glass plates 11 and 12 can also be adjusted. Note that the lower mold 922 of the forming device 902 may be configured to be in contact with the entire surface of the glass plates 11 and 12. In addition, the form of the upper mold and the lower mold is not particularly limited as long as the forming apparatus 902 is for forming a glass plate.

  When the outer glass plate 11 and the inner glass plate 12 are formed in this way, subsequently, the intermediate film 13 is sandwiched between the outer glass plate 11 and the inner glass plate 12, and this is put in a rubber bag, and suctioned under reduced pressure. Pre-adhesion at about 70-110 ° C. Other methods of pre-adhesion are also possible. For example, the intermediate film 13 is sandwiched between the outer glass plate 11 and the inner glass plate 12 and heated at 45 to 65 ° C. in an oven. Subsequently, the laminated glass is pressed by a roll at 0.45 to 0.55 MPa. Next, the laminated glass is again heated at 80 to 105 ° C. by an oven, and then pressed again by a roll at 0.45 to 0.55 MPa. Thus, the preliminary bonding is completed.

  Next, the actual bonding is performed. The pre-bonded laminated glass is fully bonded by an autoclave, for example, at 8 to 15 atm and at 100 to 150 ° C. Specifically, for example, the actual bonding can be performed at 145 ° C. at 14 atm. Thus, the laminated glass according to the present embodiment is manufactured.

  Finally, the above-described anti-fog sheet 7 is attached to the imaging window 113 formed in the mask layer 110. The size of the anti-fog sheet 7 is slightly smaller than the size of the imaging window 113, and is attached inside the information acquisition area. Specifically, it is attached to the inner surface of the inner glass plate 12. First, an antifogging laminate is prepared, and the first protective sheet 74 attached to the adhesive layer 71 is removed. Then, the exposed adhesive layer 71 is attached to the imaging window 113. Then, the second protective sheet 75 is pressed to firmly fix the anti-fog sheet 7 to the photographing window 113. Finally, when the second protective sheet 75 is removed and the anti-fog layer 73 is exposed, the mounting of the anti-fog sheet 7 is completed. The timing of attaching the anti-fog sheet 7 is not particularly limited, and may be after attaching the bracket. Alternatively, the second protective sheet 75 may be removed after attaching the anti-fog sheet 7 to the photographing window 113 and attaching the bracket.

<6. Features>
According to the windshield described above, the following effects can be obtained.
(1) First, fogging of the imaging window 113 can be prevented by attaching the anti-fog sheet 7 to the imaging window 113 of the mask layer 110. Therefore, when light is received through the imaging window 113 by the imaging device 2, it is possible to prevent problems such as hindering the passage of light due to clouding of the imaging window 113 and inaccurate measurement.

  In particular, the upper part of the interior of the vehicle where the photographing window 113 of the mask layer 110 is provided is easily cooled even when the heating is ON, and fogging is likely to occur. Therefore, it is advantageous that the anti-fog layer is laminated at such a position. In addition, since the imaging window 113 of the mask layer 110 on which the anti-fog layer is laminated is covered with a bracket or a cover, there is a problem that it is difficult for heating or warm air from the defroster to reach. Also, since it is not easy to exchange air between the space covered by the bracket and the cover and the outside, when the humidity of the air in the space reaches a saturated state, it easily adheres to the surface of the glass plate as water droplets. There is. Therefore, providing the anti-fog sheet in the space covered as described above has great significance.

(2) Further, since the mask layer 110 has a dark color, it easily absorbs heat, whereby the temperature of the periphery of the anti-fog sheet 7 tends to be high. In particular, since the mask layer 110 is covered with the cover, the humidity around the imaging window 113 increases, and the imaging window 113 is easily clouded. Therefore, providing the anti-fog sheet 7 in the photographing window 113 is particularly advantageous.

(3) The following effects are also obtained. There is a possibility that the plasticizer that has separated from the interior components (for example, a resin molded product) in the vehicle and has flowed into the air may adhere to the anti-fog layer 73. And if a plasticizer adheres to the anti-fogging layer, the anti-fogging function may be reduced. However, as described above, since it is surrounded by the bracket and the cover, it is possible to prevent the plasticizer from adhering to the anti-fog layer. As a result, in the antifogging function, particularly in the water absorbing type antifogging layer, it is possible to prevent the water absorbing function from being deteriorated. Further, in the case of the hydrophilic type, since the plasticizer easily bonds to the hydrophilic group in the anti-fog layer, it is preferable to surround the plasticizer with the bracket or the cover as described above.

  In addition, if the plasticizer adheres to the surface of the water-absorbing type anti-fog layer 73 and accumulates for a long period of time, water absorption will be impaired, and the anti-fog performance will decrease. However, if the plasticizer is wiped off with water wiping or the like, the water absorption performance is restored. On the other hand, if the plasticizer adheres to the surface of the hydrophilic type anti-fog layer, it is strongly bonded to the hydrophilic group, and the hydrophilic performance is reduced. Therefore, there is a possibility that distortion of an image through the anti-fog layer and deterioration of anti-fog performance may occur in a short period of time due to a difference in thickness of the formed water film.

(4) In addition, a method of removing fogging by heating the vicinity of the imaging window 113 of the mask layer 110 with a heating wire can be considered. However, there is a problem that it takes time from the time when current is applied to the heating wire to the time when the fogging is removed. Yes, electricity consumption is also a problem. In addition, in order to eliminate the fogging due to the heating wire, there are some differences depending on the thickness of the glass plate and the condition of the outside air, which is not uniform. Therefore, the anti-fog layer 73 that prevents fogging in advance and consumes no power is very advantageous.

(5) Further, the anti-fogging layer 73 generally has poor durability and has a problem that it is easily damaged by external force. However, as described above, by surrounding the anti-fog layer with the bracket or the cover, it is possible to prevent the occurrence of scratches.

(6) The following effects are also obtained. Although the anti-fog sheet 7 supports the anti-fog layer 73 by the base film 72, the base film 72 may be clouded by ultraviolet rays incident from the imaging window 113. When such cloudiness occurs, there is a possibility that the photographing by the photographing device 2 cannot be performed. Therefore, in the present embodiment, as described above, the laminated glass satisfies Tuv380 ≦ 0.5% and Tuv400 <3.5%, and absorbs ultraviolet rays. Can be prevented from becoming cloudy.

(7) Further, the present inventor has found that, in addition to the base film 72, the anti-fogging layer 73 may cause cloudiness under certain conditions. And it discovered that this cloudiness arises by the following mechanisms. That is, since the anti-fog layer 73 is formed of various resin materials as described above, the polymer constituting the resin (for example, the absorbent resin) may be cut when irradiated with ultraviolet rays. The anti-fogging layer 73 shrinks when exposed to a high temperature, and a part of the cut polymer is deposited on the surface of the anti-fogging layer 73. When water droplets are formed on the surface of the anti-fog layer 73 by, for example, condensation from this state, the polymer deposited on the surface dissolves in the water droplets. Thereafter, when the surface of the anti-fogging film 73 dries and the moisture evaporates, the polymer precipitates at the locations where the water droplets are formed, and a number of convex portions are generated on the surface of the anti-fogging layer 73. As a result, unevenness is formed on the surface of the anti-fog layer 73, so that light is scattered and white turbidity is visually recognized. As described above, when the windshield receives the ultraviolet rays and water droplets are generated on the surface of the anti-fog layer 73, the anti-fog layer 73 may become cloudy thereafter. When the temperature of the windshield increases, cloudiness tends to occur.

  Therefore, when the laminated glass satisfying the above-described formula (1) is used, the ultraviolet transmittance is reduced, so that the influence of the ultraviolet light on the anti-fog layer 73 can be reduced. That is, the projections formed by the polymer deposited on the surface of the anti-fog layer 73 are scarcely formed, or even if the projections are formed, the unevenness is small, so that the scattering of light can be prevented. 73 can be prevented from becoming cloudy. For example, when the amount of unevenness is 500 nm or less, white turbidity can be prevented. However, when the ultraviolet transmittance of the laminated glass 1 is further reduced, the unevenness of the surface of the anti-fog layer 73 becomes 300 nm or less, and further 100 nm or less. can do.

  The uneven surface of the antifogging layer 73 can be measured using a laser microscope. If the size of the unevenness is too small to be measured with a laser microscope, the measurement may be made from this photograph after taking a SEM photograph.

  The irregularities on the surface of the anti-fog layer 73 are generated, for example, under the following conditions. That is, the laminated glass to which the antifogging sheet is attached is irradiated with ultraviolet rays at 60 ° C. for 140 hours or 210 hours, and then stored in a constant temperature room at a temperature of 20 ° C. and a humidity of 30% for 1 hour. Subsequently, the laminated glass is stored in a constant temperature room at a temperature of 60 ° C. and a humidity of 95% for one hour to produce the laminated glass. The ultraviolet irradiation at this time can use, for example, Sunshine Weather Meter S80P (manufactured by Suga Test Instruments Co., Ltd.).

(8) In the above embodiment, since the size of the anti-fog sheet 7 is smaller than the size of the photographing window 113, the periphery of the anti-fog sheet 7 is located on the inner periphery of the photographing window 113, that is, on the mask layer 110. Is not placed. Therefore, it is possible to prevent a step from being formed on the periphery of the anti-fog sheet 7, thereby preventing air from entering between the anti-fog sheet 7 and the laminated glass 10 when the anti-fog sheet 7 is attached. be able to.

<7. Modification>
As mentioned above, although one Embodiment of this invention was described, this invention is not limited to the said Embodiment, A various change is possible unless it deviates from the meaning. The following modifications can be combined as appropriate.

<7-1>
In the above embodiment, the size of the anti-fog sheet 7 is smaller than the size of the information acquisition area, but it can be larger. Accordingly, for example, when a water-absorbing type anti-fog layer is used, the water-absorbing area increases, so that it is possible to further prevent the information acquisition region from fogging.

<7-2>
When using the photographing apparatus 2 having a camera as in the above embodiment, the optical axis of the camera often passes through the lower half area of the photographing window 113. Therefore, in the imaging window 113, it is only necessary to prevent fogging at least in the vicinity where the optical axis passes. Therefore, for example, the shape of the anti-fog sheet 7 can be determined so as to cover at least the lower half of the imaging window 113. Alternatively, the thickness of the lower half of the anti-fog layer 73 laminated on the anti-fog sheet 7 can be made larger than the thickness of the upper half. In this case, for example, the thickness of the anti-fog layer 73 may be gradually increased from the upper side to the lower side.

<7-3>
When the windshield laminated glass 10 as described above is mounted on the vehicle body, the mounting angle θ from the vertical N as shown in FIG. 9 is not particularly limited, but as the mounting angle θ is larger, for example, 45 degrees or more. If there is, the windshield is easy to cut off the wind during traveling, so that the information acquisition area is easily clouded. Therefore, it is particularly advantageous to attach an anti-fog sheet as described above.

<7-4>
Part or all of the mask layer 110 may be formed of a shielding film that can be attached to the laminated glass 10, thereby shielding the field of view from outside the vehicle. When the shielding film is attached to the outer surface of the inner glass plate 12, it can be attached before the preliminary bonding or after the final bonding.

  In addition, from the viewpoint of preventing the passage of light from fogging in the laminated glass 10, the mask layer 110 is not necessarily required, and if the anti-fog sheet is attached to a region where light passes (information acquisition region). Good.

<7-5>
The antifogging sheet in the windshield of the present invention can be replaced by removing the adhesive layer located between the glass plate and the base film and fixing the separately prepared antifogging laminate again. . However, when the bracket is adhered to the glass plate, it is not easy to replace the bracket due to bubbles or wrinkles. The anti-fog sheet 7 is attached to the photographing window 113. Since the photographing window 113 is a part of the laminated glass 10 and is formed in a curved shape, the space between the anti-fog sheet 7 and the photographing window 113 is formed. It is not easy to stick so that air does not enter.

  Therefore, for example, the anti-fog sheet 7 can be pressed using a roller device 68 as shown in FIG. As shown in the figure, the roller device 68 has a rotating shaft 65 curved in an arc shape and a plurality of rollers (three in FIG. 10) 66 inserted through the rotating shaft 65. Further, Y-shaped handle members 67 are attached to both ends of the rotating shaft 65. The rotating shaft 65 has a radius of curvature substantially along the vertical or horizontal curvature of the laminated glass 10. Each roller 66 inserted into the rotating shaft 65 is formed in a cylindrical shape, and has a through hole through which the rotating shaft 65 is inserted. The surface of the roller 66 is formed of an elastic material such as rubber so as not to damage the anti-fog sheet 7. Furthermore, the diameter and the shape of the outer peripheral surface of the three rollers 66 are adjusted so that a step is not generated between the adjacent rollers 66 and the outer peripheral surface of the three rollers 66 draws a smooth arc. I have.

  The roller device 68 as described above presses the roller 66 against the anti-fog sheet 7 from above the second protective sheet 75 after attaching the anti-fog sheet 7 to the photographing window 113, and horizontally or vertically. 68 is moved to push out air that has entered between the anti-fog sheet 7 and the photographing window 113. At this time, the moving direction of the roller device 68 depends on whether the radius of curvature of the rotating shaft 65 matches the vertical or horizontal radius of curvature of the imaging window 113. In this way, when the roller device 68 is moved several times to complete the extrusion of the air, the second protective sheet 75 is peeled off, and the attachment of the anti-fog sheet 7 is completed.

<7-6>
In the above embodiment, the photographing device 2 having a camera is used as the information acquiring device of the present invention. However, the present invention is not limited to this, and various information acquiring devices can be used. That is, there is no particular limitation as long as light irradiation and / or light reception is performed to acquire information from outside the vehicle. For example, the present invention can be applied to various devices such as a laser receiver, a light sensor, a rain sensor, an optical beacon, and a light receiving device that receives a signal from outside the vehicle. Further, an opening (information acquisition region) such as the imaging window 113 can be appropriately provided in the mask layer 110 according to the type of light, and a plurality of openings can be provided. For example, when a stereo camera is provided, as shown in FIG. 11, two imaging windows 113A and 113B are formed in the mask layer 110, and an anti-fog sheet is attached to each of the imaging windows 113A and 113B. Note that the information acquisition device may or may not be in contact with the glass.

  Further, in the above embodiment, the imaging window 113 formed in the mask layer 110 has been described as an example of the information acquisition region, but the form of the imaging window 113 is not particularly limited. For example, the imaging window 113 does not have to have a closed shape surrounded by the mask layer 110 and may have a shape in which a part of the periphery is open. In addition, the region need not be a region surrounded by the mask layer 113, and any region of the laminated glass 10 through which light from the information acquisition device passes corresponds to the information acquisition region of the present invention. In any case, an antifogging sheet is attached to a region (information acquisition region) of the glass plate through which light from the information acquisition device passes.

  Hereinafter, examples of the present invention will be described. However, the present invention is not limited to the following embodiments.

1. Test 1
(A) Preparation of Examples and Comparative Examples Windshields according to the following examples and comparative examples were prepared. The antifogging sheet is the same between the example and the comparative example, and the difference is the presence or absence of the laminated glass or the organic-inorganic composite film and the light-resistant sheet provided on the inner side surface of the laminated glass.

[Example 1]
(1) Composition of laminated glass:
The outer glass plate and the inner glass plate were made of green glass having a thickness of 2 mm, and a single-layer intermediate film was arranged between them to form a laminated glass.

(2) Mask layer:
A mask layer having the composition shown in Table 1 and having the shape shown in FIG. 1 was formed on the inner surface of the inner glass plate. The size of the shooting window was 100 mm long and 150 mm wide.
The Tuv 380 of this laminated glass was less than 0.1% (below the measurement limit), and the Tuv 400 was 3.5%.

  An organic-inorganic composite film further containing an ultraviolet absorber was applied to the surface of the inner glass plate of the laminated glass.

  This organic-inorganic composite film was applied as follows. In a mixed layer having a stirrer and a temperature control function, an ultraviolet absorbent: 2,2 ′, 4,4′-tetrahydroxybenzophenone “UVINUL 3050” (manufactured by BASF) 6.00 g, an organic polymer: polypropylene glycol “PPG700” 0.28 g of silicon compound A: tetraethoxysilane [manufactured by Tama Chemical Industry] 17.62 g, silicon compound B1: 3-glycidoxypropyltrimethoxysilane "KBM-403" [manufactured by Shin-Etsu Chemical Co., Ltd.] 13.31 g, nitric acid: concentration: 60% by mass, 0.025 g of [manufactured by Futaba Chemical], surfactant B: 0.04 g of silicone-based surfactant "BYK-345" [manufactured by BYK], infrared absorbent: Indium tin oxide fine particle dispersion [ethyl acetate containing 40% by mass of indium tin oxide fine particle dispersion] Call solution, Mitsubishi Materials Electronic Chemicals Ltd.] 2.50 g, was charged purified water 28.13G, ethanol 42.53G, to prepare a film forming solution for forming an organic-inorganic composite film by stirring at 20 ° C..

  Next, a film-forming solution was applied to the surface of the inner glass plate of the laminated glass by a flow coating method in an environment of 20 ° C. and 30% RH. After drying for 5 minutes in the same environment, the drying was performed such that the temperature of the glass plate to which the film-forming solution was applied was 180 ° C. to form an organic-inorganic composite film.

  Tuv380 of this laminated glass with an organic-inorganic composite film was less than 0.1% (below the measurement limit), and Tuv400 was 0.5%.

(3) Base film of anti-fog sheet:
A PET film (commercially available) having a thickness of 150 μm was prepared.

(4) Anti-fog layer of anti-fog sheet:
Polyvinyl acetal resin-containing solution (Sekisui Chemical Co., Ltd. "Eslek KX-5", solid content 8% by mass, acetalization degree 9 mol%, including acetal structure derived from benzaldehyde) 87.5% by mass, n-hexyltri Methoxysilane (HTMS, “KBM-3063” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.526% by mass, 3-glycidoxypropyltrimethoxysilane (GPTMS, “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.198 part by mass 2.774% by mass of tetraethoxysilane (TEOS, “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.), 5.927% by mass of alcohol solvent (“Solmix AP-7” manufactured by Nippon Alcohol Industry), 2.875 of purified water Mass%, hydrochloric acid 0.01 mass% as acid catalyst, leveling agent (Shin-Etsu Chemical Co., Ltd. "KP-341") 0.01 quality % Was placed in a glass container by stirring 3 hours at room temperature (25 ° C.), to prepare an antifogging layer forming coating solution.

  Next, a coating solution was applied on the base film by a flow coating method under an environment of room temperature of 20 ° C. and relative humidity of 30%. After drying under the same environment for 10 minutes, a (preliminary) heat treatment at 120 ° C. was performed. Thereafter, high-temperature and high-humidity treatment was performed by applying the above-described atmosphere and time, and additional heat treatment was also performed by similarly applying the above-described atmosphere and time.

(5) Adhesive layer of anti-fog sheet:
As the pressure-sensitive adhesive, a polymer prepared by copolymerizing methyl acrylate and n-butyl acrylate at a predetermined mixing ratio and adjusting the glass transition temperature Tg to −36 ° C. was used by dissolving it in toluene. This liquid was applied using a Meyer bar to form an adhesive layer.

(6) Windshield fabrication:
A material for a mask layer was screen-printed on the inner surface of the inner glass plate to form a mask layer. Next, the outer glass plate and the inner glass plate were fired at 650 ° C. in a heating furnace to form a curved surface using a forming die as shown in FIG. 8, and then gradually cooled after being carried out of the heating furnace. Subsequently, an intermediate film was disposed between the two glass plates, and the preliminary bonding and the main bonding were performed as in the above embodiment. Thereafter, the antifogging sheet having a slightly smaller size was attached to the photographing window on the inner surface of the inner glass plate.

[Example 2]
A laminated glass having a mask layer was prepared in the same manner as in Example 1, and a commercially available UV cut film for glass (3M, "Scotch Tint") as a light-resistant sheet was further provided on the outer surface of the inner glass plate of the laminated glass. Window film Purely rifle 87 ") was attached to the information acquisition area on the surface of the inner glass plate. Tuv380 of this laminated glass with a UV cut film was less than 0.1% (below the measurement limit), and Tuv400 was 0.5%.

[Comparative example]
The difference from Examples 1 and 2 is that the organic-inorganic composite film and the light-resistant sheet are not provided, and the other configurations of the glass plate and the anti-fog sheet are the same.

(B) Evaluation test The windshield according to the examples and the comparative examples was irradiated with a sunshine weather meter according to JIS-K-6783b for 1000 hours (corresponding to one year of outdoor exposure) to promote outdoor exposure. Was done.

  Next, the anti-fog sheet was removed from the windshield according to the example and the comparative example, and the haze rate of each anti-fog sheet was measured using an integrating sphere type light transmittance measuring device (“HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.). , C light source used, and light incident from the film surface side). As a result, the haze ratio of the antifogging sheet according to Example 1 was 0.6%. Similarly, the haze ratio of the anti-fog sheet according to Example 2 was 0.8%.

  On the other hand, the haze ratio of the antifogging sheet according to the comparative example was measured in the same manner, and it was 2%. Accordingly, it can be seen that the base films of the anti-fog sheets according to Examples 1 and 2 are prevented from becoming cloudy because the laminated glass having Tuv400 of 2.5% or less absorbs ultraviolet rays. Therefore, it was found that the photographing by the camera was not affected. As described above, the haze ratio at which clouding is prevented is preferably 1.5% or less, more preferably 1.0% or less, and further preferably 0.8% or less.

2. Test 2
(A) Evaluation on laminated glass Laminated glasses according to Examples 3 to 12 below were prepared. The green glass and heat ray absorbing glass shown in Table 2 below are those described in the above embodiment. The intermediate film 1 is an S-LECTM CLEAR Film manufactured by Sekisui Chemical Co., Ltd., and the intermediate film 2 is a Solar Control Film manufactured by Sekisui Chemical Co., Ltd.

Tuv380 and Tuv400 were measured for Examples 3 to 12 above. The results are as follows.

  As shown in Examples 1 and 2 above, the use of laminated glass having a low Tuv can reduce cloudiness, and therefore the same effects can be expected in Examples 3 to 12. Among them, Example 11 was tested for white turbidity as follows.

(B) Evaluation of cloudiness related to Example 11 Using the laminated glass according to Example 11, in the same manner as in Examples 1 and 2, a mask layer was laminated, an antifogging sheet was attached, and the windshield according to Example 11 was used. Was prepared. However, the organic-inorganic composite film and the light-resistant sheet as in Examples 1 and 2 were not provided. Further, a windshield according to the comparative example was also prepared.

  Next, the windshields according to Example 11 and Comparative Example were irradiated with ultraviolet rays at 60 ° C. for 140 hours or 210 hours. Thereafter, these were stored for 1 hour in a constant temperature room at a temperature of 20 ° C. and a humidity of 30%. Subsequently, these were stored in a constant temperature room at a temperature of 60 ° C. and a humidity of 95% for 1 hour. As a result, water droplets were formed on the surface of the antifogging layer due to condensation. Thereafter, the haze ratio of the antifogging sheets of Example 11 and Comparative Example was measured in the same manner as in Examples 1 and 2. The results are as shown in Table 4 below.

  Further, the surface properties of Example 11 and Comparative Example were confirmed. The results are as shown in FIG. FIG. 12 shows a diagram enlarged about 400 times. The anti-fog sheet of Example 11 did not have cloudiness, but the anti-fog sheet of Comparative Example had cloudiness. As shown in the above embodiment, the antifogging sheet is irradiated with ultraviolet light at a high temperature, and thereafter, when water droplets are generated on the antifogging layer due to dew condensation or the like, a convex portion in which a part of the polymer is precipitated on the surface of the antifogging layer. And this has been shown to cause cloudiness. Since the laminated glass according to the comparative example does not absorb ultraviolet rays sufficiently, as shown in FIG. 12, it is considered that a large number of convex portions are formed on the surface of the anti-fogging film, thereby causing cloudiness. Further, as shown in Table 4 above, the haze ratio was also high.

  On the other hand, in Example 11, as shown in FIG. 12, almost no projections were formed on the surface of the anti-fogging film, and it is considered that there was no white turbidity of the anti-fogging sheet. Also, the haze ratio was low. Further, the amount of irregularities on the surface of the anti-fogging layer of Example 11 was confirmed to be about 80 nm by SEM photograph. Therefore, even with such a small amount of unevenness, it is considered that the anti-fog layer did not have white turbidity.

Reference Signs List 1 laminated glass 11 outer glass plate 12 inner glass plate 13 interlayer film 110 mask layer 113 imaging window (information acquisition area)
2 Photographing device (information acquisition device)
7 Anti-fog sheet 71 Adhesive layer 72 Base film 73 Anti-fog layer

Claims (17)

A windshield in which an information acquisition device that acquires information from outside the vehicle by performing light irradiation and / or light reception can be arranged,
A laminated glass satisfying Tuv 380 ≦ 0.5% and Tuv 400 <3.5%;
An anti-fog sheet disposed on the inside surface of the laminated glass,
With
The laminated glass includes an inner glass plate, an outer glass plate, and an intermediate film disposed between the inner glass plate and the outer glass plate,
The laminated glass has at least one information acquisition region in which the light passes in opposition to the information acquisition device,
The anti-fog sheet, the adhesive layer, the base film, and the anti-fog layer are laminated in this order, and is fixed to at least a part of the information acquisition area of the laminated glass by the adhesive layer,
The windshield, wherein the anti-fog layer has a thickness of 1 to 20 μm and mainly contains a water-absorbing resin.   The windshield according to claim 1, wherein the laminated glass satisfies Tuv400 ≦ 2.5%.   The window according to claim 1, wherein the laminated glass further includes an ultraviolet shielding layer disposed on at least one of an inner surface of the outer glass plate and an inner surface of the inner glass plate. shield.   The windshield according to any one of claims 1 to 3, wherein the intermediate film of the laminated glass has an ultraviolet shielding function.   The windshield according to any one of claims 1 to 4, wherein at least one of the outer glass plate and the inner glass plate is made of an ultraviolet absorbing glass. On the laminated glass, a mask layer that blocks a view from outside the vehicle is laminated,
The windshield according to any one of claims 1 to 5, wherein the information acquisition region is configured by an opening formed in the mask layer.   The windshield according to claim 6, wherein the anti-fog sheet is formed smaller than the opening.   7. The windshield according to claim 6, wherein the anti-fog sheet is formed in a size exceeding a peripheral edge of the opening and covering a part of the mask layer. 8.   The windshield according to any one of claims 1 to 8, wherein the antifogging layer has a layer thickness in a lower half of the base film larger than a layer thickness in an upper half of the base film.   The windshield according to any one of claims 1 to 9, wherein the anti-fog sheet is disposed so as to cover at least a lower half of the information acquisition area.   The windshield according to any one of claims 1 to 10, wherein an attachment angle of the laminated glass to a vehicle body is 45 degrees or more. The windshield according to any one of claims 1 to 11, wherein the antifogging layer contains an alkyl group having 3 to 30 carbon atoms.   The windshield according to any one of claims 1 to 12, wherein the anti-fog layer contains inorganic oxide fine particles having an average particle size of 1 to 20 nm. The anti-fog layer contains the water-absorbing resin and inorganic oxide fine particles,
The windshield according to any one of claims 1 to 12, wherein 2 to 50 parts by weight of the inorganic oxide fine particles are contained with respect to 100 parts by weight of the water absorbent resin. The anti-fog layer contains the water-absorbing resin and metal oxide fine particles,
The windshield according to any one of claims 1 to 12, wherein the metal oxide fine particles are contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the water absorbent resin.
The windshield according to any one of claims 1 to 15, wherein the surface unevenness amount of the anti-fog layer is 500 nm or less. The windshield according to any one of claims 1 to 16, wherein the antifogging sheet has a haze ratio of 1.5% or less after irradiation with ultraviolet light for 1000 hours according to JIS-K-6783b.