JP6816145B2 - Windshield module manufacturing method - Google Patents

Description

In recent years, the safety performance of automobiles has been dramatically improved. One of them is to detect the distance to the vehicle in front and the speed of the vehicle in front in order to avoid a collision with the vehicle in front, and automatically when an abnormal approach occurs. A safety system in which the brakes operate has been proposed. In such a system, the distance to the vehicle in front is measured by using a laser radar or a camera. A laser radar or a camera is generally arranged inside a windshield, and measures by irradiating light such as infrared rays forward (for example, Patent Document 1).

As described above, the measuring device such as a laser radar or a camera is arranged on the inner surface side of the glass plate constituting the windshield, and irradiates or receives light through the glass plate. However, on cold days and cold regions, the glass plate may become cloudy. However, if the glass plate becomes cloudy, the measuring device may not be able to accurately irradiate or receive light. As a result, the inter-vehicle distance and the like may not be calculated accurately.

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

In order to solve this, for example, a method of using an anti-fog sheet as described in Patent Document 2 can be considered. That is, it is considered that fogging can be prevented by attaching this anti-fog sheet to the information acquisition region, which is the region through which light passes in the windshield.

Japanese Unexamined Patent Publication No. 2006-96331 Japanese Unexamined Patent Publication No. 2013-999879

By the way, the application of the anti-fog sheet is generally a process of attaching a bracket for a sensor or the like after the laminated glass is manufactured, but depending on the order in this process, when the anti-fog sheet is attached. , Air may get in between the laminated glass and the anti-fog sheet. If air enters in this way, the information acquisition device may not be able to correctly calculate the inter-vehicle distance. The present invention has been made to solve this problem, and an object of the present invention is to provide a method for manufacturing a windshield module capable of correctly attaching an antifogging sheet to an information acquisition area of a windshield. ..

The method for manufacturing a windshield module according to the present invention faces an information acquisition device that acquires information from outside the vehicle by irradiating and / or receiving light, and has at least one information acquisition region through which the light passes. A step of preparing a windshield in which a shielding layer defining the information acquisition area is formed on a laminated glass, a step of installing the windshield on a work table, a step of cleaning the information acquisition area, and the window. In the shield, a step of attaching an antifogging sheet to at least an area including the information acquisition area, and a step of attaching a mounting member for supporting the information acquisition device and facing the information acquisition area to the windshield. It has.

In the method for manufacturing the windshield module, when the windshield is installed on the workbench, a space can be formed below the information acquisition area.

In each of the windshield module manufacturing methods, in the step of attaching the antifogging sheet, the operator stands on the information acquisition area side of the windshield and attaches the antifogging sheet to the information acquisition area. be able to.

In each of the windshield module manufacturing methods, in the step of attaching the antifogging sheet, the antifogging sheet can be attached to the information acquisition area by a robot.

In the manufacturing method of each of the windshield modules, the shielding layer has an opening that defines the information acquisition region, and the antifogging sheet may be attached by positioning with reference to the contour of the opening. it can.

In each of the windshield module manufacturing methods, prior to the step of attaching the antifogging sheet, on the surface of the windshield opposite to the surface to which the antifogging sheet is attached, based on the contour of the shielding layer. The step of attaching the positioning jig is further provided, and in the step of attaching the antifogging sheet, positioning is performed based on the jig that is visually recognized through the laminated glass, and the antifogging sheet is attached. Can be done.

In the method for manufacturing each of the windshield modules, the antifogging sheet is formed by laminating at least an antifogging layer, a base film, and an adhesive layer in this order, and further, a first protection covering the adhesive layer. The sheet is attached, and in the step of attaching the anti-fog sheet, the squeegee is peeled off from any edge of the anti-fog sheet toward the opposite edge, and the squeegee is removed from any of the above. The anti-fog sheet can be attached to the windshield while pressing on the anti-fog sheet from the edge portion of the windshield toward the opposite edge portion.

In the method for manufacturing the windshield module, the antifogging sheet is formed by laminating at least an antifogging layer, a base film, and an adhesive layer in this order, and further, a second protection covering the antifogging layer. A sheet is attached, and a step of peeling the second protective sheet from the anti-fog sheet can be further provided after 24 hours have passed after the anti-fog sheet is attached.

In the method for manufacturing the windshield module, the antifogging sheet is formed by laminating at least an antifogging layer, a base film, and an adhesive layer in this order, and further, a first protective sheet covering the adhesive layer. And a second protective sheet that covers the anti-fog layer, and the first protective sheet and the second protective sheet can be distinguished from each other.

In the method for manufacturing the windshield module, a plurality of corners are formed on the peripheral edge of the antifogging sheet, and at least one of the plurality of corners is formed sharper than the other corners. The sharp corners can be arranged on the shielding layer.

According to the present invention, the anti-fog sheet can be correctly attached to the information acquisition area of the windshield.

It is sectional drawing of one Embodiment of the windshield which concerns on this invention. It is a top view of FIG. It is sectional drawing of laminated glass. It is a front view (a) and a cross-sectional view (b) which show the amount of doubling of a curved laminated glass. It is a schematic plan view which shows the measurement position of the thickness of the laminated glass. It is a top view of a glass plate. It is an enlarged plan view of the center mask layer. It is sectional drawing of FIG. It is a figure which shows another example of the enlarged plan view of the center mask layer. It is sectional drawing of the anti-fog laminate. It is a figure which shows the state which the water drop is attached to the antifogging layer. It is a figure which shows the state which the water drop is attached to the antifogging layer. It is the figure (a) which looked at the bracket from the outside of a car, and the figure (b) which saw from the inside of a car. It is the figure which looked at the sensor from the outside of a car. It is a side view which shows an example of the manufacturing method of a glass plate. It is a top view which shows the state which put the windshield on the installation stand. It is a side view which shows the state which the windshield is placed on the installation stand. It is a top view which shows the mounting state of the antifogging sheet. It is a top view which shows the sticking of the antifogging sheet. It is sectional drawing which shows the attachment of the antifogging sheet. It is a top view which shows the sticking of the antifogging sheet. It is a top view which shows the sticking of the antifogging sheet. It is a top view which shows the mounting state of a bracket. It is a top view which shows the other example of pasting the antifogging sheet. It is a top view which shows the sticking of the antifogging sheet. It is a top view which shows the state which attached the jig to the windshield. It is a side view which shows the state which attached the jig to the windshield. It is a side view which shows the state which the windshield is placed on the installation stand. It is a top view which shows the other example of pasting the antifogging sheet.

Hereinafter, the anti-fog sheet attachment tool according to the present invention will be described with reference to the drawings. In the following, first, an embodiment in the case where a measurement unit for the inter-vehicle distance or the like is attached to the windshield will be described, and then the attachment tool will be described. FIG. 1 is a cross-sectional view of the windshield according to the present embodiment, and FIG. 2 is a plan view of FIG.

As shown in FIGS. 1 and 2, the windshield according to the present embodiment includes a laminated glass 1 and a mask layer 2 formed on the inner surface of the vehicle of the laminated glass 1, and the mask layer 2 is provided with a mask layer 2. A measuring unit 4 for measuring the inter-vehicle distance is attached. Further, an opening 231 is formed in the mask layer 2, and light is irradiated or received from the measurement unit 4 through the opening 231. Then, on the inner surface of the laminated glass 1, an anti-fog sheet is attached to the region corresponding to the opening 231 of the mask layer 2. Hereinafter, each member will be described with reference to the drawings, but in some drawings, the anti-fog layer may be omitted.

<1. Laminated glass>
FIG. 3 is a cross-sectional view of the laminated glass. As shown in the figure, the laminated glass 1 includes an outer glass plate 11 and an inner glass plate 12, and a resin interlayer film 13 is arranged between the glass plates 11 and 12.

<1-1. Outer glass plate and inner 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 the outer glass plate 11 and the inner glass plate 12 can 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 the safety standards of the country in which the automobile is used. For example, the outer glass plate 11 can secure the required solar absorption rate, and the inner glass plate 12 can adjust the visible light transmittance so as to satisfy the safety standard. An example of clear glass, heat ray absorbing glass, and soda lime glass is shown below.

(Clear glass)
SiO ₂ : 70 to 73% by mass
Al ₂ O ₃ : 0.6 to 2.4% by mass
CaO: 7-12% by mass
MgO: 1.0 to 4.5% by mass
R ₂ O: 13 to 15% by mass (R is an alkali metal)
Total iron oxide converted to Fe ₂ O ₃ (T-Fe ₂ O ₃ ): 0.08 to 0.14% by mass

(Heat ray absorbing glass)
The composition of the heat-absorbing glass, for example, based on the composition of the clear glass, the proportion of the total iron oxide in terms of _{Fe 2 O 3 (T-Fe} 2 O 3) and 0.4 to 1.3 wt%, CeO ₂ ratio as 0-2 mass%, the proportion of TiO ₂ and 0 to 0.5 wt%, framework component of the glass (mainly, SiO ₂ and Al ₂ O ₃₎ to T-Fe ₂ O _3, CeO _The composition can be reduced by the amount of increase in ₂ and TiO ₂ .

(Soda lime glass)
SiO ₂ : 65-80% by mass
Al ₂ O ₃ : 0-5% 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% by mass
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
Total iron oxide converted to Fe ₂ O ₃ (T-Fe ₂ O ₃ ): 0.02 to 0.03% by mass

The thickness of the laminated glass according to the present embodiment is not particularly limited, but from the viewpoint of weight reduction, the total thickness of the outer glass plate 11 and the inner glass plate 12 is preferably 2.4 to 5.0 mm. It is more preferably 2.6 to 4.6 mm, and particularly preferably 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, so that the thickness of each glass plate is not particularly limited. For example, the thicknesses of the outer glass plate 11 and the inner glass plate 12 can be determined as follows.

The outer glass plate 11 is mainly required to have durability and impact resistance against external obstacles. For example, when this laminated glass is used as a windshield of an automobile, it has impact resistance against flying objects such as pebbles. is necessary. On the other hand, the larger the thickness, the heavier the weight, which is not preferable. From this viewpoint, 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 to use can be determined according to the application 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, considering the strength of the glass, it is preferably 0.6 to 2.3 mm, preferably 0.8 to 2.0 mm, and particularly 1.0 to 1.4 mm. preferable. Further, it is preferably 0.8 to 1.3 mm. As for the inner glass plate 12, which thickness is adopted can be determined according to the use of the glass.

Further, the shapes of the outer glass plate 11 and the inner glass plate 12 according to the present embodiment are curved shapes. When the laminated glass has a curved shape, it is said that the sound insulation performance deteriorates as the amount of doubling increases. The amount of doubling is an amount indicating bending of the laminated glass. For example, as shown in FIG. 4, when a straight line L connecting the center of the upper side and the center of the lower side of the laminated glass is set, the straight line L and the laminated glass are set. The largest distance from is defined as the amount of duplication D.

Here, an example of a method for measuring the thickness of the laminated glass 1 will be described. First, as shown in FIG. 5, the measurement positions are two points above and below the center line S extending vertically along the center of the laminated glass in the left-right direction. The measuring device is not particularly limited, but for example, a thickness gauge such as SM-112 manufactured by Teclock Co., Ltd. can be used. At the time of measurement, the curved surface of the laminated glass is placed on the flat surface, and the edge of the laminated glass is sandwiched between the thickness gauges for measurement. This windshield corresponds to the glass plate according to the present invention.

<1-2. Intermediate membrane>
The interlayer film 13 is formed of at least one layer, and as an example, as shown in FIG. 3, the interlayer film 13 can be composed of three layers in which a soft core layer 131 is sandwiched between outer layers 132 that are harder than this. However, the configuration is not limited to this, and it may be formed by a plurality of layers having a core layer 131 and at least one outer layer 132 arranged on the outer glass plate 11 side. For example, a two-layer interlayer film 13 including a core layer 131 and one outer layer 132 arranged on the outer glass plate 11 side, or an even number of outer layers 132 having two or more layers on both sides of the core layer 131 as a center. The arranged interlayer film 13 or the intermediate film 13 in which an odd number of outer layers 132 are arranged on one side and an even number of outer layers 132 are arranged on the other side of the core layer 131 may be used. When only one outer layer 132 is provided, it is provided on the outer glass plate 11 side as described above, in order to improve the damage resistance performance against external forces from outside the vehicle or outdoors. Further, when the number of outer layers 132 is large, the sound insulation performance is also high.

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, but for example, the outer layer 132 can be made of, for example, polyvinyl butyral resin (PVB). Polyvinyl butyral resin is preferable because it has excellent adhesiveness and penetration resistance to each glass plate. On the other hand, the core layer 131 can be made of, for example, 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 between them, the sound insulation performance can be greatly improved while maintaining the same adhesiveness and penetration resistance as the single-layer resin interlayer film.

Generally, the hardness of a polyvinyl acetal resin is controlled by (a) the degree of polymerization of polyvinyl alcohol as a starting material, (b) the degree of acetalization, (c) the type of plasticizer, (d) the addition ratio of the plasticizer, and the like. Can be done. Therefore, by appropriately adjusting at least one selected from these conditions, even if the same polyvinyl butyral resin is used, the hard polyvinyl butyral resin used for the outer layer 132 and the soft polyvinyl butyral resin used for the core layer 131 can be used. It is possible to make it separately from. Further, the hardness of the polyvinyl acetal resin can be controlled by the type of aldehyde used for acetalization, co-acetalization with a plurality of types of aldehydes, or 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 polyvinyl butyraldehyde, the core layer 131 contains an aldehyde having 5 or more carbon atoms (for example, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, etc.). A polyvinyl acetal resin obtained by acetalizing n-octylaldehyde) with polyvinyl alcohol can be used. If a predetermined Young's modulus can be obtained, it is not limited to the above resins and the like.

The total thickness of the interlayer film 13 is not particularly specified, but is preferably 0.3 to 6.0 mm, more preferably 0.5 to 4.0 mm, and 0.6 to 2.0 mm. It is particularly preferable to have. The thickness of the core layer 131 is preferably 0.1 to 2.0 mm, more preferably 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, more preferably 0.1 to 1.0 mm. In addition, the total thickness of the interlayer film 13 can be kept constant, and the thickness of the core layer 131 can be adjusted.

The thicknesses 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 175 times and displayed 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 specified and measured. At this time, in order to eliminate visual variations, the number of measurements is set to 5, and the average value is taken as the thickness of the core layer 131 and the outer layer 132.

The thicknesses of the core layer 131 and the outer layer 132 of the interlayer film 13 do not have to be constant over the entire surface, and may be wedge-shaped for laminated glass used in a head-up display, for example. In this case, the thickness of the core layer 131 and the outer layer 132 of the interlayer film 13 is measured at a portion having the smallest thickness, that is, a lowermost portion of the laminated glass. When the interlayer 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, the present invention includes, for example, the arrangement of the outer glass plate and the inner glass plate when the intermediate film 13 using the core layer 131 and the outer layer 132 whose thickness increases at a rate of change of 3 mm or less per 1 m is used. ..

The method for producing the interlayer film 13 is not particularly limited, but for example, a resin component such as the polyvinyl acetal resin described above, a plasticizer, and if necessary, other additives are blended and kneaded uniformly, and then each layer is collectively kneaded. Examples thereof include a method of extrusion molding with the above method, and a method of laminating two or more resin films produced by this method by a pressing method, a laminating method, or the like. The resin film before lamination used in the laminating method by a pressing method, a laminating method or the like may have a single-layer structure or a multi-layer structure. Further, the interlayer film 13 can be formed by one layer in addition to being formed by a plurality of layers as described above.

<1-3. Infrared transmittance of laminated glass>
As described above, the windshield according to the present embodiment is used for a front safety system of an automobile using a measurement unit such as a laser radar or a camera. In such a safety system, the vehicle in front is irradiated with infrared rays to measure the speed of the vehicle in front and the distance between vehicles. Therefore, the laminated glass is required to achieve the infrared transmittance in a predetermined range.

As such a transmittance, for example, when a general sensor is used for a laser radar, the transmittance is 20% or more and 80% or less, and at least 20% or more and 60% or less with respect to light (infrared ray) having a wavelength of 850 to 950 nm. It is said that it is useful to have it. As a method for measuring the transmittance, UV3100 (manufactured by Shimadzu Corporation) can be used as a measuring device according to JIS R3106. Specifically, the transmission of light in one direction, which is irradiated at an angle of 90 degrees to the surface of the laminated glass, is measured.

In addition, some safety systems such as those described above use an infrared camera to measure the speed and distance between vehicles in front of the vehicle without using a laser radar. In that case, for example, a general camera for laser radar is used. When using, it is useful that the wavelength is 30% or more and 80% or less, preferably 40% or more and 60% or less with respect to light (infrared ray) having a wavelength of 700 to 800 nm. The method for measuring the transmittance follows ISO9050.

<2. Mask layer>
Next, the mask layer 2 will be described. A mask layer 2 as shown in FIGS. 6 to 8 is formed on the laminated glass 1 according to the present embodiment. The mask layer 2 is laminated on the laminated glass 1, but its position is not particularly limited, and the car inner surface of the outer glass plate 11, the car outer surface of the inner glass plate 12, and the inner glass plate 12 It can be laminated on at least one of the inner surfaces of the vehicle. Among these, for example, when the mask layer 2 having substantially the same shape is formed on both the inner surface of the outer glass plate 11 and the inner surface of the inner glass plate 12, the mask layer 2 is laminated. This is preferable because the curvatures of both the glass plates 11 and 12 match. Note that FIG. 1 shows an example in which the mask layer 2 is formed on the inner surface of the inner glass plate 12 inside the vehicle.

The mask layer 2 is a dark-colored area for making the laminated glass 1 invisible from the outside, such as being coated with an adhesive when attaching the laminated glass 1 to the vehicle body. As shown in FIG. 6, the laminated glass 1 is formed. A peripheral mask layer 21 formed on the outer peripheral edge of the glass, and a center mask layer 22 extending downward from the center of the upper edge of the laminated glass 1 in the peripheral mask layer 21 are provided. Then, the measurement unit 4 described above is attached to the center mask layer 22. As will be described later, the measurement unit 4 may be arranged so that the light emitted from the sensor 5 can pass through the opening (information acquisition region) 231 and receive the reflected light from the preceding vehicle and obstacles. These mask layers 2 can be formed of various materials, but are not particularly limited as long as they can shield the field of view from the outside of the vehicle. For example, a dark ceramic such as black is applied to the laminated glass 1. Can be formed by

Next, the center mask layer 22 will be described. As shown in FIG. 7, the center mask layer 22 is formed in a rectangular shape extending in the vertical direction, and a rectangular opening 231 is formed in the center mask layer 22.

The center mask layer 22 is divided into three regions, and is formed on an upper region 221 above the opening 231 and a lower region 222 below the upper region 221 including the opening 231 and a side portion of the lower region 222. It is composed of a small rectangular side region 223.

Next, the layer structure of each region will be described. As shown in FIG. 8, the upper region 221 is formed of one layer by a first ceramic layer 241 made of black ceramic. The lower region 222 is formed of three layers including the first ceramic layer 241, the silver layer 242, and the second ceramic layer 243 laminated from the inner surface of the laminated glass 1. The silver layer 242 is made of silver, and the second ceramic layer 243 is made of the same material as the first ceramic layer 241. Further, the side region 223 is formed of two layers, a first ceramic layer 241 and a silver layer 242 laminated from the inner surface of the laminated glass 1, and the silver layer 242 is exposed inside the vehicle. The first ceramic layer 241 of the lowermost layer is common to each region, and the silver layer 242 of the second layer is common to the lower region 222 and the side region 223. The thickness of each of the ceramic layers 241 and 243 can be, for example, 10 to 20 μm in order to ensure the light-shielding property. Further, when the center mask layer 22 is formed on the inner surface of the inner glass plate 12 on the inside of the vehicle, the bracket of the measuring unit 4 is adhered to the center mask layer 22 with an adhesive, so that the adhesiveness is ensured. Such a thickness is also preferable. This is because, for example, the urethane-silicone adhesive may be deteriorated by ultraviolet rays or the like.

The peripheral mask layer 21 and the center mask layer 22 can be formed, for example, as follows. First, the first ceramic layer 241 is applied to any glass plate of the laminated glass 1. The first ceramic layer 241 is common to the peripheral mask layer 21. Next, the silver layer 242 is applied onto the first ceramic layer 241 in the regions corresponding to the lower region 222 and the side region 223. Finally, the second ceramic layer 243 is applied to the region corresponding to the lower region 222. In the lower region 222, the region where the silver layer 242 is formed corresponds to the position where the sensor of the measurement unit 4 described later is arranged. Further, the silver layer 242 exposed in the side region 223 is provided with wiring for grounding. The ceramic layers 241,243 and the silver layer 242 can be formed by a screen printing method, but can also be produced by transferring a firing transfer film to a glass plate and firing.

The ceramic layers 241 and 243 can be formed of various materials, and can have, for example, the following composition.
* 1, Main component: Copper oxide, Chromium oxide, Iron oxide and Manganese oxide * 2, Main component: Bismuth borosilicate, Zinc borosilicate

Further, the silver layer 242 is also not particularly limited, but may have, for example, the following composition.
* 1, Main component: Bismuth borosilicate, Zinc borosilicate

The screen printing conditions can be, for example, polyester screen: 355 mesh, coat thickness: 20 μm, tension: 20 Nm, squeegee hardness: 80 degrees, mounting angle: 75 °, printing speed: 300 mm / s, in a drying oven. The ceramic layer and the silver layer can be formed by drying at 150 ° C. for 10 minutes. When the first ceramic layer 241 and the silver layer 242 and the second ceramic layer 243 are laminated in this order, the screen printing and drying described above may be repeated.

The configuration of the center mask layer 22 is not particularly limited, and it is not necessary to cover the entire peripheral edge of the opening 231 with the center mask layer 22. Therefore, for example, the shape may be as shown in FIG. Further, the number of openings 231 is not particularly limited, and may be appropriately determined according to the type of the measuring unit 4 to be attached and the like.

<3. Anti-fog sheet>
Next, the anti-fog sheet will be described. As shown in FIG. 10, the antifogging sheet 3 is attached to the opening 231 and has an adhesive layer 31, a base film 32, and an antifogging layer 33 laminated in this order. Further, until the adhesive layer 31 is fixed to the opening 231 a peelable first protective sheet 34 is attached, and a peelable second protective sheet 35 is also attached to the antifogging layer 33. Hereinafter, a five-layer structure in which both protective sheets 34 and 35 are attached to the anti-fog sheet 3 will be referred to as an anti-fog laminate 30. Further, the anti-fog sheet 3 is formed in a shape corresponding to the opening 231 but can be formed in a shape slightly smaller than the opening 231, for example. Alternatively, it may be formed so as to be larger than the opening 231 and cover a part of the mask layer 2 beyond the opening 231. In the example of FIG. 12, the second protective sheet 35 is formed large, but it may be the same size as the anti-fog sheet 3. Hereinafter, each layer will be described.

<3-1. Anti-fog layer>
The antifogging layer 33 is not particularly limited as long as it exhibits the antifogging effect of the laminated glass 1, and known ones can be used. Generally, the antifogging layer 33 is a hydrophilic type that forms water generated from water vapor as a water film on the surface, a water absorbing type that absorbs water vapor, a water repellent water absorbing type that prevents water droplets from condensing on the surface, and water droplets generated from water vapor. There is a water-repellent type that repels water, but any type of antifogging layer 33 can be applied. An example is given below.

The antifogging layer 33 can be configured to contain a water repellent group and a metal oxide component, preferably further containing a water absorbing resin. The anti-fog layer 33 may further contain other functional components, if necessary. The water-absorbent resin may be of any type as long as it can absorb and retain water. The water-repellent group can be supplied to the antifogging layer from a metal compound having a water-repellent group (water-repellent group-containing metal compound). The metal oxide component can be supplied to the antifogging layer from a water-repellent group-containing metal compound or other metal compound, metal oxide fine particles, or the like. Hereinafter, each component will be described.

[Water-absorbent resin]
First, the water-absorbent resin will be described. As the water-absorbent resin, at least one selected from the group consisting of urethane resin, epoxy resin, acrylic resin, polyvinyl acetal resin, and polyvinyl alcohol resin can be exemplified. Examples of the urethane resin include a polyurethane resin composed of polyisocyanate and polyol. As the polyol, an acrylic polyol and a polyoxyalkylene-based polyol are preferable. Examples of the epoxy resin include a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, and a cyclic aliphatic epoxy resin. A preferred epoxy resin is a cyclic aliphatic epoxy resin. Hereinafter, a polyvinyl acetal resin (hereinafter, simply “polyacetal”), which is a preferable water-absorbent resin, will be described.

Polyvinyl acetal can be obtained by subjecting polyvinyl alcohol to a condensation reaction of an aldehyde to acetalize it. Acetalization of polyvinyl alcohol may be carried out by using a known method such as a precipitation method using an aqueous medium in the presence of an acid catalyst and a dissolution method using a solvent such as alcohol. Acetalization can also be carried out in parallel with the saponification of polyvinyl acetate. The degree of acetalization is preferably 2 to 40 mol%, more preferably 3 to 30 mol%, particularly 5 to 20 mol%, and in some cases 5 to 15 mol%. The degree of acetalization can be measured, for example, based on the ^13C nuclear magnetic resonance spectral method. Polyvinyl acetal having an acetalization degree in the above range is suitable for forming an antifogging layer having good water absorption and water resistance.

The average degree of polymerization of polyvinyl alcohol is preferably 200 to 4500, more preferably 500 to 4500. A high average degree of polymerization is advantageous for forming an antifogging layer having good water absorption and water resistance, but if the average degree of polymerization is too high, the viscosity of the solution becomes too high, which may hinder the formation of a film. is there. The degree of saponification of polyvinyl alcohol is preferably 75 to 99.8 mol%.

Examples of the aldehyde to be condensed with polyvinyl alcohol include aliphatic aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hexylcarbaldehyde, octylcarbaldehyde, and decylcarbaldehyde. Benzaldehyde; 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, other alkyl group-substituted benzaldehyde; chlorobenzaldehyde, other halogen atom-substituted benzaldehyde; alkyl such as hydroxy group, alkoxy group, amino group, cyano group. Substituent benzaldehyde in which a hydrogen atom is substituted with a functional group other than a group; aromatic aldehydes such as condensed aromatic ring aldehydes such as naphthaldehyde and anthralaldehyde can be mentioned. Aromatic aldehydes with strong hydrophobicity are advantageous in forming an antifogging layer having a low degree of acetalization and excellent water resistance. The use of aromatic aldehydes is also advantageous in forming a film having high water absorption while leaving a large amount of hydroxyl groups. The polyvinyl acetal preferably contains an acetal structure derived from an aromatic aldehyde, particularly benzaldehyde.

The content of the water-absorbent resin in the anti-fog layer is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 65% by mass or more, from the viewpoint of film hardness, water absorption and anti-fog property. It is 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[Water repellent group]
Next, the water repellent group will be described. The water-repellent group facilitates both the strength of the anti-fog layer and the anti-fog property, and contributes to ensuring the straightness of incident light even if water droplets are formed by making the surface of the film hydrophobic. .. In order to obtain a sufficient effect of the water-repellent group, it is preferable to use a water-repellent group having high water repellency. Preferred water repellent groups are (1) chain or cyclic alkyl groups having 3 to 30 carbon atoms, and (2) chain or cyclic groups having 1 to 30 carbon atoms in which at least a part of hydrogen atoms are replaced by fluorine atoms. It is at least one selected from alkyl groups (hereinafter sometimes referred to as "fluorine-substituted alkyl groups").

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 a straight chain alkyl group is preferable. Alkyl groups having more than 30 carbon atoms may make the antifogging layer cloudy. From the viewpoint of the antifogging property, strength and appearance balance of the film, the number of carbon atoms of the chain alkyl group is preferably 20 or less, for example, 1 to 8, and for example, 4 to 16, preferably 4 to 8. is there. Particularly preferred alkyl groups are linear alkyl groups having 4 to 8 carbon atoms, such as n-pentyl groups, n-hexyl groups, n-heptyl groups, and n-octyl groups. Regarding (2), the fluorine-substituted alkyl group may be a group in which only a part of the hydrogen atom of the 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 a group substituted with a fluorine atom, for example, a linear perfluoroalkyl group. Since the fluorine-substituted alkyl group has high water repellency, a sufficient effect can be obtained by adding a small amount. However, if the content of the fluorine-substituted alkyl group becomes too large, it may be separated from other components in the coating liquid for forming the film.

(Hydrolyzable metal compound having a water-repellent group)
In order to blend a water-repellent group into the antifogging layer, a metal compound having a water-repellent group (water-repellent group-containing metal compound), particularly a metal compound having a water-repellent group and a hydrolyzable functional group or a halogen atom ( A water-repellent group-containing hydrolyzable metal compound) or a hydrolyzate thereof may be added to the coating liquid 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, the water-repellent group-containing hydrolyzable silicon compound represented by the following formula (I) is suitable.
R _m SiY _4-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 a hydrogen atom may be substituted with a fluorine atom, and Y is a hydrolyzable functional group. It is a group or a halogen atom, and m is an integer of 1 to 3. The hydrolyzable functional group is, for example, at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group and an amino group, preferably an alkoxy group, particularly an alkoxy group having 1 to 4 carbon atoms. The alkenyloxy group is, for example, an isopropenoxy group. The halogen atom is preferably chlorine. The functional group exemplified here can also be used as the "hydrolyzable functional group" described below. m is preferably 1 to 2.

The compound represented by the formula (I) supplies the component represented by the following formula (II) when the hydrolysis and polycondensation have completely proceeded.
R _m SiO _{(4-m) / 2} (II)
Here, R and m are as described above. After hydrolysis and polycondensation, the compound represented by formula (II) actually forms a network structure in which silicon atoms are bonded to each other via oxygen atoms in the antifogging layer.

As described above, the compound represented by the formula (I) is hydrolyzed or partially hydrolyzed, and at least a part thereof is polycondensed so that silicon atoms and oxygen atoms are alternately connected and three-dimensionally. It forms a network structure of spreading siloxane bonds (Si—O—Si). A water-repellent group R is connected to the silicon atom contained in this network structure. In other words, the water repellent group R is fixed to the network structure of the siloxane bond via the bond R—Si. This structure is advantageous in uniformly dispersing the water-repellent group R in the film. The network structure may contain a silica component supplied from a silicon compound (for example, tetraalkoxysilane, silane coupling agent) other than the water-repellent group-containing hydrolyzable silicon compound represented by the formula (I). To form an antifogging layer together with a water-repellent group-containing hydrolyzable silicon compound (water-repellent group-free hydrolyzable silicon compound) having a hydrolyzable functional group or halogen atom without a water-repellent group. When blended in the coating liquid of, a network structure of siloxane bonds containing silicon atoms bonded to water-repellent groups and silicon atoms not bonded to water-repellent groups can be formed. With such a structure, it becomes easy to adjust the content of the water repellent group and the content of the metal oxide component in the antifogging layer independently of each other.

When the antifogging layer contains a water-absorbent resin, the water-repellent group improves the antifogging performance by improving the permeability of water vapor on the surface of the antifogging layer containing the water-absorbent resin. Since the two functions of water absorption and water repellency are opposite to each other, the water-absorbent material and the water-repellent material have conventionally been assigned to different layers, but the water-repellent group contained in the anti-fog layer is an anti-fog material. It eliminates the uneven distribution of water near the surface of the cloudy layer, prolongs the time until dew condensation, and improves the antifogging property of the antifogging layer. The effect will be described below.

The water vapor that has entered the antifogging layer containing the water-absorbent resin is hydrogen-bonded to the hydroxyl groups of the water-absorbent resin and is retained in the form of bound water. As the amount increases, the water vapor is retained in the form of free water, which is retained in the voids in the antifogging layer, from the form of bonded water through the form of semi-bonded water. In the anti-fog layer, 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-absorbent resin is the same, there is no difference in the number of hydroxyl groups that can be hydrogen-bonded in the membrane, but the water-repellent group reduces the rate of hydrogen bond formation. Therefore, in the antifogging layer containing a water-repellent group, water is finally retained in the film in any of the above forms, but remains water vapor to the bottom of the film by the time it is retained. Can spread. In addition, once the water is held, it dissociates relatively easily and easily moves to the bottom of the membrane in the state of water vapor. As a result, the distribution of water retention in the thickness direction of the layer becomes relatively uniform from the vicinity of the surface to the bottom of the layer. That is, since all of the antifogging layer in the thickness direction can be effectively utilized and the water supplied to the film surface can be absorbed, water droplets are less likely to condense on the surface and the antifogging property is improved.

On the other hand, in the conventional anti-fog layer containing no water-repellent group, the water vapor that has entered the film is very easily retained in the form of bonded water, semi-bonded water or free water. Therefore, the invading water vapor tends to be retained near the surface of the film. As a result, the water content in the film is extremely high near the surface and decreases rapidly toward the bottom of the film. That is, although water can still be absorbed at the bottom of the film, it is saturated with water in the vicinity of 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 layer using a water-repellent group-containing hydrolyzable silicon compound (see formula (I)), a strong siloxane bond (Si—O—Si) network structure is formed. The formation of this network structure is advantageous not only from the viewpoint of improving wear resistance but also from the viewpoint of improving hardness, water resistance and the like.

The water-repellent group may be added so that the contact angle of water on the surface of the antifogging layer is 70 degrees or more, preferably 80 degrees or more, and more preferably 90 degrees or more. For the contact angle of water, a value measured by dropping 4 mg of water droplets on the surface of the membrane is adopted. In particular, when a methyl group or an ethyl group having a slightly weak water repellency is used as the water repellent group, it is preferable to add an amount of the water repellent group in the antifogging layer so that the contact angle of water is in the above range. The upper limit of the contact angle of water is not particularly limited, but is, for example, 150 degrees or less, for example, 120 degrees or less, and further 105 degrees or less. It is preferable that the water-repellent group is uniformly contained in the anti-fog layer so that the contact angle of the water falls within the above-mentioned range in all the regions on the surface of the anti-fog layer.

Here, the relationship between the contact angle of water and the antifogging layer 33 will be described with reference to FIGS. 11 and 12. 11 and 12 show a state in which water droplets (90, 91) having different contact angles are attached to the antifogging layer 33. As shown in FIGS. 11 and 12, the area where the water droplets (90, 91) formed by condensing the same amount of water vapor on the surface of the antifogging layer 33 covers the antifogging layer 33 is the contact of water on the surface. The larger the angle, the smaller the tendency. Further, the smaller the area covered by the water droplets (90, 91), the smaller the ratio of the area where the light incident on the antifogging layer 33 is scattered. Therefore, the antifogging layer 33 in which the contact angle of water is increased due to the presence of the water-repellent group is advantageous in maintaining the straightness of the transmitted light in a state where water droplets are formed on the surface thereof.

The antifogging layer 33 preferably contains a water repellent group so that the contact angle of water is within the above-mentioned preferable range. When the water-absorbent resin is contained, the antifogging layer is in the range of 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the water-absorbent resin. It is preferable to include a water-repellent group so as to be in the range of 10 parts by mass or less, preferably 5 parts by mass or less.

[Metal oxide component]
Next, the metal oxide component will be described. The metal oxide component is, for example, an oxide component of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, and preferably an oxide component of Si (silica component). ). When the water-absorbent resin is contained, the antifogging layer is 0.01 part by mass or more, preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, still more preferably 0.2 parts by mass or more, based on 100 parts by mass of the water-absorbent resin. 1 part by mass or more, particularly preferably 5 parts by mass or more, in some cases 7 parts by mass or more, if necessary 10 parts by mass or more, and 60 parts by mass or less, particularly 50 parts by mass or less, preferably 40 parts by mass or less. It is more preferable to contain the metal oxide component so as to be more preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and in some cases 18 parts by mass or less. The metal oxide component is a component necessary for ensuring the strength of the film, particularly scratch resistance, but if the content thereof is excessive, the antifogging property of the film is lowered.

At least a part of the metal oxide component may be a hydrolyzable metal compound added to the coating liquid for forming the antifogging layer or a metal oxide component derived from the hydrolyzate thereof. Here, the hydrolyzable metal compound has a) a metal compound having a water-repellent group and a hydrolyzable functional group or a halogen atom (water-repellent group-containing hydrolyzable metal compound) and b) a water-repellent group. It is at least one selected from metal compounds having a hydrolyzable functional group or a halogen atom (hydrolyzable metal compound containing no water repellent group). The metal oxide component derived from a) and / or b) is an oxide of a metal atom constituting a hydrolyzable metal compound. The metal oxide component is a metal oxide component derived from metal oxide fine particles added to a coating liquid for forming an antifogging layer, a hydrolyzable metal compound added to the coating liquid, or the like. It may contain a metal oxide component derived from a hydrolyzate. Again, the hydrolyzable metal compound is at least one selected from the above a) and b). The above b), that is, the hydrolyzable metal compound having no water repellent group may contain at least one selected from tetraalkoxysilane and a silane coupling agent. Hereinafter, the metal oxide fine particles and the above b) will be described except for the above a) described above.

(Metal oxide fine particles)
The antifogging layer 33 may further contain metal oxide fine particles as at least a part of the metal oxide component. The metal oxide constituting the metal oxide fine particles is, for example, an oxide of at least one element selected from Si, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn, preferably silica fine particles. is there. Silica fine particles can be introduced into the membrane, for example, by adding colloidal silica. The metal oxide fine particles have an excellent effect of transmitting the stress applied to the antifogging layer to the transparent article supporting the film, and have high hardness. Therefore, the addition of the metal oxide fine particles is advantageous from the viewpoint of improving the wear resistance and scratch resistance of the antifogging layer. Further, when the metal oxide fine particles are added to the antifogging layer, fine voids are formed in the portions where the fine particles are in contact with or close to each other, and water vapor is easily taken into the film from the voids. Therefore, the addition of the metal oxide fine particles may have an advantageous effect on improving the antifogging property. The metal oxide fine particles can be supplied to the antifogging layer by adding the preformed metal oxide fine particles to the coating liquid for forming the antifogging layer.

If the average particle size of the metal oxide fine particles is too large, the film may become cloudy, and if it is too small, it becomes difficult to aggregate and uniformly disperse the metal oxide fine particles. From this point of view, the preferred average particle size of the metal oxide fine particles is 1 to 20 nm, particularly 5 to 20 nm. Here, the average particle size of the metal oxide fine particles is described in the state of primary particles. Further, the average particle size of the metal oxide fine particles is determined by measuring the particle size of 50 fine particles arbitrarily selected by observation using a scanning electron microscope and adopting the average value. If the content of the metal oxide fine particles is excessive, the water absorption amount of the entire film is reduced, and the film may become cloudy. When the antifogging layer contains a water-absorbent resin, the amount of the metal oxide fine particles is 0 to 50 parts by mass, preferably 1 to 30 parts by mass, more preferably 2 to 30 parts by mass, particularly with respect to 100 parts by mass of the water-absorbent resin. It is preferable to add 5 to 25 parts by mass, and in some cases 10 to 20 parts by mass.

(Hydrolytic metal compound having no water repellent group)
Further, the antifogging layer 33 may contain a metal oxide component derived from a hydrolyzable metal compound having no water-repellent group (hydrolyzable compound containing no water-repellent group). A preferred water-repellent group-free hydrolyzable metal compound is a hydrolyzable silicone compound having no water-repellent group. The hydrolyzable silicon compound having no water-repellent group is, for example, at least one silicon compound (however, having no water-repellent group) selected from silicon alkoxide, chlorosilane, acetoxysilane, alkenyloxysilane and aminosilane. Silicon alkoxides that do not have a water repellent group are preferred. As the alkenyloxysilane, isopropenoxysilane can be exemplified.

The hydrolyzable silicon compound having no water-repellent group may be a compound represented by the following formula (III).
SiY ₄ (III)
As described above, Y is a hydrolyzable functional group, preferably at least one selected from an alkoxyl group, an acetoxy group, an alkenyloxy group, an amino group and a halogen atom.

The water-repellent group-free hydrolyzable metal compound is hydrolyzed or partially hydrolyzed, and at least a part thereof is polycondensed to supply a metal oxide component in which a metal atom and an oxygen atom are bonded. This component firmly bonds the metal oxide fine particles and the water-absorbent resin, and can contribute to the improvement of the abrasion resistance, hardness, water resistance, etc. of the antifogging layer. When the antifogging layer contains a water-absorbent resin, the amount of the metal oxide component derived from the hydrolyzable metal compound having no water-repellent group is 0 to 40 parts by mass, preferably 0, with respect to 100 parts by mass of the water-absorbent resin. The range may be 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, particularly preferably 3 to 10 parts by mass, and in some cases 4 to 12 parts by mass.

A preferred example of a hydrolyzable silicon compound having no water repellent group is tetraalkoxysilane, more specifically tetraalkoxysilane having an alkoxy group having 1 to 4 carbon atoms. Tetraalkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane and tetra-tert-. At least one selected from butoxysilane.

If the content of the metal oxide (silica) component derived from tetraalkoxysilane is excessive, the antifogging property of the antifogging layer may decrease. This is partly due to the reduced flexibility of the anti-fog layer, which limits the swelling and contraction of the film with the absorption and release of water. When the antifogging layer contains a water-absorbent resin, the metal oxide component derived from tetraalkoxysilane is 0 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 3 with respect to 100 parts by mass of the water-absorbent resin. It is preferable to add in the range of 10 parts by mass.

Another preferred example of a hydrolyzable silicone compound that does not have a water repellent group is a silane coupling agent. Silane coupling agents are silicon compounds that have different reactive functional groups from each other. The reactive functional group is preferably a partially 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 glycidyloxyalkyltrialkoxysilanes and aminoalkyltrialkoxysilanes. 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) exhibiting hydrophilicity, although they contain an alkylene group, they are not water repellent as a whole.

The silane coupling agent firmly binds the water-absorbent resin which is an organic component and the metal oxide fine particles which are an inorganic component, and can contribute to the improvement of the abrasion resistance, hardness, water resistance and the like of the antifogging layer. However, if the content of the metal oxide (silica) component derived from the silane coupling agent is excessive, the antifogging property of the antifogging layer is lowered, and in some cases, the antifogging layer becomes cloudy. When the antifogging layer contains a water-absorbent resin, the metal oxide component derived from the silane coupling agent is 0 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the water-absorbent resin. It is preferable to add in the range of 0.1 to 2 parts by mass.

[Cross-linked structure]
Further, the antifogging layer 33 may contain a cross-linking structure derived from a cross-linking agent, preferably at least one cross-linking agent selected from an organoboron compound, an organic titanium compound and an organic zirconium compound. The introduction of the crosslinked structure improves the wear resistance, scratch resistance, and water resistance of the antifogging layer. From another point of view, the introduction of the crosslinked structure facilitates improving the durability of the antifogging layer without deteriorating its antifogging performance.

When a crosslinked structure derived from a cross-linking agent is introduced into the antifogging layer in which the metal oxide component is a silica component, the antifogging layer contains silicon as metal atoms and metal atoms other than silicon, preferably boron, titanium or zirconium. May be contained.

The type of the cross-linking agent is not particularly limited as long as it can cross-link the water-absorbent resin used. Here, only the organic titanium compound is given as an example. The organic titanium compound is, for example, at least one selected from titanium alkoxide, titanium chelate compound and titanium acylate. Titanium alkoxides are, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetraoctoxide. Titanium chelate compounds are, for example, titanium acetylacetonate, ethyl titaniumacetoacetate, titanium octylene glycol, titanium triethanolamine, and titanium lactate. The titanium lactate may be an ammonium salt (titanium lactate ammonium). 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 cross-linking agent is an organic titanium compound, particularly titanium lactate.

[Other optional ingredients]
Other additives may be blended in the antifogging layer 33. Examples of the additive include glycols such as glycerin and ethylene glycol having a function of improving antifogging property. The additive may be a surfactant, a leveling agent, an ultraviolet absorber, a colorant, an antifoaming agent, a preservative or the like.

[Film thickness]
The film thickness of the antifogging layer 33 may be appropriately adjusted according to the required antifogging characteristics and the like. The film thickness of the antifogging layer 33 is preferably 1 to 20 μm, preferably 2 to 15 μm, and particularly 3 to 10 μm.

As is clear from the above description, preferred forms of the antifogging layer 33 include the following. That is, the antifogging layer 33 preferably contains 0.1 to 60 parts by mass of the metal oxide component and 0.05 to 10 parts by mass of the water repellent group with respect to 100 parts by mass of the water-absorbent resin. At this time, the water-repellent group is a chain alkyl group having 1 to 8 carbon atoms, the water-repellent group is directly bonded to a metal atom constituting a metal oxide component, and the metal atom may be silicon. .. Further, at least a part of the metal oxide component is a metal oxide component derived from a hydrolyzable metal compound or a hydrolyzate of the hydrolyzable metal compound added to the coating liquid for forming the antifogging layer. The hydrolyzable metal compound may be at least one selected from a hydrolyzable metal compound having a water-repellent group and a hydrolyzable metal compound having no water-repellent group. Further, the hydrolyzable metal compound having no water repellent group may contain at least one selected from tetraalkoxysilanes and silane coupling agents. By making the anti-fog layer 33 in this way, it is possible to suppress fogging of the information acquisition region 23, and it becomes possible to appropriately acquire information outside the vehicle by the information acquisition device.

The above-mentioned anti-fog layer 33 is an example, and other known anti-fog layers can be used. For example, the anti-fog layers described in JP-A-2014-14802 and JP-A-2001-146585 are used. , Various things can be used.

<3-2. Base film>
The base film 32 is formed of a transparent resin film, and can be formed of, for example, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, or an acrylic resin. Then, the resin can contain an ultraviolet absorber.

Examples of the ultraviolet absorber include benzotriazole compounds [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl). Bentriazole, etc.], benzophenone compounds [2,2', 4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5, 5'-Methylenebis (2-hydroxy-4-methoxybenzophenone), etc.], hydroxyphenyltriazine compound [2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-t-) Butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4, 6-bis (2,4-di-t-butylphenyl) -s-triazine, etc.] and cyanoacrylate compounds [ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3 -(P-Phenylphenyl) acrylate, etc.] and other organic substances can be mentioned. The ultraviolet absorber may be used alone or in combination of two or more. Further, the ultraviolet absorber may be at least one organic dye selected from polymethine compounds, imidazoline compounds, coumarin compounds, naphthalimide compounds, perylene compounds, azo compounds, isoindolinone compounds, quinophthalone compounds and quinoline compounds. ..

Such a base film 32 preferably has, for example, a transmittance of 5% or less at a wavelength of 380 nm and a transmittance of 50% or less at a wavelength of 400 nm.

Further, since the base film 32 is a film that supports the antifogging layer 33, a certain degree of rigidity is required. However, if the thickness is too large, the haze rate tends to be high. Therefore, the thickness of the base film 32 is preferably, for example, 30 to 200 μm.

<3-3. Adhesive layer>
As will be described later, the adhesive layer 31 may be any as long as it can fix the base film 32 to the inner glass plate 12 with sufficient strength. Specifically, an adhesive layer such as a resin obtained by copolymerizing an acrylic-based, rubber-based, or methacrylic-based and acrylic-based monomer having tackiness at room temperature and setting a desired glass transition temperature can be used. As the acrylic monomer, methyl acrylate, ethyl acrylate, butyl acrylate, stearyl acrylate, diethylhexyl acrylate and the like can be applied, and as the methacrylic monomer, ethyl methacrylate, butyl methacrylate, methacrylic acid and the like can be applied. Isobutyl, stearyl methacrylate and the like can be applied. Further, when the construction is carried out by heat laminating or the like, an organic substance that softens at the laminating temperature may be used. For example, in the case of a resin obtained by copolymerizing a methacrylic monomer and an acrylic monomer, the glass transition temperature can be adjusted by changing the blending ratio of each monomer.

<3-4. Protective sheet>
The first protective sheet 34 protects the adhesive layer 31 until it is fixed to the opening 231 of the laminated glass 1, and is formed of, for example, a resin sheet coated with a release agent such as silicone. ing. Similarly, the second protective sheet 35 is for protecting the antifogging layer 33 until it is fixed to the photographing window of the laminated glass, and is formed of a resin sheet coated with a release agent. ing. In either case, a known general release sheet can be adopted.

<3-5. Manufacturing method of anti-fog sheet>
Next, a method for manufacturing the antifogging sheet 3 will be described. First, the antifogging layer 33 is formed on one surface of the base film 32. The anti-fog layer 33 is formed by applying a coating liquid for forming the anti-fog layer 33 on the equipment film, drying the applied coating liquid, and further performing a high-temperature and high-humidity treatment as necessary. , Can be formed. As the solvent used for preparing the coating liquid and the coating method for the coating liquid, known materials and methods may be used.

At this time, it is preferable to keep the relative humidity of the atmosphere below 40%, more preferably 30% or less. Keeping the relative humidity low can prevent the film from absorbing excessive moisture from the atmosphere. If a large amount of water is absorbed from the atmosphere, the water that has entered the matrix of the membrane and remains may reduce the strength of the membrane.

The drying step of the coating liquid preferably includes an air-drying step and a heating-drying step accompanied by heating. The air-drying step may be carried out by exposing the coating liquid to an atmosphere in which the relative humidity is kept below 40% and further below 30%. The air-drying step can be carried out as a non-heating step, in other words, at room temperature. When the coating liquid contains a hydrolyzable silicon compound, in the heat-drying step, a dehydration reaction involving silanol groups contained in the hydrolyzate of the silicon compound and hydroxyl groups present on the article proceeds, and silicon proceeds. A matrix structure (Si—O bond network) consisting 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 water-absorbent resin, the temperature applied in the heating and drying step should not be excessively high. The appropriate heating temperature in this case is 300 ° C. or lower, for example 100 to 200 ° C., and the heating time is 1 minute to 1 hour.

When forming the antifogging layer 33, a high temperature and high humidity treatment step may be carried out as appropriate. By implementing the high temperature and high humidity treatment step, it may be easier to achieve both antifogging property and film strength. The high-temperature and high-humidity treatment step can be carried out by, for example, holding in an atmosphere of 50 to 100 ° C. and a relative humidity of 60 to 95% for 5 minutes to 1 hour. The high temperature and high humidity treatment step may be carried out after the coating step and the drying step, or may be carried out after the coating step and the air drying step and before the heat drying step. In particular, in the former case, a heat treatment step may be further carried out after the high temperature and high humidity treatment step. This additional heat treatment step can be carried out, for example, by holding in an atmosphere of 80 to 180 ° C. for 5 minutes to 1 hour. In this way, the film formation of the antifogging layer 33 is completed. Then, in order to protect the antifogging layer 33, a second protective sheet 35 is attached on the antifogging layer 33.

The antifogging layer 33 formed from the coating liquid may be washed and / or wiped with a compress, if necessary. Specifically, it can be carried out by exposing the surface of the antifogging layer 33 to a stream of water or wiping it with a cloth soaked in water. Pure water is suitable as the water used for these. It is advisable to avoid using solutions containing detergents for cleaning. By this step, dust, dirt and the like adhering to the surface of the antifogging layer 33 can be removed to obtain a clean coating film surface.

Next, the adhesive layer 31 is applied to the other surface of the base film 32, and then the first protective sheet 34 is attached. In this way, the anti-fog laminate is completed. The anti-fog laminate is cut to a required size as described above, and then attached to the inner glass plate 12 at a position corresponding to the opening 231 as described later.

As the anti-fog layer 33, in addition to the above-mentioned anti-fog sheet 3 attached to the inner glass plate 12, the above-mentioned anti-fog layer 33 can be directly applied to the inner glass plate 12 to form an anti-fog layer. You can also do it.

<4. Measurement unit>
Next, the measuring unit will be described with reference to FIGS. 13 and 14. FIG. 13A is a view of the bracket viewed from the outside of the vehicle, and FIG. 13B is a view of the bracket viewed from the inside of the vehicle. Further, FIG. 14 is a view of the sensor viewed from the outside of the vehicle.

The measuring unit 4 includes a bracket (mounting member) 700 fixed to the inner surface of the laminated glass 1, a sensor (information acquisition device) 500 supported by the bracket 700, and a cover 800 (a cover 800) that covers the bracket 700 and the sensor from the inside of the vehicle. (See FIG. 17).

As shown in FIG. 13, the bracket 700 is formed in a rectangular frame shape having a mounting opening 701 in which the sensor 500 is arranged, and the rectangular main body portion 702 surrounding the mounting opening 701 and the main body portion 702. It is arranged on both sides, and includes two pairs of support portions 703 and 704 for fixing the sensor 500 and the cover 800, respectively. Here, the support portion arranged at the upper part of the main body portion 702 is referred to as a first support portion 703, and the support portion arranged at the lower portion is referred to as a second support portion 704. A flat surface is formed on the surface of the main body 702 facing the outside of the vehicle, and the adhesive 401 or the double-sided tape 402 is attached to the flat surface and fixed to the mask layer 2 or the laminated glass 1. However, the arrangement of the adhesive and the double-sided tape in FIG. 13 is an example, and may be other than this.

Various adhesives 401 can be used, and for example, urethane resin adhesives, epoxy resin adhesives, and the like can be used. However, since the epoxy resin adhesive has high viscosity, it is difficult to flow and is advantageous.

As shown in FIG. 13A, the sensor 500 is supported by the bracket 700 by both support portions 703 and 704, and is arranged so as to close the mounting opening 701. Then, as shown in FIG. 14, in the housing of the sensor 500, a recess 510 is formed on the surface facing the laminated glass 1 through the mounting opening 701. The concave portion 510 is inclined so that the upper end is the deepest and becomes shallower toward the lower end side, and the wall surface 520 at the upper end has a lens 530 of various elements such as a camera, a laser light receiving element, and an irradiation element. It is arranged, but its type and number are not particularly limited. Then, the sensor 500 photographs the outside with a camera, irradiates light from a laser, and receives light through the recess 510 and the laminated glass 1. Thereby, for example, the distance between the preceding vehicle or an obstacle and the own vehicle can be calculated based on the time until the reflected light is received by the light receiving element. The calculated distance is transmitted from the sensor to an external device and used for brake control and the like.

Further, after a harness or the like (not shown) is attached to the bracket 700, the cover 800 is attached from the inside of the vehicle as described later. As a result, the sensor 500 and the bracket 700 cannot be seen from the inside of the vehicle. In this way, the sensor 500 is housed in the space surrounded by the bracket 700, the cover 800, and the laminated glass 1. Since the center mask layer 22 is formed, the measurement unit 4 cannot be seen from the outside of the vehicle except for the opening 231. Further, the opening 231 is surrounded by the bracket 41 so that it cannot be seen from the inside of the vehicle. Further, the sensor 500 may be supported by the bracket 700 as described above, or may be supported by the cover 800.

<5. Windshield module manufacturing method>
Next, an example of a method for manufacturing the windshield module will be described. First, the windshield production line will be described. In the present invention, a laminated glass having a mask layer laminated is referred to as a windshield. However, in the following, since the mask layer is already laminated in the laminated glass manufacturing process, for convenience of explanation, Laminated glass is sometimes called a windshield.

<5-1. Windshield manufacturing ＞
As shown in FIG. 15, the heating furnace 901 and the molding apparatus 902 are arranged in this order from upstream to downstream in this production line. A roller conveyor 903 is arranged from the heating furnace 901 to the molding apparatus 902 and the downstream side thereof, and the glass plate (outer glass plate 11 or inner glass plate 12) 10 to be processed is the roller conveyor. Transported by 903. The glass plate 10 is formed in a flat plate shape before being carried into the heating furnace 901, and after the above-mentioned mask layer 2 is laminated on the glass plate 10, the glass plate 10 is carried into the heating furnace 901.

The heating furnace 901 can have various configurations, and can be, for example, an electric heating furnace. The heating furnace 901 includes a square tubular furnace body whose upstream and downstream ends are open, and a roller conveyor 903 is arranged inside the furnace from upstream to downstream. Heaters (not shown) are arranged on the upper surface, the lower surface, and the pair of side surfaces of the inner wall surface of the furnace body, respectively, and the temperature at which the glass plate 10 passing through the heating furnace 901 can be formed, for example, the softening point of the glass. Heat to the vicinity.

The molding apparatus 902 is configured to press the glass plate 10 with the upper die 921 and the lower die 922 to form the glass plate 10 into a predetermined shape. The upper mold 921 has a downwardly convex curved surface shape that covers the entire upper surface of the glass plate 10, and is configured to be movable up and down. Further, the lower mold 922 is formed in a frame shape corresponding to the peripheral edge portion of the glass plate 10, and the upper surface thereof has a curved surface shape corresponding to the upper mold 921. With this configuration, the glass plate 10 is press-molded between the upper die 921 and the lower die 922 to form a final curved surface shape. Further, a roller conveyor 903 is arranged in the frame of the lower mold 922, and the roller conveyor 903 can move up and down so as to pass through the frame of the lower mold 922. Although not shown, a slow cooling device (not shown) is arranged on the downstream side of the molding device 902 to cool the molded glass plate.

The roller conveyor 903 as described above is known, 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 can be attached to the end of each roller 931 and a chain can be wound around each sprocket to drive the roller 931. Then, by adjusting the rotation speed of each roller 931, the transport speed of the glass plate 10 can also be adjusted. The lower mold 922 of the molding apparatus 902 may be in contact with the entire surface of the glass plate 10. In addition, the molding apparatus 902 is not particularly limited in the form of the upper mold and the lower mold as long as it molds the glass plate 10.

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

Next, the main bonding is performed. The pre-bonded laminated glass is main-bonded by an autoclave, for example, at 8 to 15 atm and 100 to 150 ° C. Specifically, for example, the main bonding can be performed at 14 atm and 145 ° C. In this way, the laminated glass (windshield) according to the present embodiment is manufactured.

<5-2. Installation of anti-fog sheet>
Subsequently, as shown in FIGS. 16 and 17, the windshield is arranged on the installation table 94. At this time, the windshield is arranged on the support jig 95 on the installation table 94 with the outer glass plate 11 on the lower side. Further, the opening 231 of the windshield is arranged so as to protrude from the installation table 94. That is, the installation table 94 is not arranged below the opening 231. As a result, nothing is arranged under the opening 231 and a space is formed. Therefore, after the antifogging sheet 3 is attached, the antifogging sheet 3 is passed through the laminated glass 1 when the antifogging sheet 3 is attached. It is possible to easily confirm whether or not a defect, for example, dust or air is trapped.

Next, in the inner glass plate 12, the area around which the anti-fog sheet 3 including the opening 231 is attached (hereinafter referred to as the application area) is washed. Cleaning is performed by wiping the pasted area with, for example, a cloth impregnated with IPA, ethanol, industrial alcohol, or the like. Further, this removes dust, dirt and dirt on the surface of the sticking area on the inner glass plate 12. At this time, the entire inner glass plate 12 other than the sticking area can be cleaned.

Following this, the anti-fog sheet 3 is attached to the inner glass plate 12 exposed from the opening 231. First, the first protective sheet 34 is peeled off from the anti-fog laminate 30, and the exposed adhesive layer 31 is attached to the inner glass plate 12. The second protective sheet 35 is not peeled off, and the antifogging layer 33 is covered.

When attaching the anti-fog sheet 3, the operator stands on the upper side of the windshield, that is, the side on which the center mask layer 22 is arranged. This makes it easier to attach the anti-fog sheet 3. Then, the anti-fog sheet is positioned based on the contour of the opening 231. For example, when the anti-fog sheet 3 is formed smaller than the opening 231 by a predetermined length (for example, about 2 mm from the contour of the opening), as shown in FIG. 18, it is about 2 mm inside from the contour of the opening 231. Positioning is performed so that the contour of the anti-fog sheet 3 is arranged on the surface. Further, the reference position for positioning may be any of the contours of the opening 231. For example, any side of the opening 231, that is, any of the upper side, the lower side, the left side, and the right side may be used, or the corner of the opening 231 may be used. A portion, that is, any of the upper left corner portion, the upper right corner portion, the lower left corner portion, and the lower right corner portion can be used.

At this time, for example, the first protective sheet 34 is peeled off from the lower left corner of the anti-fog sheet 3, this corner is attached to the inside of the opening 231 and the first protective sheet 34 is peeled off toward the upper right corner. At the same time, the anti-fog sheet 3 is attached to the inner glass plate 12. Further, a squeegee 98 can be used for attaching the anti-fog sheet 3. For example, as shown in FIGS. 19 and 20, while pressing the anti-fog sheet 3 with the squeegee 98, the squeegee 98 is moved in the same direction as the first protective sheet 34 is peeled off. As a result, the air between the anti-fog sheet 3 and the inner glass plate 12 can be pushed out, and it is possible to prevent the air from accumulating between them.

The method of attaching the anti-fog sheet 3 is not limited to this, and for example, as shown in FIG. 21, the first protective sheet 34 is peeled off from the left side to the right side, and the squeegee 98 is also in the same direction. Can be moved to. Alternatively, as shown in FIG. 22, the first protective sheet 34 can be peeled off from the upper left corner toward the lower right corner, and the squeegee 98 can be moved in the same direction at the same time.

Various squeegees 98 can be used, and may be other than rod-shaped ones as described above. Further, in order to make the squeegee 98 slippery, a slippery Teflon (registered trademark) tape can be attached to the squeegee. The shape of the squeegee 98 is not particularly limited, and various shapes such as a spatula shape and a flat plate shape can be used. Further, the maximum length of the squeegee 98 is preferably longer than the left side or the right side of the opening 231 and more preferably longer than the diagonal line of the opening 231. However, in this case, when the squeegee 98 is moved, the area through which the squeegee 98 passes becomes larger than the opening 231. Therefore, if the bracket 700 is attached first, the squeegee 98 cannot be operated. Therefore, as described above, it is preferable to attach the anti-fog sheet 3 before attaching the bracket 700.

Further, the first protective sheet 34 can be divided into a plurality of pieces in order to make it easy to peel off from the adhesive layer 31. For example, a cut extending in the vertical direction is provided in the center of the left and right of the first protective sheet 34, the left side of the first protective sheet 34 is peeled off, the left side of the antifogging sheet 3 is attached, and then the right side of the first protective sheet 34 is attached. Can be peeled off and the right side of the anti-fog sheet 3 can be attached.

<5-3. Bracket mounting>
Next, mounting of the bracket will be described with reference to FIG. FIG. 23 is a view of the bracket 700 attached to the center mask layer 22 as viewed from the inside of the vehicle. As shown in the figure, the bracket 700 is attached to the center mask layer 22 so that the opening 231 of the center mask layer 22 is arranged in the attachment opening 701. In this way, the windshield module is completed.

After that, immediately before attaching the sensor 500 to the support portions 703 and 704, the second protective sheet 35 is removed to expose the antifogging layer 33, and then the sensor 500 and the cover 800 are attached to the bracket 700 in this order. The installation of the unit 4 is completed. Then, for example, the light from the sensor 500 is irradiated to the outside of the vehicle through the mounting opening 701 of the bracket 700 and the opening 231 of the mask layer 2.

However, it is preferable that the second protective sheet 35 is peeled off after about 24 hours have passed since the antifogging sheet was attached. This is because it takes a predetermined time for the adhesive layer to be fixed to the inner glass plate, and the fixing to the inner glass plate is almost completed after about 24 hours have passed.

<6. Features>
According to the windshield described above, the following effects can be obtained.

<6-1>
After the laminated glass (windshield) is completed by the main adhesion by the autoclave as described above, the laminated glass 1 is temporarily stored in the rack, and then moved to the installation table 94 and the antifogging sheet 3 is attached. However, in this process, dust, dirt, dirt, etc. often adhere to the surface of the windshield 1. Therefore, in the present embodiment, the area where the anti-fog sheet 3 is attached on the inner glass plate 12 of the windshield 1 is cleaned to remove dust and dirt. Then, after the anti-fog sheet 3 is attached, the bracket 700 is fixed. By sticking the anti-fog sheet 3 in such an order, it is possible to prevent dust and the like from entering between the inner glass plate 12 and the anti-fog sheet 3, and it is possible to prevent the sticking defect of the anti-fog sheet 3 from occurring. can do. Further, by cleaning, in addition to the above-mentioned dust, dust, dirt, etc., bubbles and the like can be removed, so that it is possible to prevent defects from occurring in the laminated glass 1 exposed through the opening 231 which is the information acquisition area. ..

<6-2>
In the above embodiment, the second protective sheet 35 is left attached to the anti-fog sheet 3 after the anti-fog sheet is attached until the cover or the like of the measurement unit 4 is attached. It is possible to prevent dust and the like from adhering to the antifogging layer 33 of the sheet 3.

<6-3>
By arranging the anti-fog sheet 3 in the opening 231 of the mask layer 2, fogging of the opening 231 can be prevented. Therefore, when the measurement unit 4 irradiates or receives light through the opening 231, the cloudiness of the opening 231 hinders the passage of light and prevents problems such as inability to perform accurate measurement. it can.

In particular, the upper part of the vehicle interior where the opening 231 of the mask layer 2 is provided tends to be cold and cloudy even when the heating is turned on. Therefore, it is advantageous that the antifogging layer 33 is provided at such a position. Further, the opening 231 of the mask layer 2 provided with the anti-fog layer 33 is surrounded by the bracket 41 or the measurement unit 4 is arranged so as to face each other. Therefore, there is a problem that warm air from heating or defroster is difficult to reach. Therefore, as described above, it is of great significance to provide the antifogging layer 33 in the region where warm air is difficult to reach.

Furthermore, it also has the following effects. The antifogging layer 33 may be separated from the interior parts (for example, resin molded product) in the vehicle, and the plasticizer that has flowed into the air may adhere to the antifogging layer 33. Then, if the plasticizer adheres to the antifogging layer 33, the antifogging function may be deteriorated. However, as described above, since the measuring unit is arranged at the opposite position of the antifogging layer 33 and further surrounded by the bracket 700, it is possible to prevent the plasticizer from adhering to the antifogging layer 33. .. As a result, in the anti-fog function, particularly the water-absorbing type anti-fog layer 33, it is possible to prevent the water absorption function from deteriorating. Further, in the hydrophilic type, since the plasticizer easily binds to the hydrophilic group in the antifogging layer, it is preferable that the measuring units 4 are arranged facing each other or surrounded by the bracket 700 as described above.

If the plasticizer adheres to the surface of the water absorption type antifogging layer 33 and accumulates for a long period of time, the water absorption will be hindered and the antifogging performance will deteriorate. However, if the plasticizer is wiped off with water, the water absorption performance will be restored. On the other hand, if a plasticizer adheres to the surface of the hydrophilic type antifogging layer 33, it will be strongly bonded to the hydrophilic group, and the hydrophilic performance will be deteriorated. Therefore, the difference in the thickness of the formed water film may cause distortion of the image through the antifogging layer 33 and deterioration of the antifogging performance in a short period of time.

<7. Modification example>
Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention. The following modifications can be combined as appropriate.

<7-1>
The shape of the antifogging sheet 3 is not particularly limited, and can be made smaller than the opening 231 of the mask layer 2 as described above, or can be made larger than the opening 231. For example, as shown in FIG. 24, the shape may be larger than the contour of the opening 231 by a predetermined length (for example, about 2 mm). As a result, the anti-fog sheet can be positioned based on the contour of the opening 231.

Alternatively, when the sensor has a camera and a laser, at least inside the opening 231 the area where the camera shoots is more prone to problems when fogging occurs than the laser, so the area where the camera shoots is anti-fog. Sheets can be pasted. For example, as shown in FIG. 25, when the anti-fog sheet 3 is attached to the area on the left side of the opening 231 where the camera is arranged, the anti-fog sheet 3 is formed so as to cover the left half of the opening 231 and the opening 231 is formed. The anti-fog sheet 3 can be attached by positioning with reference to the contour on the left side. At this time, the anti-fog sheet 3 can be sized so as to protrude to the left side of the opening 231. Similarly, the anti-fog sheet 3 can be attached by positioning with reference to the contour on the left side of the opening 231. ..

<7-2>
It is also possible to attach the jig 60 to the outer glass plate 11 side of the laminated glass 1 and position the anti-fog sheet 3 with reference to the jig 60 that transmits the laminated glass 1 when viewed from the inner glass plate 12 side. .. At this time, as shown in FIGS. 26 and 27, the jig 60 is attached to the outer glass plate 11 with reference to the center mask layer 22, and is based on the positioning mark 601 of the jig 60 that can be visually recognized from the opening 231. The anti-fog sheet 3 can be attached. As a result, the anti-fog sheet 3 does not come into contact with the jig 60, so that it is possible to prevent the anti-fog sheet 3 from becoming dirty.

<7-3>
In the above embodiment, the second protective sheet 35 is peeled off after the bracket 700 is attached, but the second protective sheet 35 can also be peeled off before the bracket 700 is attached. This is because, depending on the shape of the bracket 700, the bracket 700 may interfere and it may be difficult to peel off the second protective sheet 35.

<7-4>
The configuration of the support jig 95 in the installation table 94 is not particularly limited, and for example, as shown in FIG. 28, the windshield 1 can be supported by using the suction cup type support jig 95. In this case, it is preferable that the support jig 95 is not arranged below the opening 231 of the windshield 1. Further, the size of the installation table 94 is not particularly limited, and as shown in FIG. 28, even if it is larger than the windshield 1, a space may be formed at least below the opening 231. That is, it suffices to allow the laminated glass 1 to pass through so that it can be easily confirmed whether or not a defect at the time of attaching the antifogging sheet 3, for example, dust or air is caught.

<7-5>
In the above embodiment, the anti-fog sheet 3 is attached by the operator, but for example, it can be attached using a robot. As a result, the sticking accuracy is improved.

<7-6>
In the above embodiment, the first protective sheet 34 is peeled off to expose the adhesive layer 31, and then the anti-fog sheet 3 is attached to the windshield. At this time, the second protective sheet 35 is not accidentally peeled off. Therefore, it is preferable that the first and second protective sheets 34 and 35 can be distinguished from each other. For example, the colors of the first and second protective sheets 34 and 35 may be different, or a mark or the like may be provided on any of the first and second protective sheets 34 and 35, or the first and second protective sheets 34 may be provided. , 35 can be made of different materials. As the material, for example, one may be made of paper and the other may be made of a resin material, or one may be made of a material that does not allow characters to be written with a pen.

<7-7>
Since the anti-fog sheet 3 may be replaced, it is preferable that the anti-fog sheet 3 is configured so that it can be easily replaced. For example, when the anti-fog sheet 3 is formed into a polygonal shape such as a rectangle, as shown in FIG. 29, any one corner portion 305 is formed sharper than the other. For example, the radius of curvature can be made smaller or sharper than the other corners. Then, this sharp corner portion can be arranged outside the edge portion of the opening of the mask layer.

<7-8>
The mask layer 2 has a three-layer structure as described above, but the mask layer 2 is not limited to this. That is, in the above embodiment, the silver layer 242 is provided in order to shield the electromagnetic wave, but a method of providing a single layer in which silver and a ceramic layer are mixed, or if the electromagnetic wave can be shielded, another material such as , Copper, nickel, etc. may be laminated. Further, although the silver layer 242 is sandwiched between ceramic layers so as not to be seen from the outside, a member such as the cover described above can be used in addition to covering with the ceramic layer. Further, it is not always necessary to provide the silver layer 242 which is a shielding layer of electromagnetic waves, and at least it may be a layer which cannot be seen from the outside.

The mask layer 2 may be other than black, and is not particularly limited as long as it is a dark color such as brown, gray, or navy blue that shields the field of view from the outside of the vehicle and makes the inside of the vehicle invisible. Further, a part or all of the mask layer may be formed of a shielding film that can be attached to the laminated glass, whereby the field of view from the outside of the vehicle can be shielded. When the shielding film is attached to the outer surface of the inner glass plate 12 on the vehicle side, it can be attached before the pre-adhesion or after the main adhesion.

Further, in the laminated glass, from the viewpoint of preventing fogging of the light passage, the mask layer is not always necessary, and the fogging layer may be formed in the region through which the light passes (information acquisition region).

<7-9>
In the above embodiment, the sensor 5 for measuring the inter-vehicle distance is used as the information acquisition device of the present invention, but the present invention is not limited to this, and various information acquisition devices can be used. That is, it is not particularly limited as long as it irradiates and / or receives light in order to acquire information from the outside of the vehicle. For example, a visible light and / or infrared camera for measuring the distance between vehicles, a light receiving device that receives signals from outside the vehicle such as an optical beacon, and a camera that uses visible light and / or infrared rays that read white lines on the road as images. It can be applied to various devices such as a stereo camera and a stereo camera. When using a stereo camera, it is necessary to provide two openings.

1 Laminated glass 3 Anti-fog sheet 500 sensor (information acquisition device)
700 bracket (mounting member)
8 sticker

Claims (9)

A shield that defines the information acquisition area on a laminated glass that faces an information acquisition device that acquires information from outside the vehicle by irradiating and / or receiving light and has at least one information acquisition area through which the light passes. Steps to prepare the layered windshield,
The step of installing the windshield on the workbench and
The step of cleaning the information acquisition area and
In the windshield, a step of attaching an antifogging sheet to at least an area including the information acquisition area,
A step of attaching an attachment member for supporting the information acquisition device and facing the information acquisition area to the windshield,
Bei to give a,
A plurality of corners are formed on the peripheral edge of the antifogging sheet, and at least one of the plurality of corners is formed sharper than the other corners, and the sharp corners are formed. A method for manufacturing a windshield module , which is arranged on the shielding layer . The method for manufacturing a windshield module according to claim 1, wherein a space is formed below the information acquisition area when the windshield is installed on the workbench. In the step of attaching the anti-fog sheet,
The method for manufacturing a windshield module according to claim 1 or 2, wherein an operator stands on the information acquisition area side of the windshield and attaches the antifogging sheet to the information acquisition area. In the step of attaching the anti-fog sheet,
The method for manufacturing a windshield module according to claim 1 or 2, wherein the antifogging sheet is attached to the information acquisition area by a robot. The shielding layer has an opening that defines the information acquisition region.
The method for manufacturing a windshield module according to any one of claims 1 to 4, wherein the application of the antifogging sheet is positioned with reference to the contour of the opening. Prior to the step of attaching the anti-fog sheet,
Based on the contour of the shielding layer, the windshield is further provided with a step of attaching a positioning jig to the surface of the windshield opposite to the surface to which the antifogging sheet is attached.
The window according to any one of claims 1 to 4, wherein in the step of attaching the antifogging sheet, positioning is performed based on the jig visually recognized through the laminated glass, and the antifogging sheet is attached. How to make a shield module. The anti-fog sheet is formed by laminating at least an anti-fog layer, a base film, and an adhesive layer in this order, and further, a first protective sheet covering the adhesive layer is attached.
In the step of attaching the anti-fog sheet,
While peeling the first protective sheet from any edge of the anti-fog sheet toward the opposite edge, the squeegee is moved from any of the edges toward the opposite edge on the anti-fog sheet. The method for manufacturing a windshield module according to any one of claims 1 to 6, wherein the antifogging sheet is attached to the windshield while pressing. The anti-fog sheet is formed by laminating at least an anti-fog layer, a base film, and an adhesive layer in this order, and further, a second protective sheet covering the anti-fog layer is attached.
The windshield module according to any one of claims 1 to 7, further comprising a step of peeling the second protective sheet from the antifogging sheet 24 hours after the application of the antifogging sheet. Manufacturing method. The anti-fog sheet is formed by laminating at least an anti-fog layer, a base film, and an adhesive layer in this order, and further, a first protective sheet covering the adhesive layer and a first protective sheet covering the anti-fog layer. Equipped with 2 protective sheets
The method for manufacturing a windshield module according to any one of claims 1 to 8, wherein the first protective sheet and the second protective sheet are configured to be distinguishable.