TWI719932B - Glass laminate with protective film - Google Patents

Abstract

The present invention relates to a glass laminate with a protective film, containing a glass laminate containing a transparent substrate having a first major surface and a second major surface, an antireflective layer above the first major surface and a light-shielding layer provided above a peripheral area of the second major surface, and a protective film with an adhesive layer, in which the protective film is stuck on the glass laminate at a location that, in a front view of the glass laminate, a peripheral edge of the protective film is situated toward an outer perimeter side with respect to an inner perimeter side of the light-shielding layer, and that toward an inner perimeter side with respect to an outer perimeter side of the light-shielding layer, and an adhesion between the glass laminate and the adhesive layer is from 0.01 N/10 mm to 0.3 N/10mm.

Description

Laminated glass with protective film

The present invention relates to laminated glass with protective film.

In recent years, the use of glass plates with high-quality texture, high strength and excellent heat resistance as display device panels for the purpose of protecting display devices has increased. As a display panel for in-vehicle devices (such as car navigation systems or dashboards), or as a display panel for mobile devices (such as mobile phones), it is necessary to be equipped from the viewpoint of preventing background reflection and stain adhesion Panels with anti-reflective layer or anti-fouling layer. In addition, from the viewpoint of protecting the product when installing the panel on the display device, it is necessary to stick the protective film finally peeled from the panel on the top side (display surface) of the panel (see Patent Document 1 and Patent Document 2). Patent Document 1: WO2011/148990 Patent document 2: WO2011/118367.

On the laminated glass used as the panel of the display device, the protective film is pasted through the adhesive medium. However, when the protective film is peeled off, a situation occurs in which at least a part of the material constituting the antireflection layer or the antifouling layer formed on the main surface of the transparent substrate is peeled off by the adhesive of the adhesive layer formed on the protective film, Or the adhesive constituting the adhesive layer remains on at least a part of the surface of the laminated glass, depending on the adhesiveness of the adhesive constituting the adhesive layer of the protective film attached to the laminated glass. Due to this difficulty, the following problems may be caused: at the boundary between the protective film pasting area and the non-protecting film pasting area, the hue of the color changes, and the boundary becomes prominent and affects visual appreciation. The main reason for this problem lies in the fact that the attachment of the low-reflection layer reduces the surface reflectivity, causing small changes in the color tone to be visually easy to recognize, and because of the use of optical interference, the low-reflection layer is affected by the film thickness and refractive index on the surface. The effect of the change causes the color tone and reflectivity to change. In addition, in the case where the size of the protective film is larger than the laminated glass used as the panel, the following problems may be caused: for example, the protective film is trapped in the gap of the display device housing when the panel is installed on the display device, thereby causing difficulties from the production point of view. The laminated glass with a protective film of the present invention is a laminated glass with a protective film, which contains: Laminated glass comprising at least a transparent substrate having a first main surface and a second main surface, an anti-reflection layer above the first main surface, and a light-shielding layer provided above the peripheral area of the second main surface, and Protective film with adhesive layer, The protective film with the adhesive layer is pasted on the laminated glass at the following position: In the front view of the laminated glass, the peripheral edge of the protective film with the adhesive layer is positioned relative to the inner peripheral side of the light-shielding layer toward the outer peripheral side, and they are opposite Positioning on the outer peripheral side of the light shielding layer toward the inner peripheral side, and The adhesion between the laminated glass and the adhesive layer is 0.01 N/10 mm to 0.3 N/10 mm. In the laminated glass with the protective film of the present invention, the laminated glass preferably further contains an antifouling layer on the opposite side of the transparent substrate above the anti-reflection layer, and the adhesion between the laminated glass and the adhesive layer The performance is 0.01 N/10 mm to 0.05 N/10 mm. In the laminated glass with a protective film of the present invention, the length t is preferably defined as connecting any point on the peripheral edge of the outermost surface of the laminated glass and passing through the arbitrary point from the peripheral edge of the outermost surface of the laminated glass. When the length of the line segment at the point where the perpendicularly oriented straight line extending from the peripheral edge of the protective film crosses the nearest peripheral edge of the protective film, the length t is greater than 0 mm and less than 10 mm. In the laminated glass with the protective film of the present invention, preferably, the light-shielding layer is formed in a range from more than 0 mm to less than 30 mm from the outer peripheral side of the second main surface of the transparent substrate. In the laminated glass with a protective film of the present invention, preferably, the adhesive layer contains an adhesive containing an acrylic-based adhesive or a polyurethane-based adhesive as a main component. In the laminated glass with a protective film of the present invention, preferably, the laminated glass has a light reflectivity of 2% or less on the surface formed by the anti-reflection layer in the region where the light-shielding layer is formed, wherein the light Reflectance is measured by removing the effect from the backside reflection. In the laminated glass with the protective film of the present invention, preferably, the laminated glass has 2% or less of light on the surface formed by the anti-reflection layer and the anti-fouling layer in the area where the light-shielding layer is formed. Reflectance, where the light reflectance is measured by removing the effect from the backside reflection. In the laminated glass with a protective film of the present invention, preferably, the antifouling layer is formed of an antifouling agent containing a fluorine-containing compound. In the laminated glass with a protective film of the present invention, preferably, the first main surface of the transparent substrate has unevenness. In the laminated glass with a protective film of the present invention, preferably, the transparent substrate is a chemically toughened glass. According to the present invention as mentioned above, the adhesiveness of the adhesive constituting the adhesive layer of the protective film is adjusted to fall within a specified range, and thus it is possible to prevent the adhesive from remaining on at least a part of the outermost surface of the laminated glass And prevent at least a part of the materials constituting the anti-reflection layer, anti-fouling layer or the like from being peeled off, thereby obtaining a good appearance without visually recognizable boundaries between different tones on the surface of the display. In addition, in the laminated glass with the protective film of the present invention, the protective film with the adhesive layer is stuck on the laminated glass at the following position: the peripheral edge of the protective film is positioned toward the outer peripheral side with respect to the inner peripheral side of the light-shielding layer, and in addition , It is positioned toward the inner peripheral side with respect to the outer peripheral side of the light shielding layer, thereby enhancing the handling properties when installing laminated glass with a protective film as a display device panel.

The laminated glass with protective film of the present invention is described in detail below with reference to the drawings. Although the present invention is explained below with specific embodiments, the present invention should not be regarded as being limited in any way by the following description of these specific embodiments, and needless to say, without departing from the spirit and scope of the present invention If appropriate, various additions, omissions, modifications, substitutions and other changes can be made to multiple components. 1 to 3 are cross-sectional views illustrating exemplary embodiments of the laminated glass with protective film of the present invention. Hereinafter, a laminated glass with a protective film is sometimes referred to as "a laminated glass with a protective film". Similarly, a protective film with an adhesive layer is sometimes referred to as a "protective film attached to the adhesive layer". Incidentally, when the protective film-loaded laminated glass 1 explained in each of the first to third embodiments is provided on the image display side (viewer side) of the display panel, it can be used as a protective display The panel of the board. (First Embodiment) The first embodiment of the laminated glass with protective film of the present invention is illustrated in FIG. 1. The laminated glass 1 carrying the protective film includes a protective film 80 attached with an adhesive layer and a laminated glass 90. The laminated glass 90 includes a transparent substrate 10 having a first major surface and a second major surface, and a first surface of the transparent substrate 10 The anti-reflection layer 20 formed on the main surface and the light-shielding layer 70 formed on the peripheral portion of the second main surface of the transparent substrate 10. The protective film 80 to which the adhesive layer is attached is stuck on the laminated glass 90. In the front view of the laminated glass 90, the protective film 80 with the adhesive layer is attached to the laminated glass 90 at the following position: the peripheral edge of the protective film 80 with the adhesive layer is facing the outer peripheral side with respect to the inner peripheral side of the light shielding layer 70 It is positioned and positioned toward the inner periphery with respect to the outer periphery of the light shielding layer 70. In addition, the adhesion between the anti-reflection layer 20 formed as the outermost surface of the laminated glass 90 and the adhesive layer 40 is adjusted to fall within the range of 0.01 N/10 mm to 0.3 N/10 mm. By adjusting the adhesiveness between the adhesive layer 40 and the anti-reflection layer 20 to be formed as the main surface of the laminated glass 90 to fall within the range of 0.01 N/10 mm to 0.3 N/10 mm, it is possible to avoid forming the adhesive layer The adhesive remains on at least a part of the outermost surface of the laminated glass 90. By adjusting the adhesiveness between the adhesive layer 40 and the anti-reflection layer 20 to be formed as the main surface of the laminated glass 90 to fall within the range of 0.01 N/10 mm to 0.3 N/10 mm, it is possible to avoid forming the laminated glass At least a part of the material of the anti-reflection layer 20 formed on the outermost surface of 90 is peeled off by the adhesive constituting the adhesive layer. In addition, according to the first embodiment of the laminated glass with the protective film of the present invention, the protective film 80 to which the adhesive layer is attached is adhered to the laminated glass 90 so that the length t is defined as the peripheral edge connecting the outermost surface of the laminated glass 90 When the arbitrary point on the above and the length of the line segment that passes through the arbitrary point from the peripheral edge of the outermost surface of the laminated glass to the peripheral edge of the protective film and the line segment that intersects the nearest peripheral edge of the protective film, the The length t is greater than 0 mm and less than 10 mm (see Figure 4). In this embodiment, the light shielding layer 70 formed on the peripheral area of the second main surface of the transparent substrate 10 forms a band-shaped area having a predetermined width from the peripheral edge to the center of the second main surface of the transparent substrate 10. (Second Embodiment) The second embodiment of the laminated glass with protective film of the present invention is illustrated in FIG. 2. The laminated glass 1 carrying the protective film includes a protective film 80 attached with an adhesive layer and a laminated glass 90. The laminated glass 90 includes a transparent substrate 10 having a first major surface and a second major surface, and a first surface of the transparent substrate 10 The anti-reflection layer 20 formed on the main surface and the light-shielding layer 70 formed on the peripheral portion of the second main surface of the transparent substrate 10. The laminated glass 90 in the second embodiment of the laminated glass with a protective film of the present invention is further provided with an anti-fouling layer 30 on the main surface of the anti-reflection layer. The protective film 80 to which the adhesive layer is attached is stuck on the laminated glass 90. In the front view of the laminated glass 90, the protective film 80 with the adhesive layer is attached to the laminated glass 90 at the following position: the peripheral edge of the protective film 80 with the adhesive layer is facing the outer peripheral side with respect to the inner peripheral side of the light shielding layer 70 It is positioned and positioned toward the inner periphery with respect to the outer periphery of the light shielding layer 70. In addition, the adhesion between the antifouling layer 30 formed as the outermost surface of the laminated glass 90 and the adhesive layer 40 is adjusted to fall within the range of 0.01 N/10 mm to 0.05 N/10 mm. By adjusting the adhesion between the adhesive layer 40 and the antifouling layer 30 to be formed as the main surface of the laminated glass 90 to fall within the range of 0.01 N/10 mm to 0.05 N/10 mm, it is possible to avoid forming the adhesive layer The adhesive remains on at least a part of the outermost surface of the laminated glass 90. By adjusting the adhesiveness between the adhesive layer 40 and the antifouling layer 30 to be formed as the main surface of the laminated glass 90 to fall within the range of 0.01 N/10 mm to 0.05 N/10 mm, it is possible to avoid forming the laminated glass At least a part of the material of the antifouling layer 30 formed on the surface of the outermost layer 90 is peeled off by the adhesive constituting the adhesive layer. In addition, according to the second embodiment of the laminated glass with a protective film of the present invention, the protective film 80 to which the adhesive layer is attached is adhered to the laminated glass 90 so that the length t is defined as the peripheral edge connecting the outermost surface of the laminated glass 90 The length of the vertical line extending from the peripheral edge of the outermost surface of the laminated glass with the antifouling layer to the peripheral edge of the protective film through the arbitrary point on the above and the line segment between the point where the nearest peripheral edge of the protective film intersects with the arbitrary point When the length t is greater than 0 mm and less than 10 mm (see Figure 4). (Third Embodiment) The third embodiment of the laminated glass with protective film of the present invention is illustrated in FIG. 3. The third embodiment of the present invention is the following embodiment: in the laminated glass 90 in which the anti-reflection layer 20 is provided as presented in the first embodiment, or in the second embodiment, in which the arrangement is in this order In the laminated glass 90 with the anti-reflection layer 20 and the anti-fouling layer 30, an anti-glare layer 60 is further formed between the first main surface of the transparent substrate 10 and the anti-reflection layer 20. 3 illustrates the following embodiment: in the laminated glass with the anti-fouling layer 30 (the second embodiment), the anti-glare layer 60 is formed between the first main surface of the transparent substrate 10 and the anti-reflection layer 20. However, needless to say, the anti-glare layer 60 can also be formed in a laminated glass without the anti-fouling layer 30 (first embodiment). <Laminated glass> Laminated glass contains at least a transparent substrate having a first main surface and a second main surface, an anti-reflection layer formed on/over the first main surface of the transparent substrate, and an end surface adjacent to the second main surface of the transparent substrate A light-shielding layer formed on/over the peripheral area. The laminated glass may further contain an anti-fouling layer on/above the main surface of the anti-reflection layer. In laminated glass, an anti-glare layer can be formed between the first main surface of the transparent substrate and the anti-reflection layer. <Protective film with adhesive layer> A protective film with an adhesive layer is formed by attaching the adhesive layer to one side of the protective film. In order to protect the display panel installed on the display device during the production process and product transportation, the protective film with the adhesive layer is kept stuck on the outermost surface of the laminated glass, thereby protecting the laminated glass. When using the display device, the protective film with the adhesive layer is peeled off from the laminated glass. By adjusting the adhesiveness of the adhesive constituting the adhesive layer to be attached to the protective film, it is possible to prevent the adhesive constituting the adhesive layer from remaining on at least a part of the outermost surface of the laminated glass. By adjusting the adhesiveness of the adhesive constituting the adhesive layer to be attached to the protective film, it is possible to avoid at least a part of the material constituting the anti-reflection or antifouling layer formed on the surface of the laminated glass. The adhesive peels off. The protective film with the adhesive layer is pasted on the outermost surface of the laminated glass. The protective film with the adhesive layer is pasted on the laminated glass at the following position: when viewing the laminated glass from the front side, the peripheral edge of the protective film is positioned relative to the inner peripheral side of the light-shielding layer toward the outer peripheral side, and relative to the outer peripheral side of the light-shielding layer Position towards the inner circumference. Therefore, when installing laminated glass as a panel of a display device (such as a liquid crystal display (LCD), a plasma display panel (PDP) or an electroluminescence display (ELD)), it is possible to reduce the amount of protection film with an adhesive layer trapped in the device housing. Therefore, when installing laminated glass with a protective film on the display device, the handling properties are enhanced. The term "the peripheral edge of the protective film with the adhesive layer" refers to the edge away from the center of the protective film with the adhesive layer. Generally speaking, the protective film with the adhesive layer has a rectangular shape, and in the case of the rectangular shape, at least a part of the peripheral edge is formed by a straight line. If appropriate, the shape of the protective film with the adhesive layer changes in accordance with the shape of the laminated glass, and therefore at least a part of the peripheral edge can be formed by a curve. In addition, the protective film with the adhesive layer is pasted on the laminated glass at the following position: the length t is defined as connecting any point on the peripheral edge of the outermost surface of the laminated glass and the periphery from the outermost surface of the laminated glass through the arbitrary point When the length of the line segment at the point where the vertical straight line extending from the edge to the peripheral edge of the protective film intersects the nearest peripheral edge of the protective film with the adhesive layer, the length t is greater than 0 mm and less than 10 mm. Therefore, it is possible to enhance the handling properties when the laminated glass with the protective film is installed on the display device. The protective film is preferably placed so that its peripheral edge is located directly above the position away from the peripheral edge of the laminated glass and toward the center of the laminated glass less than 10 mm. This is because the purpose of protecting laminated glass from impact and the like becomes easy to achieve. In addition, for the purpose of enhancing the ease of peeling off the protective film with the adhesive layer from the laminated glass, a tongue segment that makes it easy to pick up the edge of the protective film can be provided, or it can be placed on the peripheral edge of the protective film with the adhesive layer. At least a part is provided with an area on which no adhesive layer is formed. Therefore, the protective film with the adhesive layer can be easily peeled off from the laminated glass. Incidentally, the tongue segment set for the purpose of making it easy to peel off can extend beyond the periphery to the extent that it does not affect the handling properties. When the laminated glass with the anti-reflection layer and/or the anti-fouling layer is combined with the protective film with the adhesive layer, manual work can be adopted. However, from the viewpoint of production efficiency, it is preferable that the protective film with the adhesive layer supplied in the form of a rolled-up reel is subjected to laminating with a rubber roller or the like, or the protective film with the adhesive layer is preliminarily protected according to the size of the laminated glass The film is cut into a sheet-shaped protective film, and then subjected to lamination by means of a labeling machine, a seal pasting machine or the like. <Adhesive layer> An adhesive layer is provided on one side of the protective film to form a protective film to which the adhesive layer is attached. The degree of adhesion of the adhesive system suitable for the adhesive layer is such that when the protective film with the adhesive layer is peeled from the laminated glass, the adhesive even resists the adhesive remaining on at least a part of the outermost surface of the laminated glass. The adhesion of the adhesive system suitable for the adhesive layer is such that when the protective film with the adhesive layer is peeled from the laminated glass, the adhesive is inhibited and even the adhesive of at least a part of the material constituting the anti-reflective layer or the anti-fouling layer of the laminated glass is peeled off. As the adhesive of the adhesive layer specified above, it is preferable to use acrylic-based adhesives, polyurethane-based adhesives, and the like in terms of adhesiveness and peeling properties. As long as the adhesive layer has an adhesiveness of 0.01 N/10 mm or more, the adhesive can be uniformly adhered to the outermost surface of the laminated glass, and the adhesive is allowed when the protective film attached to the adhesive layer is attached to the laminated glass The layer is uniformly adhered to the surface of the anti-reflective layer or the surface treatment agent of the anti-fouling layer formed on the outermost surface of the laminated glass. In addition, there is no need to worry about delaminating the protective film from the laminated glass during transportation, etc., and impairing its function as a protective film. As long as the adhesive layer has adhesion of 0.3 N/10 mm or less, the adhesive layer has moderate adhesion, and therefore there is no need to worry about causing defects so that it can be used as a laminated glass when peeling off the protective film attached to the adhesive layer At least part of the surface treatment agent of the anti-reflective layer formed on the surface of the outermost layer is peeled by the adhesive in an amount greater than required, or the adhesive of the adhesive layer constituting the protective film attached to the adhesive layer remains in the laminated glass. In at least a part of the surface layer, and therefore visibility is reduced and staining occurs. In the case where the protective film attached with the adhesive layer is pasted on the laminated glass forming the anti-reflection layer as the outermost surface, the adhesion between the adhesive layer and the anti-reflection layer is preferably 0.03 N/10 mm to 0.3 N /10 mm, and more preferably 0.05 N/10 mm to 0.15 N/10 mm. By adjusting the adhesiveness to a value within a preferable range, it is possible to inhibit the adhesive from remaining on the anti-reflection layer and prevent the material constituting the anti-reflection layer from being peeled off by the adhesive. In the case of attaching the protective film attached with the adhesive layer to the laminated glass forming the antifouling layer as the outermost surface, the adhesion between the adhesive layer and the antifouling layer is preferably 0.01 N/10 mm to 0.05 N/ 10 mm, and more preferably 0.02 N/10 mm to 0.04 N/10 mm. By adjusting the adhesiveness to a value within a preferable range, it is possible to inhibit the adhesive from remaining on the antifouling layer and prevent the material constituting the antifouling layer from being peeled off by the adhesive. Specifically, the adhesive tends to remain on the surface of the antifouling layer or the material constituting the antifouling layer is easily peeled off by the adhesive. Therefore, it should be understood that the adhesiveness between the adhesive layer and the anti-fouling layer is adjusted to a value lower than the adhesiveness between the adhesive layer and the anti-reflective layer. According to the adhesion and peeling ability of the adhesive layer of the protective film attached to the adhesive layer with respect to the anti-reflective layer or the antifouling layer, the thickness of the adhesive layer is preferably 3 μm to 50 μm, and more preferably 5 μm to 25 μm. <Protective film> There is no particular restriction on the protective film, as long as it is made of resin and has a film-like form. In addition, the protective film may have a single-layer structure or a multi-layer structure formed by laminating a plurality of layers, the plurality of layers including an antistatic layer, a hard coat layer, and an easy-adhesive layer. In addition, the protective film can be colored in any color to avoid forgetting to peel the protective film with the adhesive layer from the laminated glass. As the protective film, for example, a polyester film such as a polyethylene terephthalate film; a polyolefin film such as a polyethylene film and a polypropylene film; a polyvinyl chloride film or the like can be used. Among these films, the polyester film is better in terms of adhesion to the adhesive layer, durability, and optical characteristics. The thickness of the protective film is not particularly limited, but the thickness is preferably, for example, 5 μm to 100 μm. The thickness in the range of 15 μm to 75 μm is more preferable because the film having a thickness in this range is easy to bend and easy to peel off. On the other hand, a protective film thinner than 5 μm may not provide sufficient protection for the laminated glass, and a protective film thicker than 100 μm can increase the cost. <Transparent substrate> Examples of transparent substrates include commonly used glass plates, such as plates made from soda lime glass, borosilicate glass, aluminosilicate glass and alkali-free glass, and made from inorganic materials with various compositions The inorganic glass plate and transparent resin plate. Examples of materials for the most suitable glass plates include glass materials such as soda lime glass, quartz glass, crystal glass, and sapphire glass. Among these materials, the better one is highly transparent glass with lower iron content and less blue tint. As the material of the transparent resin board, highly transparent resin materials are suitable. Examples of transparent resin plates include polyester resins, such as polycarbonate and polyethylene terephthalate; polyolefin resins, such as polypropylene and polyvinyl chloride; acrylic resins, polyether ether, polyarylate, and triacetate Base cellulose and polymethyl methacrylate. As a transparent substrate, a glass plate is the best because it not only has high transparency, but also has light resistance, heat resistance, low refraction, high flatness accuracy, surface scratch resistance and high mechanical strength. For the purpose of increasing the safety of the glass plate, the mechanical strength can be improved. In order to improve the mechanical strength of the glass plate, the glass plate is subjected to toughening treatment in advance. Examples of toughening treatment include physical toughening by exposing the glass plate to a high-temperature atmosphere and then cooling the glass plate in the air, and by immersing the glass plate in a molten salt containing an alkali metal for storage in the molten salt And the alkali metal (ion) with a large atomic diameter replaces the alkali metal (ion) with a small atomic diameter stored in the outermost surface of the glass plate to achieve chemical toughening. Especially in the case of using a thin glass plate, the glass plate used is preferably a glass plate that has undergone chemical toughening (also referred to as chemically toughened glass). The chemically toughened glass as a transparent substrate preferably satisfies the following conditions. Specifically, preferably, the surface compressive stress of the glass substrate (hereinafter abbreviated as CS) is 400 MPa to 1,200 MPa, and more preferably 700 MPa to 900 MPa. From the viewpoint of actual strength, a CS of 400 MPa or more is sufficient. On the other hand, as long as the glass substrate has a CS of 1,200 MPa or less, the glass substrate can withstand its own compressive stress without the possibility of spontaneous cracking. In the case of using the protective film-loaded laminated glass 1 of the present invention as a display device or the like (cover glass), the CS of the glass substrate is preferably in the range of 700 MPa to 850 MPa. In addition, preferably, the depth of the stress value of the glass substrate (hereinafter referred to as DOL) is 15 μm to 50 μm, and preferably 20 μm to 40 μm. As long as the glass substrate has a DOL of 15 μm or greater, there is no need to worry about the glass substrate being easily scratched and broken. On the other hand, as long as the glass substrate has a DOL of 40 μm or less, the glass substrate can withstand its own compressive stress without the possibility of spontaneous cracking. In the case of using the protective film-loaded laminated glass 1 of the present invention as a display device or the like (cover glass), preferably, the DOL of the glass substrate is in the range of 25 μm to 35 μm. In terms of mechanical strength, sapphire glass is also suitable as a glass substrate. The transparent substrate is generally smooth and has a rectangular shape. If appropriate, the required shape of the transparent substrate can vary according to the shape of the display panel on the display device, the design of the display device, the installation position of the display device, and the like. In other words, the shape of the transparent substrate is not limited to smooth geometry and rectangular shape. For example, the transparent substrate may be a patterned glass with concave and convex on the surface, and it may have a polygonal shape, a circular shape, or an elliptical shape. In addition, the transparent substrate can be not only a flat glass plate but also a glass plate with a curved surface. The term "peripheral edge of the transparent substrate" refers to the end side away from the center of the transparent substrate. Generally speaking, the transparent substrate has a rectangular shape, and in the case of the rectangular shape, at least a part of the peripheral edge is formed by a straight line. If appropriate, the shape of the transparent substrate changes in accordance with the shape of the display panel or the like, and therefore at least a part of the peripheral edge can be formed by a curve. The size of the transparent substrate is appropriately selected according to the size of the display panel or the purpose of using the display device. For example, in the case of being used as a cover glass for a mobile device, the size of the transparent substrate is preferably in the range of 30 mm × 50 mm to 300 mm × 400 mm, and its thickness is in the range of 0.1 mm to 2.5 mm; and In the case of use in a vehicle navigation system, control panel, instrument panel or the like, the size of the transparent substrate is preferably in the range of 50 mm × 100 mm to 2,000 mm × 1,500 mm and its thickness is 0.5 mm to 4 mm Within range. However, the transparent substrate is not particularly limited with respect to its thickness, and the glass plate can be used as the transparent substrate as long as the thickness is 10 mm or less. Regarding mechanical strength, transparency, etc., the thickness of a glass plate used as a transparent substrate is usually about 0.1 mm to 6 mm. Especially in the case of using a glass plate as a transparent substrate in a vehicle-mounted display device, the safety of the glass plate is required, and therefore, from the viewpoint of mechanical strength, its thickness is preferably in the range of 0.2 mm to 2 mm. In the case of using chemically toughened glass for the purpose of efficient chemical toughening treatment, the suitable thickness of the glass substrate is usually 5 mm or less, and preferably 3 mm or less. In the case of using a transparent resin board, the appropriate thickness of the board is 2 mm to 10 mm. The smaller the thickness of the substrate, the more light absorption is reduced, and therefore in terms of improving visibility and transparency, the use of glass plates is better. In addition, it is not necessary that the transparent substrate must have a single-layer structure formed of a single layer, and it may have a multilayer structure formed of multiple layers, such as a laminated glass structure. <Anti-reflective layer> The anti-reflective layer is a layer formed for the purpose of improving the image quality of the display by suppressing the reflection of ambient light, and it is usually formed on/over the first main surface of the transparent substrate. In the case where the anti-glare treatment has been performed on the first main surface of the transparent substrate, the anti-reflection layer 20 is appropriately formed on/over the anti-glare layer 60 produced by the anti-glare treatment. The anti-reflective layer has no particular limitation on its structure, as long as the structure allows light reflection to be reduced to a certain range. For example, the anti-reflection layer may have a laminated structure including a low refractive index layer and a high refractive index layer. In this context, the high refractive index layer refers to a layer having a refractive index of, for example, 1.9 or higher, as measured using light with a wavelength of 550 nm, and a low refractive index layer refers to a layer having a refractive index as measured using 550 nm light For example, the layer is 1.6 or lower. Regarding the number of the high refractive index layer and the low refractive index layer in the anti-reflection layer, it may take a form including one high refractive index layer and one low refractive index layer, or it may be formed to have more than one high refractive index layer and low refractive index layer. structure. In the case of adopting a form including each of a high refractive index layer and a low refractive index layer, it is appropriate that the high refractive index layer and the low refractive index layer are stacked on the main surface of the transparent substrate in the stated order. On the other hand, in the case of forming a structure having one or more high-refractive index layers and low-refractive index layers, a form including high-refractive index layers and low-refractive index layers alternately stacked in the stated order is appropriately adopted. For enhancing the anti-reflection performance, preferably, the anti-reflection layer is a laminate in which two or more layers are stacked on top of each other. The build-up layer preferably has a total of 2 to 8 layers stacked on top of each other, more preferably a total of 2 to 6 layers stacked on top of each other, and further preferably a total of 2 to 4 layers stacked on top of each other. As mentioned above, the preferred laminate in this article is a laminate in which high refractive index layers and low refractive index layers are alternately stacked, and the total number of high refractive index layers and low refractive index layers is within the range specified above. In addition, other layers can be added within a range that does not affect the optical characteristics. For example, in order to prevent the diffusion of Na from the glass substrate, a SiO ₂ film may be inserted between the glass and the first layer. The main components of the high refractive index layer and the low refractive index layer are not particularly limited, and they can be selected after considering the required degree of anti-reflection and productivity. Examples of the main components in the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅₎ , aluminum oxide (Al ₂ O ₃ ) And silicon nitride (SiN). One or more types selected from these materials can be preferably used as the main component in the high refractive index layer. Examples of the main components in the low refractive index layer include silicon _{oxide (especially silicon dioxide SiO 2} ), materials containing Si-Sn mixed oxides, materials containing Si-Zr mixed oxides, and materials containing Si-Al mixed oxides. material. One or more types selected from these materials can be preferably used in the low refractive index layer. From the viewpoint of productivity and refractive index, preferably, the high refractive index layer is composed of a species selected from niobium oxide, tantalum oxide, or silicon nitride, and the low refractive index layer is composed of silicon oxide. The anti-reflective layer can be suitably formed by directly forming an inorganic thin layer on the surface on which it is to be formed, by using an etching technique or the like to perform surface treatment or a dry process (e.g., chemical vapor deposition (CVD)) It is formed by a process or a physical vapor deposition (PVD) process, especially a vacuum deposition process or a sputtering process as one of the physical vapor deposition processes. It may also take a form in which an anti-reflection layer and an anti-fouling layer are provided on/above the first main surface of the transparent substrate in the stated order. In this case, when it is intended to make it easy to apply the anti-fouling layer to the anti-reflection layer, the anti-reflection layer may be formed by a wet process. As an example of an anti-reflection layer formed by a wet process, a layer containing low refractive index particles can be mentioned, especially a layer containing low refractive index particles in a matrix component used as a binder. Alternatively, the anti-reflection layer can be provided by using a method of pasting a transparent resin film with anti-reflection function on the transparent substrate. The thickness of the anti-reflection layer is preferably 100 nm to 500 nm. It is advantageous to adjust the thickness of the anti-reflection layer to 100 nm or more, which is why a thickness allows the reflection of ambient light to be effectively reduced. <Antifouling layer> The antifouling layer has at least oil repellency or lipophilicity. The anti-fouling layer can prevent the adhesion of different stains. The stains include not only fingerprint marks but also sweat and dust, making it easy to erase the stains or making the stains inconspicuous, and thus maintain the display The surface is clean. In addition, the anti-fouling layer can allow fingers to slide smoothly without obstruction during touch panel operation. Regarding the properties of the anti-fouling layer, preferably, by providing an anti-fouling layer on/above the anti-reflective layer, the anti-fouling layer is formed as the outermost surface of the laminated glass. As a method of forming an antifouling layer, for example, a vacuum evaporation method (dry method) in which a fluorine-containing organic compound or the like is evaporated in a vacuum chamber and deposited on the surface of the anti-reflective layer, or a fluorine-containing organic compound or the like is dissolved A method of preparing a solution with a predetermined concentration in an organic solvent and applying the solution to the surface of the anti-reflection layer (wet method). If appropriate, the dry method can be selected from ion beam assisted deposition, ion plating, sputtering, or plasma CVD, and the wet method can be appropriately selected from spin coating, dip coating, casting, and slit coating. Bu method or spray method. Both the dry method and the wet method can be adopted. Regarding scratch resistance, a dry film forming method is preferably used. The main ingredients in the antifouling layer (antifouling agent) can be appropriately selected from fluorine-containing compounds (fluorine-containing organic compounds) that can impart antifouling, water-repellent, and oil-repellent properties, and the like. Examples of such compounds include fluorine-containing organosilicon compounds and fluorine-containing hydrolyzable compounds. The use of the fluorine-containing organic compound is not particularly limited, as long as it can impart stain resistance, water repellency, and oil repellency. (Fluorine-containing organosilicon compound coating) In the case where an anti-reflection layer is formed on the main surface of the transparent substrate or on the treated surface of the anti-glare layer, it is preferable to provide the anti-fouling layer on the surface of the anti-reflection layer. Fluorine organosilicon compound coating. On the other hand, in the case of using a glass substrate that has undergone surface treatment (such as anti-glare treatment or chemical toughening treatment) and has no anti-reflection layer on the surface as a transparent substrate, it is preferable to directly use this surface treatment. A coating of fluorine-containing organosilicon compound is formed on the surface. As an example of a method of forming a fluorine-containing organosilicon compound coating, the following methods can be mentioned: by using spin coating, dip coating, casting, slit coating, spraying, etc. (Such as perfluoroalkyl group or fluoroalkyl group with perfluoro(polyoxyalkylene) chain) of silane coupling agent, and then subject the coated composition to heat treatment; or vacuum evaporation method, in which fluorine-containing organosilicon The compound undergoes vapor deposition and then heat treatment. In order to obtain a high-adhesion fluorine-containing organosilicon compound coating, preferably, the coating is formed by using a vacuum evaporation method. The formation of the fluorine-containing organosilicon compound coating by using a vacuum evaporation method is preferably implemented by using a composition for coating formation containing a fluorine-containing hydrolyzable silicon compound. (Fluorine-containing hydrolyzable silicon compound) When it comes to anti-fouling layer, there is no specific restriction on the fluorine-containing hydrolyzable silicon compound used to form the fluorine-containing organosilicon compound coating, as long as the obtained fluorine-containing organosilicon compound coating has anti-fouling properties (Including water repellency and oil repellency). Specific examples of this fluorine-containing hydrolyzable silicon compound include those each having at least one group selected from the group consisting of perfluoropolyether groups, perfluoroalkylene groups, and perfluoroalkyl groups. The antifouling layer can also be provided by using a method of laminating transparent resin films with antifouling function. Generally, the thickness of the anti-fouling layer formed on the anti-reflective layer is not particularly limited, but it is preferably 2 nm to 20 nm, more preferably 2 nm to 15 nm, and further preferably 3 to 10 nm. As long as the anti-fouling layer has a thickness of 2 nm or greater, the anti-fouling layer can produce a state where the surface of the anti-reflective layer is uniformly covered by the anti-fouling layer, and can easily obtain scratch resistance that can withstand actual use. On the other hand, as long as its thickness is 20 mm or less, the antifouling layer in the laminated state can maintain optical characteristics such as light reflectance and haze in good condition. <Anti-glare layer> When it is intended to impart anti-glare properties to laminated glass, the anti-glare layer may be provided on/above the first main surface of the transparent substrate. In order to impart anti-glare properties, irregularities may be formed in the main surface of the transparent substrate. The main surface with concavities and convexities may be at least one main surface of the transparent substrate, and the concavities and convexities are preferably formed in the first main surface of the transparent substrate. For the method of forming the bumps, generally known methods are applicable. For example, in the case of using a glass substrate as a transparent substrate, a method of applying chemical or physical surface treatment to the main surface of the glass substrate to form unevenness with a desired surface roughness, or a wet coating method is applicable. As a specific example of the method of chemically implementing the anti-glare treatment, a method of giving a frosting treatment can be mentioned. The frosting treatment can be performed by, for example, immersing the glass substrate as the material to be treated in a mixed solution containing hydrogen fluoride and ammonium fluoride. As an example of the method of physically implementing the anti-glare treatment, there can be mentioned sandblasting, in which a pressurized air stream loaded with crystalline silicon dioxide powder, silicon carbide powder, or the like is delivered to the main surface of the glass substrate; or using it A method of rubbing the main surface of the glass substrate with a crystalline silicon dioxide powder, silicon carbide powder or the like is placed on it. Among the above-mentioned treatments, the method of imparting anti-glare treatment to the glass substrate is preferably the frosting treatment, because it hardly causes the formation of tiny cracks in the surface of the processed material, so it hardly causes The mechanical strength is reduced. The main surface of the glass substrate that has undergone the chemical or physical anti-glare treatment as mentioned above is preferably subjected to an etching treatment to fix the surface profile. For the etching treatment, for example, a chemical etching method in which a glass plate is immersed in an aqueous hydrogen fluoride solution as an etching solution can be used. After the anti-glare treatment and subsequent etching treatment as mentioned above, the main surface of the glass substrate preferably has a surface roughness (root mean square roughness, RMS) of 0.01 μm to 0.5 μm. The surface roughness (RMS) is more preferably 0.01 μm to 0.3 μm, and still more preferably 0.02 μm to 0.2 μm. By adjusting the surface roughness (RMS) to fall within the range specified above, the turbidity value of the glass substrate can be controlled to fall within the range of 1% to 30% after the anti-glare treatment, so as to provide anti-reflection The transparent substrate 10 of the layer imparts excellent anti-glare properties. Incidentally, the turbidity value is the value specified in JIS K 7136 (2000). Regarding the method of forming the anti-glare layer, the anti-glare layer can be provided by laminating a transparent resin film having an anti-glare function and a transparent substrate. <Light-shielding layer> A light-shielding layer is formed on/over at least a part of the peripheral area of the second main surface of the transparent substrate. The purpose of forming the light-shielding layer is to shield the wiring members and other components placed on the peripheral area of the display panel, so that it is impossible to visually recognize any area of the display panel except the image display area from the observer side, and to enhance the design quality of the display device . The light-shielding layer can improve the visibility and appearance of the display. The term "peripheral area of the transparent substrate" refers to a belt-shaped area having a predetermined width from the edge excluding the center of the transparent substrate toward the center of the transparent substrate. The light-shielding layer is formed on the entire peripheral area or on at least a part of the peripheral area. Generally speaking, the light-shielding layer is adjacent to the peripheral edge of the transparent substrate and is a belt-shaped area with a predetermined width. Therefore, the outer peripheral side of the light-shielding layer is usually almost the same as the peripheral edge of the second main surface of the transparent substrate on which the light-shielding layer is formed. The term "inner peripheral side of the light-shielding layer" refers to the end side closer to the center of the transparent substrate in the light-shielding layer area having a predetermined width. The light-shielding layer forming area is usually shaped according to the shape of the transparent substrate. In the case where the transparent substrate has a rectangular shape, at least a part of the outer peripheral side of the light shielding layer is formed in a straight line. The inner peripheral side of the light shielding layer can be formed in a straight line or a curved line. In addition, an operating state display area can be formed in a part of the light shielding layer forming area to display the state of the display device or to receive operating light (for example, infrared radiation) from a remote controller. The light-shielding layer is formed on/above the peripheral area of the second main surface of the transparent substrate. Preferably, the light shielding layer is formed in a range from more than 0 mm to less than 30 mm from the outer peripheral side of the second main surface of the transparent substrate. The light-shielding layer can be formed by printing with black ink. Examples of printing methods include barcode process, reverse coating process, gravure coating process, die coating process, roll coating process, and screen printing process. Among these processes, the screen printing process is better because it not only allows easy and simple printing, but also allows printing on multiple types of substrates and printing according to each of different substrate sizes. Black ink can be used without specific restrictions. As examples of usable black inks, inorganic inks containing fired ceramics or the like and organic inks containing coloring materials such as pigments or dyes and organic resins can be mentioned. The light-shielding layer formed by printing with ceramics containing colored pigments is preferable because of its high opacity. The light-shielding layer is usually formed in black, but any color other than black can also be used as long as it has high opacity. Alternatively, the light-shielding layer can be formed by laminating a transparent film and a transparent substrate having a light-shielding function. Examples of ceramics incorporated into the inorganic black ink include oxides such as chromium oxide and iron oxide; carbides such as chromium carbide and tungsten carbide, carbon black and mica. The black printing area 6 can be obtained by melting an ink containing ceramics and silicon dioxide as listed above, printing the molten ink with a desired pattern on the substrate, and then firing the printed ink. This inorganic ink needs to undergo melting and firing processes, and it is usually used as a special ink for glass. The organic ink may be a composition containing black dyes or pigments and organic resins. Examples of organic resins include homopolymers, such as epoxy resin, acrylic resin, polyethylene terephthalate, polyether ether, polyarylate, polycarbonate, phenol resin, polyurethane, polymethyl Methyl acrylate, polyvinyl resin, polyvinyl butyral, polyetheretherketone, polyethylene, polyester, polypropylene, polyamide and polyimide; and transparent ABS (acrylonitrile-butadiene-benzene Ethylene) resins and resins including copolymers formed from any of the monomers of these resins and any monomers that can be copolymerized with these monomers. The use of dyes or pigments is not particularly limited, as long as they are black. The use of organic inks is better than the use of inorganic inks because the firing temperature of organic inks is lower than that of inorganic inks. In addition, the use of organic inks containing pigments is better in terms of chemical resistance. <Light reflectivity> The laminated glass of the present invention includes a transparent substrate, an anti-reflection layer formed on/over the first main surface of the transparent substrate, and a light-shielding layer formed on/over at least a part of the peripheral area of the second main surface of the transparent substrate . The light reflectivity of the laminated glass of the present invention is preferably 2% or less in the area where the light shielding layer is formed. The light reflectivity is measured for the light incident from the side of the anti-reflection layer and is measured by the transparent substrate and the light shielding layer. The interface removal of the layer is determined by the effect of backside reflection. The light reflectivity of laminated glass refers to the light reflectivity of the outermost surface of the laminated glass on the first main surface side, that is, when the laminated glass does not have an anti-fouling layer, it refers to the light reflectivity of the anti-reflective layer. When laminated glass has an anti-fouling layer, it refers to the total light reflectivity of the anti-reflective layer and the anti-fouling layer. The method usually implemented as a method to remove the effect of backside reflection in the case of measuring only specular reflection is the following method: toughen the second main surface of the transparent substrate with sandpaper or the like and use black markers or the like to further reduce the reflection Rate, thereby eliminating the specular reflection of the second main surface. However, this method is insufficient in the case of measuring in the SCI mode, which also includes diffuse reflected light. This is because the diffused light from the second main surface exists even after the aforementioned treatment. However, in this case, the effect of backside reflection can be removed by the following calculation. When the reflectance of the first main surface provided with the low-reflection layer to be obtained is expressed as R1, the reflectance of the transparent substrate is expressed as R0 and considering the incident from the first main surface, the interface between the second main surface and the air Reflected out and then transmitted through the first main surface, the SCI mode reflectance measured from the first main surface side in the second main surface area corresponding to the second main surface without a light-shielding layer (this reflectance is expressed as Rg) Expressed as the following equation: Rg = R1 + (1-R1) × R0 × (1-R1). Since R0 can be obtained by measuring the refractive index on a transparent substrate by using, for example, an ellipsometer, the measured values Rg and R0 become known quantities to allow the measurement of R1. Incidentally, in fact, the term about the light that repeats the round trip inside the transparent substrate also exists after the second term in the aforementioned equation, but the transparent substrate usually has a low R0 value of about 4%, and therefore these subsequent terms are as small as Can be ignored. Since the laminated glass in the present invention has a low light reflectivity of 2% or less and the adhesive layer has an appropriately adjusted adhesiveness, the laminated glass has low ambient light reflection and satisfactorily avoids the light-shielding layer formation area. The protection of the non-uniform color of the anti-reflective layer peeling off the surface of the anti-reflective layer caused by the adhesive residue or the adhesive, and the area where the protective film attached to the adhesive layer is stuck and the adhesive layer is not attached to it The boundary between the regions of the film does not cause changes in the color tone. Therefore, the laminated glass of the present invention can ensure satisfactory visibility. The light reflectance is preferably 1.5% or lower, and more preferably 1% or lower. In these situations, more significant effects can be achieved. By controlling the light reflectivity of the laminated glass to preferably as low as 2% or less, and by appropriately adjusting the adhesiveness of the adhesive used in the adhesive layer, it is possible to satisfactorily prevent the laminated glass from suffering from The color of the peeling off of the anti-reflective layer caused by the adhesive residue and the adhesive is not uniform, and when the laminated glass is installed on the display device, not only satisfactory display visibility and low ambient light reflection on the display surface can be obtained , And can also obtain excellent design quality and beautiful appearance. In addition, even in the case of forming an anti-fouling layer as the outermost surface of the laminated glass, as long as the thickness of the anti-fouling layer is small enough (for example, 20 nm or less), the anti-fouling layer in the laminated state has no significant effect on the light reflectivity. . By removing the effect of backside reflection, the total light reflectivity of the anti-reflection layer and the anti-fouling layer is controlled to be preferably 2% or lower, and by adjusting the adhesive layer to have proper adhesion, Satisfactorily prevent the color unevenness of the laminated glass from peeling off the antifouling layer skin caused by the adhesive residue and the adhesive, and when the laminated glass is installed on the display device, not only satisfactory display visibility can be obtained Performance and low ambient light reflection on the display surface, and can also obtain excellent design quality and beautiful appearance. Examples In the following examples and comparative examples, we will mainly explain the specific materials and program combinations used. Prepare a glass substrate with an anti-fouling film according to the following procedure. First, Dragontrail (trademark, manufactured by Asahi Glass Co., Ltd., also abbreviated as "DT" hereinafter), a glass for chemical toughening, is used as a transparent substrate. (1) Anti-glare treatment According to the following procedure, the first main surface of the glass substrate is subjected to anti-glare treatment by frosting treatment. First, stick the acid-resistant protective film to the surface of the glass substrate that does not require anti-glare treatment. Then, the obtained glass substrate was immersed in a 3 wt% hydrogen fluoride solution for 3 minutes to remove the dirt adhering to the surface of the glass substrate. In addition, the glass substrate from which the dirt has been removed is subjected to frosting treatment by immersing it in a mixed solution containing 15 wt% hydrogen fluoride and 15 wt% potassium fluoride for 3 minutes, and the frosting is performed on the first main surface of the glass plate化处理。 Treatment. The turbidity of the anti-glare treated glass substrate was adjusted by immersing in a 10% hydrogen fluoride solution. (2) Chemical toughening treatment The anti-glare treated glass substrate is subjected to chemical toughening treatment according to the following procedure. First, the anti-glare treated glass substrate was immersed in the molten salt of potassium nitrate melted by heating at 450°C for 2 hours, then rose from the molten salt, and further subjected to gradually cooling to room temperature for 1 hour, from This obtains chemically toughened glass. The thus obtained chemically toughened glass substrate has a surface compressive stress (CS) of 730 MPa and a depth of stress layer (DOL) of 30 μm. After the above steps, the chemically toughened glass was immersed in an alkali solution (SUNWASH TL-75, manufactured by Lion Specialty Chemicals Co., Ltd.) for 4 hours. (3) Formation of the light-shielding layer Next, screen printing is performed on the second main surface of the glass substrate that has undergone anti-glare treatment and chemical toughening treatment according to the following procedures. On the 4 side surfaces of the outer peripheral area of the second main surface of the glass substrate, printing was performed in the shape of a black frame with a width of 2 cm to form a light shielding layer. More specifically, black ink (GLSHF, trade name, manufactured by Teikoku Printing Inks Mfg. Co., Ltd.) was applied at a thickness of 5 μm by means of a screen printer, and then dried by keeping it at 150°C for 10 minutes. This forms the first printing layer. After that, the black ink was applied to the first printing layer in a thickness of 5 μm, and then dried by keeping it at 150° C. for 40 minutes in the same manner as mentioned above, thereby forming the second printing layer. Therefore, a light-shielding layer having a laminated structure of the first and second printing layers is formed, and thus a glass substrate with the light-shielding layer provided on the outer peripheral area of one main surface of the glass substrate is obtained. (4) Formation of the high refractive index layer An anti-reflection layer is formed on the first main surface side of the anti-glare treated glass substrate in the following manner. First, when the argon gas mixture containing 10 vol% oxygen is received into the thin film forming equipment, by using a niobium oxide target (NBO target, brand name, manufactured by AGC Ceramics Co., Ltd.) at a pressure of 0.3 Pa, Pulse sputtering is performed under the conditions of a frequency of 20 kHz, a power density of 3.8 W/cm ² and an inverted pulse width of 5 μsec to form a glass substrate with a refractive index (n) of 2.3 and a thickness of 13 nm. High refractive index layer (first layer) composed of niobium oxide (Nb ₂ O _{5 ).} In Example 4, a high refractive index layer was formed on the first main surface side of the glass substrate in a manner similar to the above, but silicon nitride (SiN) was used instead of niobium oxide (Nb ₂ O ₅ ). More specifically, the high refractive index layer made of silicon nitride is formed in the following manner. When the argon gas mixture containing 50 vol% nitrogen is received into the vacuum chamber, a silicon target is used at a pressure of 0.3 Pa, a frequency of 20 kHz, a power density of 3.8 W/cm ² and an inverted pulse width of 5 μsec. Under the conditions, pulse sputtering is performed to form a high refractive index layer composed of silicon nitride (SiN) with a refractive index (n) of 2.0 and a thickness of 15 nm. The refractive index layer is on the surface of the glass substrate. (5) The formation of the low refractive index layer is when the argon gas mixture containing 40 vol% oxygen is received into the equipment, by using a silicon target at a pressure of 0.3 Pa, a frequency of 20 kHz, and a power density of 3.8 W/cm ² , Pulse sputtering is performed under the conditions of inverted pulse width of 5 μsec and pulse width of 5 μsec, thereby forming a low refractive index layer _{composed of silicon oxide (SiO 2) with a refractive index (n) of 1.45.} (6) Formation of the anti-reflection layer The anti-reflection layer is formed by alternately forming the high refractive index layer and the low refractive index layer. (7) Formation of antifouling layer The antifouling layer is formed into a film in the following manner. First, the material used to form the fluorine-containing organosilicon compound film is introduced into the heating vessel as the antifouling layer material. Then, the heating vessel is subjected to degassing for 10 hours or more with the aid of a vacuum pump to remove the solvent from the solution, thereby providing a composition for forming a fluorine-containing organosilicon compound film (hereinafter referred to as a composition for forming an antifouling layer)物). After that, the heating vessel containing the composition for forming the antifouling layer was heated to 270°C, and after reaching 270°C, this condition was maintained for 10 minutes until the temperature stabilized. Then, the glass substrate provided with the anti-reflective layer 20 is placed in a vacuum chamber, and the nozzle connected to the heating vessel containing the composition for forming the anti-fouling layer is fed to the anti-reflective layer of the glass substrate for forming The composition of the antifouling layer, thereby forming a film. In the vacuum chamber, the film thickness is measured by a monitor group equipped with a quartz oscillator while the film is being formed, and the process is continued until the thickness of the fluorine-containing organosilicon compound film on the low refractive index layer reaches 4 nm. After that, the glass substrate was taken out from the vacuum chamber and mounted on the hot plate so that the surface of the fluorine-containing organosilicon compound film was facing upward and heat-treated in the air at 150°C for 60 minutes. In this way, a laminated glass having an anti-fouling layer formed on the anti-reflection layer is obtained. (8) Sticking of the protective film attached to the adhesive layer Next, the protective film attached to the adhesive layer is placed on the main surface of the glass substrate on which the antifouling layer is formed, obtained in the foregoing manner. At this time, stick the adhesive layer of the protective film so that its periphery is positioned 2 mm away from the inside of the laminated glass periphery. The layering may be implemented by, for example, cutting the protective film in advance to a size that is 2 mm smaller than the size of the glass substrate on either side. Therefore, a laminated glass with a protective film is obtained, wherein the laminated glass has an anti-reflection layer, an anti-fouling layer, and an anti-glare layer, and in addition, the protective film attached with the adhesive layer is pasted to the main surface side of the laminated glass, so that the protective film The periphery is positioned 2 mm away from the inside of the laminated glass periphery. Will be mentioned in the description of each example and Table 1 for the following examples and comparative examples, each having an anti-reflective layer, an anti-fouling layer, and an anti-glare layer, and a protective film with an adhesive layer to be adhered to laminated glass Laminated glass. Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Substrate DT DT DT DT DT DT DT DT Substrate thickness 1.3 mm 2 mm 1.3 mm 1.3 mm 1.3 mm 1.3 mm 1.3 mm 1.3 mm Anti-glare treatment executed executed Not implemented executed executed executed executed executed Chemical toughening executed executed executed executed executed executed executed executed Anti-reflective layer (thickness) Nb ₂ O ₅ (13nm) Nb ₂ O ₅ (13nm) Nb ₂ O ₅ (13nm) SiN (15 nm) Nb ₂ O ₅ (13nm) Nb ₂ O ₅ (13nm) Nb ₂ O ₅ (13nm) Nb ₂ O ₅ (13nm) SiO ₂ (35 nm) SiO ₂ (35 nm) SiO ₂ (120 nm) SiO ₂ (70 nm) SiO ₂ (35 nm) SiO ₂ (120 nm) SiO ₂ (35 nm) SiO ₂ (35 nm) Nb ₂ O ₅ (115 nm) Nb ₂ O ₅ (115 nm) SiN (17 nm) Nb ₂ O ₅ (115 nm) Nb ₂ O ₅ (115 nm) Nb ₂ O ₅ (115 nm) SiO ₂ (90 nm) SiO ₂ (90 nm) SiO ₂ (105 nm) SiO ₂ (90 nm) SiO ₂ (90 nm) SiO ₂ (90 nm) SiN (15 nm) SiO ₂ (50 nm) SiN (120 nm) SiO ₂ (80 nm) Antifouling layer KY-185 KY-185 OPTOOL DSX KY-195 - - KY-185 KY-185 wrap EC-9005ASL UA-3004ASL Y16FAS EC-610B2L EC-9005ASL Y16FAS SAF-010 TTG-3370 Substrate type PET PET Based on polyethylene Based on polyethylene PET PET Based on polypropylene PET Adhesive material Based on acrylic Based on polyurethane Based on acrylic Based on acrylic Based on acrylic Based on polyurethane - Based on acrylic Length(t) 2 mm 2 mm 2 mm 2 mm 2 mm 2 mm 2 mm 2 mm Turbidity 2% 25% 0% 2% 2% 2% 2% 2% Light reflectivity 0.30% 0.30% 0.80% 1% 0.30% 0.80% 0.30% 0.30% Adhesion 0.012N/10mm 0.015N/10mm 0.05N/10mm 0.02N/10mm 0.11N/10mm 0.3N/10mm 0.008N/10mm 0.1N/10mm Visibility unevenness No unevenness No unevenness No unevenness No unevenness No unevenness No unevenness Uneven adhesion Uneven color on both sides of the border KY-185: produced by Shin-Etsu Chemical Co. Ltd. OPTOOL DSX: produced by Daikin Industries Ltd. KY-195: produced by Shin-Etsu Chemical Co. Ltd. EC-9005ASL: produced by Sumiron Co., Ltd. UA -3004ASL: produced by Sumiron Co., Ltd. Y16FAS: produced by Sun A. Kaken Co., Ltd. EC-610B2L: produced by Sumiron Co., Ltd. SAF-010: produced by Futamura Chemical Co. Ltd. TTG- 3370: Produced by Sumiron Co., Ltd. (Example 1) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, and then the turbidity was adjusted to 2% by controlling the etching time, and further subjected to (2) Chemical toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are alternately performed to form an anti-reflection layer, so that the number of stacked layers is four (4). Regarding the thickness of each layer, the thickness of the first niobium oxide layer is 13 nm, the thickness of the second silicon oxide layer is 35 nm, the thickness of the third niobium oxide layer is 115 nm, and the thickness of the fourth silicon oxide layer is 90 nm . Thereafter, the antifouling layer was formed by using KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a vapor phase evaporation material, and EC-9005ASL (manufactured by Sumiron Co., Ltd.) was pasted to it , It is a PET protective film with an adhesive layer composed of an acrylic-based adhesive. The thickness of the protective film substrate is 25 μm. (Example 2) In the same manner as in the case of Example 1, a DT substrate with a thickness of 2.0 mm was subjected to (1) anti-glare treatment, and then the turbidity was adjusted to 25% by controlling the etching time, and further subjected to (2) chemical Toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are alternately performed to form an anti-reflection layer, so that the number of stacked layers is four (4). Regarding the thickness of each layer, the thickness of the first niobium oxide layer is 13 nm, the thickness of the second silicon oxide layer is 35 nm, the thickness of the third niobium oxide layer is 115 nm, and the thickness of the fourth silicon oxide layer is 90 nm . Thereafter, the antifouling layer was formed by using KY-185 (produced by Shin-Etsu Chemical Co., Ltd.) as the vapor phase evaporation material, and UA-3004ASL (produced by Sumiron Co., Ltd.) was pasted to it , It is a PET protective film with an adhesive layer composed of polyurethane-based adhesives. (Example 3) A DT substrate with a thickness of 1.3 mm was subjected to (2) chemical toughening treatment without undergoing anti-glare treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are carried out in the order described to form an anti-reflection layer, so that the number of layers is two (2 ). The thickness of the first niobium oxide layer is 13 nm and the thickness of the second silicon oxide layer is 120 nm. After that, OPTOOL DSK (Daikin Industries Ltd.) was used to form the antifouling layer, and Y16FAS (produced by Sun A. Kaken Co., Ltd.) was adhered to it, which has an adhesive composed of an acrylic-based adhesive Layer of protective film based on polyethylene. (Example 4) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, then its haze was adjusted to 2% by controlling the etching time, and further subjected to (2) chemical toughening treatment. After that, (3) the formation of the light-shielding layer. Then, alternately implement (A) the formation of a high refractive index layer made of silicon nitride and (B) the formation of a low refractive index layer made of silicon oxide to form an anti-reflection layer, so that the number of layers is eight (8) . Regarding the thickness of each layer, the thickness of the first silicon nitride layer is 15 nm, the thickness of the second silicon oxide layer is 70 nm, the thickness of the third silicon nitride layer is 17 nm, and the thickness of the fourth silicon oxide layer is 105 nm, the thickness of the fifth silicon nitride layer is 15 nm, the thickness of the sixth silicon oxide layer is 50 nm, the thickness of the seventh silicon nitride layer is 120 nm, and the thickness of the eighth silicon oxide layer is 80 nm. Thereafter, KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used to implement the formation of an antifouling layer, and EC-610B2L (manufactured by Sumiron Co., Ltd.) was adhered to it, which was made of acrylic-based The adhesive layer is composed of a polyethylene-based protective film. (Example 5) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, then its haze was adjusted to 2% by controlling the etching time, and further subjected to (2) chemical toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are alternately performed to form an anti-reflection layer, so that the number of stacked layers is four (4). Regarding the thickness of each layer, the thickness of the first niobium oxide layer is 13 nm, the thickness of the second silicon oxide layer is 35 nm, the thickness of the third niobium oxide layer is 115 nm, and the thickness of the fourth silicon oxide layer is 90 nm . After that, EC-9005ASL (manufactured by Sumiron Co., Ltd.) was pasted, that is, a PET protective film with an adhesive layer composed of acrylic-based adhesives, and no anti-fouling layer was formed. (Example 6) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, then its haze was adjusted to 2% by controlling the etching time, and further subjected to (2) chemical toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) the formation of a high refractive index layer made of niobium oxide and (B) the formation of a low refractive index layer made of silicon oxide are carried out in the order described to form the anti-reflection layer 20, so that the number of stacked layers is two ( 2). The thickness of the first niobium oxide layer is 13 nm and the thickness of the second silicon oxide layer is 120 nm. After that, paste Y16-FAS (produced by Sun A. Kaken Co., Ltd.), which is a PET protective film with an adhesive layer composed of polyurethane-based adhesives without forming any anti-fouling layer . (Comparative Example 1) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, then its haze was adjusted to 2% by controlling the etching time, and further subjected to (2) chemical toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are alternately performed to form an anti-reflection layer, so that the number of stacked layers is four (4). Regarding the thickness of each layer, the thickness of the first niobium oxide layer is 13 nm, the thickness of the second silicon oxide layer is 35 nm, the thickness of the third niobium oxide layer is 115 nm, and the thickness of the fourth silicon oxide layer is 90 nm . After that, KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used to form an antifouling layer, and SAF-010 (manufactured by Futamura Chemical Co., Ltd.) was adhered to it, which has an adhesive Polypropylene-based protective film for the adhesive layer composed of adhesive. (Comparative Example 2) A DT substrate with a thickness of 1.3 mm was subjected to (1) anti-glare treatment, then its haze was adjusted to 2% by controlling the etching time, and further subjected to (2) chemical toughening treatment. After that, (3) the formation of the light-shielding layer is implemented. Then, (A) formation of a high refractive index layer made of niobium oxide and (B) formation of a low refractive index layer made of silicon oxide are alternately performed to form an anti-reflection layer, so that the number of stacked layers is four (4). Regarding the thickness of each layer, the thickness of the first niobium oxide layer is 13 nm, the thickness of the second silicon oxide layer is 35 nm, the thickness of the third niobium oxide layer is 115 nm, and the thickness of the fourth silicon oxide layer is 90 nm . Thereafter, KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used to form the antifouling layer, and TTG-3370 (manufactured by Sumiron Co., Ltd.) was adhered to it, which was made of acrylic-based The PET protective film of the adhesive layer composed of the adhesive. <Evaluation method> The following evaluations were performed for each laminated glass with a protective film attached to the adhesive layer, which were obtained in Examples 1 to 6 and Comparative Examples 1 and 2, respectively. The obtained evaluation results are shown in Table 1. (Turbidity) According to JIS-K-7136 (2000), a turbidity meter HZ-V3 (product of Suga Test Instruments Co., Ltd.) was used to perform turbidity measurement. (Light reflectance) The term light reflectance refers to the reflex stimulation value Y defined in JIS Z8701 (1999). In the present invention, a spectrophotometer (Model CM-2600d, a product of KONIKA MINOLTA, INC.) is used to measure the reflected light according to the SCI mode, where the regular reflected light and the diffuse reflected light are measured together under the D65 light source, and freely Measure the reflectivity to calculate the light reflectivity. (Evaluation of color non-uniformity) The evaluation of color non-uniformity is carried out in the following manner. The substrate is held at a brightness level of 2,000 lux under a fluorescent lamp placed in a room isolated from external light, such as a dark small room. In this case, check whether there is color unevenness by visual observation from a variety of different angles. (Adhesiveness) The adhesiveness is measured as follows. On the substrate, cut the packaged laminated film into strips with a width of 10 mm. One strip was subjected to a 90° peel test. In the test, a peeling force measuring instrument (FA PLUS, a product of IMADA Co., Ltd.) was used and the peeling speed was set to 0.84 mm/sec. The test is performed 3 times by using other strips, and the average value of the measured data is used. <Measurement results> Examples (Examples 1 to 6) of laminated glass with protective film of the present invention and examples of laminated glass for comparison (Comparative Examples 1 and 2) are shown in Table 1. The laminated glass formed in Examples 1, 2 and 4 contains an anti-glare layer, an anti-reflective layer and an anti-fouling layer. The laminated glass formed in Example 3 contains an anti-reflective layer and an anti-fouling layer, and is formed in Examples 5 and 6. The laminated glass contains an anti-glare layer and an anti-reflection layer. In these laminated glasses, by adjusting the adhesiveness of the adhesive layer attached to each protective film to fall within a specified range, after peeling off the protective film with the adhesive layer from the laminated glass, before the laminated glass In the view, no unevenness is observed in the light-shielding layer forming area, and there is neither a color tone change at the boundary between the protective film pasted area and the non-protective film pasted area, nor the appearance of a clear boundary. Therefore, a significant improvement in visual appreciation has been achieved. Regarding laminated glass each with an anti-glare layer and an anti-reflection layer (Examples 5 and 6), the adhesiveness of the adhesive layer was adjusted to fall within the range of 0.01 N/10 mm to 0.3 N/10 mm. After the glass peels off each protective film with the adhesive layer, in the front view of the laminated glass, no unevenness is observed in the light-shielding layer formation area, and there is neither the protective film adhesion area and the non-protective film adhesion area between The hue of the color at the boundary changes and there is no obvious boundary appearance. Therefore, a significant improvement in visual appreciation has been achieved. Regarding the laminated glass each having an anti-glare layer, an anti-reflective layer, and an anti-fouling layer (Examples 1, 2 and 4) and a laminated glass having an anti-reflective layer and an anti-fouling layer (Example 3), the adhesiveness of the adhesive layer was adjusted To fall within the range of 0.01 N/10 mm to 0.05 N/10 mm, the content may not be observed in the light-shielding layer formation area in the front view of the laminated glass after peeling off each protective film with the adhesive layer from each laminated glass To be uneven, and in addition, there is neither a color tone change at the boundary between the protective film pasted area and the non-protective film pasted area nor the appearance of a clear boundary. Therefore, a significant improvement in visual appreciation has been achieved. The laminated glass formed in Comparative Example 1 is a laminated glass having an anti-glare layer, an anti-reflection layer, and an anti-fouling layer. In this case, the adhesiveness of the adhesive layer was 0.008 N/10 mm, and after the protective film with the adhesive layer was peeled off from the laminated glass, unevenness was observed in the light-shielding layer formation area in the front view of the laminated glass . Therefore, the visual appreciation is degraded. The laminated glass formed in Comparative Example 2 is a laminated glass having an anti-glare layer, an anti-reflection layer, and an anti-fouling layer. In this case, the adhesiveness of the adhesive layer is 0.1 N/10 mm, and after the protective film with the adhesive layer is peeled off from the laminated glass, in the front view of the laminated glass, it is noticed that there are irregularities in the area where the light-shielding layer is formed. Uniformity, and in addition, there are changes in the color tone at the boundary between the protective film pasted area and the non-protective film pasted area and the appearance of a clear boundary. Therefore, the visual appreciation is degraded. In each laminated glass with a protective film of the present invention, between the area where the protective film is adhered and the area where the protective film is not adhered, even after the protective film is peeled off, there is no change in visual appreciation. Therefore, the laminated glass with the protective film of the present invention is suitable as a panel of a display device and can not only ensure satisfactory display visibility, but also ensure excellent design quality and beautiful appearance. This application is based on Japanese Patent Application No. 2015-247616 filed on December 18, 2015, the content of which is incorporated herein by reference. Industrial Applicability The laminated glass with a protective film of the present invention can be suitably used as a display panel (cover glass), and it can be used not only to protect the panel of a display product, but also to improve manufacturing when it is installed on a display device. Convenience.

1: Laminated glass with protective film 10: Transparent substrate 20: Anti-reflective layer 30: Antifouling layer 40: Adhesive layer 50: Protective film 60: Anti-glare layer 70: shading layer 80: Attach the protective film of the adhesive layer 90: laminated glass t: length

Regarding the description in the drawings, the same or corresponding components or components are represented by the same or corresponding numbers or symbols, and therefore, repeated descriptions may be omitted. In addition, unless otherwise specified, the drawings are not intended to show the relative proportions of components or components. Therefore, if appropriate, specific dimensions can be selected according to the non-limiting embodiments mentioned below. 1 is a cross-sectional view illustrating an example of laminated glass with a protective film, in which a transparent substrate has an anti-reflection layer on the first main surface and a light-shielding layer on the second main surface, and has an adhesive layer for protection The film is stuck on the surface of the anti-reflection layer. 2 is a cross-sectional view illustrating another example of laminated glass with a protective film, in which a transparent substrate has an anti-reflection layer and an anti-fouling layer on the first main surface in this order, and a light-shielding layer on the second main surface , And a protective film with an adhesive layer is stuck on the surface of the antifouling layer. 3 is a cross-sectional view illustrating another example of laminated glass with a protective film, in which a transparent substrate has an anti-glare layer, an anti-reflection layer, and an anti-fouling layer on the first main surface in this order and on the second main surface A protective film with a light-shielding layer and an adhesive layer is stuck on the surface of the antifouling layer. Fig. 4 is a front view of the laminated glass on which the protective film with the adhesive layer is pasted.

1: Laminated glass with protective film

10: Transparent substrate

20: Anti-reflective layer

40: Adhesive layer

50: Protective film

70: shading layer

80: Attach the protective film of the adhesive layer

90: laminated glass

t: length

Claims (11)

A laminated glass with a protective film, which contains: Laminated glass comprising at least a transparent substrate having a first main surface and a second main surface, an anti-reflection layer above the first main surface, and a light-shielding layer provided above the peripheral area of the second main surface, and Protective film with adhesive layer, The protective film with the adhesive layer is stuck on the laminated glass at the following position: in the front view of the laminated glass, the peripheral edge of the protective film with the adhesive layer is located relative to the inner peripheral side of the light-shielding layer toward the outer periphery Side and relative to the outer peripheral side of the light-shielding layer toward the inner peripheral side, The protective film with the adhesive layer is provided with tongue segments that make it easy to pick up the edges of the protective film, and The adhesion between the anti-reflection layer and the adhesive layer is 0.01 N/10 mm to 0.3 N/10 mm. For the laminated glass with a protective film of claim 1, wherein the length t is defined as connecting any point on the peripheral edge of the outermost surface of the laminated glass and passing through any point from the peripheral edge of the main surface of the laminated glass to the protective film When the length of the line segment at the point where the perpendicularly oriented straight line extending from the peripheral edge intersects the nearest peripheral edge of the protective film, the length t is greater than 0 mm and less than 10 mm. For the laminated glass with protective film of claim 1 or 2, wherein the light-shielding layer in the peripheral area of the second main surface of the transparent substrate is arranged more than 0 mm to less than the outer peripheral side of the second main surface of the transparent substrate Within 30 mm. The laminated glass with a protective film of claim 1 or 2, wherein the adhesive layer contains an adhesive mainly composed of acrylic resin or polyurethane resin. The laminated glass with a protective film of claim 1 or 2, wherein the laminated glass has a light reflectivity of 2% or less on the surface formed by the anti-reflection layer in the area where the light-shielding layer is formed, wherein the light reflects The rate is measured by removing the effect from the backside reflection. The laminated glass with a protective film of claim 1 or 2, wherein the first main surface of the transparent substrate has a concave-convex shape. The laminated glass with protective film of claim 1 or 2, wherein the transparent substrate is chemically toughened glass. The laminated glass with a protective film of claim 1 or 2, wherein at least a part of the peripheral edge of the protective film with an adhesive layer is provided with an area where no adhesive layer is formed. The laminated glass with protective film of claim 1 or 2, wherein the transparent substrate has a curved shape. A display front panel for vehicle-mounted equipment, which comprises a laminated glass with a protective film as claimed in any one of claims 1 to 9. A display device for in-vehicle equipment, which is provided with a display front panel for in-vehicle equipment as in claim 10.

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