JP6806193B2 - Glass laminate with protective film - Google Patents

Description

The present invention relates to a glass laminate with a protective film.

In recent years, glass plates having high texture, high strength, and excellent heat resistance have been increasingly used as display front plates for protecting display devices.
Anti-reflection layers and anti-fouling layers are formed on the front panels of displays used in in-vehicle devices such as car navigation devices and instrument panels, and the front panels of displays used in mobile devices such as mobile phones from the viewpoint of anti-reflection and anti-fouling. There is a demand for a display front plate.

Furthermore, from the viewpoint of product protection when assembling the display front plate to the display device, it is required to attach a protective film to be used by finally peeling off the protective film on the display outermost surface side of the front plate. There is. (See Patent Document 1 and Patent Document 2)

WO2011 / 148990 WO2011 / 118367

In a glass laminate used as a front plate used in a display device, a protective film is attached to the glass laminate via an adhesive.

However, depending on the adhesive strength of the adhesive constituting the adhesive layer added to the protective film attached to the glass laminate when the protective film is peeled off, the antireflection layer or antifouling layer formed on the main surface of the transparent substrate. At least a part of the material forming the adhesive layer may be peeled off by the adhesive of the adhesive layer added to the protective film, or the adhesive constituting the adhesive layer may remain on at least a part of the surface of the glass laminate. ..

As a result, there is a problem that the color tone changes at the boundary between the portion where the protective film is attached and the portion where the protective film is not attached, the boundary becomes conspicuous, and the visual perception deteriorates. This is because the reflectance of the surface is lowered by adding a low-reflection layer, making it easy to see subtle color changes, and because the low-reflection layer uses optical interference. The main cause is that the color and reflectance are changed due to the influence of changes in the film thickness and refractive index of the surface.

Further, when the front plate is assembled to the display device, if the protective film is larger than the glass laminate used as the front plate, there is a problem that the protective film is caught in the gap of the display device housing when assembling. was there.

The glass laminate with a protective film of the present invention has a transparent substrate having a first main surface and a second main surface, an antireflection layer on the first main surface, and a peripheral portion of the second main surface. A glass laminate having at least a light-shielding layer and a protective film with an adhesive layer. The protective film with an adhesive layer is bonded to the glass laminate and is a protective film with an adhesive layer. In front view of the glass laminate, the outer peripheral edge of the protective film with an adhesive layer is bonded to the outer peripheral side from the inner peripheral side of the light-shielding layer and to the inner peripheral side from the outer peripheral side of the light-shielding layer. The adhesive strength between the laminate and the adhesive layer is 0.01 to 0.3 N / 10 mm.

The glass laminate with a protective film of the present invention has an adhesive strength of 0.01 to 0.05 N / 10 mm between the glass laminate having an antifouling layer on the antireflection layer and the adhesive layer. It is a feature.

In the glass laminate with a protective film of the present invention, a straight line perpendicular to an arbitrary point on the outermost outer peripheral edge of the glass laminate and an arbitrary point and a straight line perpendicular to the outer peripheral edge of the main surface of the glass laminate is formed on the outer circumference of the protective film. The length t of the line segment extending with respect to the end and connecting the outer peripheral end of the protective film with the intersecting point is more than 0 mm and less than 10 mm.

As described above, according to the present invention, the adhesive remains on at least a part of the outermost surface of the glass laminate by setting the adhesive strength of the adhesive constituting the adhesive layer of the protective film with the adhesive layer within a predetermined range. In addition, it was possible to prevent at least a part of the material such as the antireflection layer and the antifouling layer from peeling off, and it was possible to secure a good appearance in which the color boundary of the display surface could not be visually recognized.

Further, according to the present invention, in the glass laminate with a protective film, the outer peripheral edge of the protective film with an adhesive layer is located on the outer peripheral side from the inner peripheral side of the light-shielding layer and on the inner peripheral side from the outer peripheral side of the light-shielding layer. By being attached to the display device, the handleability when the glass laminate with the protective film is attached to the device as the front plate of the display device is improved.

In the description in the drawings, the same or corresponding members or parts are designated by the same or corresponding reference numerals, so that duplicate description is omitted. Further, the drawings are not intended to show relative ratios between members or parts unless otherwise specified. Therefore, the specific dimensions can be appropriately selected in light of the following non-limiting embodiments.

An example of a glass laminate with a protective film, which has an antireflection layer on the first main surface of a transparent substrate, a light-shielding layer on the second main surface, and a protective film with an adhesive layer bonded to the surface of the antireflection layer. It is sectional drawing which shows. An antireflection layer and an antifouling layer are provided in this order on the first main surface of the transparent substrate, a light-shielding layer is provided on the second main surface of the transparent substrate, and a protective film with an adhesive layer is attached to the surface of the adhesive layer. It is sectional drawing which shows an example of the combined glass laminate with a protective film. An antiglare layer, an antireflection layer, and an antifouling layer are provided in this order on the first main surface of the transparent substrate, a light-shielding layer is provided on the second main surface of the transparent substrate, and an adhesive layer is provided on the surface of the antifouling layer. It is sectional drawing which shows an example of the glass laminate with the protective film which attached the protective film attached. It is a front view of the glass laminate to which the protective film with an adhesive layer is attached.

Hereinafter, the glass laminate with a protective film of the present invention will be described in detail with reference to the drawings. The present invention will be described below with reference to specific embodiments, but the present invention is not limited to the contents of the following embodiments, and various configurations are provided without departing from the spirit of the present invention. It goes without saying that addition, omission, modification, replacement, and other changes can be made as appropriate. 1 to 3 are cross-sectional views showing an example of an embodiment of the glass laminate with a protective film of the present invention.

The glass laminate 1 with a protective film shown in the first to third embodiments serves as a front plate for protecting the display panel by being provided on the image display side (observer side) of the display panel.

(First Embodiment)
The first embodiment of the glass laminate with a protective film of the present invention is as shown in FIG.

The glass laminate 1 with a protective film includes a transparent substrate 10 having a first main surface and a second main surface, an antireflection layer 20 formed on the first main surface of the transparent substrate 10, and a transparent substrate. A glass laminate 90 having a light-shielding layer 70 on the peripheral edge of a second main surface of 10 and a protective film 80 with an adhesive layer are provided.

The protective film 80 with an adhesive layer is bonded to the glass laminate 90, and in the front view of the glass laminate 90, the outer peripheral edge of the protective film 80 with an adhesive layer is the inner circumference of the light-shielding layer 70. The adhesive force between the antireflection layer 20 and the adhesive layer 40 formed on the outermost surface of the glass laminate 90 is bonded to the outer peripheral side from the side and the position on the inner peripheral side from the outer peripheral side of the light shielding layer 70. It is 0.01 to 0.3 N / 10 mm.

By adjusting the adhesive force between the antireflection layer 20 and the adhesive layer 40 formed on the main surface of the glass laminate 90 to 0.01 to 0.3 N / 10 mm, the adhesive forming the adhesive layer is glass. It can be prevented from remaining on at least a part of the outermost surface of the laminated body 90.

By adjusting the adhesive force between the antireflection layer 20 and the adhesive layer 40 formed on the main surface of the glass laminate 90 to 0.01 to 0.3 N / 10 mm, the adhesive forming the adhesive layer makes the glass. At least a part of the material forming the antireflection layer 20 on the outermost surface of the laminate 90 can be prevented from peeling off.

Further, according to the first embodiment of the glass laminate with a protective film of the present invention, an arbitrary point on the outermost surface of the glass laminate 90 and an outer peripheral edge of the main surface of the glass laminate passing through the arbitrary points. With an adhesive layer so that the length t of the line segment connecting the outer peripheral edge of the protective film and the intersecting point is more than 0 mm and less than 10 mm by extending a straight line perpendicular to the outer peripheral edge of the protective film. The protective film 80 is attached to the glass laminate 90. (See Fig. 4)

Here, the light-shielding layer 70 formed on the peripheral edge of the second main surface of the transparent substrate 10 is directed from the outer peripheral edge of the second main surface of the transparent substrate 10 toward the central portion of the second main surface. It is formed in a strip-shaped region having a predetermined width.

(Second Embodiment)
A second embodiment of the glass laminate with a protective film of the present invention is as shown in FIG.

The glass laminate 1 with a protective film includes a transparent substrate 10 having a first main surface and a second main surface, an antireflection layer 20 formed on the first main surface of the transparent substrate 10, and a transparent substrate. A glass laminate 90 having a light-shielding layer 70 on the peripheral edge of a second main surface of 10 and a protective film 80 with an adhesive layer are provided.

The glass laminate 90 in the second embodiment of the glass laminate with a protective film of the present invention further includes an antifouling layer 30 on the main surface of the antireflection layer.

The protective film 80 with an adhesive layer is bonded to the glass laminate 90, and in the front view of the glass laminate 90, the outer peripheral edge of the protective film 80 with an adhesive layer is the inner circumference of the light-shielding layer 70. The adhesive force between the antifouling layer 30 and the adhesive layer 40 formed on the outermost surface of the glass laminate 90 is bonded to the outer peripheral side from the side and the inner peripheral side from the outer peripheral side of the light shielding layer 70. It is 0.01 to 0.05 N / 10 mm.

By adjusting the adhesive force between the antifouling layer 30 and the adhesive layer 40 formed on the main surface of the glass laminate 90 to 0.01 to 0.05 N / 10 mm, the adhesive that forms the adhesive layer is glass. It can be prevented from remaining on at least a part of the outermost surface of the laminated body 90.

By adjusting the adhesive force between the antifouling layer 30 and the adhesive layer 40 formed on the main surface of the glass laminate 90 to 0.01 to 0.05 N / 10 mm, the adhesive forming the adhesive layer makes the glass. At least a part of the material forming the antifouling layer 30 on the outermost surface of the laminate 90 can be prevented from peeling off.

Further, according to the second embodiment of the glass laminate with a protective film of the present invention, the glass laminate provided with an antifouling layer passes through an arbitrary point on the outermost peripheral edge of the outermost surface of the glass laminate 90 and an arbitrary point. The length t of the line segment that extends a straight line perpendicular to the outer peripheral edge of the main body surface with respect to the outer peripheral edge of the protective film and connects the point intersecting with the outer peripheral edge of the protective film is more than 0 mm and less than 10 mm. As described above, the protective film 80 with an adhesive layer is attached to the glass laminate 90. (See Fig. 4)

(Third Embodiment)
A third embodiment of the glass laminate with a protective film of the present invention is as shown in FIG.

In the third embodiment of the present invention, the glass laminate 90 provided with the antireflection layer 20 shown in the first embodiment, and the antireflection layer 20 and the antifouling layer 60 shown in the second embodiment are used. This is an embodiment in which the antiglare layer 60 is formed between the first main surface of the transparent substrate 10 and the antireflection layer 20 in the glass laminates provided in order.

FIG. 3 shows an embodiment in which the antiglare layer 60 is formed between the first main surface of the transparent substrate 10 and the antireflection layer 20 in the glass laminate provided with the antifouling layer 60 (Embodiment 2). However, it goes without saying that the antiglare layer 60 can be formed even on a glass laminate (Example 1) that does not have the antifouling layer 60.

<Glass laminate>
The glass laminate comprises a transparent substrate having a first main surface and a second main surface, an antireflection layer formed on the first main surface of the transparent substrate, and a second main surface of the transparent substrate. It is provided with at least a light-shielding layer formed on the edge portion adjacent to the end face.

The glass laminate may further include an antifouling layer on the main surface of the antireflection layer.

In the glass laminate, an antiglare layer may be formed between the first main surface of the transparent substrate and the antireflection layer.

<Protective film with adhesive layer>
By providing an adhesive layer on one side of the protective film, a protective film with an adhesive layer is formed.

In order to protect the display panel assembled to the display device in the manufacturing process or product transportation, a protective film with an adhesive layer is attached to the outermost surface of the glass laminate to protect the glass laminate.

When using the display device, the protective film with an adhesive layer is peeled off from the glass laminate and used.

By adjusting the adhesive strength of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer provided in the protective film with a pressure-sensitive adhesive layer, it is possible to prevent the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer from remaining on at least a part of the outermost surface of the glass laminate. it can.

A material that forms an antireflection layer or an antifouling layer on the outermost surface of a glass laminate by the adhesive that forms the adhesive layer by adjusting the adhesive force of the adhesive that forms the adhesive layer provided in the protective film with an adhesive layer. It is possible to suppress peeling of at least a part of.

The protective film with an adhesive layer is attached to the outermost surface of the glass laminate. The outer peripheral edge of the protective film with an adhesive layer is bonded to the outer peripheral side from the inner peripheral side of the light-shielding layer and to the inner peripheral side from the outer peripheral side of the light-shielding layer in the front view of the glass laminate, thereby laminating the glass. When assembling the body as a front plate of a display device such as a liquid crystal display (LCD), a plasma display panel (PDP), or an electroluminescence display (ELD), a protective film with an adhesive layer is sandwiched in the device housing, etc. It is possible to suppress the problem of the above, and it is possible to improve the handleability when assembling the glass laminate with the protective film to the device.

The outer peripheral edge of the protective film with an adhesive layer is an edge away from the center of the protective film with an adhesive layer. Normally, the protective film with an adhesive layer has a rectangular shape, but in the case of a rectangular shape, at least a part of the outer peripheral end is formed by a straight line. Since the protective film with an adhesive layer is appropriately changed according to the shape of the glass laminate, at least a part of the outer peripheral end may be formed by a curved line.

Further, in the protective film with an adhesive layer, a straight line perpendicular to an arbitrary point on the outermost peripheral edge of the outermost surface of the glass laminate and a straight line passing through the arbitrary point from the outer peripheral edge of the main surface of the glass laminate is directed to the outer peripheral edge of the protective film. The glass laminate with the protective film is formed by extending and bonding the length t of the line segment connecting the nearest outer peripheral edge of the protective film with the adhesive layer to the point where it intersects at a position of more than 0 mm and less than 10 mm. Handleability when assembling to the device can be improved.

It is preferable that the outer peripheral edge of the protective film is located at a position less than 10 mm from the outer peripheral edge of the glass laminate toward the central portion of the glass laminate so that the purpose of protecting the glass laminate from impact or the like can be easily achieved.

Further, in order to increase the peelability of the protective film with the adhesive layer, a tab portion is provided to make it easier to grasp the end portion of the protective film, or an adhesive layer is provided on at least a part of the outer peripheral edge of the protective film with the adhesive layer. The protective film with an adhesive layer can be easily peeled off from the glass laminate by providing a portion that does not form the adhesive layer. The tab portion created for the purpose of facilitating the above-mentioned peelability may protrude to the outer peripheral portion as long as the handleability is not impaired.

When the glass laminate having the antireflection layer or the antifouling layer and the protective film with the adhesive layer are bonded by hand, the protective film with the adhesive layer supplied as a roll-shaped roll may be used as a rubber roll or the like. The manufacturing efficiency is improved by using a label sticker or a sticker sticker to stick the protective film with an adhesive layer by cutting it in advance according to the dimensions of the glass laminate to make a single-wafer protective film. Preferred from the point of view.

<Adhesive layer>
The adhesive layer is provided on one side of the protective film to form a protective film with an adhesive layer.

The pressure-sensitive adhesive of the pressure-sensitive adhesive layer preferably has a degree of adhesiveness that prevents the pressure-sensitive adhesive from remaining on at least a part of the outermost surface of the glass laminate when the protective film with the pressure-sensitive adhesive is peeled off from the glass laminate.

The adhesive of the adhesive layer has an adhesiveness that suppresses peeling of at least a part of the material forming the antireflection layer and the antifouling layer of the glass laminate when the protective film with the adhesive layer is peeled from the glass laminate. It is preferable to have.

As the pressure-sensitive adhesive for such a pressure-sensitive adhesive layer, acrylic-based or polyurethane-based pressure-sensitive adhesives are preferably used from the viewpoint of adhesiveness and peelability.

When the adhesive strength of the adhesive layer is 0.01 N / 10 mm or more, the adhesive adheres uniformly to the outermost surface of the glass laminate, and when the protective film with the adhesive layer is peeled off, it adheres to the outermost surface of the glass laminate. The adhesive layer can be uniformly adhered to the surface of the surface treatment material of the antireflection layer or the antifouling layer to be formed. In addition, there is no risk of impairing the function as a protective film, such as the protective film peeling off from the glass laminate during transportation.

When the adhesive strength of the adhesive layer is 0.3 N / 10 mm or less, the adhesive strength of the adhesive layer is appropriate, and the antireflection layer formed on the outermost surface of the glass laminate when the protective film with the adhesive layer is peeled off. The surface treatment material is peeled off at least in part by the adhesive, or the adhesive forming the adhesive layer of the protective film with the adhesive layer remains on at least a part of the outermost surface of the glass laminate. There is no risk of deterioration of properties or defects such as dirt.

When a protective film with an adhesive layer is attached to a glass laminate having an antireflection layer formed on the outermost surface of the glass laminate, the adhesive strength between the adhesive layer and the antireflection layer is 0.03 to 0.3 N / 10 mm. It is preferably 0.05 to 0.15 N / 10 mm, and more preferably 0.05 to 0.15 N / 10 mm.

By adjusting the adhesive strength to a preferable value, it is possible to prevent the adhesive from remaining and the material forming the antireflection layer from being peeled off by the adhesive.

Further, when the protective film with an adhesive layer is attached to the glass laminate having the antifouling layer formed on the outermost surface of the glass laminate, the adhesive strength between the adhesive layer and the antifouling layer is 0.01 to 0.05 N. It is preferably / 10 mm, and more preferably 0.02 to 0.04 N / 10 mm.

By adjusting the adhesive strength to a preferable value, it is possible to prevent the adhesive from remaining and the material forming the antifouling layer from being peeled off by the adhesive.

In particular, since the adhesive tends to remain on the surface of the antifouling layer or the material forming the antifouling layer is easily peeled off by the adhesive, the adhesive strength of the adhesive layer is higher than that of the adhesive with the antireflection layer. It is preferable that the value is also low.

The thickness of the adhesive layer is preferably 3 μm to 50 μm, preferably 5 μm to 25 μm, from the viewpoint of adhesiveness and peelability between the antireflection layer and the antifouling layer and the adhesive layer formed on the protective film with the adhesive layer. More preferably.

<Protective film>
The protective film is not particularly limited as long as it is in the form of a resin film. Further, the protective film may have a single-layer structure, or may have a multi-layer structure in which a plurality of layers such as an antistatic layer, a hard coat layer, and an easy-adhesion layer are laminated. Further, the protective film may be colored in order to prevent the protective film with the adhesive layer from being forgotten to be peeled off from the glass laminate.

As the protective film, for example, a polyester film such as polyethylene terephthalate, a polyethylene film, a polyolefin film such as polypropylene, a polyvinyl chloride film or the like can be used. Among these, a polyester-based film is preferable from the viewpoint of adhesion to the adhesive layer, durability and optical properties.

The thickness of the protective film is also not particularly limited. For example, it is preferably 5 μm to 100 μm, and when it is 15 μm to 75 μm, the protective film is easily bent and peeled off, which is more preferable. If it is less than 5 μm, the glass laminate may not be sufficiently protected, and if it exceeds 100 μm, the cost may increase.

<Transparent substrate>
Examples of the transparent substrate include general glass plates such as soda lime glass, borosilicate glass, aluminosilicate glass, and non-alkali glass, inorganic glass made of inorganic materials having various compositions, and transparent resin plates.

Examples of the optimum glass plate material include glass materials such as soda lime glass, quartz glass, quartz glass, and sapphire glass, and highly transparent glass having a lower iron content and less bluish tint is more preferable.

As the material of the transparent resin plate, a highly transparent resin material is preferable, and as the transparent resin plate, for example, a polyester resin such as polycarbonate or polyethylene terephthalate, a polyolefin resin such as polypropylene, a polyvinyl chloride, an acrylic resin, etc. Examples thereof include polyether sulfone, polyacrylicate, triacetyl cellulose, polymethyl methacrylate and the like.

As the transparent substrate, a glass plate is most preferable from the viewpoint of high transparency, light resistance, heat resistance, low refractive index, high flatness accuracy, surface scratch resistance, and high mechanical strength.

The mechanical strength may be increased in order to increase the safety of the glass plate. In order to increase the mechanical strength of the glass plate, the glass plate is preliminarily strengthened.

As the strengthening treatment, physical strengthening in which the glass plate is exposed to high temperature and then air-cooled, or the glass plate is immersed in a molten salt containing an alkali metal, and an alkali having a small atomic diameter existing on the outermost surface of the glass plate is present. Chemical strengthening that replaces the metal (ion) with a large atomic alkali metal (ion) present in the molten salt can be mentioned.

In particular, when a thin glass plate is used, it is preferable to use a chemically strengthened glass plate (hereinafter, also referred to as “chemically strengthened glass”).

The chemically strengthened glass as a transparent substrate preferably satisfies the following conditions. That is, the surface compressive stress (hereinafter referred to as CS) of the glass substrate is preferably 400 MPa or more and 1200 MPa or less, and more preferably 700 MPa or more and 900 MPa or less. When CS is 400 MPa or more, it is sufficient as a practical strength.

Further, if the CS is 1200 MPa or less, it can withstand its own compressive stress and there is no concern that it will break naturally. When the glass laminate 1 with a protective film of the present invention is used as a front plate (cover glass) of a display device or the like, the CS of the glass substrate is preferably 700 MPa or more and 850 MPa or less.

Further, the depth of the stress value of the glass substrate (hereinafter referred to as DOL) is preferably 15 to 50 μm, more preferably 20 to 40 μm. If the DOL is 15 μm or more, there is no concern that it will be easily scratched and destroyed.

Further, if the DOL is 40 μm or less, it can withstand the compressive stress of the substrate itself, and there is no concern that it will break naturally. When the glass laminate 1 with a protective film of the present invention is used as a front plate (cover glass) of a display device or the like, the DOL of the glass substrate is preferably 25 μm or more and 35 μm or less.

Further, sapphire glass is also preferable from the viewpoint of mechanical strength.

The shape of the transparent substrate is usually a smooth and rectangular shape. The shape of the transparent substrate is appropriately changed according to the shape of the display panel of the display device, the design of the display device, the mounting position of the display device, and the like.

That is, the shape of the transparent substrate is not limited to a smooth shape or a rectangular shape. For example, it may be a template glass having an uneven surface, or may have a polygonal shape, a circular shape, or an elliptical shape. Further, not only flat glass but also glass having a curved surface shape may be used.

The outer peripheral edge of the transparent substrate is an edge away from the center of the transparent substrate. Normally, the transparent substrate has a rectangular shape, but in the case of a rectangular shape, at least a part of the outer peripheral edge is formed by a straight line. Since the shape of the transparent substrate is appropriately changed depending on the shape of the display panel and the like, at least a part of the outer peripheral end may be formed by a curved line.

The size of the transparent substrate is appropriately determined depending on the size of the display panel and the application of the display device. For example, when used as a cover glass for mobile devices, it has a size of 30 mm × 50 mm to 300 mm × 400 mm and a thickness of 0.1 to 2.5 mm, and is a display device such as a display device, a car navigation system, a console panel, or an instrument panel. In the case of, it is preferable that the size is 50 mm × 100 mm to 2000 mm × 1500 mm and the thickness is 0.5 to 4 mm.

The thickness of the transparent substrate is not particularly limited, and glass having a thickness of 10 mm or less can be used. In the case of a glass plate, it is usually about 0.1 to 6 mm from the viewpoint of mechanical strength and transparency. In particular, when used in an in-vehicle display device, the transparent substrate is required to be safe, and therefore 0.2 to 2 mm is preferable from the viewpoint of mechanical strength.

When chemically tempered glass is used, the thickness of the glass substrate is usually preferably 5 mm or less, more preferably 3 mm or less, in order to effectively perform the chemical tempering treatment. In the case of a transparent resin plate, 2 to 10 mm is preferable.

Since the thinner the thickness, the lower the absorption of light can be suppressed, it is preferable to use a glass plate from the viewpoint of improving visibility and transparency. The transparent substrate is not necessarily limited to a single-layer structure composed of a single layer, and may be a multilayer structure composed of a plurality of layers such as laminated glass.

<Anti-reflective layer>
The antireflection layer is a layer formed to suppress reflection by external light and improve the display quality of a display image, and is usually formed on the first main surface of a transparent substrate.

When the first main surface of the transparent substrate is subjected to antiglare treatment, it is preferable to form the antireflection layer 20 on the antiglare layer 60 that has been antiglare treated.

The configuration of the antireflection layer is not particularly limited as long as it can suppress the reflection of light within a predetermined range, and for example, a configuration in which a high refractive index layer and a low refractive index layer are laminated can be used. Here, the high refractive index layer means, for example, a layer having a refractive index of 1.9 or more for light having a wavelength of 550 nm, and a low refractive index layer means a layer having a refractive index of 1.6 or less for light having a wavelength of 550 nm. ..

The number of layers of the high refractive index layer and the low refractive index layer in the antireflection layer may be a form including one layer each, or may include two or more layers each. In the case of a configuration including one high refractive index layer and one low refractive index layer, it is preferable that the high refractive index layer and the low refractive index layer are laminated in this order on the main surface of the transparent substrate. Further, in the case of a configuration including two or more layers each having a high refractive index layer and a low refractive index layer, it is preferable that the high refractive index layer and the low refractive index layer are alternately laminated in this order.

In order to enhance the antireflection performance, the antireflection layer is preferably a laminated body in which a plurality of layers are laminated, and the laminated body is, for example, a laminated body in which two or more layers and eight or less layers are laminated as a whole. It is preferable that two or more and six or less layers are laminated, and more preferably two or more and four or less layers are laminated. As described above, the laminated body is preferably one in which high refractive index layers and low refractive index layers are alternately laminated, and the total number of layers of high refractive index layers and low refractive index layers is in the above range. It is preferable to be in. Further, the layer may be added within a range that does not impair the optical characteristics. For example, in order to prevent Na diffusion from the glass substrate, a SiO ₂ film may be inserted between the glass and the first layer.

The materials constituting the high refractive index layer and the low refractive index layer are not particularly limited, and can be selected in consideration of the required degree of antireflection and productivity. Examples of the material constituting the high refractive index layer include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TIO ₂ ), zirconium oxide (ZrO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), and aluminum oxide (Al ₂ ). O ₃ ), silicon nitride (SiN) and the like can be mentioned. One or more selected from these materials can be preferably used. Materials constituting the low refractive index layer include silicon oxide (particularly silicon dioxide SiO ₂ ), a material containing a mixed oxide of Si and Sn, a material containing a mixed oxide of Si and Zr, and Si and Al. Examples of the material containing the mixed oxide of the above. One or more selected from these materials can be preferably used.

From the viewpoint of productivity and refractive index, it is preferable that the high refractive index layer is one selected from niobium oxide, tantalum oxide, and silicon nitride, and the low refractive index layer is a layer made of silicon oxide.

The antireflection layer can be obtained by a method of directly forming an inorganic thin film on the surface, a method of surface treatment by a method such as etching, or a dry method, for example, a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a physical vapor deposition method. It can be suitably formed by a kind of vacuum deposition method or sputter method.

The antireflection layer and the antifouling layer may be formed in this order on the first main surface of the transparent substrate. In this case, the antireflection layer may be formed by a wet method in order to easily apply the antifouling layer to the antireflection layer. Examples of the wet method include those containing low refractive index fine particles, and specifically, those containing low refractive index fine particles in a matrix component serving as a binder.

Alternatively, the antireflection layer can be provided by a method of attaching a transparent resin film having an antireflection function to the transparent substrate.

The thickness of the antireflection layer is preferably 100 to 500 nm. It is preferable that the thickness of the antireflection layer is 100 nm or more because the reflection of external light can be effectively suppressed.

<Anti-fouling layer>
The antifouling layer has at least one property of oil repellency and lipophilicity. It has functions such as suppressing the adhesion of various stains such as sweat and dust as well as fingerprint marks, making it easier to wipe off stains, and making stains less noticeable, and keeps the display surface clean. In addition, it is possible to obtain smooth finger slipperiness without getting caught when operating the touch panel.

It is preferable that the antifouling layer is formed on the outermost surface of the glass laminate by forming the antifouling layer on the antireflection layer from the viewpoint of the characteristics of the antifouling layer.

As a method for forming the antifouling layer, a vacuum vapor deposition method (dry method) in which a fluorine-containing organic compound or the like is evaporated in a vacuum chamber and adhered to the surface of the antireflection layer, or a fluorine-containing organic compound or the like is dissolved in an organic solvent. A method (wet method) or the like can be used in which the compound is adjusted to a predetermined concentration and then applied to the surface of the antireflection layer.

The dry method can be appropriately selected from the ion beam assisted vapor deposition method, the ion plate method, the sputtering method, the plasma CVD method and the like, and the wet method can be appropriately selected from the spin coating method, the dip coating method, the casting method, the slit coating method, the spray method and the like. ..

Both the dry method and the wet method can be used. From the viewpoint of scratch resistance, it is preferable to use a dry film forming method.

The constituent material of the antifouling layer can be appropriately selected from fluorine-containing organic compounds that can impart antifouling property, water repellency, and oil repellency. Specific examples thereof include a fluorine-containing organosilicon compound and a fluorine-containing hydrolyzable property. The fluorine-containing organic compound can be used without particular limitation as long as it imparts antifouling property, water repellency and oil repellency.

(Fluorine-containing organosilicon compound coating)
When the antireflection layer is formed on the main surface of the transparent substrate or the treated surface of the antiglare layer, the fluorine-containing organosilicon compound coating forming the antifouling layer may be formed on the surface of the antireflection layer. preferable. Further, when a glass substrate that has been subjected to surface treatment such as antiglare treatment or chemical strengthening treatment as the transparent substrate and does not have an antireflection layer formed is used, the fluorine-containing organosilicon compound coating is the surface to which these surface treatments have been applied. It is preferably formed directly on.

As a method for forming a fluorine-containing organosilicon compound film, a composition of a silane coupling agent having a fluoroalkyl group such as a perfluoroalkyl group; a fluoroalkyl group containing a perfluoro (polyoxyalkylene) chain is spin-coated. , A method of applying by a dip coating method, a casting method, a slit coating method, a spray coating method or the like and then heat-treating, or a vacuum vapor deposition method in which a fluorine-containing organosilicon compound is vapor-deposited and then heat-treated. In order to obtain a fluorine-containing organosilicon compound film having high adhesion, it is preferably formed by a vacuum vapor deposition method. The formation of the fluorine-containing organosilicon compound film by the vacuum vapor deposition method is preferably performed using a film-containing composition containing a fluorine-containing hydrolyzable silicon compound.

(Fluorine-containing hydrolyzable silicon compound)
In the antifouling layer, the fluorine-containing hydrolyzable silicon compound used for forming the fluorine-containing organosilicon compound film is such that the obtained fluorine-containing organosilicon compound film has antifouling properties such as water repellency and oil repellency. There are no particular restrictions.

Specific examples thereof include a fluorine-containing hydrolyzable silicon compound having one or more groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group.

The antifouling layer may be provided by a method of laminating a transparent resin film having an antifouling function.

Usually, the layer thickness of the antifouling layer formed on the antireflection layer is not particularly limited, but is preferably 2 to 20 nm, more preferably 2 to 15 nm, and preferably 3 to 10 nm. More preferred.

When the layer thickness is 2 nm or more, the surface of the antireflection layer is uniformly covered by the antifouling layer, and the scratch resistance is simple and practical. Further, when the layer thickness is 20 nm or less, the optical characteristics such as the visual reflectance and the haze value in the state where the antifouling layer is laminated are good.

<Anti-glare layer>
An antiglare layer may be provided on the first main surface of the transparent substrate in order to impart antiglare properties to the glass laminate.

In order to impart antiglare properties, an uneven shape is formed on the main surface of the transparent substrate. The main surface having the uneven shape is at least one main surface of the transparent substrate, and it is preferable to provide the uneven shape on the first main surface of the transparent substrate.

A known method can be applied as a method for forming the uneven shape. For example, when a glass substrate is used as the transparent substrate, a method of chemically or physically surface-treating the main surface of the glass substrate to form an uneven shape having a desired surface roughness, a wet coat, or the like can be used.

Specific examples of the method of chemically performing the antiglare treatment include a method of performing a frost treatment. The frost treatment can be realized, for example, by immersing a glass substrate as an object to be treated in a mixed solution of hydrogen fluoride and ammonium fluoride.

Further, as a method of physically performing the antiglare treatment, for example, sandblasting treatment in which crystalline silicon dioxide powder, silicon carbide powder or the like is sprayed on the main surface of the glass substrate with pressurized air, crystalline silicon dioxide powder, silicon carbide, etc. A method of rubbing a brush to which powder or the like is attached with a water-moistened brush can be used.

Among these, the frost treatment is preferable as a method for performing the antiglare treatment on the glass substrate because microcracks on the surface of the object to be treated are unlikely to occur and the mechanical strength is unlikely to decrease.

The main surface of the glass substrate that has been chemically or physically antiglare-treated in this way is preferably etched in order to adjust the surface shape. As the etching process, for example, a method of immersing a glass substrate in an etching solution which is an aqueous solution of hydrogen fluoride and chemically etching can be used.

The surface roughness (root mean square roughness, RMS) of the main surface of the glass substrate after the antiglare treatment and the etching treatment are preferably 0.01 to 0.5 μm. The surface roughness (RMS) is more preferably 0.01 to 0.3 μm, still more preferably 0.02 to 0.2 μm. By setting the surface roughness (RMS) in the above range, the haze value of the glass substrate after the antiglare treatment can be adjusted to 1 to 30%, and as a result, the obtained transparent substrate 10 with an antireflection layer is excellent. Anti-glare property can be imparted. The haze value is a value defined by JIS K 7136.

As a method of forming the antiglare layer, a transparent resin film having an antiglare function may be attached to a transparent substrate.

<Shading layer>
A light-shielding layer is formed on at least a part of the peripheral edge of the second main surface of the transparent substrate. The light-shielding layer hides the wiring members and the like arranged on the peripheral edge of the display panel so that the area other than the image display area of the display panel cannot be seen from the observer side, and the design of the display device is improved. Formed on the display to enhance the visibility and aesthetics of the display.

The peripheral portion of the transparent substrate means a band-shaped region having a predetermined width from an end portion away from the center of the transparent substrate toward the central portion of the transparent substrate. The light-shielding layer is formed on the entire circumference of the peripheral edge portion or at least a part of the peripheral edge portion.

The outer peripheral side of the light-shielding layer is usually a band-shaped region in which the light-shielding layer is in contact with the outer peripheral edge of the transparent substrate and has a predetermined width, and is substantially the outer peripheral edge of the second main surface of the transparent substrate on which the light-shielding layer is formed. It is the same.

The inner peripheral side of the light-shielding layer means an edge near the center of the transparent substrate in the light-shielding layer region having a predetermined width. Usually, the region where the light-shielding layer is formed is formed according to the shape of the transparent substrate. When the transparent substrate has a rectangular shape, at least a part of the outer peripheral side of the light-shielding layer is formed by a straight line. The inner peripheral side of the light-shielding layer may be formed by a straight line or a curved line.

Further, an operation state display unit for displaying the operation state of the display and a light transmission area for receiving operation light such as infrared rays from the remote controller may be formed in a part of the light-shielding layer formation area.

The light-shielding layer is formed on the peripheral edge of the second main surface of the transparent substrate. The light-shielding layer is preferably provided in a region of more than 0 mm and less than 30 mm from the outer peripheral side of the second main surface of the transparent substrate.

The light-shielding layer is formed by a method of printing black ink. Examples of the printing method include a bar code method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, a screen method, etc., which can be easily printed and can be printed on various substrates. The screen printing method is preferable because it can be printed according to the size of the material.

Black ink can be used without particular limitation. As the black ink, an inorganic ink containing a fired ceramic body or the like and an organic ink containing a colorant such as a dye or pigment and an organic resin can be used. It is preferable to form a light-shielding layer by using ceramic printing containing a coloring pigment because the light-shielding property is high.

The light-shielding layer is usually formed in black, but is not limited to black as long as the light-shielding property is high.

A light-shielding layer can also be formed by laminating a transparent film having a light-shielding function on a transparent substrate.

Ceramics contained in the black inorganic 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 unit 6 is obtained by melting the ink composed of the ceramics and silica, printing in a desired pattern, and then firing. This inorganic ink requires melting and firing steps, and is generally used as a glass-only ink.

The organic ink is a composition containing a black dye or pigment and an organic resin. Organic resins include epoxy resin, acrylic resin, polyethylene terephthalate, polyether sulfone, polyarylate, polycarbonate, transparent ABS resin, phenol resin, acrylonitrile-butadiene-styrene resin, polyurethane, polymethyl methacrylate, polyvinyl, Examples thereof include homopolymers such as polyvinyl butyral, polyether ether ketone, polyethylene, polyester, polypropylene, polyamide, and polyimide, and resins composed of copolymers of monomers of these resins and copolymerizable monomers. Further, the dye or pigment can be used without particular limitation as long as it is black.

Since the firing temperature of the inorganic ink and the organic ink is low, it is preferable to use the organic ink. Further, from the viewpoint of chemical resistance, an organic ink containing a pigment is preferable.

<Visual reflectance>
The glass laminate of the present invention has a transparent substrate, an antireflection layer formed on the first main surface of the transparent substrate, and a light-shielding layer formed on at least a part of the peripheral edge of the second main surface of the transparent substrate. And have. Then, in the glass laminate of the present invention, the visual reflection measured by removing the back surface reflection at the interface between the transparent substrate and the light-shielding layer with respect to the incident light from the antireflection layer side in the region having the light-shielding layer. The rate is 2% or less.

As a method of removing the back surface reflection, when measuring only the specular reflection, the second main surface is exposed to sandpaper or the like, and the reflectance is further lowered by black magic or the like to reduce the reflectance from the second main surface. A method of eliminating reflections is commonly used. However, this is insufficient when measuring in the SCI mode including diffuse reflection light. This is because the diffused light from the second main surface exists even after the above treatment. In this case, the back surface reflection can be removed by calculation as follows.
Assuming that the reflectance of the first main surface having a low reflection layer and the desired first main surface is R1 and the reflectance of the transparent substrate is R0, the light is incident from the first main surface and at the interface between the second main surface and air. Considering the light that is reflected and transmitted through the first main surface, the reflectance of the SCI mode measured from the side of the first main surface in the region where the second main surface is not provided with the light shielding layer. (Let's be Rg) is Rg = R1 + (1-R1) × R0 × (1-R1)
Will be. Since R0 can be calculated by measuring the refractive index of the transparent substrate with, for example, an ellipsometer, R1 can be calculated because the measured values Rg and R0 are known.
Actually, there is light that repeats reciprocating in the transparent substrate according to the second term or less in the above equation, but R0 is as low as about 4% in a normal transparent substrate, so that it is negligibly small.

The glass laminate of the present invention has a visual reflectance of 2% or less, and further, since the adhesive strength of the adhesive layer is appropriately adjusted, there is little reflection, and the adhesive remains in the light-shielding layer forming region. Color unevenness due to peeling of the antireflection layer due to the adhesive or the adhesive is sufficiently suppressed, and the color tone does not change between the portion where the adhesive layer protective film is attached and the portion where the adhesive layer protective film is not attached, and the visibility is improved.

When the visual reflectance is preferably 1.5% or less, more preferably 1% or less, a more remarkable effect is exhibited.

The glass laminate of the present invention has a visual reflectance of 2% or less, and by appropriately adjusting the adhesive force of the adhesive, color unevenness due to residual adhesive or peeling of the antireflection layer by the adhesive When the glass laminate is assembled to the display device, it is possible to obtain excellent design and aesthetics as well as good display visibility with less reflection on the display surface.

Further, even when the antifouling layer is formed on the outermost surface of the glass laminate, if the layer thickness of the antifouling layer is 20 nm or less, the visual reflectance is large even when the antifouling layer is laminated. Does not affect. The visual reflectance after removing the back reflection of the antireflection layer and the antifouling layer is 2% or less, and the adhesive strength of the adhesive layer is appropriately adjusted to prevent residual adhesive and prevent the adhesive. Color unevenness due to peeling of the dirty layer is sufficiently suppressed, and when the glass laminate is assembled to the display device, it is possible to obtain excellent design and aesthetics as well as good display visibility with less reflection on the display surface.

In the following examples and comparative examples, combinations of materials and procedures specifically used will be mainly described.

A glass substrate with an antifouling film was manufactured by the following procedure.
First, as a transparent substrate, chemically strengthened glass and Dragon Trail (registered trademark, manufactured by AGC Inc., hereinafter also referred to as "DT") were used.

(1) Anti-glare treatment The first main surface of the glass substrate was subjected to anti-glare treatment by frost treatment according to the following procedure. First, an acid-resistant protective film was attached to the surface of the glass substrate that was not subjected to the antiglare treatment. Then, this glass substrate was immersed in a 3% by weight hydrogen fluoride solution for 3 minutes to remove stains adhering to the surface of the glass substrate. Next, the glass substrate was immersed in a mixed solution of 15% by weight hydrogen fluoride and 15% by weight potassium fluoride for 3 minutes, and the second main surface of the glass substrate was frosted.

The haze value was adjusted by immersing the glass substrate after the antiglare treatment in a 10% hydrogen fluoride solution.

(2) Chemical strengthening treatment The antiglare-treated glass substrate was chemically strengthened by the following procedure. First, the glass substrate subjected to the antiglare treatment is immersed in potassium nitrate heated and melted at 450 ° C. for 2 hours, then the substrate is pulled up from the molten salt and slowly cooled to room temperature in 1 hour to obtain a chemically strengthened substrate. Obtained. In this way, a chemically strengthened glass substrate having a surface compressive stress (CS) of 730 MPa and a stress layer depth (DOL) of 30 μm was obtained.

The substrate was then immersed in an alkaline solution (Sunwash TL-75, manufactured by Lion Corporation) for 4 hours.

(3) Formation of Light-shielding Layer Next, on the glass substrate subjected to the antiglare treatment and the chemical strengthening treatment, screen printing was performed on the second main surface of the glass substrate by the following procedure.

A 2 cm wide black frame was printed on the four sides of the outer peripheral portion of the second main surface of the glass substrate to form a light-shielding layer. First, a black ink (GLSHF (trade name, manufactured by Teikoku Printing Inks)) was applied to a thickness of 5 μm by a screen printing machine, and then held at 150 ° C. for 10 minutes to dry to form a first printing layer. .. Next, black ink was applied to a thickness of 5 μm on the first print layer in the same procedure as above, and then held at 150 ° C. for 40 minutes to dry to form a second print layer. In this way, a light-shielding layer in which the first printing layer and the second printing layer were laminated was formed, and a glass substrate provided with a light-shielding layer on the outer peripheral portion of one main surface was obtained.

(4) Formation of High Refractive Index Layer An antireflection layer was formed on the first main surface side of the glass substrate subjected to the antiglare treatment by the following method. First, while introducing a mixed gas in which 10% by volume of oxygen gas is mixed with argon gas into the thin film forming apparatus, a pressure of 0.3 Pa is used using a niobium oxide target (manufactured by AGC Ceramics Co., Ltd., trade name: NBO target). Pulse sputtering was performed under the conditions of frequency 20 kHz, power density 3.8 W / cm ² , and inversion pulse width 5 μsec, and from niobium oxide (Nb2O5) having a thickness of 12 nm and a refractive index (n) of 2.3 on an optical member. A high refractive index layer (first layer) was formed.

Further, in forming the high refractive index layer on the first main surface side of the glass substrate, silicon nitride (SiN) is used instead of niobium oxide (Nb ₂ O ₅ ) to form the high refractive index layer on the glass substrate. It was formed on the first main surface side.

The high refractive index layer made of silicon nitride was formed by the following method. Conditions of pressure 0.3 Pa, frequency 20 kHz, power density 3.8 W / cm ² , and inverting pulse width 5 μsec while introducing a mixed gas in which nitrogen gas is mixed with argon gas so as to be 50% by volume in a vacuum chamber. Then, pulse sputtering was performed using a silicon target to form a high refractive index layer made of silicon nitride on the entire surface of the glass substrate on which the high refractive index layer should be formed.

(5) Formation of low refractive index layer Using a silicon target while introducing a mixed gas in which 40% by volume of oxygen gas is mixed with argon gas, the pressure is 0.3 Pa, the frequency is 20 kHz, and the power density is 3. Pulse sputtering was performed under the condition of 8 W / cm ² and the inverting pulse width of 5 μsec under the condition of the pulse width of 5 μsec to form a low refractive index layer made of silicon oxide (SiO ₂ ) having a refractive index (n) of 1.45.

(6) Formation of Antireflection Layer An antireflection layer was formed by alternately forming a high refractive index layer and a low refractive index layer.

(7) Formation of antifouling layer An antifouling layer was formed by the following method. First, as a material for the antifouling layer, a material for forming a fluorine-containing organosilicon compound film was introduced into a heating container. After that, the inside of the heating container was degassed with a vacuum pump for 10 hours or more to remove the solvent in the solution to obtain a composition for forming a fluorine-containing organosilicon compound film (hereinafter referred to as an antifouling layer forming composition). ..

Next, the heating container containing the antifouling layer forming composition was heated to 270 ° C., and after reaching 270 ° C., the state was maintained for 10 minutes until the temperature became stable. Next, after the glass substrate on which the antireflection layer 20 is formed is installed in the vacuum chamber, the antireflection layer of the glass substrate is provided from a nozzle connected to a heating container containing the antifouling layer forming composition. A composition for forming an antifouling layer was supplied toward the above, and a film was formed.

The film formation was carried out while measuring the film thickness with a crystal oscillator monitor installed in the vacuum chamber until the film thickness of the fluorine-containing organosilicon compound film on the low-reflection film became 4 nm. Next, the glass substrate taken out from the vacuum chamber was placed on a hot plate with the fluorine-containing organosilicon compound film surface facing upward, and heat-treated at 150 ° C. in the air for 60 minutes.

In this way, a glass laminate in which an antifouling layer was formed on the antireflection layer was obtained.

(8) Adhesion of Protective Film with Adhesive Layer Next, the protective film with adhesive layer was installed on the main surface of the glass substrate with antifouling film obtained above. At that time, they were bonded so as to be 2 mm inside from the outer peripheral edge of the glass laminate. This can be done, for example, by processing the film into a shape 2 mm smaller than the substrate shape in advance and then laminating the film.

In this way, a protective film with an adhesive layer attached to the main surface side of the glass laminate is provided with an antireflection layer, an antifouling layer, and an antiglare layer attached 2 mm inward from the end. A laminate was obtained.

The antireflection layer, the antifouling layer, the glass laminate forming the antiglare layer, and the protective film with an adhesive layer to be bonded to the glass laminate used in Examples and Comparative Examples will be described in each Example. And Table 1.

(Example 1)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobide oxide, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is four. This was done to form an antireflection layer. The thickness of each layer was 13 nm for the first niobium oxide layer, 35 nm for the second silicon oxide layer, 115 nm for the third niobium oxide layer, and 90 nm for the fourth silicon oxide layer.

After that, an antifouling layer was formed using KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a vapor deposition material, and a PET protective film of EC-9005 ASL (manufactured by Sumiron Co., Ltd.) having an adhesive layer with an acrylic adhesive was attached. did. The thickness of the protective film base material is 25 μm.

(Example 2)
Similar to Example 1, the DT having a thickness of 2.0 mm is subjected to (1) antiglare treatment, and the haze is adjusted to 25% by adjusting the etching time, and (2) chemical strengthening treatment is performed. gave. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobide oxide, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is four. This was done to form an antireflection layer. The thickness of each layer was 13 nm for the first niobium oxide layer, 35 nm for the second silicon oxide layer, 115 nm for the third niobium oxide layer, and 90 nm for the fourth silicon oxide layer.

After that, an antifouling layer was formed using KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a vapor deposition material, and a PET protective film of UA-3004ASL (manufactured by Sumiron Co., Ltd.) having an adhesive layer made of a polyurethane-based adhesive was attached. did.

(Example 3)
The DT having a thickness of 1.3 mm was subjected to (1) chemical strengthening treatment without antiglare treatment. Next, (2) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobium oxide and (B) a low refractive index layer made of silicon oxide were formed in this order to form an antireflection layer having two layers. .. The thickness of each layer was 13 nm for the first niobium oxide layer and 120 nm for the second silicon oxide layer.

Then, an antifouling layer was formed with Optool DSX (manufactured by Daikin Co., Ltd.), and a polyethylene-based protective film of Y16FAS (manufactured by Sun A. Kaken Co., Ltd.) having an adhesive layer made of an acrylic adhesive was attached.

(Example 4)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of silicon nitride, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is eight. This was done to form an antireflection layer. The thickness of each layer is 15 nm for the first silicon nitride layer, 70 nm for the second silicon oxide layer, 17 nm for the third silicon nitride layer, 105 nm for the fourth silicon oxide layer, and the fifth layer. The silicon nitride layer was 15 nm, the sixth silicon oxide layer was 50 nm, the seventh silicon nitride layer was 120 nm, and the eighth silicon oxide layer was 80 nm.

Then, an antifouling layer was formed with KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a polyethylene-based protective film of EC-610B2L (manufactured by Sumiron Co., Ltd.) having an adhesive layer made of an acrylic adhesive was attached.

(Example 5)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobium oxide and (B) a low refractive index layer made of silicon oxide are formed in this order to form an antireflection layer 20 having two layers. It was. The thickness of each layer was 13 nm for the first niobium oxide layer and 120 nm for the second silicon oxide layer.

After that, the antifouling layer was not formed, and a PET protective film of EC-9005ASL (manufactured by Sumiron) having an adhesive layer made of an acrylic adhesive was attached.

(Example 6)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobide oxide, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is four. This was done to form an antireflection layer. The thickness of each layer was 13 nm for the first niobium oxide layer, 35 nm for the second silicon oxide layer, 115 nm for the third niobium oxide layer, and 90 nm for the fourth silicon oxide layer.

After that, the antifouling layer was not formed, and a PET protective film of Y16-FAS (manufactured by Sun A. Kaken Co., Ltd.) having an adhesive layer made of a polyurethane-based adhesive was attached.

(Comparative Example 1)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobide oxide, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is four. This was done to form an antireflection layer. The thickness of each layer was 13 nm for the first niobium oxide layer, 35 nm for the second silicon oxide layer, 115 nm for the third niobium oxide layer, and 90 nm for the fourth silicon oxide layer.

Then, an antifouling layer was formed with KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a polypropylene-based protective film manufactured by Futamura Chemical Co., Ltd. having an adhesive layer with an adhesive was attached.

(Comparative Example 2)
The DT having a thickness of 1.3 mm was subjected to (1) antiglare treatment, and the haze was adjusted to 2% by adjusting the etching time, and (2) chemical strengthening treatment was performed. Next, (3) a light-shielding layer was formed. Next, (A) a high refractive index layer made of niobide oxide, (B) a low refractive index layer made of silicon oxide, and an antireflection layer are alternately formed so that the number of layers is four. This was done to form an antireflection layer. The thickness of each layer was 13 nm for the first niobium oxide layer, 35 nm for the second silicon oxide layer, 115 nm for the third niobium oxide layer, and 90 nm for the fourth silicon oxide layer.

Then, an antifouling layer was formed with KY-185 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a PET protective film of TTG-3370 (manufactured by Sumiron Co., Ltd.) having an adhesive layer made of an acrylic adhesive was attached.

<Evaluation method>
The following evaluations were carried out on the glass laminates with the protective film with the adhesive layer obtained in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 1.

(Haze)
The haze was measured according to JIS-K-7136 using a haze meter HZ-V3 (manufactured by Suga Test Instruments Co., Ltd.).

(Visual reflectance)
The visual reflectance is a reflection stimulus value Y defined in JIS Z8701. In the present invention, a spectrophotometer (manufactured by Konica Minolta, model: CM-2600d) is used to measure and measure the reflected light by the SCI method, which measures the specular reflected light and the diffuse reflected light together under the light source of D65. The specular reflectance was calculated using the obtained reflectance.

(Evaluation of color unevenness)
The color unevenness evaluation was carried out as follows. First, the substrate was held at a position of 2000 lux under fluorescent light in a room where outside light did not enter, for example, in a black booth. In that state, it was visually confirmed that there was no color unevenness from various angles.

(Adhesion)
Adhesion was measured as follows. First. The packaged laminated film is cut into strips having a width of 10 mm on the base material. Next, one of them was used for a 90-degree peeling test. The peeling speed was set to 0.84 mm / sec using a peeling force measuring device FA PLUS (manufactured by IMADA). This was done three times in another strip and the average value was adopted.

<Measurement result>
Table 1 shows Examples (Examples 1 to 6) and Comparative Examples (Comparative Examples 1 and 2) of the glass laminate with a protective film according to the present invention.

A glass laminate having an antiglare layer, an antireflection layer and an antifouling layer (Examples 1 to 4), and a glass laminate having an antiglare layer and an antireflection layer (Examples 5 to 6) have an adhesive layer. By adjusting the adhesive strength of the adhesive layer of the protective film to a predetermined value, when the protective film with the adhesive layer is peeled off from the glass laminate, unevenness in the light-shielding layer forming region is not observed in the front view of the glass laminate. , The color tone did not change at the boundary between the part where the protective film was attached and the part where the protective film was not attached, and the boundary was not conspicuous, and the visibility was significantly improved.

In the glass laminate having the antiglare layer and the antireflection layer (Examples 5 to 6), the adhesive strength of the adhesive layer is adjusted to 0.01 to 0.3 N / 10 mm, so that the glass laminate is changed to the adhesive layer. When the protective film with adhesive is peeled off, unevenness is not observed in the light-shielding layer forming region in the front view of the glass laminate, and the color tone changes between the part where the protective film is attached and the part where the protective film is not attached. It was not noticeable and the visibility was significantly improved.

In the glass laminate having the antiglare layer, the antireflection layer and the antifouling layer (Examples 1 to 4), the adhesive strength of the adhesive layer is adjusted to 0.01 to 0.05 N / 10 mm, so that the glass laminate is formed. When the protective film with the adhesive layer is peeled off from the body, no unevenness is observed in the light-shielding layer forming region in the front view of the glass laminate, and the color changes between the part where the protective film is applied and the part where the protective film is not applied. However, the boundary was not conspicuous, and the visibility was significantly improved.

Comparative Example 1 is a glass laminate having an antiglare layer, an antireflection layer, and an antifouling layer. When the adhesive strength of the adhesive layer is 0.008 N / 10 mm, when the protective film with the adhesive layer is peeled off from the glass laminate, unevenness is visually recognized in the light-shielding layer forming region in the front view of the glass laminate, and the visibility is visible. Has deteriorated.

Comparative Example 2 is a glass laminate having an antiglare layer, an antireflection layer, and an antifouling layer. When the adhesive strength of the adhesive layer is 0.1 N / 10 mm, when the protective film with the adhesive layer is peeled off from the glass laminate, unevenness occurs in the light-shielding layer forming region in the front view of the glass laminate, and the protective film. The color changed between the part where and the part where was not pasted, the boundary was conspicuous, and the visibility deteriorated.

The glass laminate with a protective film of the present invention is suitable as a front substrate of a display device because the visual appearance of the portion where the protective film is attached and the portion where the protective film is not attached does not change even after the protective film with the adhesive layer is peeled off. It is possible to obtain excellent design and aesthetics as well as good display visibility.

The glass laminate with a protective film of the present invention is suitably used as a display front plate (cover glass), and is useful not only for product protection of the display front plate but also for improving manufacturing ease when assembling to a display device.

1 ... Glass laminate with protective film, 10 ... Transparent substrate, 20 ... Antireflection layer, 30 ... Antifouling layer, 40 ... Adhesive layer, 50 ... Protective film, 60 ... Antiglare layer, 70 ... Light-shielding layer, 80 ... Adhesive Protective film with layer, 90 ... Glass laminate

Claims (7)

A transparent substrate having a first main surface and a second main surface,
An antifouling layer on the first main surface,
A glass laminate having at least a light-shielding layer on the peripheral edge of the second main surface, and
A glass laminate with a protective film provided with a protective film with an adhesive layer.
The protective film with an adhesive layer is bonded to the glass laminate and
In the protective film with an adhesive layer, the outer peripheral edge of the protective film with an adhesive layer is on the outer peripheral side from the inner peripheral side of the light-shielding layer and the inner circumference from the outer peripheral side of the light-shielding layer in the front view of the glass laminate. It is pasted on the side position,
Ri adhesive strength 0.01~0.05N / 10mm der between the adhesive layer and the antifouling layer,
The antifouling layer is formed by a silane coupling reaction.
A glass laminate with a protective film. The glass laminate with a protective film according to claim 1, wherein the first main surface of the transparent substrate has an uneven shape. The protection is provided by extending a straight line perpendicular to an arbitrary point on the outer peripheral edge of the outermost surface of the glass laminate and the outer peripheral edge of the main surface of the glass laminate through an arbitrary point with respect to the outer peripheral edge of the protective film. The glass laminate with a protective film according to claim 1 or 2, wherein the length t of the line segment connecting the point intersecting with the nearest outer peripheral edge of the film is more than 0 mm and less than 10 mm. The light-shielding layer on the peripheral edge of the second main surface of the transparent substrate is provided in a region of more than 0 mm and less than 30 mm from the outer peripheral end of the second main surface of the transparent substrate. Item 3. The glass laminate with a protective film according to any one of Items 1 to 3. The glass laminate with a protective film according to any one of claims 1 to 4, wherein the adhesive layer is made of an adhesive containing an acrylic resin or a polyurethane resin as a main component. The glass laminate with a protective film according to claim 1, wherein the antifouling layer is made of an antifouling agent containing fluorine. The glass laminate with a protective film according to any one of claims 1 to 6, wherein the transparent substrate is chemically tempered glass.

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