Glass substrate with colored layer, cover glass, display device, and method for producing glass substrate with colored layer

Abstract

This colored layer-equipped glass substrate is provided with a glass substrate having a main surface, and a colored layer disposed in contact with the main surface, wherein the colored layer contains a colorant, a cured resin, and a non-curable resin. Furthermore, this method for producing a glass substrate with a colored layer is a method for producing a glass substrate with a colored layer provided with a glass substrate having a main surface and a colored layer disposed in contact with the main surface, the method comprising: preparing a glass substrate having a main surface, preparing a transfer member having a transfer base material and a colored layer precursor film; the transfer member is laminated on the glass substrate such that the main surface of the glass substrate is in contact with the colored layer precursor film, and the colored layer precursor film disposed in contact with the main surface of the glass substrate is cured to form the colored layer. The colored layer precursor film contains a colorant, a curable resin, and a non-curable resin.

Description

Technical Field

[0001] The present invention relates to a glass substrate with a coloring layer, a cover glass, a display device, and a method for manufacturing a glass substrate with a coloring layer. Background Art

[0002] Conventionally, as a cover glass for a display device of a display, a glass substrate with a coloring layer (light-shielding portion) in which a coloring layer for shielding wirings and the like around the display is provided on one main surface of the glass substrate is known. In addition, in recent years, in displays such as in-vehicle display devices, in order to improve visibility and designability, an appearance design with a curved surface is sometimes adopted, and accordingly, the need for a cover glass with a curved surface has been increasing.

[0003] Patent Document 1 describes an invention related to a curved surface screen printing apparatus and a curved surface screen printing method for printing a predetermined pattern on a plate-shaped substrate with a curved surface.

[0004] Patent Document 2 describes a transparent plate with a decorative layer, which includes a transparent plate made of a material that transmits visible light and has two main surfaces, and a decorative layer provided on one main surface.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2020 / 162469

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2019-010871 Summary of the Invention

[0009] The inventors of the present invention have developed a new method for forming a coloring layer by a transfer decoration method as a method for providing a coloring layer as a light-shielding portion on a cover glass corresponding to a more complex shape of a display. It has been found that there are problems with the durability of the formed coloring layer when the coloring layer is formed by the transfer decoration method.

[0010] Therefore, an object of the present invention is to provide a glass substrate with a coloring layer, a cover glass, and a display device having a coloring layer with excellent durability. Another object of the present invention is to provide a method for manufacturing a glass substrate with a coloring layer having a coloring layer with excellent durability formed by a transfer decoration method.

[0011] The inventors of the present invention have conducted in-depth research and as a result, have found that the above problems can be solved by the following configuration.

[0012] 〔1〕A glass substrate with a coloring layer, comprising: a glass substrate having a main surface, and a coloring layer disposed in contact with the main surface, the coloring layer including a colorant, a cured resin, and a non-curable resin.

[0013] 〔2〕The glass substrate with a coloring layer according to 〔1〕, wherein the cured resin is a cured product of a curable resin and a curing agent.

[0014] 〔3〕The glass substrate with a coloring layer according to 〔2〕, wherein the curing agent is a heat curing agent or a photo curing agent.

[0015] 〔4〕The glass substrate with a coloring layer according to 〔2〕, wherein the curing agent is a heat curing agent.

[0016] 〔5〕The glass substrate with a coloring layer according to any one of 〔2〕 to 〔4〕, wherein the curing agent contains blocked isocyanate.

[0017] 〔6〕The glass substrate with a coloring layer according to any one of 〔2〕 to 〔5〕, wherein the coloring layer further contains at least one selected from methyl ethyl ketoxime, diethyl malonate, ε - caprolactam, 3,5 - dimethylpyrazole, and acetone oxime.

[0018] 〔7〕The glass substrate with a coloring layer according to 〔4〕, wherein the curing temperature of the heat curing agent is 80 to 200 °C.

[0019] 〔8〕The glass substrate with a coloring layer according to any one of 〔1〕 to 〔7〕, wherein the non - curable resin contains a tackifier.

[0020] 〔9〕The glass substrate with a coloring layer according to any one of 〔2〕 to 〔4〕 and 〔7〕, wherein the non - curable resin contains a tackifier, and the content of the tackifier is greater than 0% by mass and 150% by mass or less relative to the content of the curable resin.

[0021] 〔10〕The glass substrate with a coloring layer according to any one of 〔2〕 to 〔4〕, 〔7〕, and 〔9〕, wherein the curable resin further contains at least one selected from acrylic resin, polyester resin, and epoxy resin.

[0022] 〔11〕The glass substrate with a coloring layer according to any one of 〔2〕 to 〔4〕, 〔7〕, and 〔9〕, wherein the curable resin contains acrylic resin.

[0023] 〔12〕A glass substrate with a coloring layer, comprising: a glass substrate having a main surface, and a coloring layer disposed in contact with the main surface, and the extraction amount of the non - cured component of the coloring layer measured by the extraction test described below is 5% by mass to 40% by mass.

[0024]

[13] The glass substrate with a colored layer according to

[12] , wherein the extraction amount of the uncured component of the colored layer is 10% by mass to 25% by mass.

[0025]

[14] The glass substrate with a colored layer according to

[12] , wherein the extraction amount of the uncured component of the colored layer is 10% by mass to 19% by mass.

[0026]

[15] The glass substrate with a colored layer according to any one of [1] to

[14] , wherein the thickness of the colored layer is 5 to 20 μm.

[0027]

[16] The glass substrate with a colored layer according to any one of [1] to

[15] , which satisfies Requirement 1 and Requirement 2 described below.

[0028]

[17] The glass substrate with a colored layer according to any one of [1] to

[16] , wherein when observing the glass substrate with a colored layer from the glass substrate side, no bubbles are observed between the glass substrate and the colored layer.

[0029]

[18] The glass substrate with a colored layer according to any one of [1] to

[17] , wherein the glass substrate with a colored layer has an opening portion on the main surface of the glass substrate where the colored layer is not disposed, and the slope of the end portion of the colored layer adjacent to the opening portion is 0.1 or more.

[0030]

[19] The glass substrate with a colored layer according to any one of [1] to

[18] , wherein at least a part of the region of the main surface where the colored layer is disposed is a curved surface.

[0031]

[20] A cover glass, which is a cover glass for a display having the glass substrate with a colored layer according to any one of [1] to

[19] , the colored layer has an opening portion, and at least one layer selected from an antiglare layer, an antireflection layer, and an antifouling layer is laminated on the main surface layer of the glass substrate on the side opposite to the main surface on which the colored layer is laminated.

[0032]

[21] A display device, which includes the cover glass according to

[20] and a display, and the main surface of the cover glass on the colored layer side faces the display.

[0033] 〔22〕A method for manufacturing a glass substrate with a colored layer, which is a method for manufacturing a glass substrate with a colored layer having a glass substrate with a main surface and a colored layer disposed in contact with the main surface, includes preparing a glass substrate with a main surface, preparing a transfer member having a transfer substrate and a colored layer precursor film, laminating the transfer member on the glass substrate such that the main surface of the glass substrate is in contact with the colored layer precursor film, and curing the colored layer precursor film disposed in contact with the main surface of the glass substrate to form the colored layer. The colored layer precursor film contains a colorant, a curable resin, and a non-curable resin.

[0034] 〔23〕The method for manufacturing a glass substrate with a colored layer according to 〔22〕, wherein the colored layer precursor film further contains a curing agent.

[0035] 〔24〕The method for manufacturing a glass substrate with a colored layer according to 〔23〕, wherein the curing agent is a heat-curing agent. After laminating the transfer member on the glass substrate, the colored layer precursor film is heated to a temperature equal to or higher than the curing temperature of the heat-curing agent to cure the colored layer precursor film. The curing temperature of the heat-curing agent is 80 to 200 °C.

[0036] 〔25〕The method for manufacturing a glass substrate with a colored layer according to 〔23〕 or 〔24〕, wherein the content of the curing agent is 0.5 to 30% by mass based on the colored layer precursor film.

[0037] 〔26〕The method for manufacturing a glass substrate with a colored layer according to any one of 〔22〕 to 〔25〕, wherein the prepared glass substrate and the transfer member are disposed in a chamber such that the main surface of the glass substrate faces the colored layer precursor film. The chamber is divided by the transfer member into a first space containing the glass substrate and a second space not containing the glass substrate. The transfer substrate is heated to soften it, and the pressure in the first space is made lower than the pressure in the second space, thereby bringing the colored layer precursor film into contact with the main surface of the glass substrate.

[0038] 〔27〕The method for manufacturing a glass substrate with a colored layer according to any one of 〔22〕 to 〔26〕, wherein a part of the colored layer disposed on the main surface of the glass substrate is irradiated with laser to remove the colored layer irradiated with the laser.

[0039] According to the present invention, it is possible to provide a glass substrate with a colored layer, a cover glass, and a display device having a colored layer with excellent durability. In addition, according to the present invention, a method for manufacturing a glass substrate with a colored layer having a colored layer with excellent durability can be provided by a transfer decoration method. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It is a cross-sectional view showing an example of the configuration of a laminate including a glass substrate with a colored layer.

[0041] Figure 2A It is a cross-sectional view showing an example of the structure of the glass substrate included in the glass substrate with a colored layer.

[0042] Figure 2B It is a cross-sectional view showing an example of the structure of the glass substrate included in the glass substrate with a colored layer.

[0043] Figure 2C It is a cross-sectional view showing an example of the structure of the glass substrate included in the glass substrate with a colored layer.

[0044] Figure 3 It is a top view showing an example of the configuration of the glass substrate with a colored layer.

[0045] Figure 4 It is a diagram showing an example of the structure near the end of the colored layer.

[0046] Figure 5 It is a schematic diagram showing an example of the configuration of a laser irradiation device that irradiates a part of the colored layer with laser light.

[0047] Figure 6 It is a cross-sectional view showing an example of the configuration of a display device. Detailed implementation

[0048] Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. Various modifications and substitutions can be added to the following embodiments without departing from the scope of the present invention.

[0049] The meanings of the terms in this specification are as follows.

[0050] A numerical range expressed using "~" means a range including the values described before and after "~" as the lower limit value and the upper limit value. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. In addition, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the value shown in the examples.

[0051] In this specification, each component can be used alone with one substance belonging to each component, or two or more can be used in combination. Here, when two or more substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.

[0052] In this specification, a combination of two or more preferred modes is a more preferred mode.

[0053] A unit refers to the general term for an atomic group based on one molecule of the above monomer formed directly by the polymerization of monomers and an atomic group obtained by chemically converting a part of the above atomic group. The content (mol%) of each unit relative to all the units contained in the polymer is determined by analyzing the polymer using nuclear magnetic resonance method, and can also be determined based on the feeding amount of the components used in the manufacture of the polymer.

[0054] (Meth)acrylic acid refers to the general term for acrylic acid and methacrylic acid.

[0055] The glass transition temperature (Tg) is the midpoint glass transition temperature of the polymer measured by differential scanning calorimetry (DSC) method.

[0056] The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured using size exclusion chromatography (gel permeation chromatography) with polystyrene as the reference substance. In addition, the ratio of Mw to Mn represents the molecular weight distribution, also known as Mw / Mn.

[0057] Transparent means that the average transmittance of visible light (wavelength 400 - 700 nm) is 80% or more.

[0058] A flat area refers to a part where the average radius of curvature exceeds 10000 mm.

[0059] A curved surface area refers to a part where the average radius of curvature is 10000 mm or less.

[0060] [Glass substrate with a coloring layer]

[0061] Hereinafter, the glass substrate with a coloring layer of the present invention will be described with reference to the accompanying drawings.

[0062] Figure 1 It is a cross-sectional view showing an example of the structure of the glass substrate with a coloring layer of the present invention. Figure 1 A laminate 10 having a glass substrate 2, a coloring layer 3, an AG layer 4, an AR layer 5, and an AFP layer 6 in this order is shown. The glass substrate with a coloring layer 1 is composed of the glass substrate 2 and the coloring layer 3 disposed in contact with the first main surface 21 of the glass substrate 2. The glass substrate 2 has a first main surface 21 and another main surface opposite to the first main surface 21, that is, a second main surface 22. The AG layer 4, the AR layer 5, and the AFP layer 6 are disposed on the second main surface 22 side of the glass substrate 2.

[0063] In Figure 1In this case, the coloring layer 3 is disposed in contact with a part of the first main surface 21 of the glass substrate 2, and an opening 7 is formed in a portion of the first main surface 21 where the coloring layer 3 is not disposed. When the laminate 10 is mounted on the display device, the first main surface 21 having the coloring layer 3 disposed thereon faces the display device, and the second main surface 22 faces the observer.

[0064] The laminate having a glass substrate with a coloring layer is not limited to Figure 1 the manner shown. For example, the laminate may not have any of the AG layer, AR layer, and AFP layer. In addition, the laminate having a glass substrate with a coloring layer may also have a functional layer other than the AG layer, AR layer, and AFP layer.

[0065] 〔First Embodiment〕

[0066] The glass substrate with a coloring layer according to the first embodiment of the present invention is a glass substrate with a coloring layer having a glass substrate with a main surface and a coloring layer disposed in contact with the main surface of the glass substrate, and the coloring layer contains a cured resin and a non-curable resin.

[0067] Hereinafter, each component included in the glass substrate with a coloring layer of the present embodiment will be described in detail.

[0068] <Glass Substrate>

[0069] The glass substrate is a transparent glass member and has at least one main surface.

[0070] The glass substrate is formed of ordinary glass. Examples of the glass forming the glass substrate include non-alkali glass, soda-lime glass, soda-lime silicate glass, aluminosilicate glass, borosilicate glass, lithium aluminosilicate glass, and borosilicate glass. Among them, aluminosilicate glass or lithium aluminosilicate glass is preferred in terms of easily introducing a large stress through strengthening treatment to obtain high-strength glass even when the thickness is thin.

[0071] In particular, when performing the chemical strengthening treatment described later on the glass substrate, it is preferable to use a chemical strengthening glass based on aluminosilicate glass (for example, "Dragontrail (registered trademark)") series.

[0072] The shape of the glass substrate can be a flat shape as Figure 1 shown, or can be a shape having one or more bent portions or curved portions as Figures 2A to 2C shown later.

[0073] All regions of the main surface of the glass substrate can be flat, or at least a part thereof can be curved. When at least a part of the main surface is curved, all regions of the main surface can be composed of curved surfaces, or the main surface can be composed of a curved surface portion and a flat surface portion.

[0074] The glass substrate can be any shape among flat shapes including polygons such as rectangles, circles, and ellipses, shapes in which part or all of these shapes are bent, and three-dimensional shapes.

[0075] All of the regions with the colored layer in the main surface can be flat, or at least a part of the above regions can be a curved surface. The regions with the colored layer can be entirely composed of a curved surface, or can be composed of a curved surface and a flat surface. The colored layer disposed on the curved surface deforms following the shape of the curved surface.

[0076] When using a glass substrate with at least a part of the main surface being a curved surface as a cover glass for automotive interior components, display devices, etc., by moderately bending the parts disposed on these display surfaces, the viewing angle from the user becomes smaller and the visibility is improved.

[0077] It should be noted that the "curved surface" of the main surface refers to a region where the first curvature radius R1 described below is 10000 mm or less.

[0078] The first curvature radius R1 of the curved surface is determined as follows. Among the tangent directions at an arbitrary point P on the curved surface, the tangent direction selected in a manner that satisfies the following conditions is set as the X direction, the tangent direction orthogonal to the X direction is set as the Y direction, and the normal direction of the main surface is set as the Z direction. The X direction is the tangent direction orthogonal to the Z direction in the plane of the main surface where the curvature radius is the smallest among the planes passing through the above point P and including the Z direction. When there are multiple directions with the smallest first curvature radius R1, at least one of them is set as the X direction to determine the first curvature radius R1.

[0079] The first curvature radius R1 of the curved surface can be appropriately set according to the use and type of the glass substrate, etc. The first curvature radius R1 is preferably 1 mm or more, preferably 50 mm or more, more preferably 100 mm or more, and further preferably 200 mm or more. The first curvature radius R1 of the curved surface is 10000 mm or less, preferably 5000 mm or less, more preferably 3000 mm or less.

[0080] The curved surface forming at least a part of the main surface of the glass substrate can be bent or curved only in the X direction, or can be a compound curved shape bent or curved in the X direction and a tangent direction other than the X direction (for example, the Y direction). When bent or curved in a tangent direction other than the X direction of the main surface, its curvature radius is preferably 1 to 10000 mm, more preferably 50 to 5000 mm, further preferably 100 to 3000 mm, and particularly preferably 200 to 3000 mm.

[0081] The curvature radius of the curved surface of the above glass substrate can be the same or different in any direction and position within the plane.

[0082] The shape of the glass substrate can be referred to WO 2022 / 070611 A1.

[0083] In particular, it is preferable that at least a part of the region of the glass substrate where the colored layer is disposed has a complex curved shape, or a shape that is bent or curved only in the X direction and the bending angle in the X direction is 45 degrees or more.

[0084] If the shape of the glass substrate is the above shape, it is difficult to form (print) the colored layer by the existing methods for forming the colored layer of the cover panel of the display device, i.e., screen printing or inkjet printing. In contrast, according to the manufacturing method of the glass substrate with a colored layer based on the transfer decoration method of the present embodiment, a colored layer with excellent durability can also be formed on the glass substrate of the above shape, and a cover panel with high quality can be provided.

[0085] The above bending angle is defined as follows based on the shape of the cross-section of the glass substrate including the bending direction such as the X direction. Figures 2A to 2C FIGS. are cross-sectional views showing an example of the structure of the glass substrate of the glass substrate with a colored layer, and showing the cross-sectional shape of the glass substrate along the X direction. When there are a plurality of bending angles in the X direction according to the following definition, it is preferable that at least one bending angle is 45 degrees or more.

[0086] (i) Figure 2A The cross-sectional shape of the shown glass substrate 2A is a shape (V-shaped) composed of a bent portion 41 without an inflection point and two flat portions 42 disposed to sandwich the bent portion 41. When it is such a shape, the angle formed by one flat portion 42 and the other flat portion 42 is defined as the bending angle θ.

[0087] (ii) Figure 2B The cross-sectional shape of the shown glass substrate 2B is a shape composed of a bent portion 51 without a flat portion, and is a shape without an inflection point (U-shaped). When it is such a shape, the angle formed by two tangents T drawn at the midpoints 52 of the ends and the points of curvature change closest to the ends at both ends of the glass substrate 2B is defined as the bending angle θ.

[0088] (iii) When the cross-sectional shape of the glass substrate is a shape composed of one flat portion and a bent portion that is bent in the in-plane direction (X direction) without an inflection point, the angle formed by the flat portion and the tangent T drawn at the midpoint of the end on the bent portion side and the point of curvature change closest to the end is defined as the bending angle θ.

[0089] (iv) Figure 2CThe cross-sectional shape of the glass substrate 2C shown is a shape (S-shaped) formed by a bent portion 61 that has no flat portion and has an inflection point Q in the in-plane direction (X direction). When it is such a shape, at one end of the glass substrate 2C, a tangent line T1 is drawn at the midpoint 62 between the end and the closest curvature change point to the end, and a tangent line T2 is drawn at the inflection point Q. The angle formed by the tangent line T1 and the tangent line T2 at this time is taken as the bending angle θ.

[0090] (v) When the cross-sectional shape of the glass substrate is a shape formed by a flat portion and a bent portion having an inflection point Q, the angle formed by the tangent line T at the inflection point Q and the flat portion is taken as the bending angle θ.

[0091] It should be noted that the "flat portion" refers to a region where the radius of curvature R1 exceeds 10000 mm in the above cross-section, and the "bent portion" refers to a region where the radius of curvature R1 is 10000 mm or less in the above cross-section.

[0092] In addition, the "curvature change point" refers to a point where the change in the radius of curvature R at each position in an interval with a length of 50 mm or less exceeds 5%.

[0093] When the glass substrate is a plate-like member having two opposite main surfaces, the thickness of the glass substrate is preferably 0.2 to 5.0 mm, more preferably 0.8 to 3.0 mm, and further preferably 1.0 to 2.5 mm. By making the thickness within this range, it is possible to achieve both lightweight and strength of the glass substrate, and the designability of the appearance can be improved when the glass substrate with a coloring layer is used as a cover panel of an in-vehicle display device.

[0094] In addition, the size of the glass substrate can be appropriately selected according to the use. When the glass substrate with a coloring layer is used as a cover glass of an in-vehicle display device, the length of the short side of the glass substrate is, for example, 50 to 500 mm, preferably 100 to 300 mm, and the length of the long side of the glass substrate is, for example, 50 to 1500 mm, preferably 100 to 1200 mm.

[0095] The shape, size, etc. when observing the glass substrate from the normal direction of the main surface (top view) can be appropriately determined according to the display of the display device on which the glass substrate with a coloring layer is mounted, for example.

[0096] The glass substrate is preferably strengthened by chemical strengthening treatment. When performing the chemical strengthening treatment, chemically strengthened glass is used as the glass material.

[0097] As a method of chemical strengthening treatment, typically, the following methods can be cited: impregnating a glass substrate formed into a specified shape in a molten salt containing an alkali metal such as KNO3, performing ion exchange treatment, and then cooling to near room temperature. The treatment conditions such as the temperature of the molten salt and the impregnation time may be set in such a way that the surface compressive stress (CS) of the compressive stress layer and the depth of the compressive stress layer (DOL) reach the desired values.

[0098] The surface compressive stress (CS) of the compressive stress layer is preferably 500 MPa or more, more preferably 600 MPa or more, and still more preferably 700 MPa or more. On the other hand, CS is preferably 1300 MPa or less.

[0099] The depth of the compressive stress layer (DOL) is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and particularly preferably 25 μm or more. In addition, DOL is preferably 50 μm or less, more preferably 40 μm or less.

[0100] <Coloring layer>

[0101] The coloring layer is a layer disposed in contact with the main surface of the glass substrate and contains at least a colorant, a cured resin, and a non-curable resin.

[0102] It should be noted that "in contact" in the "layer disposed in contact with the main surface of the glass substrate" means that there is no adhesive layer between the main surface of the glass substrate and the coloring layer.

[0103] Figure 3 is a top view showing an example of the configuration of a glass substrate with a coloring layer. Figure 3 In, the glass substrate 1 with a coloring layer is observed from the normal direction of the first main surface 21 of the glass substrate 2 (the side where the coloring layer 3 is disposed).

[0104] The coloring layer 3 is disposed close to the peripheral portion of the first main surface 21. Here, the peripheral portion of the first main surface 21 refers to a belt-shaped region from the outer peripheral end of the first main surface 21 toward the central portion of the first main surface 21. The coloring layer 3 is disposed around the entire circumference of the peripheral portion of the first main surface 21, and the opening 7 is the region of the central portion of the first main surface 21 surrounded by the coloring layer 3.

[0105] In Figure 3 the boundary line 8 is the boundary between the coloring layer 3 and the opening 7 observed from the normal direction of the first main surface 21 of the glass substrate 2.

[0106] In addition, Figure 3The shown end portion 3A is the region in the coloring layer 3 adjacent to the opening portion 7. Specifically, the end portion 3A refers to the continuous region in the coloring layer 3 from the demarcation line 8 to the position where the thickness of the coloring layer 3 (the distance from the first main surface 21 to the surface on the side opposite to the glass substrate 2) reaches 95% of the average thickness of the coloring layer 3.

[0107] By configuring the coloring layer and the opening portion in this way, in a display device having a glass substrate with a coloring layer as a cover glass, the display of the display is visually recognized by the observer through the opening portion, while on the other hand, components such as wiring components around the display are shielded by the coloring layer and not visually recognized by the observer.

[0108] The shape of the coloring layer may also be other than the Figure 3 shown shape. For example, the coloring layer may be disposed on a part of the peripheral portion of the main surface of the glass substrate. In addition, the coloring layer may not be in contact with the outer peripheral end portion of the main surface of the glass substrate.

[0109] When the coloring layer is strip-shaped, the width of the coloring layer in the in-plane direction may not be constant. In addition, the shape of the coloring layer is not limited to strip-shaped, and the shape and size of the coloring layer can be appropriately set according to the purpose. In addition, Figure 3 Although the shown opening portion 7 is surrounded by the coloring layer 3 in the in-plane direction for a full circle, as long as it is an area on the main surface of the glass substrate where the coloring layer is not disposed, it can be an opening portion. The opening portion may also be in contact with the outer peripheral end portion of the glass substrate in one or more intervals in the in-plane direction. For example, the opening portion may be an area sandwiched by strip-shaped coloring layers disposed along two opposite sides on the main surface of a rectangular glass substrate and is an area in contact with the outer peripheral end portion of the glass substrate on the other two opposite sides.

[0110] As described above, in a display device using a glass substrate with a coloring layer as a cover glass, the coloring layer can shield components such as wiring circuits disposed in the peripheral portion of the display from the observer's field of view, improving the visibility and aesthetics of the display. The coloring layer is sometimes used to improve the design of the display device and can also function as a decorative layer having characters, patterns, etc.

[0111] Hereinafter, each component included in the coloring layer will be described in detail.

[0112] (Colorant)

[0113] The colorant can be either a pigment or a dye. In addition, a colorant of an appropriate color can be used according to the purpose of the coloring layer. For example, when forming a coloring layer used as a light-shielding film, a black colorant can be used, or a plurality of colorants with different colors can be mixed and used to form patterns such as a wood grain style.

[0114] As the colorant, a pigment is preferred. For example, when the coloring layer is black, as the colorant, a black pigment is preferred. As the black pigment, for example, carbon black, titanium black, titanium carbon, iron oxide, titanium oxide, and graphite can be mentioned, with graphite or carbon black being preferred, and carbon black being more preferred.

[0115] The colorant can be used alone as one kind, or two or more kinds can be used in combination.

[0116] The content of the colorant is preferably 20 to 75% by mass, more preferably 30 to 70% by mass, relative to the total amount of the coloring layer.

[0117] (Cured resin)

[0118] The coloring layer contains a cured resin.

[0119] The cured resin refers to a cured product obtained by curing a curable resin.

[0120] The cured resin can be a cured product of a curable resin and a curing agent, or a cured product (condensate) obtained by reacting a curable resin with heat, light, acid, alkali, etc.

[0121] As the cured resin, a cured product of a curable resin and a curing agent is preferred.

[0122] -Curable resin-

[0123] As the curable resin, for example, acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin, phenolic resin, and urea resin can be mentioned. Among them, a resin selected from acrylic resin, polyester resin, and epoxy resin is preferred, and acrylic resin is more preferred in terms of being easily removed by laser trimming described later and having excellent transparency of the glass substrate after the removal of the coloring layer (hereinafter, also referred to as "excellent laser trimability").

[0124] Acrylic resin is a polymer having units derived from (meth)acrylate. The acrylic resin can have reactive groups such as carboxyl group, hydroxyl group, sulfonic group, and epoxy group.

[0125] The acrylic resin can be a compound having one or more (meth)acryloyl groups and having reactive groups such as carboxyl group, hydroxyl group, sulfonic group, and epoxy group.

[0126] The reactive group is preferably a group that can react with an isocyanate group (for example, carboxyl group, hydroxyl group, epoxy group).

[0127] Polyester resin is a polymer in which units derived from polycarboxylic acid and units derived from polyol are connected by ester bonds. The polyester resin can have units other than the above two kinds of units (for example, units derived from hydroxycarboxylic acid compounds).

[0128] As polycarboxylic acids, for example, aromatic polycarboxylic acids and aliphatic polycarboxylic acids can be cited. As polycarboxylic acids, aromatic polycarboxylic acids are preferably used, and more preferably both aromatic polycarboxylic acids and aliphatic polycarboxylic acids are used. The number of carbon atoms of the polycarboxylic acid is preferably 8 to 15. The number of carboxyl groups in the polycarboxylic acid is preferably 2 to 4, and more preferably 2.

[0129] As the polyol, a polyol having 2 to 10 carbon atoms is preferred. The number of hydroxyl groups in the polyol is preferably 2 to 4, and more preferably 2.

[0130] Epoxy resin is a compound having two or more epoxy groups in the molecule. As the epoxy resin, an aromatic compound having a glycidyloxy group such as bisphenol A-diglycidyl ether and its oligomer are preferably used.

[0131] The weight average molecular weight (Mw) of the above-mentioned curable resin is preferably 10,000 to 80,000, and more preferably 15,000 to 50,000.

[0132] - Curing agent -

[0133] As the curing agent, for example, a heat curing agent and a photo curing agent can be cited.

[0134] The curing agent can be appropriately selected according to the type of reactive group possessed by the curable resin. The curing agent can be used alone or in combination of two or more. The colored layer can contain both a heat curing agent and a photo curing agent.

[0135] The heat curing agent is a curing agent that does not have reactivity with the curable resin at a temperature lower than a specified curing temperature, but exhibits reactivity with the curable resin by changing its molecular structure by heating to a temperature above the specified curing temperature.

[0136] As the curing agent, a heat curing agent is preferred.

[0137] As the heat curing agent, for example, isocyanate compounds, aziridine compounds, epoxy compounds, metal chelate compounds, amine compounds, acid anhydrides, imidazole compounds, phenol compounds, phosphorus compounds, sulfonium salts, azo compounds, and organic peroxides can be cited. Among them, isocyanate compounds, imidazole compounds or phenol compounds are preferred, isocyanate compounds or imidazole compounds are more preferred, and isocyanate compounds are further preferred.

[0138] As the above-mentioned isocyanate compounds, for example, polyisocyanates such as toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and adducts, biurets, and urethane bodies of these polyisocyanates can be cited.

[0139] As a thermal curing agent, it is preferably a blocked compound formed by bonding a prescribed blocking agent to a functional group reactive with a reactive group possessed by a curable resin. The reaction of such a blocked compound with the curable resin is suppressed in an environment at a temperature lower than the curing temperature.

[0140] As the blocked compound, for example, blocked isocyanate can be cited.

[0141] Preferably, the curing agent contains blocked isocyanate.

[0142] As the blocking agent, a compound that bonds to the functional group of the thermal curing agent and dissociates from the functional group by heating to a temperature equal to or higher than a prescribed curing temperature can be used. For example, the following compounds can be cited.

[0143] · Lactam compounds such as ε-caprolactam and δ-valerolactam.

[0144] · Oxime compounds such as acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime.

[0145] · Pyrazole compounds such as pyrazole and 3,5-dimethylpyrazole.

[0146] · Amine compounds such as diphenylpropylamine, aniline ethyleneimine, and diisopropylamine.

[0147] · Active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone.

[0148] · Phenol compounds such as phenol, cresol, and ethylphenol.

[0149] · Alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol.

[0150] · Thiol compounds such as butyl mercaptan and dodecyl mercaptan.

[0151] · Amide compounds such as acetanilide and acetamide.

[0152] In terms of more excellent curing speed, the curing temperature of the thermal curing agent is preferably 80 to 200 °C, more preferably 100 to 180 °C, and further preferably 110 to 160 °C.

[0153] The curing temperature of the thermal curing agent is measured by differential scanning calorimetry (DSC) according to a known method. When the thermal curing agent is commercially available, the curing temperature can be the catalog value.

[0154] A photo-curing agent is a curing agent that exhibits reactivity with a curable resin by changing its molecular structure upon irradiation with light such as ultraviolet light.

[0155] As a photoinitiator, for example, a photo radical generator and a photo cation generator (photoacid generator) that generates a Bronsted acid or a Lewis acid by light irradiation can be cited. As the photo radical generator, for example, an acetophenone compound, a benzophenone compound, and an acylphosphine compound can be cited. As the photo cation generator, for example, a sulfonium salt compound and an iodine salt compound.

[0156] The content of the curing agent is appropriately adjusted according to the content of the curable resin and the number of reactive groups, and is preferably 0.5 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.5 to 10% by mass with respect to the colored layer precursor film described later.

[0157] If the content of the curing agent is above the above lower limit value, the colored layer is sufficiently cured and the adhesion of the colored layer is more excellent. In addition, if the content of the curing agent is below the above upper limit value, the reliability (moisture and heat resistance, boiling resistance, low temperature resistance, high temperature resistance, durability) of the colored layer is more excellent.

[0158] (Non-curable resin)

[0159] The colored layer contains a non-curable resin. It should be noted that the non-curable resin is a resin component different from the colorant and the curable resin contained in the colored layer.

[0160] The weight average molecular weight (Mw) of the non-curable resin is, for example, less than 20,000, preferably 400 to 15,000, and more preferably 500 to 10,000.

[0161] The glass transition temperature (Tg) of the non-curable resin is preferably 30 to 200 °C, more preferably 50 to 150 °C, and further preferably 60 to 130 °C in terms of being sufficiently leveled at the interface with the glass substrate and having excellent adhesion to the glass substrate.

[0162] From the viewpoint of adhesion to the glass substrate, the non-curable resin preferably has a functional group selected from a hydroxyl group and a carboxyl group.

[0163] As the non-curable resin, for example, a tackifier (tackifier, adhesion-imparting agent) can be cited, and preferably the non-curable resin contains a tackifier. In terms of more excellent adhesion to the glass substrate, the colored layer preferably contains a tackifier.

[0164] As the tackifier, for example, a rosin-based resin, a terpene-based resin, and a petrochemical-based resin can be cited.

[0165] As the rosin-based resin, for example, a rosin resin, a rosin ester resin, a polymerized rosin ester resin, an acid-modified polymerized rosin ester resin, a rosin-modified phenolic resin, and their hydrides can be cited.

[0166] As terpene resins, for example, terpene resin, terpene phenolic resin, aromatic modified terpene resin, and their hydrides can be cited.

[0167] As petrochemical resins, for example, acrylic resins obtained by polymerizing acrylic monomers as the main component, styrene resins obtained by polymerizing styrene monomers such as styrene and α-methylstyrene as the main component, styrene-acrylic resins obtained by copolymerizing acrylic monomers and styrene monomers, and their hydrides can be cited.

[0168] It should be noted that the presence of a tackifier in the colored layer can be confirmed by the following method. When polar groups contained in the above-mentioned tackifier are detected in the non-cured components extracted from the colored layer by the method described in the following (extraction test) using a thermal cracking GC-Mass (gas chromatography-mass spectrometer), NMR (nuclear magnetic resonance) analyzer, etc., it can be regarded that the colored layer contains a tackifier. As polar groups, for example, acrylic resin, hydroxyl group, carbonyl group, and ester group can be cited.

[0169] As the tackifier contained in the colored layer, in terms of making the slope of the end portion of the colored layer closer to the normal direction of the main surface through laser trimming described later and being able to manufacture a glass substrate with a colored layer having more excellent visibility when used in a display device, and in terms of excellent laser trimming properties, acrylic resin, styrene-acrylic resin, or terpene phenolic resin is more preferably used.

[0170] Among them, in terms of more excellent adhesion between the glass substrate and the colored layer, acrylic resin is preferred.

[0171] The weight average molecular weight (Mw) of the tackifier is, for example, less than 20,000, preferably 400 to 15,000, and more preferably 500 to 10,000.

[0172] In terms of the interface with the glass substrate being sufficiently leveled and having excellent adhesion with the glass substrate, the glass transition temperature (Tg) of the tackifier is preferably 30 to 200 °C, more preferably 50 to 150 °C, and further preferably 60 to 130 °C.

[0173] The non-curable resin can be used alone as one kind, or two or more different kinds can be used in combination.

[0174] The content of the non-curable resin (more preferably the tackifier) relative to the curable resin is preferably greater than 0% by mass and 150% by mass or less, more preferably 5 to 130% by mass, further preferably 10 to 100% by mass, and further preferably 10 to 60% by mass.

[0175] If the content of the tackifier is above the above lower limit value, flexibility can be imparted to the colored layer, and it can be sufficiently leveled at the glass interface during transfer, so the adhesion is more excellent. In addition, if the content of the tackifier is 150% by mass or less relative to the content of the curable resin, the durability of the colored layer is excellent. If it is 130% by mass or less, the durability is more easily improved. If it is 100% by mass or less, the density of the colorant in the colored layer is high, and heat generation points are likely to increase, so the laser trimming property is also improved. If it is 60% by mass or less, the laser trimming property is further improved.

[0176] In addition, the content of the non-curable resin (more preferably the tackifier) relative to the colored layer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.

[0177] The colored layer may also contain other components other than the above components within the range that does not impair the effects of the present invention. As the above other components, additives such as component B described later, plasticizers, non-volatile components, mold release agents, adhesion aids, antioxidants, and dispersants can be cited.

[0178] The colored layer may contain at least one component B selected from methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 3,5-dimethylpyrazole, and acetone oxime, and preferably contains component B.

[0179] The content of the above component B relative to the colored layer is preferably 0.5 to 30% by mass, more preferably 2 to 25% by mass.

[0180] (Thickness of the colored layer)

[0181] The thickness of the colored layer is preferably 5 to 20 μm, more preferably 5 to 15 μm, further preferably 5 to 13 μm, and even more preferably 8 to 10 μm. When the thickness of the colored layer is within the above range, the light-shielding property and visibility can be improved in a well-balanced manner, and poor contact of various components can be more appropriately suppressed, and the adhesion can be improved.

[0182] The thickness of the colored layer and the cross-sectional profile of the colored layer along the normal direction described later can be measured using a non-contact measuring device of the stage scanning type laser detector method (for example, "NH-3MAs" manufactured by Mitaka Kohki Co., Ltd.). A more detailed measuring method is described in the examples described later.

[0183] (End cross-sectional shape)

[0184] For the case where the glass substrate with the colored layer has an opening portion, which is an area where the colored layer is not disposed, on the main surface of the glass substrate (refer to Figure 3 ), the structure of the end portion of the colored layer adjacent to the opening portion (hereinafter, simply referred to as "end portion") will be described.

[0185] Figure 4 It is a diagram showing an example of the structure near the end of the colored layer. Figure 4 It shows a cross-section of a glass substrate with a colored layer and includes the shape of the main surface of the glass substrate and the surface of the colored layer in a cross-section extending in a direction perpendicular to the normal direction of the main surface of the glass substrate and perpendicular to the dividing line between the opening and the colored layer (when the dividing line is a curve, the tangent line is the extending direction) (hereinafter, also referred to as "cross-sectional profile"). From this cross-sectional profile, for the colored layer including the end near the above-mentioned dividing line, the relationship between the in-plane direction distance of the main surface and the thickness of the colored layer can be understood. As Figure 4 shown, the end 3A of the colored layer 3 is the region from the position corresponding to the dividing line 8 (refer to Figure 3 ) to the position where the thickness of the colored layer 3 reaches 95% of the average thickness T of the colored layer 3.

[0186] When the glass substrate with a colored layer has an opening, the slope of the end of the colored layer is preferably 0.1 or more, more preferably 0.5 or more, and further preferably 1.0 or more.

[0187] That is, the glass substrate with a colored layer preferably has an opening on the main surface of the glass substrate where the colored layer is not disposed, and the slope of the end of the colored layer adjacent to the opening is 0.1 or more.

[0188] If the slope of the end is within the above range, in the colored layer, the region with a thinner film thickness and lower light-shielding property becomes narrower, further suppressing light leakage at the end and making the boundary clearer. Therefore, the visibility is more excellent when the glass with a colored layer is used in a display device.

[0189] As Figure 4 shown, the slope of the end of the colored layer is obtained by setting two points P1 and P2 with different thicknesses on the surface of the end 3A and calculating the ratio (Lt / Lh) of the thickness direction distance Lt between the two points P1 and P2 to the in-plane direction distance Lh. Here, point P1 is the point where the thickness of the colored layer 3 (the distance from the main surface of the glass substrate 2 to the surface of the colored layer 3 on the side opposite to the glass substrate 2) reaches 10% of the average thickness T of the colored layer 3, and point P2 is the point where the thickness of the colored layer 3 reaches 50% of the average thickness T of the colored layer 3.

[0190] The colored layer with the slope of the end within the above range can be formed, for example, by performing laser trimming described later and adjusting the conditions of laser trimming when manufacturing the glass substrate with a colored layer.

[0191] It is also possible to provide at least one layer selected from an AG layer, an AR layer, and an AFP layer on the glass substrate with a colored layer of the present embodiment.

[0192] Refer to again Figure 1The AG layer 4, AR layer 5, and AFP layer 6 will be described.

[0193] <AG Layer>

[0194] The AG (Anti-Glare) layer 4 is an anti-glare layer that imparts anti-glare properties to the laminate 10.

[0195] The AG layer 4 is a layer with an uneven shape formed on the second main surface 22 side of the glass substrate 2. The uneven shape can be directly formed on the second main surface 22 of the glass substrate 2 or can be formed by a layer made of a material different from that of the glass substrate 2. The surface roughness (root mean square roughness, RMS) of this uneven shape is preferably 15 to 1000 nm, more preferably 10 to 500 nm.

[0196] The AG layer can be a layer composed of an uneven shape imparted by performing an anti-glare treatment and an etching treatment on the second main surface of the glass substrate. In addition, the AG layer can also be formed by forming a coating film in which particles having an arbitrary refractive index are dispersed on the second main surface of the glass substrate, or by laminating a transparent resin film having an uneven shape.

[0197] <AR Layer>

[0198] The AR (Anti-Reflection) layer 5 is an anti-reflection layer provided on one side of the second main surface 22 of the glass substrate 2. The AR layer 5 brings an effect of reducing the reflectance to the laminate 10, and in addition to reducing the sense of dizziness caused by the incidence of light, it also improves the visibility of a display device using the laminate 10 provided with the AR layer 5.

[0199] The configuration of the AR layer is not particularly limited as long as it can suppress light reflection. For example, it can also be a configuration in which a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550 nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550 nm are alternately laminated.

[0200] In Figure 1 In the example shown, although the AR layer 5 is disposed in contact with the AG layer 4, the AR layer can also be directly disposed on the second main surface 22 of the glass substrate 2.

[0201] <AFP Layer>

[0202] The AFP (Anti-Finger-Print) layer 6 is an anti-fouling layer having a function of suppressing the adhesion of various dirt such as fingerprint marks, sweat, and dust and making the dirt less likely to become obvious.

[0203] The AFP layer 6 is provided on one side of the second main surface 22 of the glass substrate 2. Figure 1 The shown AFP layer 6 is provided on the outermost surface of the laminate 10. Thus, the characteristics of the anti-fouling layer that keeps the display surface clean are fully exhibited.

[0204] The AFP layer is composed of, for example, a fluorine-containing compound capable of imparting antifouling properties, water repellency, and oil repellency. As the fluorine-containing compound, a fluorine-containing organic compound (a compound having a fluorine-containing organic group) is preferred. As the fluorine-containing organic compound, for example, a fluorine-containing organosilicon compound can be cited.

[0205] The above-described AG layer, AR layer, and AFP layer are each an example, and the composition of each layer can be appropriately changed within the range of having the functions of each layer. In addition, in the laminate, the AG layer, AR layer, and AFP layer are not necessarily formed, and a part of the AG layer, AR layer, and AFP layer may not be provided depending on the composition of the laminate.

[0206] <Properties of the Glass Substrate with a Coloring Layer>

[0207] (Non-cured Components of the Coloring Layer)

[0208] The extraction amount of the non-cured components of the coloring layer measured by the following extraction test is preferably 5% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and further preferably 10% to 25% by mass. When the extraction amount of the non-cured components of the coloring layer is within the above range, the adhesion and durability (hot water resistance) between the glass substrate and the coloring layer are more excellent.

[0209] The extraction test method for measuring the extraction amount of the above non-cured components will be described in detail in the second embodiment below.

[0210] (Hot Water Resistance)

[0211] The glass substrate with a coloring layer preferably satisfies the following requirement 1.

[0212] Requirement 1: When the glass substrate with a coloring layer is immersed in boiling water under atmospheric pressure and taken out after 1 hour from the immersion, no peeling of the coloring layer from the glass substrate is observed.

[0213] The detailed method of the hot water durability test for confirming whether requirement 1 is satisfied is described in the examples below.

[0214] (Cross-Cutting Test)

[0215] The glass substrate with a coloring layer preferably satisfies the following requirement 2, and more preferably satisfies the following requirement 3.

[0216] Requirement 2: Immerse the glass substrate with a colored layer in boiling water under atmospheric pressure. After 1 hour from the immersion, when performing the cross-cut test according to JIS K5600-5-6, no peeling of the colored layer from the glass substrate is observed, or the ratio of the area of the region peeled from the glass substrate to the total area of the colored layer is 15% or less.

[0217] That is, when performing the cross-cut test according to JIS K5600-5-6 on the glass substrate with a colored layer that has undergone the above-mentioned hot water durability test, no peeling of the colored layer from the glass substrate is observed, or the ratio of the area of the region peeled from the glass substrate to the total area of the colored layer is 15% or less.

[0218] Requirement 3: More preferably, no peeling of the colored layer from the glass substrate is observed in the glass substrate with a colored layer that has undergone the above-mentioned cross-cut test, or the ratio of the area of the region peeled from the glass substrate to the total area of the colored layer is 5% or less.

[0219] The glass substrate with a colored layer further preferably satisfies both of the above-mentioned Requirement 1 and Requirement 2, and particularly preferably satisfies both of the above-mentioned Requirement 1 and Requirement 3.

[0220] In terms of more excellent appearance and design, it is preferable that no bubbles are observed between the glass substrate and the colored layer when visually observing the glass substrate with a colored layer from the side opposite to the side where the colored layer is disposed with respect to the glass substrate.

[0221] That is, it is preferable that no bubbles are observed between the glass substrate and the above-mentioned colored layer when observing the glass substrate with a colored layer from the glass substrate side.

[0222] As a method for reducing bubbles between the glass substrate and the colored layer, for example, a method of performing an annealing treatment (post-heating treatment) after laminating the colored layer on the main surface of the glass substrate can be cited.

[0223] 〔Second Embodiment〕

[0224] The glass substrate with a colored layer of the second embodiment of the present invention is a glass substrate with a colored layer that includes a glass substrate having a main surface and a colored layer disposed in contact with the main surface of the glass substrate, and the extraction amount of the non-cured component of the colored layer measured by the following extraction test is 5% by mass to 40% by mass.

[0225] (Extraction Test)

[0226] (i) Measure the initial weight of the colored layer.

[0227] (ii) Immerse the colored layer in an ethanol solution with a concentration of 99.5% by volume for 2 weeks. The ethanol solution for immersing the colored layer is changed once a day.

[0228] (iii) After drying the solid components remaining undissolved in the ethanol solution, the weight of the dried solid components is measured, and the extraction amount of the non-cured components is calculated according to the following formula (1).

[0229] Extraction amount of non-cured components [mass%] = (Initial weight of the colored layer [g] - Weight of the solid components [g]) / Initial weight of the colored layer [g] × 100 (Formula 1)

[0230] A more specific description of the above extraction test method is given.

[0231] First, the colored layer is taken from the glass substrate with the colored layer. The taking method preferably uses a method that can suppress chemical modification of the colored layer, such as scraping with a metal tool (such as a thin plate and a spatula, etc.).

[0232] The weight of the sample of the colored layer taken from the glass substrate with the colored layer is measured. Next, the sample is wrapped in a non-woven fabric bag. A sufficient amount of ethanol solution (concentration 99.5 vol%) relative to the sample of the colored layer is charged into a flask equipped with a condenser tube, and the above bag-wrapped sample is immersed in the ethanol solution. The ethanol solution is replaced with fresh ethanol solution every 1 day (24 hours), and the sample is immersed in the ethanol solution for 2 weeks. After 2 weeks, the bag is taken out from the flask, and the solid components remaining in the bag after the extraction test are completely dried, and the weight of the dried solid components is measured.

[0233] The weight of the sample of the colored layer before immersion in the ethanol solution (initial weight of the colored layer) and the weight of the solid components obtained by drying after immersion in the ethanol solution measured in the above extraction test are substituted into the above formula (1), thereby calculating the extraction amount of the non-cured components of the colored layer (unit: mass%). It should be noted that the extraction amount of the non-cured components of the colored layer refers to the ratio of the amount of non-cured components extracted from the colored layer into the ethanol solution through the extraction test to the total mass of the colored layer before the extraction test.

[0234] The extraction amount of the non-cured components of the colored layer measured by the above extraction test is preferably 5 mass% to 30 mass% with respect to the entire colored layer, more preferably 10 to 25 mass%, more preferably 10 to 23 mass%, more preferably 10 to 20 mass%, still more preferably 10 to 19 mass%, and most preferably 10 to 18 mass%. When the extraction amount of the non-cured components is 25 mass% or less, the durability of the colored layer is more excellent. When it is 19 mass% or less, the density of the colorant in the colored layer is high, and heat generation points are likely to increase, so the laser trimming property is also improved. When it is 19 mass% or less, the laser trimming property is further improved.

[0235] Regarding the uncured components extracted through the above extraction tests, it is assumed that most of them are composed of uncured resins and include unreacted portions of curable resins and / or curing agents, as well as colorants as part of them. On the other hand, not all of the uncured resins contained in the resin layer are extracted as uncured components. For example, it is considered that the uncured resins introduced into the cured resin network are difficult to extract.

[0236] Therefore, it is considered that the extracted portion of the above uncured components reflects the amount of easily elutable components, in other words, easily flowing components, in the uncured resins. It is speculated that by making the extraction amount of the uncured components within the above range, the fluidity during the formation of the colored layer is improved, and a glass substrate with a colored layer having excellent adhesion between the colored layer and the glass substrate is obtained.

[0237] Hereinafter, each component included in the glass substrate with a colored layer of the present embodiment will be described in detail.

[0238] As the colored layer included in the glass substrate with a colored layer of the present embodiment, for example, a colored layer containing a colorant and a cured resin can be cited. In the present embodiment, it is preferable that the colored layer contains a colorant, a cured resin, and an uncured resin.

[0239] In the present embodiment, regarding the components such as colorants, cured resins, and uncured resins that the colored layer may contain, as well as the characteristics of the colored layer, the preferred modes thereof are also included as described in the first embodiment.

[0240] In addition, regarding the glass substrate with a colored layer of the present embodiment, the glass substrate, each layer other than the glass substrate and the colored layer, and the characteristics of the glass substrate with a colored layer, the preferred modes thereof are also included as described in the first embodiment.

[0241] In the following description, unless otherwise specified, both the first embodiment and the second embodiment will be described.

[0242] [Manufacturing Method of Glass Substrate with Colored Layer]

[0243] As a manufacturing method of the glass substrate with a colored layer, as long as it is a method capable of directly forming a colored layer on the main surface of the glass substrate, it can be any method. For example, a method of forming a colored layer on the main surface of the glass substrate by a transfer decoration method can be cited.

[0244] As a method for manufacturing a glass substrate with a colored layer based on a transfer decoration method, for example, the following method for manufacturing a glass substrate with a colored layer can be cited: Prepare a glass substrate having a main surface, prepare a transfer member having a transfer substrate and a precursor film of the colored layer, laminate the transfer member on the glass substrate such that the main surface of the glass substrate is in contact with the precursor film of the colored layer, and cure the precursor film of the colored layer disposed in contact with the main surface of the glass substrate, thereby forming a colored layer.

[0245] The precursor film of the colored layer described above contains, for example, a colorant, a curable resin, and a non-curable resin. The precursor film of the colored layer may further contain a curing agent.

[0246] Hereinafter, the method for manufacturing a glass substrate with a colored layer based on the transfer decoration method will be described in detail.

[0247] The glass substrate is manufactured, for example, through each process of cutting, machining, and polishing a large-sized sheet glass.

[0248] As a method for cutting the sheet glass, for example, cutting based on a diamond blade, a scribe break method, a laser cutting method, and chemical cutting based on etching can be cited. For machining or polishing, a grindstone can be used, or a polishing wheel or brush made of cloth, leather, rubber, etc. other than a grindstone can also be used. At this time, abrasives such as cerium oxide, alumina, silicon carbide, and colloidal silica can also be used. Among them, from the viewpoint of dimensional stability, a grindstone is preferably used as the polishing tool.

[0249] In terms of more excellent strength of the glass substrate, it is preferable to perform chemical strengthening treatment on the glass component obtained through the above processes. The method of chemical strengthening treatment is as described above.

[0250] In parallel with the preparation of the glass substrate, a transfer member having a transfer substrate and a precursor film of the colored layer is prepared.

[0251] As a method for preparing the transfer member, for example, the following method can be cited: A coating film is formed on the surface of the transfer substrate using a composition containing components constituting the colored layer (hereinafter, also referred to as "composition A"), and the coating film is dried as needed, thereby manufacturing a transfer member having a transfer substrate and a precursor film of the colored layer disposed on the surface of the transfer substrate.

[0252] The transfer substrate is appropriately selected according to the method of forming the precursor film of the colored layer and transferring it to the glass substrate. As the transfer substrate, a resin substrate is preferable in terms of flexibility, heat resistance, surface cleanliness, and smoothness.

[0253] Examples of the resin constituting the transfer substrate include thermoplastic resins such as polyethylene terephthalate resin, polyethylene resin, and polypropylene resin. For the purpose of facilitating peeling after transfer, etc., a functional layer may be provided on the surface of the transfer substrate, or surface treatments such as adhesion treatment and corona treatment may be performed on the surface of the transfer substrate.

[0254] The thickness of the transfer substrate is, for example, 10 to 300 μm, preferably 20 to 250 μm, and more preferably 40 to 200 μm.

[0255] In addition, when the transfer substrate is softened when laminating the transfer member on the glass substrate as described later, the glass transition temperature (Tg) of the resin constituting the transfer substrate is preferably 70 to 180 °C, and more preferably 100 to 150 °C.

[0256] Composition A is a composition containing the components constituting the colored layer and is used in the formation of the colored layer precursor film and the colored layer. That is, the colored layer is a layer formed using Composition A containing a colorant, a curable resin, and a non-curable component.

[0257] Examples of Composition A include a composition containing a colorant, a curable resin, a non-curable resin, and a solvent. Composition A may contain a curing agent and preferably contains a curing agent.

[0258] Regarding the colorant, curable resin, curing agent, and non-curable resin contained in Composition A, the preferred embodiments thereof also include the contents already described as the components of the colored layer of the glass substrate with a colored layer constituting the first embodiment.

[0259] It should be noted that for the colorant, curable resin, curing agent, and non-curable resin, the preferred ranges of the contents in the colored layer or the colored layer precursor film are directly applied as the preferred ranges of the contents relative to the total content of the solid components of Composition A.

[0260] The solvent contained in Composition A is appropriately selected according to the components other than the solvent and the type of the transfer substrate. Examples include alcohol solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents.

[0261] Examples of alcohol solvents include isopropyl alcohol, methanol, and ethanol. Examples of ester solvents include ethyl acetate. Examples of ketone solvents include methyl ethyl ketone. Examples of aromatic hydrocarbon solvents include toluene and xylene. Examples of aliphatic hydrocarbon solvents include hexane.

[0262] The content of the solvent in Composition A is preferably 20 to 80% by mass, and more preferably 30 to 60% by mass, relative to the total mass of Composition A.

[0263] That is, the total content of the components other than the solvent in Composition A (hereinafter also referred to as "solid component concentration") is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, relative to the total mass of Composition A.

[0264] Composition A can be prepared by a known method. The above components contained in Composition A can be mixed separately, or two or more of the above components can be mixed to prepare a preliminary composition and then mixed with other components or other preliminary compositions to prepare Composition A.

[0265] As a method of forming a coating film of Composition A on the surface of the transfer substrate using Composition A, known coating film forming methods can be employed. For example, screen printing, inkjet printing, offset printing, flexographic printing, stencil printing, gravure printing, roller printing, curtain coating, die coating, gravure coating, microgravure coating, reverse coating, roll coating, flow coating, and spraying can be mentioned.

[0266] When Composition A contains a solvent, it is preferable to dry the coating film to evaporate the solvent. Drying of the coating film can be carried out by a known method such as heating of the coating film.

[0267] When Composition A contains a thermosetting agent, it is preferable that the heating temperature during drying of the coating film of Composition A is lower than the curing temperature of the thermosetting agent.

[0268] The coating film of Composition A can also be used as a precursor film for the colored layer without drying.

[0269] The precursor film for the colored layer formed on the transfer substrate can have a pattern corresponding to the target colored layer.

[0270] The patterned precursor film for the colored layer can be formed by the above-described coating film forming method.

[0271] The thickness of the precursor film for the colored layer in the transfer member is preferably 5 to 20 μm, more preferably 5 to 15 μm, and further preferably 8 to 15 μm.

[0272] Next, the transfer member is laminated on the glass substrate such that the main surface of the glass substrate is in contact with the precursor film for the colored layer possessed by the transfer member.

[0273] When laminating the transfer member on the glass substrate, the transfer member before lamination can be heated, and the transfer member having a softened transfer substrate and precursor film for the colored layer is laminated on the glass substrate. By laminating the softened transfer substrate, it becomes easier to form a colored layer having a desired pattern shape. In particular, when the main surface of the glass substrate on which the colored layer is disposed has a curved surface, it is preferable to heat and soften the transfer substrate when laminating the transfer member on the glass substrate in terms of more excellent adhesion between the glass substrate and the colored layer.

[0274] When laminating the transfer member on the glass substrate, the glass substrate before lamination can also be heated.

[0275] The heating temperature of the transfer member before lamination is, for example, 80 to 180°C, preferably 100 to 160°C.

[0276] In addition, when the colored layer precursor film contains a thermosetting agent, the heating temperature of the transfer member before lamination is preferably lower than the curing temperature of the thermosetting agent, and more preferably a temperature 10°C or more lower than the curing temperature of the thermosetting agent. By setting the heating temperature within these ranges, the colored layer precursor film can be adhered to the main surface of the glass substrate without curing.

[0277] As a method for heating the transfer member, for example, irradiation with infrared rays, superheated steam, and contact with a hot plate can be cited. The glass substrate can also be heated by the same method.

[0278] The lamination of the glass substrate and the transfer member is preferably performed by a vacuum pressure forming method.

[0279] More specifically, the method is as follows: The prepared glass substrate and transfer member are arranged in a chamber such that the main surface of the glass substrate faces the colored layer precursor film. The chamber is divided by the transfer member into a first space containing the glass substrate and a second space not containing the glass substrate. The transfer substrate is heated to soften it, and the air pressure in the first space is made lower than the air pressure in the second space, whereby the colored layer precursor film comes into contact with the main surface of the glass substrate.

[0280] If the glass substrate and the transfer member are laminated by the above method, the softened transfer member will deform along the main surface of the glass substrate. Therefore, the adhesion of the colored layer precursor film (and the colored layer) adhered to the main surface of the glass substrate to the main surface is more excellent. In particular, when at least a part of the main surface of the glass substrate is a curved surface, the above adhesion can also be obtained, which is therefore preferable.

[0281] The heating temperature and heating method of the transfer substrate in the vacuum pressure forming method are as described above. As a heating method of the transfer substrate, the following method is preferred: In the second space of the vacuum pressure forming machine, the hot plate arranged opposite to the transfer substrate is brought into contact with the transfer substrate.

[0282] In addition, when laminating the glass substrate and the transfer member by the vacuum pressure forming method, the glass substrate can also be heated.

[0283] As a method for making the air pressure in the first space (glass substrate side) lower than the air pressure in the second space, a method of decompressing the first space is preferred, and a method of decompressing the first space and pressurizing the second space is more preferred.

[0284] When the air pressure in the first space when the coloring layer precursor film is in contact with the main surface of the glass substrate is, for example, 1 MPa or less, preferably 0.2 MPa or less, more preferably 0.1 MPa or less, and still more preferably 0.05 MPa or less. The air pressure in the first space is preferably 10 Pa or more.

[0285] In addition, when pressurizing the second space, the air pressure in the second space is, for example, 0.01 MPa or more, preferably 0.05 MPa or more, more preferably more than 0.1 MPa, and still more preferably more than 0.2 MPa. The air pressure in the second space is preferably less than 1 MPa.

[0286] Details of the method for laminating the glass substrate and the transfer member based on the vacuum pressure forming method can be referred to the known method.

[0287] Next, the coloring layer precursor film disposed in contact with the main surface of the glass substrate is cured, thereby manufacturing a glass substrate with a coloring layer.

[0288] The curing treatment is appropriately selected according to the components constituting the coloring layer precursor film.

[0289] When the coloring layer precursor film contains a thermal curing agent, the coloring layer precursor film is cured by heating the laminated coloring layer precursor film to a temperature above the curing temperature of the thermal curing agent. The heating temperature at this time is preferably a temperature 10 °C or more higher than the curing temperature of the thermal curing agent. The heating temperature is preferably 200 °C or less.

[0290] When the coloring layer precursor film contains a photo-curing agent, the coloring layer precursor film is cured by irradiating the coloring layer precursor film with light of a specified wavelength. As a method of curing the coloring layer precursor film by light irradiation, the wavelength, irradiation amount, irradiation time, etc. of the irradiated light are appropriately selected according to the type of the photo-curing agent and the composition of the coloring layer precursor film, etc. For example, a method of irradiating ultraviolet rays of about 0.3 to 30 mW / cm 2 for about 1 to 30 minutes can be cited.

[0291] When manufacturing a glass substrate with a coloring layer by the above-described transfer decoration method, the transfer substrate can also be used as a protective member without being peeled off, but it is usually peeled off.

[0292] The peeling of the transfer substrate can be performed before curing the coloring layer precursor film, or the transfer substrate can be peeled off from the glass substrate with a coloring layer after curing the coloring layer precursor film. In terms of more excellent adhesion between the coloring layer and the main surface of the glass substrate, it is preferable to peel off the transfer substrate after curing the coloring layer precursor film.

[0293] In the case of laminating a glass substrate and a transfer member by vacuum pressure forming, a device that has been subjected to vacuum pressure forming can also be used to cure the precursor film of the colored layer and peel the transfer substrate from the glass substrate with the colored layer.

[0294] <Laser trimming>

[0295] In the manufacture of a glass substrate with a colored layer, it is also possible to perform a process of irradiating a part of the colored layer disposed on the main surface of the glass substrate with a laser after forming the colored layer and removing the irradiated colored layer (hereinafter, also referred to as "laser trimming").

[0296] Especially when manufacturing a glass substrate with a colored layer having an opening, it is preferable to perform the above-mentioned laser trimming to remove the excess portion of the colored layer and form an end portion of the colored layer adjacent to the opening. This is because: an opening having a desired shape can be easily formed at an accurate position, and the slope of the end portion of the colored layer is closer to the normal of the main surface, the boundary between the opening and the colored layer becomes clearer, and the visibility when using the glass with the colored layer in a display device is more excellent.

[0297] Figure 5 It is a schematic diagram showing an example of the configuration of a laser irradiation device that irradiates a part of the colored layer with a laser.

[0298] Figure 5 The shown laser irradiation device 30 irradiates the colored layer 3 with an absorbable laser L and performs ablation processing on the colored layer 3. The laser irradiation device 30 includes a laser oscillator 31, a scanner 32, and a condenser lens 33. The laser oscillator 31 emits a laser L having an absorbable wavelength to the colored layer 3 at a specified irradiation timing based on a control signal from a control device (not shown). The condenser lens 33 condenses the laser L emitted from the laser oscillator 31 and guides it to the colored layer 3. The scanner 32 is disposed between the laser oscillator 31 and the condenser lens 33 and makes the optical axis of the laser L emitted from the laser oscillator 31 face the condenser lens 33. The scanner 32 includes a mirror (not shown) and rotates the mirror around an axis, thereby scanning the laser L deflected by the mirror onto the colored layer 3. Thus, as Figure 5 shown, the excess portion 3B of the colored layer 3 irradiated with the laser L is removed to form an end portion 3A.

[0299] It should be noted that the configuration of the laser irradiation device and the processing method of laser trimming are not limited to Figure 5 the shown configuration. For example, in Figure 5 , the laser L is irradiated onto the colored layer 3 from the first main surface 21 side where the colored layer 3 is disposed, but the laser irradiation device may also be disposed on the second main surface side of the glass substrate, and the laser transmitted through the glass substrate may be irradiated onto the colored layer.

[0300] The conditions for laser trimming are set as follows.

[0301] The wavelength of the laser L is appropriately selected according to the absorption wavelength of the colorant contained in the colored layer, preferably 300 to 1100 nm, more preferably 500 to 1100 nm.

[0302] The irradiation interval of the laser L is preferably less than 100 μm, more preferably less than 70 μm. In addition, the scanning speed is preferably 1000 to 8000 mm / s, more preferably 1000 to 4000 mm / s. The irradiation interval is the interval of the laser L that is intermittently irradiated onto the colored layer during the scanning time on the colored layer, and is calculated by dividing the scanning speed by the irradiation frequency of the laser L.

[0303] After manufacturing the glass substrate with the colored layer by the above method, a process of applying at least one selected from an AG layer, an AR layer, and an AFP layer to the main surface (second main surface) of the glass substrate on the side opposite to the main surface directly provided with the colored layer can be carried out.

[0304] The manufacturing methods of the AG layer, the AR layer, and the AFP layer are appropriately selected from known methods.

[0305] [Use]

[0306] <Cover glass>

[0307] The glass substrate with the colored layer of the present invention can be used as a cover glass for a display, for example. The glass substrate with the colored layer can be used alone as a cover glass for a display, and preferably at least one functional layer selected from an AG layer, an AR layer, and an AFP layer is laminated on the second main surface on the side opposite to the first main surface where the colored layer is disposed on the glass substrate. In addition, when used as a cover glass for a display, it is preferable that the glass substrate with the colored layer has an opening.

[0308] The cover glass for a display having a glass substrate with a colored layer can protect an object while ensuring the visibility of the display image of the display.

[0309] <Display device>

[0310] As an embodiment of the display device of the present invention, a display device including a cover glass having a glass substrate with a colored layer and a display, and the main surface on the colored layer side of the cover glass facing the display can be cited.

[0311] Refer to Figure 6 A vehicle-mounted display device used in a vehicle, which is an example of the display device having the above-mentioned cover glass for a display, will be described.

[0312] Figure 6The in-vehicle display device 101 shown has: a glass substrate 1 with a coloring layer, a housing 102, a display 103, and an adhesive layer 104.

[0313] The in-vehicle display device 101 is, for example, a vehicle navigation device, an instrument panel, or a rear-seat entertainment audio-visual (RSE) device for allowing a passenger in the rear seat to view and listen to images or the like.

[0314] The in-vehicle display device 101 has a housing 102 that houses each part. The display 103 is disposed inside the housing 102. As the display 103, for example, a liquid crystal panel, an organic EL (electroluminescence) panel, and an electronic ink type panel can be cited. The display 103 may also have a touch panel or the like.

[0315] The display 103 can display, for example, a navigation system screen, various measuring instruments such as a speedometer, and images such as a start button.

[0316] In the in-vehicle display device 101, the glass substrate 1 with a coloring layer is attached to the display 103 by the adhesive layer 104. Thus, the glass substrate 1 with a coloring layer functions as a cover glass for the display 103.

[0317] As the adhesive layer 104, for example, a layer made of a transparent resin obtained by curing a liquid curable resin composition can be cited. The adhesive layer 104 can be an OCA (Optical Clear Adhesive) film or tape. The thickness of the adhesive layer 104 is preferably 5 μm or more, more preferably 50 μm or more. On the other hand, the thickness of the adhesive layer 104 is preferably 400 μm or less, more preferably 200 μm or less.

[0318] The mode of the display device having the glass substrate with a coloring layer of the present invention as a cover glass is not limited to Figure 6 the mode shown. For example, at least a part of the glass substrate with a coloring layer may have a curved surface.

[0319] In addition, the glass substrate with a coloring layer of the present invention can be used as a cover glass for a display device in a panel display (such as a liquid crystal display and an organic EL display) and a portable device or the like in addition to the in-vehicle display device.

[0320] Examples

[0321] Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples. Examples 1 to 7 and Example 11 are examples, and Examples 8 to 10 are comparative examples.

[0322] [Example 1]

[0323] The glass substrate with a coloring layer of Example 1 was produced as follows.

[0324] Prepare a rectangular aluminosilicate glass (AGC Inc.'s "Dragontrail (registered trademark)") with a thickness of 1.3 mm, a length of 100 mm, and a width of 200 mm as the glass substrate.

[0325] (Preparation of Composition A)

[0326] Use the following ink agent, curing agent, non-curable resin, and solvent as raw materials to prepare Composition A1.

[0327] · Ink agent I-1: "INQ-HF 979 Ink" manufactured by Teikoku Ink Manufacturing Co., Ltd.

[0328] · Curing agent: A blocked isocyanate compound containing methyl ethyl ketoxime (MEKO) ("BK1175" manufactured by SAPICI Co., Ltd., curing temperature T1: about 150 °C)

[0329] · Non-curable resin: Acrylic tackifier ("UH-2170" manufactured by Toagosei Co., Ltd., weight average molecular weight (Mw): 14000)

[0330] · Solvent: Methyl ethyl ketone (MEK)

[0331] First, dissolve the above non-curable resin in the above solvent to prepare a premix b1. In addition, mix the above ink agent and the above curing agent to prepare Composition a1. Mix and stir the composition a1 and the premix b1 at a ratio of composition a1: premix b1 of 50:7 by mass ratio, and thus prepare Composition A1 as the composition for forming a colored layer.

[0332] (Manufacture of Transfer Member)

[0333] Prepare a resin substrate made of an olefin resin with a thickness of 0.1 mm, a length of 300 mm, and a width of 210 mm ("DECOFIT (registered trademark) Q01CK" manufactured by Toray Industries, Inc., glass transition temperature Tg: about 70 °C) as the transfer substrate.

[0334] Print the prepared Composition A1 onto the surface of the above resin substrate by screen printing. Dry the formed coating film at 70 °C for 30 minutes to produce a transfer member having a resin substrate and a precursor film of a colored layer formed on the surface of the resin substrate. The thickness of the formed precursor film of the colored layer is 0.01 mm, and the shape in plan view is a rectangle with a length of 250 mm and a width of 200 mm.

[0335] (Manufacture of Glass Substrate with Colored Layer)

[0336] Place the glass substrate on the setting table provided in the chamber of a vacuum pressure forming machine. Set the fabricated transfer member above the glass substrate with the coloring layer precursor film facing the glass substrate. After heating to 100 °C the transfer substrate of the transfer member using a preheating plate, move the setting table upward, thereby bringing the heated transfer member into contact with the glass substrate. Next, reduce the air pressure in the first space containing the glass substrate, which is divided by the transfer member, in the chamber to approximately 400 Pa. At this time, the air pressure in the second space is the atmospheric pressure.

[0337] After restoring the air pressure in the first space to the atmospheric pressure, peel the resin substrate from the coloring layer precursor film, and heat the laminate of the glass substrate and the coloring layer precursor film at 160 °C for 30 minutes. Thereby, cure the coloring layer precursor film to form a coloring layer, and manufacture a glass substrate with a coloring layer having a coloring layer disposed in contact with the main surface of the glass substrate.

[0338] (Laser trimming)

[0339] Perform laser trimming as described above: irradiate the coloring layer of the manufactured glass substrate with a coloring layer through the glass substrate, and remove the irradiated coloring layer.

[0340] Laser trimming is performed using a laser irradiation device (manufactured by Keyence Corporation) under the conditions of a laser wavelength of 1064 nm and a laser irradiation interval of approximately 100 μm.

[0341] Remove a part of the coloring layer by laser trimming to form a rectangular opening portion with a length of 10 mm and a width of 10 mm.

[0342] [Examples 2 to 11]

[0343] In Examples 2 to 7 and Example 11, according to the preparation method of Composition A described in Example 1, change the types and amounts used of the ink agent, curing agent, non-curable resin, and solvent so as to have the compositions shown in Table 1 below, and respectively prepare Compositions a2 to a7, Composition a11, Premixes b2 to b7, and Premix b11. Substitute the prepared respective compositions and respective premixes for Composition a1 and Premix b1, thereby respectively prepare Compositions A2 to A7 and A11 described in Table 1 below. Compositions a2 to a7, Composition a11, Premixes b2 to b7, and Premix b11 are mixed at the mixing ratios shown in Table 1 below.

[0344] In addition, in Examples 8 to 10, according to the preparation method of composition a1 described in Example 1, the types and usage amounts of the ink agent and the curing agent were changed so as to achieve the compositions shown in Table 1 described later, and compositions a8 to a10 were prepared respectively. The prepared compositions a8 to a10 were directly used as the coloring layer forming compositions A8 to A10.

[0345] The ink agent, curing agent, non-curable resin, and solvent used in the preparation of each composition are shown below.

[0346] - Ink agent -

[0347] · Ink agent I-2: "HF GV3 RX01710 Black" manufactured by Seiko Advance Co., Ltd.

[0348] · Ink agent I-3: "1300HK" manufactured by Seiko Advance Co., Ltd.

[0349] It should be noted that ink agents I-1, I-2, and I-3 each contain carbon black (CB) as a colorant and the curable resin shown in Table 1 described later.

[0350] - Curing agent -

[0351] · Isocyanate compound ("106 curing agent" manufactured by Teikoku Ink Manufacturing Co., Ltd.)

[0352] - Non-curable resin -

[0353] · Acrylic tackifier ("UC-3000" manufactured by Toagosei Co., Ltd., weight average molecular weight (Mw): 10000)

[0354] · Styrene-acrylic tackifier ("UC-3080" manufactured by Toagosei Co., Ltd., weight average molecular weight (Mw): 14000)

[0355] · Terpene-phenol tackifier ("YS POLYSTER G-125" manufactured by Yasuhara Chemical Co., Ltd., weight average molecular weight (Mw): 600)

[0356] - Solvent -

[0357] · Butyl acetate

[0358] Using the prepared compositions A2 to A11, and heating the transfer substrate at the temperature described in Table 1 described later before bringing the transfer member into contact with the glass substrate, except for this, according to the production method of the transfer member in Example 1 and the production method of the glass substrate with a coloring layer, glass substrates with a coloring layer were manufactured respectively.

[0359] In Examples 1 to 7, 9, and 11, the formed colored layer adheres to the main surface of the glass substrate over the entire surface. On the other hand, after bringing the transfer member into contact with the glass substrate, in the step of peeling off the resin substrate, in Example 8, the entire formed colored layer precursor film is peeled off from the glass substrate, and in Example 10, about 20 area% or more of the total area of the formed colored layer precursor film is peeled off from the glass substrate.

[0360] Laser trimming was performed on the colored layer of the glass substrate with the colored layer manufactured in Examples 1 to 7, 9, and 11 in the same manner as in Example 1.

[0361] [Measurement]

[0362] The following measurements were made on the colored layer of the glass substrate with the colored layer in Examples 1 to 7, 9, and 11. The measurement results are shown in Table 1 below.

[0363] The thickness of the colored layer was measured in a non-contact manner using a measurement device of the stage scanning type laser detector method (“NH-3MAs” manufactured by Mitaka Kohki Co., Ltd.). Specifically, five positions were randomly selected in the region other than the end portion of the colored layer, and the thickness of the colored layer based on the first main surface of the glass substrate (the distance from the first main surface of the glass substrate to the surface of the colored layer in the normal direction of the first main surface) was measured. The arithmetic mean of the obtained measurement values was calculated as the average thickness of the colored layer (unit: μm).

[0364] Using the above measurement device, a cross-section of the glass substrate with the colored layer was obtained, and the cross-sectional profile of the end portion adjacent to the opening of the colored layer in the cross-section including the direction perpendicular to the boundary line between the opening and the colored layer and in the direction extending along the normal direction of the main surface of the glass substrate (refer to Figure 4 ).

[0365] In the cross-sectional profile of the end portion of the obtained colored layer, the ratio (Lt / Lh) of the thickness direction distance Lt between the two points P1 where the thickness reaches 10% of the average thickness of the colored layer and the point P2 where the thickness reaches 50% of the average thickness of the colored layer to the in-plane direction distance Lh between the two points was calculated as the slope of the end portion. The slope of the end portion in Examples 1 to 3, 5 to 7, and 11 is 0.1 or more.

[0366] For the glass substrate with the colored layer, an OD value (Optical Density) was measured at a position 20 μm shifted in the in-plane direction of the colored layer from the boundary line between the opening and the colored layer using an OD measurement device (“LV-OD” manufactured by Lambda Vision Co., Ltd.).

[0367] The larger the OD value, the higher the light-shielding property of the colored layer. As long as the OD value exceeds 5, it can be evaluated that the light-shielding property is good.

[0368] <Extraction amount of non-cured component>

[0369] Use a thin metal plate to scrape the colored layer from the glass substrate with the colored layer to collect a sample of the colored layer and measure its weight. Then, according to the above extraction test method, put the obtained sample of the colored layer into a bag, immerse it in ethanol solution with a concentration of 99.5 vol% for 2 weeks, take out the bag from the ethanol solution, completely dry the solid component remaining in the bag, and measure the weight of the solid component. According to the initial weight of the colored layer before immersion in the ethanol solution and the measured weight of the solid component obtained by drying after immersion in the ethanol solution, use the above formula 1 to calculate the extraction amount of the non-cured component (unit: mass%).

[0370] [Evaluation]

[0371] The glass substrates with colored layers of Examples 1 to 7, Example 9, and Example 11 were evaluated as follows. In addition, for Example 10, a cross-cut test was performed on a part of the colored layer remaining on the manufactured glass substrate with the colored layer. The evaluation results are shown in Table 1 below.

[0372] <Hot water durability test>

[0373] Put water into a beaker and boil it under atmospheric pressure. Immerse the glass substrates with colored layers of each example in the boiling water and keep the state of boiling water for 1 hour. After 1 hour from the start of immersion, take out the glass substrates with colored layers, wipe off the moisture, and visually observe whether the colored layer peels off from the glass substrate. It should be noted that in this test and the cross-cut test described later, the glass substrates with colored layers without laser trimming were used.

[0374] Based on the observation results, evaluate the hot water resistance according to the following criteria.

[0375] ○: No peeling of the colored layer is observed.

[0376] ×: Peeling of the colored layer is observed.

[0377] <Cross-cut test>

[0378] Cut the colored layer of the glass substrate with the colored layer that has undergone the above hot water durability test into a grid pattern with a width of 1 mm to form 100 meshes. Stick a transparent tape on the area of the colored layer where the meshes are formed and then peel it off.

[0379] Observe the meshes after peeling off the transparent tape, and evaluate the adhesion based on the obtained observation results according to the following criteria.

[0380] ◎: No peeling was observed in any mesh.

[0381] ○: Small peeling was observed at the intersection of the cuts. The ratio of the area of the peeled area to the total area of the colored layer is 5% or less.

[0382] △: Peeling was observed along the intersection of the cuts and / or the cutting line. The ratio of the area of the peeled area to the total area of the colored layer is greater than 5% and 15% or less.

[0383] ×: Local or entire surface peeling was observed. The ratio of the area of the peeled area to the total area of the colored layer is greater than 15%.

[0384] <Laser trimming property>

[0385] For the glass substrates with colored layers manufactured in Examples 1 to 7 and Example 11, a haze meter was used to measure the haze of the glass substrate of the opening after removing the colored layer by laser trimming.

[0386] ◎: The haze is 1.0% or less.

[0387] ○: The haze is greater than 1.0% and 5.0% or less.

[0388] △: The haze is greater than 5.0% and 30.0% or less.

[0389] ×: The haze is greater than 30.0%.

[0390] The composition of the composition used in the formation of the colored layer, the heating temperature of the transfer substrate, the measurement results of the formed colored layer, and the above evaluation results are shown in Table 1.

[0391] In the table, in the column of "Curing agent content [mass%]" of the "Colored layer precursor film", the content of the curing agent is expressed as a mass percentage relative to the total mass of the colored layer precursor film. In the column of "Ratio of non-curable resin / curable resin [mass%]", the ratio of the content of the non-curable resin contained in the colored layer precursor film to the content of the curable resin is expressed as a mass percentage.

[0392] [Table 1]

[0393] Table 1

[0394]

[0395] As shown in Table 1 above, the hot water resistance of the colored layers of the glass substrates with colored layers having a main surface and a colored layer disposed in contact with the main surface and containing a colorant, a cured resin, and a non-curable resin, that is, the glass substrates of Examples 1 to 7 and Example 11, is excellent.

[0396] In addition, a glass substrate having a main surface and a colored layer disposed in contact with the main surface, and the glass substrate with the colored layer having an extraction amount of uncured components of the colored layer of 5% by mass to 40% by mass has excellent hot water resistance.

[0397] In contrast, in the glass substrate with a colored layer in Example 9 where the colored layer does not contain a non-curable resin, the hot water resistance is insufficient.

[0398] Industrial applicability

[0399] According to the present invention, it is possible to provide a glass substrate with a colored layer, a cover glass, and a display device having a colored layer with excellent durability. In addition, it is possible to provide a method for manufacturing a glass substrate with a colored layer having a colored layer with excellent durability based on a transfer decoration method.

[0400] The present invention has been described in detail with reference to specific embodiments, but those skilled in the art can obviously make various changes and modifications without departing from the spirit and scope of the present invention.

[0401] This application is based on Japanese Patent Application (Japanese Patent Application No. 2022-197301) filed on December 9, 2022, and Japanese Patent Application (Japanese Patent Application No. 2022-212353) filed on December 28, 2022, the contents of which are incorporated herein by reference.

[0402] Symbol description

[0403] 1 Glass substrate with a colored layer

[0404] 2, 2A, 2B, 2C Glass substrate

[0405] 3 Colored layer

[0406] 3A End portion

[0407] 3B Excess portion

[0408] 4 AG layer

[0409] 5 AR layer

[0410] 6 AFP layer

[0411] 7 Opening

[0412] 8 Demarcation line

[0413] 10 Laminate

[0414] 21 First main surface

[0415] 22 Second main surface

[0416] 30 Laser irradiation device

[0417] 31 Laser oscillator

[0418] 32 Scanner

[0419] 33 Condensing lens

[0420] 41, 51, 61 Bending part

[0421] 42 Flat part

[0422] 52, 62 Midpoint

[0423] 101 Vehicle-mounted display device

[0424] 102 Housing

[0425] 103 Display

[0426] 104 Adhesive layer

Claims

1. A glass substrate with a coloring layer, comprising: a glass substrate having a main surface, and a coloring layer disposed in contact with the main surface, The coloring layer contains a colorant, a cured resin, and a non-curable resin.

2. The glass substrate with a coloring layer according to claim 1, wherein, The cured resin is a cured product of a curable resin and a curing agent.

3. The glass substrate with a coloring layer according to claim 2, wherein, The curing agent is a thermal curing agent or a photo-curing agent.

4. The glass substrate with a coloring layer according to claim 2, wherein, The curing agent is a thermal curing agent.

5. The glass substrate with a coloring layer according to claim 2, wherein, The curing agent contains blocked isocyanate.

6. The glass substrate with a coloring layer according to claim 2, wherein, The coloring layer further contains at least one selected from methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 3,5-dimethylpyrazole, and acetone oxime.

7. The glass substrate with a coloring layer according to claim 4, wherein, The curing temperature of the thermal curing agent is 80 to 200 °C.

8. The glass substrate with a coloring layer according to claim 1, wherein, The non-curable resin contains a tackifier.

9. The glass substrate with a coloring layer according to claim 2, wherein, The non-curable resin contains a tackifier, Relative to the content of the curable resin, the content of the tackifier is greater than 0% by mass and 150% by mass or less.

10. The glass substrate with a coloring layer according to claim 2, wherein, The curable resin contains at least one selected from acrylic resins, polyester resins, and epoxy resins.

11. The glass substrate with a coloring layer according to claim 2, wherein, The curable resin contains an acrylic resin.

12. A glass substrate with a coloring layer, comprising: a glass substrate having a main surface, and a coloring layer disposed in contact with the main surface, The extraction amount of the non-cured component of the coloring layer measured by the following extraction test is 5% by mass to 40% by mass, Extraction test: (i) Measure the initial weight of the coloring layer, (ii) Immerse the coloring layer in an ethanol solution with a concentration of 99.5% by volume for 2 weeks, and change the ethanol solution for the coloring layer once a day, (iii) After drying the solid components remaining undissolved in the ethanol solution, measure the weight of the dried solid components, and calculate the extraction amount of the non-cured component from the following formula, Extraction amount of non-cured component = (Initial weight of coloring layer - Weight of solid components) / Initial weight of coloring layer × 100, the unit of the extraction amount is % by mass, and the unit of weight is g.

13. The glass substrate with a coloring layer according to claim 12, wherein, The extraction amount of the non-cured component of the coloring layer is 10% by mass to 25% by mass.

14. The glass substrate with a coloring layer according to claim 12, wherein, The extraction amount of the non-cured component of the coloring layer is 10% by mass to 19% by mass.

15. The glass substrate with a coloring layer according to any one of claims 1 to 14, wherein, The thickness of the coloring layer is 5 to 20 μm.

16. The glass substrate with a coloring layer according to any one of claims 1 to 14, wherein, The following requirements 1 and 2 are satisfied, Requirement 1: When the glass substrate with the coloring layer is immersed in boiling water under atmospheric pressure and taken out after 1 hour from the immersion, no peeling of the coloring layer from the glass substrate is observed in the glass substrate with the coloring layer. Requirement 2: When the glass substrate with the coloring layer is immersed in boiling water under atmospheric pressure and, after 1 hour from the immersion, a cross-cut test according to JIS K5600-5-6 is performed, no peeling of the coloring layer from the glass substrate is observed, or the ratio of the area of the region peeled from the glass substrate to the total area of the coloring layer is 15% or less.

17. The glass substrate with a coloring layer according to any one of claims 1 to 14, wherein, When observing the glass substrate with the coloring layer from the glass substrate side, no bubbles are observed between the glass substrate and the coloring layer.

18. The glass substrate with a coloring layer according to any one of claims 1 to 14, wherein, The glass substrate with the coloring layer has an opening portion on the main surface of the glass substrate where the coloring layer is not disposed, The slope of the end portion of the coloring layer adjacent to the opening portion is 0.1 or more.

19. The glass substrate with a coloring layer according to any one of claims 1 to 14, wherein, At least a part of the region of the main surface where the coloring layer is disposed is a curved surface.

20. A cover glass is a cover glass for a display that has a glass substrate with a coloring layer as described in any one of claims 1 to 14, wherein the coloring layer has an opening, and at least one layer selected from an antiglare layer, an antireflection layer, and an antifouling layer is laminated on the main surface of the glass substrate on the side opposite to the main surface where the coloring layer is disposed.

21. A display device includes the cover glass described in claim 20 and a display, wherein the main surface of the cover glass on the coloring layer side faces the display.

22. A method for manufacturing a glass substrate with a coloring layer, the glass substrate with a coloring layer including: a glass substrate having a main surface, and a coloring layer disposed in contact with the main surface, wherein the manufacturing method is as follows: Prepare a glass substrate having a main surface, prepare a transfer member having a transfer substrate and a coloring layer precursor film, laminate the transfer member on the glass substrate such that the main surface of the glass substrate is in contact with the coloring layer precursor film, and cure the coloring layer precursor film disposed in contact with the main surface of the glass substrate to form the coloring layer, wherein the coloring layer precursor film includes a colorant, a curable resin, and a non-curable resin.

23. The manufacturing method of the glass substrate with a coloring layer according to claim 22, wherein, The coloring layer precursor film further contains a curing agent.

24. The manufacturing method of the glass substrate with a coloring layer according to claim 23, wherein, The curing agent is a thermosetting agent, after laminating the transfer member on the glass substrate, heat the coloring layer precursor film at a temperature equal to or higher than the curing temperature of the thermosetting agent to cure the coloring layer precursor film, wherein the curing temperature of the thermosetting agent is 80 to 200°C.

25. The manufacturing method of the glass substrate with a coloring layer according to claim 23, wherein, The content of the curing agent is 0.5 to 30% by mass relative to the coloring layer precursor film.

26. The manufacturing method of the glass substrate with a coloring layer according to any one of claims 23 to 25, wherein, Set the prepared glass substrate and the transfer member in a chamber such that the main surface of the glass substrate faces the coloring layer precursor film, divide the chamber by the transfer member into a first space containing the glass substrate and a second space not containing the glass substrate, heat the transfer substrate to soften it, reduce the air pressure in the first space below the air pressure in the second space, thereby bringing the coloring layer precursor film into contact with the main surface of the glass substrate.

27. The manufacturing method of the glass substrate with a coloring layer according to any one of claims 23 to 25, wherein, Irradiate a part of the coloring layer disposed on the main surface of the glass substrate with laser light to remove the irradiated coloring layer.

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