Adhesive decorative sheet and exterior member

Abstract

To provide an adhesive decorative sheet capable of suppressing air pockets between an adherend and an adhesive layer.SOLUTION: An adhesive decorative sheet 10 used as an exterior member, comprises a release sheet 1, an adhesive layer 2, and a decorative sheet 3 in this order in a thickness direction. A surface of the release sheet side of the adhesive layer has a plurality of linear grooves that intersect in a grid pattern when viewed from the thickness direction, and has a plurality of adhesive areas enclosed by the linear grooves, where a diameter of the inscribed circle of the adhesive areas is 0.6 mm or less, the adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to an adhesive decorative sheet and an exterior member. [Background technology]

[0002] In the field of building materials for houses, stores, and the like, decorative sheets with designs applied using printing technology are now widely used not only for interior materials such as floors, ceilings, walls, and furniture, but also for exterior materials such as exterior walls.

[0003] In the manufacture of exterior components, an adhesive decorative sheet having a decorative sheet, an adhesive layer, and a release sheet may be used. Specifically, the release sheet is peeled off from the adhesive decorative sheet, the adhesive surface of the adhesive layer is placed against the adherend, and the two are brought into close contact with each other to manufacture the exterior component. In addition, since exterior components are exposed to harsher environments than interior components, the decorative sheet is more likely to deteriorate. Therefore, repairs may be performed by removing the deteriorated parts and attaching the decorative sheet.

[0004] When attaching such a decorative adhesive sheet to an adherend, it is necessary to adhere it so that no air remains between the adherend and the adhesive layer after the release sheet is peeled off. If air remains between the adherend and the adhesive layer, the appearance will deteriorate and the adhesive strength will decrease.

[0005] For this reason, a method for suppressing air accumulation between the adherend and the adhesive layer has been proposed. For example, Patent Document 1 discloses an adhesive-attached decorative sheet having a laminated structure of a synthetic resin decorative sheet body, an adhesive layer, and a release sheet, characterized in that the release sheet has linearly continuous convex stripes protruding from the adhesive layer bonding surface in a pattern in which a large number of roughly polygonal shapes are randomly arranged, and when the release sheet is peeled off, the back surface of the adhesive layer has air release grooves linearly continuous in the surface direction in a pattern randomly arranged corresponding to the convex stripes. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4156530 Summary of the Invention [Problem to be solved by the invention]

[0007] Adhesive decorative sheets used in the manufacture of exterior components are required to suppress air trapping more than ever before. For example, when a conventional adhesive decorative sheet with an air release groove formed on the adhesive surface of the adhesive layer is used to attach the decorative sheet to an adherend, air trapping appears to be eliminated when observed visually from the decorative sheet side. On the other hand, when the interface between the adherend and the adhesive layer is observed under a microscope, minute air traps may be seen. There is concern that such minute air traps may cause swelling, lifting, and peeling when used outdoors where there is a large temperature difference, or in repair and restoration work that is strongly affected by the base treatment and construction environment.

[0008] The present disclosure has been made in consideration of the above-mentioned circumstances, and has as its main object to provide an adhesive decorative sheet that is capable of suppressing air trapping between an adherend and an adhesive layer. [Means for solving the problem]

[0009] The present disclosure provides an adhesive decorative sheet for use in an exterior member, comprising a release sheet, an adhesive layer, and a decorative sheet, in that order in the thickness direction, wherein the surface of the adhesive layer facing the release sheet has a plurality of linear grooves that intersect in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, the diameter of the inscribed circle of the adhesive region being 0.6 mm or less, and the adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

[0010] The present disclosure provides an exterior component having an adherend, an adhesive layer, and a decorative sheet, in that order in the thickness direction, wherein the surface of the adhesive layer facing the adherend has a plurality of linear grooves that intersect in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, the diameter of the inscribed circle of the adhesive region is 0.6 mm or less, and the adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz. Effect of the Invention

[0011] The present disclosure has the effect of providing an adhesive decorative sheet that is capable of suppressing air trapping between the adherend and the adhesive layer. [Brief description of the drawings]

[0012] [Figure 1] 1 is a schematic cross-sectional view illustrating an example of an adhesive decorative sheet according to the present disclosure. [Diagram 2] 2 is a schematic plan view illustrating an example of an adhesive surface of an adhesive layer in the present disclosure. FIG. [Diagram 3] 1 is a schematic cross-sectional view illustrating an example of an adhesive decorative sheet according to the present disclosure. [Figure 4] 2 is a schematic cross-sectional view illustrating an example of an exterior member according to the present disclosure. FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The following describes the embodiments with reference to the drawings. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. In addition, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form in order to make the description clearer, but this is merely an example and should not be interpreted as being limiting.

[0014] In this specification, when describing a mode in which another component is disposed on a certain component, the term "above" or "below" includes both a case in which another component is disposed directly above or below a certain component so as to be in contact with the component, and a case in which another component is disposed above or below a certain component via another component, unless otherwise specified. In addition, in this specification, when describing a mode in which another component is disposed on the surface of a certain component, the term "on the surface" or "on the surface side" includes both a case in which another component is disposed directly above or below a certain component so as to be in contact with the component, and a case in which another component is disposed above or below a certain component via another component, unless otherwise specified.

[0015] The adhesive decorative sheet and exterior member according to the present disclosure will be described in detail below.

[0016] A. Adhesive decorative sheet The adhesive decorative sheet of the present disclosure is used for an exterior member. Fig. 1(a) is a schematic cross-sectional view illustrating an example of an adhesive decorative sheet of the present disclosure. Fig. 1(b) is a schematic plan view of a surface 2S (hereinafter also referred to as an adhesive surface) of an adhesive layer 2 on the release sheet 1 side of the adhesive decorative sheet 10 of Fig. 1(a). Fig. 1(c) is a schematic cross-sectional view illustrating a state after the release sheet 1 has been peeled off from the adhesive decorative sheet 10 of Fig. 1(a). The adhesive decorative sheet 10 shown in Fig. 1(a) is arranged such that a release sheet 1, an adhesive layer 2, and a decorative sheet 3 are arranged in a thickness direction D. T As shown in FIG. 1(b), the surface 2S of the adhesive layer 2 on the release sheet 1 side is in the thickness direction D T When viewed from the outside, it has a plurality of linear grooves H that intersect in a lattice pattern, and a plurality of adhesive regions X that are surrounded by the linear grooves H, and the diameter d of the inscribed circle of the adhesive region X is 0.6 mm or less. Furthermore, the adhesive layer 2 has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

[0017] According to the adhesive decorative sheet of the present disclosure, the diameter of the inscribed circle of the multiple adhesive regions X surrounded by the linear grooves H is within a predetermined range, so that minute air is unlikely to accumulate in the center of the adhesive region X (the region surrounded by the linear grooves H and in contact with the adherend), and the accumulated air is easily discharged to the outside through the linear grooves H. Furthermore, the inventors of the present application have found that by adjusting the storage modulus E' at low frequencies of the adhesive layer, it becomes easy to discharge air through the linear grooves H from the time the adhesive layer is attached to the adherend until it becomes compatible with the adherend (the adhesive layer follows the minute unevenness of the adherend). Specifically, since the storage modulus E' of the adhesive layer at a temperature of 25°C and a frequency of 0.05 Hz is within a predetermined range, even if some minute air gets mixed between the adhesive region X and the adherend when it is attached to the adherend, the accumulated air can be discharged through the linear grooves H in the process of fitting to the adherend after attachment. For example, residual air generated during pasting can be discharged to the outside within 24 hours after pasting. When using a temperature-dependent measurement mode of a dynamic viscoelasticity measuring device (DMA), the frequency may be set to 1.0 Hz. With the storage modulus E' at such a frequency, it is not possible to evaluate the ease of escape of minute air pockets that are too small to be seen with the naked eye. The inventors of the present application have focused on a new problem of suppressing minute air pockets that are too small to be seen with the naked eye, and as a result, have found that it is possible to evaluate the ease of escape of minute air pockets by focusing on the storage modulus on the lower frequency side than before, and have found that the above problem can be solved for the first time.

[0018] Hereinafter, each component of the adhesive decorative sheet according to the present disclosure will be described.

[0019] 1. Adhesive layer In the present disclosure, the adhesive layer is disposed between the release sheet and the decorative sheet. The surface of the adhesive layer facing the release sheet has a plurality of linear grooves intersecting in a lattice pattern, and a plurality of adhesive regions surrounded by the linear grooves.

[0020] In the present disclosure, the term "lattice-like" refers to a figure formed by the intersection of a plurality of parallel lines. For example, in FIG. 1(b), a linear groove group H1 extending in the D1 direction intersects with a linear groove group H2 extending in the D2 direction, and the interval between the linear groove groups H1 and H2 is the same. In addition, in FIG. 2(a), a linear groove group H3 extending in the D1 direction intersects with a linear groove group H4 extending in a direction inclined at +60° with respect to the D1 direction, and a linear groove group H5 extending in a direction inclined at -60° with respect to the D1 direction. In addition, the interval between the linear groove groups H3, H4, and H5 are the same. In FIG. 2(c), a linear groove group H1 extending in the D1 direction and a linear groove group H2 extending in the D2 direction intersect with each other, and the interval between the linear groove groups H1 is greater than the interval between the linear groove groups H2.

[0021] The surface (adhesive surface) of the adhesive layer facing the release sheet has a plurality of adhesive regions surrounded by linear grooves. The adhesive regions are regions that come into contact with the adherend when attached to the adherend, and are, for example, surfaces perpendicular to the thickness direction. Examples of the planar shape of the adhesive regions X include, but are not limited to, a square ( FIG. 1(b) ), an equilateral triangle ( FIG. 2(a) ), a rectangle ( FIG. 2(b) ), a parallelogram, and the like.

[0022] In the present disclosure, the diameter of the inscribed circle of the adhesive region X is 0.6 mm or less, and may be 0.5 mm or less. By having the diameter of the inscribed circle of the adhesive region X in the above range, air is less likely to accumulate in the center of the adhesive region X, and the accumulated air is easily discharged to the outside through the linear groove. On the other hand, the diameter of the inscribed circle of the adhesive region X may be 0.3 mm or more. If the diameter of the inscribed circle of the adhesive region X is too small, the adhesive strength decreases. Note that the inscribed circle of the adhesive region is a circle that is tangent to the four sides constituting the square when the adhesive region is a square, a circle that is tangent to the three sides constituting the equilateral triangle when the adhesive region is an equilateral triangle, and a circle that is tangent to the two long sides of the four sides when the adhesive region is a rectangle.

[0023] The diameter of the inscribed circle of the above-mentioned adhesive region X is determined by peeling the release sheet from the adhesive decorative sheet, observing the adhesive surface of the adhesive layer under an optical microscope at 50x magnification, and averaging the values ​​measured at three adhesive regions X.

[0024] The adhesive layer in the present disclosure has a storage modulus E' of 100,000 Pa or less, or may be 90,000 Pa or less, or may be 80,000 Pa or less, at a temperature of 25°C and a frequency of 0.05 Hz. By having the storage modulus E' in the above range, even if air gets mixed in between the adhesive region X and the adherend when the adhesive layer is attached to the adherend, if the storage modulus E' at a frequency of 0.05 Hz is low, the air trapped in the adhesive layer can be discharged through the linear groove H in the process of the adhesive layer conforming to the adherend after attachment (the adhesive layer conforms to the minute unevenness of the adherend). On the other hand, the storage modulus E' at a frequency of 0.05 Hz may be, for example, 50,000 Pa or more, or may be 60,000 Pa or more.

[0025] The storage modulus E' and loss modulus E'' described below of the adhesive layer are measured by measuring the storage modulus E' and loss modulus E'' of the adhesive at a frequency of 0.05 Hz and 25°C by the compression method using a frequency-dependent measurement mode of a dynamic viscoelasticity measuring device (DMA) on the following test piece. The following test piece can be produced by rolling the adhesive applied to a release paper into a cylindrical shape in one direction. (Test piece) Bulk adhesive samples with a maximum cross-sectional diameter of 15mm and a maximum length of 15mm

[0026] The storage modulus of the adhesive layer can be adjusted by the type of monomer of the adhesive resin constituting the adhesive layer, the molecular weight of the adhesive resin, the polymerization degree of the adhesive resin, etc. For example, in general, resins with a glass transition temperature of -30°C or less and a weight average molecular weight of 200,000 or more are used for acrylic adhesives, and the storage modulus E' tends to increase when the molecular weight is increased. The storage modulus E' tends to increase when the polymerization degree is increased, and the temperature dependence and frequency dependence tend to become stable.

[0027] The adhesive layer in the present disclosure may have a loss modulus E'' at a temperature of 25°C and a frequency of 0.05 Hz of 55,000 Pa or less, 50,000 Pa or less, or 40,000 Pa or less. On the other hand, the loss modulus E'' may be, for example, 20,000 Pa or more, or 30,000 Pa or more.

[0028] The adhesive layer preferably has a permanent adhesive strength to a SUS plate of 25 N / 25 mm or more, more preferably 30 N / 25 mm or more. Since the outdoor environment in which the exterior member is used is harsher than the indoor environment, if the adhesive strength is low, lifting, peeling, etc. may occur during long-term use. By having a permanent adhesive strength to a SUS plate within the above range, it is possible to use the product for a long period of time while suppressing lifting and peeling, even in a usage environment in which the product is constantly exposed to the outdoor environment.

[0029] The permanent adhesive strength of the adhesive layer to the SUS plate is a value measured by the following method in accordance with JIS Z 0237:2009 (Test method for adhesive tapes and adhesive sheets), Method 1 (temperature 23°C, humidity 50%, test method in which the tape and sheet are peeled off at 180° to a stainless steel test plate). The adhesive decorative sheet is cut to a width of 25 mm, the release sheet is peeled off to prepare a sample piece, and the sample piece is pressed against the SUS plate by a 2 kg roller moving back and forth once, and left to stand for 24 hours in an environment of 23°C ± 5°C, and the adhesive strength (permanent adhesive strength) is measured by peeling off the adhesive layer and the SUS plate in a 180° direction at a speed of 300 mm / min using a tensile tester. The SUS plate used is a SUS304, surface finish BA, SUS plate with a thickness of 1.5 mm, width of 100 mm, and length of 150 mm. The permanent adhesive strength is, for example, 50 N / 25 mm or less, and may be 40 N / 25 mm or less.

[0030] The permanent adhesive strength of the adhesive layer can be adjusted by the type of monomer constituting the adhesive resin, the molecular weight of the adhesive resin, the degree of polymerization of the adhesive resin, etc. For example, by selecting a resin having a structure that can maintain a low glass transition temperature while maintaining a high molecular weight, and further optimizing the molecular weight and degree of polymerization, it is possible to set the permanent adhesive strength to a peak value.

[0031] The thickness T2 of the adhesive layer is not particularly limited, but may be, for example, 20 μm or more, and may be, for example, 30 μm or more. On the other hand, the thickness T2 of the adhesive layer is, for example, 80 μm or less, and may be, for example, 70 μm or less. As shown in FIG. 1(a), the thickness T2 of the adhesive layer refers to the distance from the surface of the adhesive layer 2 facing the decorative sheet 3 to the adhesive region X on the surface 2S (adhesive surface) of the adhesive layer 2 facing the release sheet 1.

[0032] Groove depth D H may be, for example, 5 μm or more, or 10 μm or more. H is, for example, 30 μm or less, and may be 20 μm or less.

[0033] Depth D of groove H relative to thickness T2 of adhesive layer H Percentage of (D H / T2) is, for example, 0.2 or more, and may be 0.4 or more. H / T2) is, for example, 0.8 or less, and may be 0.6 or less.

[0034] Groove width W H is, for example, 20 μm or more, and may be 40 μm or more. On the other hand, the width W H is, for example, 80 μm or less, and may be 60 μm or less.

[0035] The adhesive layer preferably contains one or more resins having adhesiveness (pressure-sensitive adhesiveness). The adhesive layer preferably contains a crosslinking agent (curing agent) as necessary. In this case, the adhesive layer may be a cured product of a resin composition. The cured product of the resin composition may be a one-component cured product or a two-component cured product. Examples of resins having adhesiveness (pressure-sensitive adhesiveness) include acrylic resins, urethane resins, polyester resins, silicone resins, and vinyl resins. Among these, acrylic resins, urethane resins, and silicone resins are preferred.

[0036] The acrylic resin may be present as a crosslinked body in which acrylic resins are crosslinked by a crosslinking agent, or may contain a simple acrylic resin together with the crosslinked body, or may be present as a simple acrylic resin. Examples of the curing agent include an isocyanate curing agent and an amine curing agent.

[0037] 2.Release sheet The adhesive decorative sheet of the present disclosure has a release sheet on the surface of the adhesive layer opposite to the decorative sheet. As shown in Fig. 1(c), the surface of the release sheet 1 on the adhesive layer 2 side preferably has a plurality of linear projections P intersecting in a lattice pattern corresponding to the linear grooves H of the adhesive layer 2, and a bottom region Y overlapping the above-mentioned adhesive region X. In other words, the release sheet 1 also functions as a shaping member for forming the linear grooves H on the adhesive surface 2S of the adhesive layer 2.

[0038] The release sheet preferably includes a substrate such as paper or a resin film. Examples of the paper include fine paper and craft paper. Examples of the resin film include polyethylene, polyester, polypropylene, and the like. The release sheet may have a substrate and a resin layer disposed on at least one surface of the substrate. The resin layer is preferably disposed on the adhesive layer side of the substrate. As the resin contained in the resin layer, for example, a thermoplastic resin such as a polyolefin resin such as polypropylene or polyethylene can be used. In addition, a thermosetting or ionizing radiation curable resin (including an ultraviolet curable resin, etc.) such as an alkyd resin, a melamine resin such as a methylol melamine resin or a methoxymethylol melamine resin, a silicone resin, or an acrylic resin can also be used. These resins may be used alone or in combination of two or more. The thickness of the resin layer is preferably 10 μm or more, more preferably 20 μm or more, from the viewpoint of durability. In addition, the thickness of the resin layer is preferably 100 μm or less, more preferably 50 μm or less, from the viewpoint of material cost.

[0039] The thickness T1 of the release sheet is, for example, 100 μm or more, and may be 120 μm or more. On the other hand, it may be, for example, 200 μm or less, and may be 180 μm or less. The thickness T1 of the release sheet refers to the distance from the surface of the release sheet 1 opposite the adhesive layer 2 to the bottom region Y on the adhesive layer side, as shown in FIG. 1(c). The release surface of the release sheet (the surface of the release sheet on the adhesive layer side) may be subjected to a release treatment using a silicone-based release agent or the like.

[0040] 3. Decorative sheets The adhesive decorative sheet in the present disclosure has a decorative sheet on the surface of the adhesive layer opposite to the release sheet. Figures 3(a) and 3(b) are schematic cross-sectional views illustrating the adhesive decorative sheet in the present disclosure. As shown in Figure 3(a), the decorative sheet 3 preferably has a base layer 31, a design layer 32, and a surface protective layer 33 in this order from the adhesive layer 2 side. As shown in Figure 3(b), the decorative sheet 3 preferably has a base layer 31, a design layer 32, a transparent resin layer 34, and a surface protective layer 33 in this order from the adhesive layer 2 side. Although not particularly shown, the decorative sheet may be a transfer type decorative sheet.

[0041] (a) Base material layer The decorative sheet has, for example, a base material layer. By having the base material layer, the decorative sheet has improved performance such as mechanical strength, suitability for post-processing, and design, and therefore the usability as a sheet is improved.

[0042] The substrate layer is not particularly limited, and may be, for example, a resin substrate. The type of substrate layer is appropriately selected depending on the application of the decorative sheet.

[0043] Examples of the resin used in the resin substrate include various synthetic resins and various natural resins. Examples of the synthetic resin include thermoplastic resins and curable resins. Considering the manufacturing suitability, handling suitability, and post-processing suitability of the decorative sheet, thermoplastic resins are preferred.

[0044] Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABS resins); polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins.

[0045] Natural resins include, for example, natural rubber, rosin, and amber.

[0046] Examples of the curable resin include ionizing radiation curable resins and thermosetting resins.

[0047] The substrate layer may contain additives as necessary. In the case of a resin substrate, examples of additives include inorganic fillers, flame retardants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, light stabilizers, and colorants. Various additives can be used alone or in combination. The content of the additives is not particularly limited as long as it does not impair the surface properties and processing properties, and can be appropriately set according to the required properties.

[0048] The substrate layer may be a single layer or a laminate of two or more layers. In the case of a laminate, the substrate layer may have two or more layers of the same type of substrate, or may have two or more layers of different types of substrate.

[0049] In the present disclosure, the base material layer can also serve as a design layer described below.

[0050] The substrate layer may be transparent or opaque. When the substrate layer is opaque, the substrate layer can serve as a design layer.

[0051] The substrate layer may be colored. When the substrate layer is colored, the substrate layer may be a design layer. The coloring is not particularly limited, and may be transparent or opaque (hiding), and may be selected arbitrarily.

[0052] When the base layer is colored, it may contain a colorant. Examples of colorants include inorganic pigments such as white pigments such as titanium white, iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo-based black pigment, and perylene-based black pigment; metal pigments made of scaly foil such as aluminum and brass; and pearlescent (pearl) pigments made of scaly foil such as titanium dioxide-coated mica and basic lead carbonate. For example, when the surface hue of the adherend on which the decorative sheet is laminated varies, in order to conceal the surface hue and improve the stability of the color tone of the decorative layer, an inorganic pigment such as a white pigment may be used.

[0053] The substrate layer may be surface-treated to enhance adhesion with layers in contact with the substrate layer, such as adhesion with a design layer and adhesion with an adhesive layer. Examples of the surface treatment include physical surface treatments such as oxidation and roughening, and chemical surface treatments. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of the roughening method include sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of substrate layer, but in consideration of the effect and operability of the surface treatment, corona discharge treatment is generally preferred.

[0054] When the substrate layer is a laminate, an adhesive layer or a primer layer may be disposed between adjacent layers in order to improve the adhesion between the layers.

[0055] The thickness of the substrate layer is not particularly limited and is appropriately selected according to the material of the substrate layer. In the case of a substrate layer containing a resin, the thickness of the substrate layer is, for example, 10 μm or more and 300 μm or less, may be 20 μm or more and 200 μm or less, or may be 40 μm or more and 100 μm or less.

[0056] (b) Design layer The decorative sheet in the present disclosure may have a design layer on one side of the substrate layer. In addition, when the decorative sheet has a transparent resin layer described below, the design layer may be between the substrate layer and the transparent resin layer. By providing the design layer, the design of the decorative sheet is improved. In addition, when the decorative sheet is viewed in a plan view along the thickness direction, the design layer may be disposed on the entire surface of the decorative sheet, or may be disposed on a part of the decorative sheet.

[0057] Examples of the design layer include a solid layer (a layer where ink is applied solidly) and a picture layer (a layer where ink is printed). Examples of the picture (pattern) in the picture layer include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-stained patterns, geometric figures, letters, symbols, abstract patterns, and floral patterns.

[0058] The design layer usually contains a colorant and a binder resin. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black, metal pigments such as aluminum and brass, and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0059] Examples of binder resins include urethane-based resins, acrylic polyol-based resins, acrylic-based resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins.

[0060] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, curing agents, plasticizers, catalysts, etc., as necessary. The thickness of the design layer is, for example, 0.5 μm or more and 20 μm or less, or may be 1 μm or more and 10 μm or less, or may be 2 μm or more and 5 μm or less.

[0061] The design layer can be formed, for example, by coating an ink containing a colorant, a binder resin and a solvent, followed by drying. As the coating method, gravure printing is preferred.

[0062] (c) Surface protective layer The decorative sheet in the present disclosure may have a surface protective layer on the side of the design layer opposite to the substrate layer. The decorative sheet may have the surface protective layer as the outermost layer. By having the surface protective layer, durability (e.g., scratch resistance, stain resistance, weather resistance) can be imparted. On the other hand, the decorative sheet may not have a surface protective layer.

[0063] The surface protective layer contains a resin component. The resin component mainly functions as a binder resin. The surface protective layer preferably contains at least one of a resin composition and a cured product thereof as the resin component. The cured product may be a cured product obtained by curing a curable resin composition with ionizing radiation, or a cured product obtained by curing a curable resin composition with heat.

[0064] Examples of the curable resin composition include an ionizing radiation curable resin composition and a heat curable resin composition. From the viewpoint of scratch resistance and production efficiency, an ionizing radiation curable resin composition is preferred. That is, the surface protective layer preferably contains a cured product of an ionizing radiation curable resin composition as a resin component.

[0065] Specific examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition. Among them, an electron beam curable resin composition has advantages such as less odor and less coloring because it does not require a polymerization initiator.

[0066] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and hardens by irradiation with ionizing radiation, and specific examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. Other specific examples of the ionizing radiation curable functional group include an epoxy group and an oxetanyl group. In this specification, a (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In this specification, a (meth)acrylate refers to an acrylate or a methacrylate. In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Specific examples of ionizing radiation include ultraviolet rays (UV) and electron beams (EB). Other specific examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0067] The ionizing radiation curable resin composition may contain only one type of ionizing radiation curable compound, or may contain two or more types. The type of ionizing radiation curable compound is not particularly limited, and a known polymerizable monomer or a known polymerizable oligomer (polymerizable prepolymer) can be used.

[0068] The ionizing radiation curable compound preferably contains a compound having two or more ethylenically unsaturated bond groups. In particular, the ionizing radiation curable compound preferably contains a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. The polyfunctional (meth)acrylate compound may be a monomer or an oligomer.

[0069] The polyfunctional (meth)acrylate compound may be a bifunctional (meth)acrylate monomer, or may be a trifunctional or higher functional (meth)acrylate monomer. Examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or higher functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid modified tri(meth)acrylate.

[0070] Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

[0071] Urethane (meth)acrylates are obtained, for example, by the reaction of polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates. Epoxy (meth)acrylates are obtained, for example, by the reaction of epoxy resins with (meth)acrylic acid. At least one of polybasic acids and phenols may be further used in this reaction. The epoxy resins may be bifunctional or trifunctional or higher. Examples of epoxy resins include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0072] The ionizing radiation curable compound may contain silicone (meth)acrylate. The use of silicone (meth)acrylate improves the contamination resistance of the surface protective layer. Examples of silicone (meth)acrylate include silicone oils containing polysiloxane. The silicone (meth)acrylate may be modified silicone oils in which a (meth)acrylic group is introduced at the end of polysiloxane. The content of silicone (meth)acrylate may be, for example, 1 part by mass or more and 7 parts by mass or less, or 2 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the ionizing radiation curable compound (excluding silicone (meth)acrylate).

[0073] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, and thioxanthone. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0074] On the other hand, a thermosetting resin composition is a composition that contains at least a thermosetting resin. This resin composition is cured by heating. Examples of the thermosetting resin include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. The thermosetting resin composition may contain additives such as a curing agent and a curing catalyst, if necessary.

[0075] The surface protective layer may further contain at least one of an antioxidant, a light stabilizer, an ultraviolet absorber, an antibacterial agent, an antiviral agent, and an antiallergen agent as an additive. Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Among them, the phosphorus-based antioxidant can effectively suppress discoloration of the surface protective layer due to light. Examples of the light stabilizer include a hindered amine-based compound. The hindered amine-based compound usually has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule. Examples of the hindered amine-based compound include an NH-type hindered amine-based compound, an NR-type hindered amine-based compound, and an NOR-type hindered amine-based compound. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber.

[0076] The thickness of the surface protective layer is not particularly limited, but is, for example, 1 μm or more and 50 μm or less. If the surface protective layer is thin, it may not be possible to provide sufficient durability, and if the surface protective layer is thick, the visibility of the design layer may be reduced. The thickness of the surface protective layer may be 3 μm or more and 40 μm or less, or 5 μm or more and 35 μm or less.

[0077] The method for forming the surface protective layer may be, for example, a method in which a mixture containing a resin component and an additive is applied to the surface of the resin layer, dried, and cured. Alternatively, the mixture may be applied to the surface of a substrate having releasability, dried, and cured to form a surface protective layer, and the surface protective layer may be transferred onto the resin layer.

[0078] The decorative sheet may have an embossed pattern on the outermost surface on the surface protective layer side with respect to the base layer. In particular, it is preferable that the embossed pattern is arranged on the surface of the surface protective layer opposite the base layer. Examples of the embossed pattern include wood grain duct grooves, stone plate surface irregularities, cloth surface texture, matte finish, sand grain, hairline, and stripe grooves. When the decorative sheet has a transparent resin layer described later, it is preferable that the embossed pattern is arranged on the surface of the transparent resin layer on the surface protective layer side.

[0079] The embossed pattern can be formed, for example, by heating the decorative sheet and pressing an embossing plate against it. The heating temperature of the decorative sheet is, for example, 80° C. or more and 260° C. or less, or may be 85° C. or more and 200° C. or less, or may be 100° C. or more and 180° C. or less.

[0080] (d) Other layers As shown in Fig. 3(a), the decorative sheet of the present disclosure preferably has at least a base layer 31, a design layer 32, and a surface protective layer 33. The decorative sheet of the present disclosure may have other layers in addition to these layers. Examples of the other layers include a transparent resin layer, an adhesive layer, a separator layer, and a primer layer.

[0081] (d-1) Transparent resin layer The decorative sheet of the present disclosure can increase the strength of the decorative sheet by having a transparent resin layer. The transparent resin layer may be transparent enough to allow the design layer to be visually recognized, and may be colorless and transparent, colored, transparent, or translucent.

[0082] Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, and vinyl chloride resins. In consideration of processability, polyolefin resins and vinyl chloride resins are preferred. The resins may be used alone or in combination.

[0083] The transparent resin layer contains additives as necessary. Examples of the additives include weather resistance agents such as ultraviolet absorbers and light stabilizers. The weather resistance agent may be appropriately selected from those described above.

[0084] Taking into consideration processability, the thickness of the transparent resin layer is, for example, 20 μm or more and 150 μm or less, or may be 40 μm or more and 120 μm or less, or may be 60 μm or more and 100 μm or less.

[0085] Examples of methods for forming the transparent resin layer include a method of applying a resin composition and a method of laminating a resin film by dry lamination.

[0086] (d-2) Interlayer adhesive layer The decorative sheet may have an interlayer adhesive layer disposed between layers of the decorative sheet. The position of the interlayer adhesive layer is not particularly limited. The interlayer adhesive layer may be disposed between the base layer and the design layer. In addition, when the decorative sheet has a transparent resin layer, the interlayer adhesive layer may be disposed between the design layer and the transparent resin layer.

[0087] The interlayer adhesive layer contains a resin. Examples of the resin include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-(meth)acrylic acid copolymer (EMAA), acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, cellulose derivative, and rubber resin.

[0088] The thickness of the interlayer adhesive layer is, for example, 0.1 μm or more and 10 μm or less. In addition, as a method for forming the interlayer adhesive layer, for example, a method of coating a resin composition containing a resin and a solvent and then drying it can be mentioned.

[0089] (d-3) Primer layer The decorative sheet of the present disclosure may have a primer layer in order to improve interlayer adhesion between the multiple layers that make up the decorative sheet.

[0090] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.

[0091] Examples of binder resins include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin. These can be used alone or in combination of multiple types.

[0092] The binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the above-mentioned resin to crosslink and harden it. For example, a resin obtained by crosslinking and hardening a polyol-based resin such as an acrylic polyol resin with an isocyanate-based curing agent is preferred, and a resin obtained by crosslinking and hardening an acrylic polyol resin with an isocyanate-based curing agent is more preferred.

[0093] The thickness of the primer layer is, for example, 0.5 μm or more, may be 1 μm or more, or may be 2 μm or more, and the thickness of the primer layer is, for example, 10 μm or less, may be 8 μm or less, or may be 6 μm or less.

[0094] The primer layer can be formed by applying a resin composition, and then drying and curing the composition as necessary.

[0095] 4. Manufacturing method of adhesive decorative sheet The method for producing an adhesive decorative sheet in the present disclosure is not particularly limited, but may, for example, include a step of embossing the release sheet to form linear protrusions that intersect in a grid pattern on the first surface of the release sheet (embossing step), a step of forming an adhesive layer on the first surface of the release sheet to produce a laminated member (adhesive layer formation step), and a step of adhering the adhesive layer side of the laminated member to the back surface of the decorative sheet (adhesion step).

[0096] (1) Embossing process In this process, the release sheet is embossed to form, for example, linear projections P intersecting in a grid pattern and a bottom region Y on the first surface of the release sheet. Prior to embossing, at least the first surface of the release sheet may be subjected to a release treatment using a silicone-based release agent or the like. The conditions for embossing, such as pressure, temperature, speed, and tension, are appropriately set according to the thickness of the release sheet and the desired embossing depth.

[0097] (2) Adhesive layer formation process In this step, a laminated member is produced by forming an adhesive layer on the first surface of the release sheet. The adhesive layer may be formed by melting and applying an adhesive, or may be provided by laminating an adhesive film and then melting it.

[0098] (3) Adhesion process In this step, the adhesive layer side of the laminated member is brought into close contact with the back surface of the decorative sheet. The back surface of the decorative sheet refers to the surface of the decorative sheet on the base layer side with respect to the design layer. This results in an adhesive decorative sheet.

[0099] 5.Applications The adhesive decorative sheet in the present disclosure is used for exterior members. Specifically, it can be used for the manufacture, repair, and regeneration of exterior members. Specifically, the adhesive decorative sheet in the present disclosure can be used when manufacturing a new exterior member by, for example, attaching it to the entire surface of one surface of an adherend after peeling off the release sheet. In addition, in an exterior member that has been installed for many years or has deteriorated due to environmental conditions, for example, the decorative sheet can be partially removed from one surface of the exterior member and attached to this removed portion to repair the deteriorated surface. In addition, in an exterior member that has deteriorated, for example, the decorative sheet can be removed from the entire surface of the exterior member and attached to the removed area to regenerate the exterior member. The adhesive decorative sheet in the present disclosure is preferably used for repairing or regenerating an exterior member. In repair and regeneration installation, which are strongly affected by the base treatment and installation environment, minute air pockets cause swelling, lifting, and peeling, so the effect of the present disclosure is significantly obtained.

[0100] B. Exterior materials 4 is a schematic cross-sectional view illustrating an example of an exterior member according to the present disclosure. The exterior member 100 according to the present disclosure is configured by arranging an adherend 40, an adhesive layer 2, and a decorative sheet 3 in a thickness direction D T The surface 2S of the adhesive layer 2 on the adherend 40 side is in the thickness direction D T When viewed from the outside, it has a plurality of linear grooves H that intersect in a lattice pattern and a plurality of adhesive regions X surrounded by the linear grooves H, the diameter of the inscribed circle of the adhesive region X is 0.6 mm or less, and the adhesive layer 2 has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

[0101] According to the exterior member of the present disclosure, the diameter of the inscribed circle of the adhesive region X surrounded by the linear groove H on the surface of the adhesive layer facing the adherend is within a predetermined range, so that air is less likely to accumulate in the center of the adhesive region X (the region surrounded by the linear groove H and in contact with the adherend), and the accumulated air is easily discharged to the outside through the linear groove. Furthermore, the inventors of the present application have found that by adjusting the storage modulus E' at low frequencies of the adhesive layer, it becomes easy to discharge air through the linear groove H from the time when the adhesive layer is attached to the adherend until it becomes compatible with the adherend (the adhesive layer follows the minute unevenness of the adherend). Specifically, since the storage modulus E' of the adhesive layer at a temperature of 25°C and a frequency of 0.05 Hz is within a predetermined range, even if some air gets mixed between the adhesive region X and the adherend when the adhesive layer is attached to the adherend, the accumulated air can be discharged through the linear groove H during the process of fitting to the adherend after attachment. For example, residual air generated during application can be expelled to the outside within 24 hours after application. Therefore, the exterior member according to the present disclosure is one in which air accumulation between the adherend and the adhesive layer is suppressed.

[0102] 1.Adherend Examples of the adherend include wood members, resin members, metal members, and ceramic members.

[0103] The adherend may be a wooden member. Examples of the wooden member include wood fiberboards. Examples of the wood fiberboard include wood veneer, wood plywood, laminated lumber, particle board, and MDF (medium density fiberboard). Examples of the material of the wooden member include wood such as cedar, cypress, pine, and lauan.

[0104] The adherend may be a metal member. Examples of metals used for the metal member include iron, aluminum, copper, and alloys containing one or more of these metals.

[0105] The adherend may be a resin member. Examples of resins used in the resin member include vinyl chloride resins, (meth)acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenol resins, cellulose resins, rubber, polycarbonate resins, and melamine resins. The resin member may contain fibers such as carbon fibers, glass fibers, aramid fibers, Zylon fibers, boron fibers, and polyethylene fibers. The strength of the resin member can be improved by containing fibers.

[0106] The adherend may be a ceramic member. The material of the ceramic member may be a ceramic such as glass or porcelain, a non-cement ceramic material such as gypsum, or a non-ceramic ceramic material such as ALC (aerated lightweight concrete).

[0107] The shape of the adherend is not particularly limited, and may be, for example, a plate, a sheet, or a three-dimensional shape. The adherend may have a flat surface, a curved surface, or both a flat surface and a curved surface. The adherend may have at least one of a convex portion, a concave portion, a convex streak portion, a concave streak portion, and a through portion.

[0108] 2. Adhesive layer The adhesive layer in the present disclosure is the same as that described above in "A. Adhesive decorative sheet," and therefore will not be described here.

[0109] 3. Decorative sheets The decorative sheet in this disclosure is similar to that described above in "A. Adhesive decorative sheet," and so a description thereof will be omitted here.

[0110] 4. Exterior materials The exterior member in the present disclosure can be manufactured by peeling off the release sheet from the above-mentioned "A. Adhesive decorative sheet", placing the surface of the adhesive layer (adhesive surface) against the adherend, and adhering them together. For example, when the above-mentioned adhesive decorative sheet is used for manufacturing or regenerating an exterior member, the exterior member may have an adhesive layer and a decorative sheet disposed on the entire surface of one surface of the adherend. When the above-mentioned adhesive decorative sheet is used for repairing an exterior member, the adhesive layer and the decorative sheet may be disposed on a portion of one surface of the adherend. In this case, the exterior member has a decorative sheet X having a damaged portion and an adhesive decorative sheet disposed so as to cover the damaged portion. Any decorative sheet can be used as the decorative sheet X.

[0111] The exterior member in the present disclosure is, for example, a building material (an exterior member of an architectural structure). The building material is used, for example, in houses, offices, stores, hospitals, clinics, general roads and highways, agricultural houses, and the like. Examples of uses of the exterior member include exterior walls, roofs, eaves ceilings, door pockets, window frames, doors, door frames, handrails, fences, and clothes drying racks. Specific uses of the exterior member include soundproof walls or windbreak walls on general roads and highways, balcony partitions, fences, roof members for terraces or carports, transparent members constituting agricultural houses, and the like.

[0112] In addition, the exterior member in the present disclosure is used as, for example, exterior members of vehicles, ships and aircraft, exterior members of industrial machines, and exterior members of various lenses, in addition to building materials (exterior members of architectural structures). Exterior members of vehicles include, for example, window materials such as side windows, rear windows, roof windows, front windows and quarter windows; headlight covers, turn signal lamp lenses, reflectors; and pillars. Exterior members of vehicles include, for example, automobiles, railroad cars, construction machines, and light vehicles such as golf carts. Exterior materials of industrial machines include, for example, window materials for visibility in machine tools. Exterior lenses include, for example, traffic light lenses.

[0113] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0114] [Example 1] (Making decorative sheets) A design layer was formed on one side of a substrate layer (a 60 μm thick colored polypropylene resin sheet) that had been subjected to corona discharge treatment on both sides, using a printing ink made of a two-liquid curing acrylic-urethane resin. Next, an interlayer adhesive layer made of a urethane resin adhesive was formed on the design layer. Next, a composition A containing 0.12 parts by mass of a hydroxyphenyltriazine ultraviolet absorber (product name: TINUVIN460, manufactured by BASF) per 100 parts by mass of polypropylene resin was hot-melt extruded on the interlayer adhesive layer using a T-die extruder to form a transparent resin layer with a thickness of 80 μm.

[0115] Next, the surface of the transparent resin layer was subjected to a corona discharge treatment, and then the following composition B was applied onto the transparent resin layer and dried to form a primer layer having a thickness of 4 μm. <Composition B> A composition obtained by mixing a composition consisting of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol with hexamethylene diisocyanate in a mass ratio of 100:5.

[0116] Next, composition C containing 2 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber (product name: TINUVIN460, manufactured by BASF) and 3 parts by mass of a hindered amine light stabilizer (product name: TINUVIN123, manufactured by BASF) per 100 parts by mass of an ionizing radiation curable resin composition consisting of a trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000 was applied onto the primer layer, and the ionizing radiation curable resin composition was cured by irradiating with an electron beam to form a surface protective layer having a thickness of 5 μm. This resulted in a decorative sheet having a substrate layer, a design layer, an adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer in this order.

[0117] (Manufacture of adhesive decorative sheets) The first surface of the release sheet (release paper with a release treatment applied to the first surface) was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer with a thickness T of 235 μm. The adhesive used was adhesive A (two-component curing acrylic adhesive, Nikkei Shinka, NT-138). Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the adhesive decorative sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was a square, and the diameter of the inscribed circle of the adhesive area was 0.5 mm.

[0118] [Example 2] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. The adhesive used was adhesive B (a two-component curing acrylic adhesive). Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 0.5 mm.

[0119] [Example 3] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. Adhesive D (two-component curing acrylic adhesive) was used as the adhesive. Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 0.5 mm.

[0120] [Comparative Example 1] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. The adhesive used was adhesive C (a two-component curing acrylic adhesive). Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 0.5 mm.

[0121] [Comparative Example 2] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. Adhesive B was used as the adhesive. Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 1.3 mm.

[0122] [Comparative Example 3] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. Adhesive C was used as the adhesive. Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 1.3 mm.

[0123] [Comparative Example 4] (Manufacture of adhesive decorative sheets) The first surface of the release sheet was embossed to form linear protrusions intersecting in a lattice pattern. Next, an adhesive was applied to the first surface of the release sheet to obtain an adhesive layer having a thickness of 35 μm. Adhesive D was used as the adhesive. Next, the surface of the adhesive layer was bonded to the surface of the decorative sheet facing the base layer. This resulted in an adhesive decorative sheet. The surface of the adhesive layer facing the release sheet had linear grooves (groove depth 15 μm, width 45 μm) intersecting in a lattice pattern, the adhesive area surrounded by the linear grooves was square, and the diameter of the inscribed circle of the adhesive area was 1.3 mm.

[0124] [Storage modulus E', loss modulus E'' and loss tangent] The storage modulus E′, loss modulus E″ and loss tangent tan δ at 25° C. / 0.05 Hz were determined by the method described above using the frequency-dependent measurement mode of a dynamic viscoelasticity measuring device (RSA3 (manufactured by TA Instrument)).

[0125] [Permanent adhesive strength] The permanent adhesive strength (peel strength, 24-hour value) of the adhesive layer to the SUS plate was measured by the method described above.

[0126] [Air pocket] The release sheet was peeled off from the adhesive decorative sheet obtained above, and the adhesive surface of the adhesive layer was placed opposite an acrylic plate with a thickness of 2 mm and attached using a squeegee. The state of air pockets on the adhesive surface immediately after attachment and 24 hours after attachment was observed under a microscope from the back side of the acrylic plate, and evaluated according to the following criteria. Evaluation criteria A: There was absolutely no air pocket. B: Air pockets were observed in an area ratio of less than 50%. C: Air pockets were observed in an area ratio of 50% or more.

[0127] [Lifting / peeling] The release sheet was peeled off from the adhesive decorative tape obtained above, and the adhesive layer side was placed opposite the corner of an exterior beam manufactured by LIXIL Corporation and attached to the tape. The edge of the sheet was then exposed to an outdoor environment for one year, after which the state of lifting and peeling at the edge of the sheet was visually checked. Evaluation criteria A: No lifting or peeling was observed at the edge of the sheet. B: Some lifting or peeling was observed at the edge of the sheet.

[0128] [Table 1]

[0129] As shown in Table 1, in Examples 1 to 3 in which the size of the adhesive region was within a predetermined range and the storage modulus E' of the adhesive layer at a temperature of 25°C and a frequency of 0.05 Hz was equal to or less than a predetermined value, air retention was suppressed 24 hours after application compared to the comparative example. It was also confirmed that Examples 1 and 2 were able to suppress lifting and peeling even in outdoor environments compared to Example 3.

[0130] Thus, in the present disclosure, for example, the following inventions are provided:

[0131] [1] An adhesive decorative sheet for use in exterior components, The adhesive sheet has a release sheet, an adhesive layer, and a decorative sheet in this order in the thickness direction, the surface of the adhesive layer facing the release sheet has a plurality of linear grooves intersecting in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, and the diameter of the inscribed circle of the adhesive region is 0.6 mm or less; The adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

[0132] [2] The adhesive decorative sheet according to [1], wherein the adhesive layer has a permanent adhesive strength to a SUS plate of 25 N / 25 mm or more.

[0133] [3] The adhesive decorative sheet according to [1] or [2], wherein the diameter of the inscribed circle of the adhesive region is 0.3 mm or more.

[0134] [4] An adhesive decorative sheet according to any one of [1] to [3], wherein the adhesive region has a square shape in a plan view.

[0135] [5] The adhesive decorative sheet according to any one of [1] to [4], wherein the decorative sheet has, from the adhesive layer side, a base layer, a design layer, and a surface protective layer in this order.

[0136] [6] The adhesive decorative sheet according to [5], wherein the decorative sheet has a transparent resin layer between the design layer and the surface protective layer.

[0137] [7] An adhesive decorative sheet according to any one of [1] to [6], wherein the surface of the release sheet facing the adhesive layer has a plurality of linear protrusions that intersect in a grid pattern and correspond to the linear grooves of the adhesive layer.

[0138] [8] An exterior member having an adherend, an adhesive layer, and a decorative sheet in this order in a thickness direction, The surface of the adhesive layer facing the adherend has a plurality of linear grooves intersecting in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, and the diameter of the inscribed circle of the adhesive region is 0.6 mm or less; The pressure-sensitive adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz. [Explanation of symbols]

[0139] 1...Release sheet 2…adhesive layer 3. Decorative sheet 10...Adhesive decorative sheet 40…Adherent 100…Exterior material

Claims

1. An adhesive decorative sheet for use in exterior components, The adhesive sheet has a release sheet, an adhesive layer, and a decorative sheet in this order in the thickness direction, the surface of the adhesive layer facing the release sheet has a plurality of linear grooves intersecting in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, and the diameter of an inscribed circle of the adhesive region is 0.6 mm or less; The adhesive decorative sheet, wherein the adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

2. 2. The adhesive decorative sheet according to claim 1, wherein the adhesive layer has a permanent adhesive strength to a stainless steel plate of 25 N / 25 mm or more.

3. 2. The adhesive decorative sheet according to claim 1, wherein the diameter of the inscribed circle of the adhesive region is 0.3 mm or more.

4. The adhesive decorative sheet according to claim 1 , wherein the adhesive area has a square shape in a plan view.

5. The adhesive decorative sheet according to claim 1 , wherein the decorative sheet has, from the adhesive layer side, a base layer, a design layer, and a surface protective layer in this order.

6. The adhesive decorative sheet according to claim 5 , wherein the decorative sheet has a transparent resin layer between the design layer and the surface protective layer.

7. The adhesive decorative sheet according to claim 1 , wherein the surface of the release sheet facing the adhesive layer has a plurality of linear projections that intersect in a lattice pattern and correspond to the linear grooves of the adhesive layer.

8. An exterior member having an adherend, an adhesive layer, and a decorative sheet in this order in a thickness direction, the surface of the adhesive layer facing the adherend has a plurality of linear grooves intersecting in a lattice pattern when viewed from the thickness direction, and has a plurality of adhesive regions surrounded by the linear grooves, and the diameter of an inscribed circle of the adhesive region is 0.6 mm or less; The adhesive layer has a storage modulus E' of 100,000 Pa or less at a temperature of 25°C and a frequency of 0.05 Hz.

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