Laminate

Abstract

To provide a laminate exhibiting excellent anti-fouling property due to its surface shape having a wrinkle structure.SOLUTION: A laminate has a surface shape having a wrinkle structure and exhibiting a contact angle to water measured in accordance with JIS R3257:1999 regulation of 90.0 degrees or over.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a laminate. [Background technology]

[0002] So-called decorative materials and decorative sheets have traditionally been used as articles for decorating and protecting the surfaces of, for example, interior building components such as walls, ceilings, and floors; exterior components such as exterior walls, eaves ceilings, roofs, fences, and fences; fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets and the like for home appliances and office automation equipment; and interior or exterior vehicle components. Such decorative materials and decorative sheets have, for example, a surface layer with desired functions, and various properties are required, including surface properties such as stain resistance, scratch resistance, strength, and weather resistance, as well as processability.

[0003] Among the above surface properties, in order to improve the antifouling property, it has been proposed to increase the water repellency of the surface. For example, Patent Document 1 proposes a decorative sheet that exhibits stain resistance due to an olefin resin layer containing a silicone polymer-incorporated olefin resin formed by chemically bonding a high-molecular-weight silicone polymer, and Patent Document 2 proposes a decorative sheet that exhibits stain resistance due to a transparent surface protective layer formed from an aqueous composition containing an aqueous emulsion of a (meth)acrylic resin composition and an aqueous dispersion of an isocyanate.Furthermore, Patent Document 3 proposes a decorative sheet having a surface protective layer obtained by crosslinking and curing an ionizing radiation-curable resin composition containing a monofunctional silicone (meth)acrylate with an average molecular weight of 100 to 3000, in order to provide a decorative sheet that has excellent stain resistance and water repellency and whose water repellency does not decrease over time. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-129420 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-98660 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-276464 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0005] The methods for improving stain resistance disclosed in Patent Documents 1 to 3 involve improving water repellency with a water repellent such as a silicone polymer, thereby achieving excellent stain resistance. However, while such methods can achieve a certain degree of improvement in stain resistance, they have limitations. Using a large amount of water repellent to improve stain resistance may result in failure to satisfy surface performance other than stain resistance, such as scratch resistance, strength, and weather resistance, depending on the application, and also increases costs. Therefore, methods for improving stain resistance using water repellents are currently unable to fully address the demand for further improvements in stain resistance.

[0006] Therefore, an object of the present disclosure is to provide a laminate that exhibits excellent antifouling properties due to a surface shape having a wrinkled structure. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that the above-mentioned problems can be solved by adopting a surface shape in a laminate that has a wrinkled structure and a predetermined contact angle with water. That is, in order to solve the above-mentioned problems, the present disclosure provides the following laminate: a laminate having a wrinkled structure and a surface shape in which the contact angle with water measured in accordance with the provisions of JIS R3257:1999 is 90.0 degrees or more; to provide. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a laminate that exhibits excellent antifouling properties due to a surface shape having a wrinkled structure. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic plan view illustrating an embodiment of a laminate according to the present disclosure. [Figure 2] FIG. 2 is a cross-sectional view showing one embodiment of a surface layer of a laminate of the present disclosure. [Figure 3] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present disclosure. [Figure 4] 1 is an optical microscope image of the surface of the laminate obtained in Example 1. [Figure 5] 1 is an optical microscope image of the surface of the laminate obtained in Comparative Example 1. [Figure 6] 1 is an optical microscope image of the surface of the laminate obtained in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0010] The laminate according to the present disclosure will be specifically described below. Note that the present disclosure is not limited to the following embodiments and may be implemented with any modifications within the scope that does not impair the effects of the invention. In addition, in this specification, the numerical values ​​associated with "greater than or equal to," "less than or equal to," and "to" in describing a numerical range are numerical values ​​that can be arbitrarily combined. For example, when a certain numerical range is described as "A to B" and "C to D," the numerical ranges "A to D" and "C to B" are also included.

[0011] [Laminate] The laminate of the present disclosure is characterized by having a wrinkled structure and a surface shape (hereinafter sometimes simply referred to as a "specific surface shape") in which the contact angle with water measured in accordance with the provisions of JIS R3257:1999 is 90.0 degrees or more.

[0012] The laminate of the present disclosure exhibits excellent stain resistance by adopting a specific surface shape having a wrinkled structure as a surface shape, and the wrinkled structure results in a contact angle with water of 90.0 degrees or more. A contact angle with water of 90.0 degrees or more is generally considered to indicate water repellency. By providing a water-repellent surface shape, even if water containing a stain-causing substance adheres to the surface of the laminate, the water is repelled, thereby removing the stain-causing substance, thereby achieving excellent stain resistance. In addition, surfaces with excellent water repellency generally also exhibit excellent oil repellency. Therefore, the laminate of the present disclosure exhibits excellent stain resistance even if the stain-causing substance is oily. In other words, the laminate of the present disclosure exhibits excellent stain resistance regardless of the type of stain-causing substance due to the water repellency exhibited by the wrinkled structure.

[0013] The laminate of the present disclosure achieves stain resistance due to water repellency by employing a wrinkled structure, even without using a water repellent agent or even with an extremely small amount of water repellent agent, as in Patent Documents 1 to 3. Therefore, with the laminate of the present disclosure, there is no need to consider the balance between water repellency achieved by using a water repellent agent and surface performance such as scratch resistance, strength, and weather resistance. Therefore, the laminate of the present disclosure exhibits water repellency through its wrinkle structure, thereby not only providing excellent stain resistance, but also, as secondary effects, providing excellent surface performance other than stain resistance, such as scratch resistance, strength, and weather resistance, all while keeping costs down. The configuration of the laminate of the present disclosure will be described below.

[0014] [Surface shape] The surface shape of the laminate of the present disclosure has a wrinkled structure, and the contact angle with water measured in accordance with the provisions of JIS R3257:1999 is 90.0 degrees or more. If the contact angle with water of the surface shape is less than 90.0 degrees, the water repellency will be insufficient, and excellent antifouling properties will not be obtained. Therefore, even if a laminate has a surface shape with a wrinkled structure, if the contact angle with water is less than 90.0 degrees, it cannot be said to have a specific surface shape and will not achieve excellent antifouling properties, and therefore does not fall under the category of the laminate of the present disclosure.

[0015] The contact angle of the surface shape with water is preferably 90.5 degrees or more, more preferably 91.0 degrees or more, and even more preferably 91.3 degrees or more. When the contact angle with water is within the above range, the antifouling properties are improved.

[0016] The shape of the wrinkle structure of the surface shape is not particularly limited as long as the contact angle with water is 90.0 degrees or more, but it is preferable that the surface has the following properties.

[0017] (Ra (arithmetic mean roughness)) As for the surface shape properties, it is preferable that the Ra (arithmetic mean roughness), which is a parameter in the height direction of the profile curve as defined in JIS B0601:2013, is 2.00 μm or more. Ra (arithmetic mean roughness) is one of the parameters in the height direction of the profile curve and is the average value of the height difference from the mean plane in the profile curve over a reference length. The larger the Ra (arithmetic mean roughness) value, the greater the tendency for the convex portions in the wrinkle structure of the surface shape and the height difference of the corresponding concave portions to increase. As the height difference increases, the convex portions become more prominent, making it more likely that the contact angle with water will be 90.0 degrees or more, improving antifouling properties.

[0018] In the laminate of the present disclosure, the Ra (arithmetic mean roughness) of the surface profile is preferably 2.00 μm or more, more preferably 2.40 μm or more, and even more preferably 2.50 μm or more. There is no particular upper limit, but taking into consideration ease of production and the like, it is preferably 5.00 μm or less, more preferably 4.00 μm or less, and even more preferably 3.70 μm or less. In measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm. Furthermore, in this specification, the Ra (arithmetic mean roughness) is the average value of measurements taken at any 10 points on the laminate.

[0019] (RSm (average length of curved elements)) As a surface shape characteristic, it is preferable that RSm (average length of curved elements), a horizontal parameter of the profile curve as defined in JIS B0601:2013, be 50.00 μm or less. RSm (average length of curved elements) is a horizontal parameter of the profile curve and is the average length of the profile curve elements over a reference length. The smaller RSm, the more closely the vertices of the convex portions in the wrinkle structure of the surface shape tend to be located. The closer the distance between one convex portion and another convex portion, the less likely water and other substances will penetrate between these convex portions. As a result, the contact angle with water is more likely to be 90.0 degrees or more, improving stain resistance.

[0020] In the laminate of the present disclosure, the RSm (average length of curved elements) of the surface shape is preferably 50.00 μm or less, more preferably 47.50 μm or less, and even more preferably 45.00 μm or less. Taking into consideration ease of manufacture, the lower limit is preferably 20.00 μm or more, more preferably 30.00 μm or more, and even more preferably 35.00 μm or more. In measuring RSm (average length of curved elements) in this specification, the cutoff value is 0.8 mm. Furthermore, in this specification, the RSm (average length of curved elements) is the average value of measurements taken at any 10 locations on the laminate.

[0021] (Spc (arithmetic mean curvature of the apex of the protrusion)) The surface shape characteristics are as follows: Spc (arithmetic mean curvature of the apex of the protrusion) specified in JIS B0601:2013 is 4000 mm -1 Spc (arithmetic mean curvature of the peaks of protrusions) is one of the three-dimensional surface texture parameters defined in JIS B0601:2013, and is the mean curvature (average sharpness) of the tip of the peak, calculated from the arithmetic mean value of the curvature radii of the peaks (peaks of protrusions) of the parts classified as peaks (convex parts) in the feature image included in the reference area. Spc is the reciprocal (mm) of the radius (mm -1) The larger the Spc, the larger the mean curvature (the smaller the radius), and the sharper the tip shape. As a result, the contact angle with water is more likely to be 90.0 degrees or more, improving antifouling properties.

[0022] In the laminate of the present disclosure, the Spc (arithmetic mean curvature of the apex of the protrusion) of the surface shape is preferably 4000 mm -1 More than 4150mm, preferably -1 More than 4300mm, more preferably -1 The upper limit is preferably 7000 mm, taking into consideration ease of manufacture. -1 Less than or equal to 6000 mm, preferably -1 Less than 5000 mm, more preferably -1 The cutoff value for measuring Spc (arithmetic mean curvature of the apexes of the protrusions) in this specification is 0.8 mm. In addition, in this specification, the Spc (arithmetic mean curvature of the apexes of the protrusions) is the average value of measurements taken at any 10 points on the laminate.

[0023] (Wrinkle structure) The shape of the wrinkle structure of the surface of the laminate of the present disclosure is not particularly limited as long as the wrinkles constituting the wrinkle structure form a contact angle with water of 90.0 degrees or more, but the following shapes are preferred: When the wrinkles constituting the wrinkle structure have the following shapes, the contact angle with water is more likely to be 90.0 degrees or more.

[0024] In the laminate of the present disclosure, the wrinkle structure is preferably configured with an uneven shape caused by irregular wrinkles. The irregular wrinkles are preferably configured with a plurality of convex portions formed by a plurality of protrusions and concave portions formed by being surrounded by the plurality of protrusions, and the protrusions preferably have linear protrusions. In this specification, "linear protrusions" (hereinafter also referred to as "linear protrusions") means that the ratio of the length to the width of the protrusions (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more, and the method for determining the length and width is as described below. In the present disclosure, more preferred irregular wrinkles are wrinkles that are composed of a plurality of protrusions formed by a plurality of linear protrusions and a recess formed by being surrounded by the plurality of linear protrusions.

[0025] A specific embodiment of the wrinkle structure is, for example, that shown in Figure 1. Figure 1 also shows that the surface shape of the surface of the laminate has irregular wrinkles in a planar view, and that the irregular wrinkles are configured to include a plurality of protrusions 3 formed by a plurality of curved linear protrusions and recesses 2 formed by being surrounded by the plurality of protrusions (a plurality of protrusions 3), and that at least a portion of the curved protrusions 3 are each formed by a meandering linear protrusion, and that the meandering recesses 2 are formed so as to be surrounded by the meandering linear protrusions. By having a surface shape of the laminate of the present disclosure have a wrinkle structure formed by irregular wrinkles, for example as shown in Figure 1, the water contact angle is likely to be 90.0 degrees or more, and the stain resistance is improved.

[0026] Here, "curved" means that there is one or more portions where the extension direction of the continuous linear protrusions 3 reverses from one side to the other in a planar view. Examples of portions where the extension direction reverses from one side to the other include a form having an inflection point when the linear protrusions 3 are approximated by a continuous curve when the width of the planar view shape is ignored (when the width is considered to be 0). Further, examples include a form having a portion that is approximated by a V-shaped folded line or two sides of a triangle sandwiching one vertex when the linear protrusions 3 are approximated by a straight line when the width of the planar view shape is ignored.

[0027] Furthermore, "meandering" means that there are at least two or more portions where the extension direction of the continuous linear protrusions 3 reverses from one side to the other in a planar view (hereinafter also referred to as "reversed portions"). When the linear protrusions 3 are followed in their extension direction, the extension direction of the linear protrusions 3 alternately reverses in opposite directions at two adjacent portions. For example, when the width of the planar view shape of the linear protrusions 3 is ignored and the linear protrusions 3 are approximated by a continuous curve, an example of such a shape is one having a portion that can be approximated by the Roman letter "S." Furthermore, when the width of the planar view shape of the linear protrusions 3 is ignored and the linear protrusions 3 are approximated by a straight line, an example of such a shape is one having a portion that can be approximated by the Roman letter "W."

[0028] In this specification, "irregular" means a shape that does not have a fixed rule or is not arranged according to a fixed rule, i.e., is not patterned. A typical example of a non-irregular shape (regular shape) is a shape that is arranged with a fixed periodicity in a specific direction, such as a so-called "lenticular lens," in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction. Therefore, in the present disclosure, the irregular wrinkles that may be present in the wrinkle structure that forms the surface shape include a shape in which the shape of a single protrusion itself is irregular and not formed according to a fixed rule such as periodicity, a shape in which the shapes of multiple convex portions formed by multiple protrusions are irregular and not formed and arranged according to a fixed rule, and a shape in which the concave portion surrounded by such multiple protrusions is also irregular.

[0029] In the wrinkle structure that forms the surface shape, if any of the shape of a single protrusion (a single convex portion), the shape and arrangement of each of the multiple protrusions (multiple convex portions), and the shape of a concave portion surrounded by the multiple protrusions is irregular, the surface shape is more likely to have a specific surface shape and the antifouling properties are improved. For the same reason, it is more preferable that all of them are irregular.

[0030] As described above, the surface shape of the laminate of the present disclosure has a wrinkled structure, and is essentially an uneven shape. The convex and concave portions in the uneven shape are defined based on the median value of the height distribution of the concave and convex shape, with regions with heights exceeding this median value being defined as convex portions and regions with heights equal to or less than this median value being defined as concave portions. For example, by utilizing the density difference (i.e., brightness difference) of an image having a density that corresponds 1:1 to the height of the surface of the laminate, the darkest portion of the density distribution image may be defined as gradation 255 and the lightest portion of the density distribution image as gradation 0 (the median density value for the median height is 127), and the gradations 0 to 255 may be binarized to define concave portions as gradations 0 to 127 and convex portions as gradations 128 to 255.

[0031] The surface shape of the laminate of the present disclosure preferably has a wrinkled structure on at least a part thereof, and more preferably has a wrinkled structure over the entire surface. As shown in Figure 1, the wrinkle structure forming the surface shape of the laminate of the present disclosure is preferably composed of a plurality of convex portions formed by a plurality of protrusions that are irregular but have a certain degree of uniformity, and concave portions surrounded by the convex portions. Therefore, in the convex portions (protrusions) shown in Figure 1, a shape in which the width or height changes drastically is not considered to be a preferable embodiment for obtaining excellent antifouling properties. Specific embodiments of the shapes of the convex portions (protrusions) and concave portions that constitute the wrinkle structure of the surface shape of the laminate of the present disclosure, which can be effective in improving antifouling properties by making the surface shape a specific surface shape, are described below.

[0032] Fig. 2 is a cross-sectional view showing one embodiment of a laminate, in which the laminate is cut along a plane parallel to its thickness direction (Z direction in the figure). That is, Fig. 2 schematically shows the cross-sectional shape of wrinkles (protrusions and recesses) that constitute the wrinkle structure of the laminate of the present disclosure. The shape of the recess may be, for example, acute-angled as shown in 2a in Figure 2, semicircular or semi-elliptical as shown in 2b, or a combination of these.Furthermore, a shape such as 2c in Figure 2, in which one protrusion has a recess in a part thereof, may also be used. On the other hand, the shape of the convex portion is semicircular or semielliptical, although the width varies as shown in 3a and 3b in FIG.

[0033] Regarding the shape of the wrinkles that constitute the wrinkle structure of the surface shape, the height of the convex portions (height of the protrusions) is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of about 10 μm or less. Furthermore, the width of the convex portions is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, with an upper limit of preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. When the height and width of the convex portions are within the above ranges, the surface shape is likely to have a specific shape in relation to the concave portions, improving the antifouling properties. Here, the above dimensions of the convex portions are the average values ​​of 10 convex portions (protrusions) at 10 arbitrary locations (100 μm square area × 10 locations) on the surface shape of the laminate of the present disclosure, i.e., a total of 100 convex portions. Also, as shown in FIG. 1, the width of one convex portion (protrusion) is not the same but varies between wide and narrow, so the width of one convex portion (protrusion) is the average value of the widths at five arbitrary locations on that one convex portion (protrusion). The same applies to the height of the convex portions (protrusions).

[0034] The depth of the recesses is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of about 10 μm or less. The width of the recesses is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, with an upper limit of preferably 10 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. When the depth and width of the recesses are within the above ranges, the surface shape is likely to be a specific surface shape in relation to the protrusions, and antifouling properties are improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0035] The distance from the top of the convex portion to the bottom of the concave portion (height difference between the convex portion and the concave portion) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. When the distance is within the above range, the surface shape is likely to be a specific surface shape, and the antifouling properties are improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0036] The proportion of the convex portions is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, with the upper limit being preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. When the proportion of the convex portions is within the above range, the surface shape is likely to have a specific shape in relation to the proportion of the concave portions surrounded by the convex portions, and the antifouling properties are improved. Here, the occupancy ratio of the convex portions is the average value of the occupancy ratio of the convex portions at 10 arbitrary locations (100 μm square area×10 locations) of the laminate.

[0037] The protrusions and recesses may have portions that are approximately the same in direction and width, but it is preferable that the length is short. If the length of the protrusions and recesses is short, the surface shape is more likely to be a specific surface shape, and the antifouling properties are improved. Specifically, the length of the continuous convex and concave portions of approximately the same width and direction is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, with the lower limit being preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, making it easier to achieve a contact angle with water of 90.0 degrees or more and excellent stain resistance. Here, of any 10 convex portions and concave portions (i.e., a total of 100 convex portions and concave portions) in any 10 locations (100 μm square areas × 10 locations) of the laminate, it is preferable that 80% or more of them satisfy the above conditions, more preferably 85% or more, even more preferably 90% or more, and even more preferably 95% or more. Furthermore, in this specification, the "substantially the same" in "substantially the same" means roughly the same, without branching, meaning a difference of ±3° in the direction, and a difference of ±5% in the width.

[0038] The number of convex portions (projections) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, with the upper limit being preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. When the number of convex portions is within the above range, the surface shape is likely to be a specific surface shape, and the antifouling properties are improved. The number of convex portions is the average value of the number of convex portions in 10 locations (100 μm square area×10 locations) of the laminate.

[0039] [Surface layer] The laminate of the present disclosure preferably includes a surface layer, and the surface shape is formed by the surface of the surface layer. Preferred methods for forming the above-mentioned surface shape in the laminate of the present disclosure include employing a surface layer as one of the layers constituting the laminate, employing a cured product of a resin composition as a material constituting the surface layer, employing an irradiation treatment with ionizing radiation as a method for forming the surface layer, and adjusting the thickness of the surface layer, etc. Among the methods for forming the surface shape, the surface layer will be described below.

[0040] The thickness of the surface layer is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more, with the upper limit being preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 100 μm or less. Adjusting the thickness of the surface layer is one of the important means for easily forming a wrinkled structure, making the contact angle with water 90.0 degrees or more through the wrinkled structure, and facilitating the development of antifouling properties. That is, when the thickness of the surface layer is within the above range, the surface shape is easily formed into a specific surface shape, and the antifouling properties are improved. Furthermore, when the thickness of the surface layer is within the above range, the surface layer is easily formed, the usability as a laminate is improved, and surface properties such as scratch resistance, strength, and weather resistance, as well as processability, are easily obtained. In this specification, the thickness of the surface layer is determined by measuring the thickness at 20 points on an image of the cross section of the laminate taken using a scanning electron microscope (SEM), and averaging the values ​​at 20 points. The accelerating voltage of the SEM is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of the other layers.

[0041] The surface layer may be provided partially or over the entire surface, but considering the effect of the wrinkled structure making the contact angle with water 90.0 degrees or more and exhibiting antifouling properties, it is preferable that the surface layer be provided over the entire surface. When the surface layer is provided partially, the laminate of the present disclosure preferably has a substrate, which will be described later, as a layer other than the surface layer.

[0042] (Resin composition) The surface layer is preferably a layer formed from a cured product of a resin composition. By forming the surface layer from a cured product of a resin composition, it is easy to form a specific surface shape and the antifouling properties are improved. The resin composition preferably used to form the surface layer may be any composition containing a resin that forms a cured product by curing and that forms the surface layer.

[0043] (resin) The surface layer is a layer that can be provided on the outermost surface of the laminate, and by having a specific surface shape, it becomes a layer that exhibits antifouling properties. Therefore, an ionizing radiation curable resin is preferred as a resin that easily forms a specific surface shape, i.e., a wrinkled structure, and a surface shape that has a contact angle with water of 90.0 degrees or more due to the wrinkled structure. In addition, an ionizing radiation curable resin is preferred in consideration of the ease with which the surface layer can be formed and the ease with which surface properties such as scratch resistance, strength, and weather resistance, as well as processability, can be improved.

[0044] An ionizing radiation-curable resin is a resin having an ionizing radiation-curable functional group, which is a group that crosslinks and cures upon irradiation with ionizing radiation. Preferred examples of such groups include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, or an allyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group. In this specification, the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0045] Ionizing radiation curable resins include electron beam curable resins and ultraviolet curable resins, with ultraviolet curable resins being preferred. The surface shape is easily formed into a specific shape, improving antifouling properties. Furthermore, other surface properties, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved. Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins, and it is preferable to use polymerizable monomers and polymerizable oligomers.

[0046] The polymerizable monomer is preferably a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule. The (meth)acrylate monomer is a monomer having at least a (meth)acryloyl group as an ionizing radiation-curable functional group, and examples thereof include monofunctional (meth)acrylate monomers having one ionizing radiation-curable resin and polyfunctional (meth)acrylate monomers having two or more ionizing radiation-curable resins, and either can be used.

[0047] The polymerizable monomers can be used alone or in combination of multiple types, and it is preferable to use two or more polymerizable monomers in combination. By using two or more polymerizable monomers in combination, the surface shape is easily formed into a specific surface shape, and the antifouling property is improved. In addition, surface properties other than the antifouling property, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved.

[0048] When two or more polymerizable monomers are used in combination, a combination of a monofunctional monomer and a polyfunctional monomer, or a combination of two or more polyfunctional monomers is preferred, and a combination of a polyfunctional monomer and a polyfunctional monomer is more preferred. When a polyfunctional monomer is used, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.

[0049] When a monofunctional monomer and a polyfunctional monomer are used in combination, the upper limit of the number of functional groups in the polyfunctional monomer is most preferably 2 or less, that is, the number of functional groups in the polyfunctional monomer is most preferably 2. In this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers. Furthermore, when two or more types of polyfunctional monomers are used, it is most preferable to combine a monomer having two functional groups with a monomer having four functional groups. In this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers.

[0050] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.

[0051] Other polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecule, such as novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0052] Among the above polymerizable oligomers, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers are preferred, with urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers being more preferred, and urethane (meth)acrylate oligomers being even more preferred. By using these polymerizable oligomers, the surface shape tends to be specific, improving antifouling properties. Furthermore, surface properties other than antifouling properties, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved.

[0053] For the same reason, these polymerizable oligomers may be used alone or in combination of two or more types, and it is preferable to use one type of polymerizable oligomer alone, although it goes without saying that two or more types of polymerizable oligomers may be used in combination.

[0054] The number of functional groups in the polymerizable oligomer is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. When the number of functional groups is within the above range, the surface shape is likely to be a specific surface shape, and the antifouling properties are improved. In addition, surface properties other than the antifouling properties, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved.

[0055] For the same reason, the weight-average molecular weight of these polymerizable oligomers is preferably 1,000 to 7,500, more preferably 1,500 to 6,500, even more preferably 1,750 to 5,000, and even more preferably 1,900 to 4,000. Here, the weight-average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0056] The resin may be a resin having a functional group having a substituent such as a hydrocarbon group, such as a linear or branched alkyl group or an alkenyl group, an alicyclic hydrocarbon group, such as a cycloalkyl group or a cycloalkenyl group, or an aromatic hydrocarbon group, such as an aryl group, or, in the case where some of these groups are heteroatoms, hydroxyl groups, alicyclic hydrocarbon groups, or aromatic hydrocarbon groups, a hydrocarbon group or the like. Among the above, hydrophobic resins are preferred because they improve antifouling properties, and resins having aromatic hydrocarbon groups are particularly preferred.

[0057] In the laminate of the present disclosure, the resin forming the surface layer preferably contains at least one selected from the polymerizable monomer and polymerizable oligomer. In this case, the content of the polymerizable monomer or polymerizable oligomer in the resin forming the surface layer is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, i.e., the resin is preferably at least one selected from the polymerizable monomer and polymerizable oligomer.

[0058] As described above, the resin forming the surface layer preferably contains at least one selected from the above-mentioned polymerizable monomer and polymerizable oligomer, more preferably contains a polymerizable monomer and a polymerizable oligomer, even more preferably contains at least one selected from the polymerizable monomer and the polymerizable oligomer, and particularly preferably contains a polymerizable monomer and a polymerizable oligomer.

[0059] When a polymerizable monomer and a polymerizable oligomer are used, the content of the polymerizable oligomer relative to 100 parts by mass of the total of the polymerizable monomer and the polymerizable oligomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, with the upper limit being preferably 75 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less. When the content of the polymerizable oligomer is within the above range, the surface shape is likely to be a specific surface shape, and the antifouling properties are improved. In addition, surface properties other than antifouling properties, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved.

[0060] For the same reason, when a monofunctional monomer and a polyfunctional monomer are used as polymerizable monomers, the content of the polyfunctional monomer is preferably 15 parts by mass or more, with the upper limit being preferably 50 parts by mass or less, more preferably 45 parts by mass or less, per 100 parts by mass of the resin. The content of the monofunctional monomer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, with the upper limit being preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less, per 100 parts by mass of the resin.

[0061] (components other than resin) Since the surface layer is a layer provided on the surface of the laminate of the present disclosure, it is preferable that it not only has antifouling properties but also surface properties other than antifouling properties, such as scratch resistance, strength, and weather resistance. Therefore, the resin composition preferably used to form the surface layer may contain various additives according to the desired surface properties as components other than the above resin. That is, in the laminate of the present disclosure, the surface layer may contain various additives according to the desired surface properties. Preferred examples of such various additives include photopolymerization initiators, photopolymerization accelerators, and weatherproofing agents.

[0062] The photopolymerization initiator and photopolymerization accelerator are particularly preferably used when the resin is an ultraviolet-curable resin that is cured by ultraviolet light. The inclusion of these additives promotes the formation of a wrinkled structure, which in turn increases the contact angle with water to 90.0 degrees or more, making it easier to achieve excellent antifouling properties. Furthermore, the accelerated curing of the resin composition improves the surface properties, particularly the scratch resistance and strength.

[0063] The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0064] The content of the photopolymerization initiator relative to 100 parts by mass of the resin forming the surface layer is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and the upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1.5 parts by mass or less, and still more preferably 1.0 part by mass or less. When the content of the photopolymerization initiator is within the above range, the effect of using the photopolymerization initiator efficiently can be obtained. The content of the photopolymerization accelerator is the same as that of the photopolymerization initiator.

[0065] As the weatherproofing agent, various weatherproofing agents such as ultraviolet absorbers and light stabilizers are preferably used. As the ultraviolet absorber, any ultraviolet absorber commonly used in decorative sheets can be used without any particular limitation, and examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers.

[0066] As the light stabilizer, any light stabilizer commonly used in decorative sheets can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers. Furthermore, these ultraviolet absorbers and light stabilizers may have a reactive functional group with an ethylenic double bond in the molecule, such as a (meth)acryloyl group, a vinyl group, or an allyl group. These weathering agents such as ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more kinds.

[0067] The content of the ultraviolet absorber relative to 100 parts by mass of the resin forming the surface layer is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, even more preferably 2.0 parts by mass or more, and even more preferably 3.0 parts by mass or more, with the upper limit being preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and even more preferably 6.0 parts by mass or less. When the content of the ultraviolet absorber is within the above range, the effect of using the ultraviolet absorber efficiently can be obtained. The content of the light stabilizer is the same as that of the ultraviolet absorber.

[0068] In addition, a water repellent may be used to improve the stain resistance. Examples of water repellents include silicone-based water repellents, fluorine-based water repellents, wax emulsion-based water repellents, etc. The content of the water repellent per 100 parts by mass of the resin forming the surface layer is preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.6 parts by mass or less, with the lower limit being 0.1 parts by mass or more. The antifouling properties exhibited by the laminate of the present disclosure are obtained by making the contact angle with water 90.0 degrees or more due to the wrinkle structure of the surface shape. In other words, the laminate of the present disclosure exhibits excellent antifouling properties even without using a water repellent. Therefore, although a water repellent can be used, the smaller the amount used, the better.

[0069] The resin composition preferably used to form the surface layer may contain a wrinkle structure stabilizer. Use of a resin composition containing a wrinkle structure stabilizer makes it easier for the surface to have a specific surface shape, improving the stain resistance.

[0070] As the wrinkle structure formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of organic materials that can be used to form organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, and polyester-based resin. Examples of inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and among these, silica is preferred because of its excellent transparency.

[0071] The shape of the wrinkle structure formation stabilizer is not particularly limited, but examples thereof include spherical, polyhedral, scaly, and amorphous shapes.

[0072] The average particle size of the wrinkle formation stabilizer is preferably the smaller of 100% or less of the thickness of the surface layer or 30 μm or less. When the average particle size is within this range, the formation of a wrinkle structure in the surface layer is promoted, and the wrinkle structure makes the contact angle with water 90.0 degrees or more, making it easier to achieve excellent stain resistance. For the same reason, it is preferable to use as the wrinkle structure formation stabilizer at least one of wrinkle structure formation stabilizer 1 having an average particle size of 1 μm or more and an upper limit of the smaller of 100% or less of the thickness of the surface layer or 30 μm or less, and wrinkle structure formation stabilizer 2 having an average particle size of less than 1 μm. For example, as the wrinkle structure formation stabilizer, one or more types of wrinkle structure formation stabilizer 1 may be used, one or more types of wrinkle structure formation stabilizer 2 may be used, or one or more types of wrinkle structure formation stabilizer 1 may be used in combination with one or more types of wrinkle structure formation stabilizer 2.

[0073] The average particle size of wrinkle structure formation stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.8 μm or more. On the other hand, the upper limit is preferably 90% or less of the thickness of the surface layer, more preferably 80% or less of the thickness of the surface layer, and even more preferably 70% or less of the thickness of the surface layer, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less. The average particle size of the wrinkle structure formation stabilizer 1 may be the smaller of any combination of the upper limit relative to the thickness of the surface layer and the upper limit of the absolute value. For example, the upper limit may be the smaller of either 90% or less of the thickness of the surface layer or 20 μm or less, or the smaller of either 90% or less of the thickness of the surface layer or 10 μm or less.

[0074] The average particle size of the wrinkle structure formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more, with the upper limit being preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less. In this specification, the average particle size of the wrinkle structure formation stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

[0075] The content of the wrinkle formation stabilizer relative to 100 parts by mass of the resin forming the surface layer is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, and even more preferably 1.0 part by mass or more. When the content of the wrinkle formation stabilizer is within the above range, the formation of a wrinkle structure in the surface layer is promoted, and the wrinkle structure results in a contact angle with water of 90.0 degrees or more, making it easier to obtain excellent stain resistance. On the other hand, the upper limit is preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, taking into account surface properties such as scratch resistance, strength, and weather resistance, as well as processability.

[0076] [Layer structure] The laminate of the present disclosure is composed of a plurality of layers as described above, and the layers constituting the laminate may include the following layers in addition to the surface layer described above.

[0077] (More realistic layer structure) For practical reasons, the laminate of the present disclosure preferably has a layer structure having, for example, a substrate as a layer other than the surface layer. In this case, as shown in Fig. 2, it is preferable that the laminate has a substrate 5 and a surface layer 4, and that the surface shape is present on the surface of the surface layer 4 opposite to the substrate 5, and that the surface shape is configured to be the surface of the laminate 1. As the layer structure of the laminate of the present disclosure, a structure having a substrate 5 and a surface layer 4 is the simplest and most preferred layer structure. As shown in FIG. 3, typical preferred layers other than the surface layer 4 and the base material 5 include a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, and a primer layer 9.

[0078] (base material) The laminate preferably has a substrate in addition to the surface layer. By having the substrate, various performances such as mechanical strength, post-processing suitability, and designability are improved, thereby improving the usability of the laminate. In addition, since the substrate can function as a support, the surface layer can be easily formed, for example, by applying the resin composition to the substrate and curing it.

[0079] The shape of the substrate is not particularly limited and may be various shapes such as a film, sheet, plate, polyhedron, polygonal prism, cylinder, cone, sphere, spheroid, etc. Although films, sheets, and plates are referred to as films, sheets, and plates in the order of relatively thinnest thickness, there is no significance in strictly distinguishing between these three types in this specification, and differences between these three types do not cause differences in interpretation of the rights of the present invention.

[0080] The substrate used in the present disclosure can be any substrate that is typically used as a substrate for articles such as decorative materials and decorative sheets, and representative examples include substrates made of fibrous materials such as paper, nonwoven fabric and woven fabric, resins, wood-based materials, metals, non-metallic inorganic materials, etc. The substrate may be a single-layer substrate or a substrate having two or more layers made of the above materials. When the substrate has two or more layers, it is preferable that the substrate has two or more layers made of different materials, and that the performances of the materials in each layer are mutually complementary.

[0081] Furthermore, when the substrate is a substrate having two or more layers, the laminate may be configured such that an adhesive layer, a pressure-sensitive adhesive layer, or a primer layer (also referred to as an "anchor layer" or "easy-adhesion layer") is further provided between each constituent layer of the laminate as a layer for strengthening the adhesive strength between adjacent layers.

[0082] Examples of fibrous substrates include paper substrates such as kraft paper, titanium paper, linter paper, parchment paper, paraffin paper, glassine paper, parchment paper, wallpaper backing paper, tissue paper, wood-free paper, Japanese paper, paperboard, and plasterboard base paper. Furthermore, paper substrates may further contain various resins, such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin (either impregnated after papermaking or embedded during papermaking), to improve interfiber or interlayer strength and to prevent fluffing. Examples of such paper substrates include inter-paper reinforced paper and resin-impregnated paper. Examples of substrates in which a resin layer is laminated to a fibrous material layer include wallpaper rolls, which are commonly used in the building materials field and in which various resin layers, such as vinyl chloride resin, olefin resin, and acrylic resin, are laminated to the surface of wallpaper backing paper.

[0083] Examples of substrates for nonwoven or woven fabrics include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon; organic fibers made of various synthetic resins such as polyester resin, acrylic resin, polyethylene, and polypropylene; protein-based or cellulose-based natural fibers such as silk, cotton, and hemp; nonwoven or woven fabrics made of various fibers such as glass fiber and carbon fiber; and composites of these.

[0084] Examples of the resin substrate include substrates made of various resins such as synthetic resins, natural resins, etc. As the synthetic resin, thermoplastic resins and curable resins can be used. Examples of thermoplastic resins include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin-based thermoplastic elastomers, and ionomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane, and celluloid; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene resins (ABS resins); and resin substrates made of thermoplastic resins such as polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins. Examples of the curable resin include the ionizing radiation curable resin that can form the surface layer described above, and other thermosetting resins. Examples of natural resins include natural rubber, pine resin, and amber.

[0085] Examples of wood-based substrates include wood substrates made from various types of wood, such as cedar, cypress, pine, zelkova, oak, walnut, lauan, teak, rubber tree, etc. The wood substrates can be in the form of a film or sheet called veneer, or in the form of a board, such as a single board, plywood, laminated wood, particle board, or fiberboard.

[0086] Examples of metals include aluminum, aluminum-containing alloys such as duralumin, iron-containing alloys such as iron, carbon steel, and stainless steel, copper-containing alloys such as copper, brass, and bronze, gold, silver, chromium, nickel, cobalt, tin, and titanium. Furthermore, as the metal substrate made of a metal, it is also possible to use those metals that have been subjected to a treatment such as plating. Non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as porcelain, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, and andesite.

[0087] The substrate may be colored or uncolored (it may be transparent), and if it is colored, there are no particular restrictions on the coloring mode, and it may be transparently colored or opaquely colored (hiding colored), which can be selected as desired.

[0088] When the substrate is colored, 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 complexes, azomethine azo-based black pigments, and perylene-based black pigments; metal pigments consisting of scaly foil flakes such as aluminum and brass; and pearlescent pigments consisting of scaly foil flakes such as titanium dioxide-coated mica and basic lead carbonate. For example, when the surface hue of the adherend to which the article is attached varies, an inorganic pigment such as a white pigment can be used to conceal the surface hue and improve the color stability of the picture layer and the large-area decorative layer provided as desired.

[0089] In the case of coloring synthetic resins, any of the following methods can be used: adding a colorant to the resin (mixing or kneading), applying a coating film of a paint containing the resin and the colorant, etc. In the case of coloring paper, nonwoven fabric, or woven fabric, any of the following methods can be used: mixing with pulp or fiber materials, or forming a coating film, or a combination of these. In the case of coloring wood, it can be done by dyeing with a dye or by forming a coating film, or by a combination of these. In the case of coloring metals, in addition to forming a coating film, electrolytic coloring methods that form a metal oxide film on the surface using anodization can be used. In addition, in the case of non-metallic inorganic materials, it can be done by forming a coating film or by adding a dye to the substrate, or by a combination of these.

[0090] The substrate may contain additives as needed. Examples of additives, mainly in the case of resins, include inorganic substances such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of additives added is not particularly limited as long as it does not impair surface properties, processing properties, and the like, and can be appropriately set depending on the required properties, etc.

[0091] From the viewpoint of improving the weather resistance of the laminate of the present disclosure, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the above additives. Examples of the ultraviolet absorber and light stabilizer include those exemplified above as those that can be contained in the surface layer. These ultraviolet absorbers, weathering agents such as light stabilizers, and other various additives may be used alone or in combination of two or more kinds.

[0092] The shape and dimensions of the substrate are not particularly limited and may be appropriately selected depending on the application, desired performance, and processability. When the substrate is in the form of a film, sheet, or plate, the thickness is a typical dimension in the design of the article. There are no particular restrictions on the thickness, but it is generally sufficient to set it to about 10 μm or more and 10 cm or less from the viewpoints of manufacturing processability, mechanical strength, ease of use and handling, and economic efficiency. Furthermore, when it is in the form of a film or sheet, the thickness is preferably 20 μm or more, more preferably 40 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. When the substrate is in the form of a plate, its thickness is preferably 1 mm or more and 2 cm or less. In addition, when the base material is paper, the basis weight is usually 20 g / m 2 More than 150g / m 2 Less than 30 g / m 2 More than 100g / m 2 The following is more preferred:

[0093] The substrate may have the primer layer formed thereon in order to improve adhesion to other layers, such as the surface layer, constituting the laminate, and to improve adhesion to an adherend when the laminate is attached to the adherend to be used as a decorative sheet. In addition, one or both sides of the substrate may be subjected to a surface treatment such as a physical surface treatment, such as an oxidation method or a roughening method, or a chemical surface treatment. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc. Examples of roughening methods include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but in consideration of the effect and operability of the surface treatment, corona discharge treatment is generally preferred.

[0094] [Other layers] In addition to the surface layer and substrate, the laminate of the present disclosure may optionally include other layers, such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer. A cross-sectional view of one embodiment of a laminate having these layers is shown in Figure 3. The laminate 1 shown in Figure 3 includes, in order, a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a surface layer 4.

[0095] (primer layer) As described above, the laminate may have a primer layer in order to improve the interlayer adhesion between the multiple layers that make up the laminate. For example, when a surface layer and a substrate are present, a primer layer can be provided between the surface layer and the substrate, or when a transparent resin layer is present, as shown in Figure 3, a primer layer can be provided between the transparent resin layer and the surface layer to improve interlayer adhesion.

[0096] 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.

[0097] Preferred examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins, and these can be used alone or in combination.

[0098] The binder resin may be a resin obtained by crosslinking and curing the above-mentioned resin with the addition of a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent. For example, a resin obtained by crosslinking and curing 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 curing an acrylic polyol resin with an isocyanate-based curing agent is more preferred.

[0099] The thickness of the primer layer is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and the upper limit is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm or less.

[0100] The laminate of the present disclosure may also have a primer layer (also referred to as a "rear primer layer") on the side opposite to the side on which the surface layer of the substrate is provided, for the purpose of improving adhesion to the adherend, etc.

[0101] (Transparent resin layer) The laminate may have a transparent resin layer to increase its strength and to protect the decorative layer, if any, described later. Providing a transparent resin layer is particularly effective when the laminate is used as a flooring material or a frequently used fitting material such as a window frame, a door, a door frame, or a handrail. The transparent resin layer may be provided on the side opposite to the surface having the surface shape of the surface layer, for example, between the substrate and the surface layer, or, if a decorative layer is provided, between the decorative layer and the surface layer to protect the decorative layer (see Figure 3).

[0102] 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. Among these, polyolefin resins and vinyl chloride resins are preferred in terms of processability. Two or more of these resins may be laminated or mixed together for use.

[0103] The transparent resin layer may be transparent enough to allow the substrate side to be visible from the transparent resin layer, and if a decorative layer is provided, may be transparent enough to allow the decorative layer to be visible, and may be colorless and transparent, colored and transparent, or translucent. That is, in this specification, "transparent" means not only colorless and transparent, but also colored and transparent and translucent.

[0104] The transparent resin layer may contain additives such as weather resistance agents, such as ultraviolet absorbers and light stabilizers, and colorants. The additives, such as weather resistance agents and colorants, may be appropriately selected from those already described. Considering protection of the decorative layer, processability, etc., the thickness of the transparent resin layer is preferably 20 μm to 150 μm, more preferably 40 μm to 120 μm, and even more preferably 60 μm to 100 μm.

[0105] (decorative layer) The laminate may have a decorative layer to accommodate a desired design. The decorative layer may be provided on the surface opposite to the surface having the surface shape of the surface layer, for example, between the substrate and the surface layer. If a transparent resin layer is provided, the decorative layer, the transparent resin layer, and the surface layer may be provided in this order (see Figure 3).

[0106] The decorative layer may be, for example, a colored layer that covers the entire surface (a so-called solid colored layer, "6a" in Fig. 3), or a patterned layer formed by printing various patterns using ink and a printing machine ("6b" in Fig. 3). Also, as shown in Fig. 3, it may be a combination of a solid colored layer 6a and a patterned layer 6b.

[0107] The design (pattern) of the design layer is not particularly limited and may be any desired design, such as wood grain patterns such as tree rings and vessel grooves on the surface of a wooden board, stone grain patterns on the surface of stone slabs such as marble and granite, fabric grain patterns on the surface of fabric, leather grain patterns on the surface of leather, geometric patterns, letters, figures, and combinations of these.

[0108] The ink used for the decorative layer is a mixture of a binder resin with an appropriate amount of pigment, colorant such as dye, extender pigment, solvent, stabilizer, plasticizer, catalyst, hardener, ultraviolet absorber, light stabilizer, etc. The binder resin for the decorative layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

[0109] As the colorant, a pigment having excellent hiding power and weather resistance is preferred. The pigment may be the same as those exemplified as the pigments that can be used for the substrate. The content of the colorant is preferably 5 to 90 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin constituting the decorative layer.

[0110] The decorative layer may contain additives such as ultraviolet absorbers, weather resistance agents such as light stabilizers, and colorants. The thickness of the decorative layer may be selected appropriately depending on the desired pattern, and considering the need to conceal the base color of the substrate and improve the design, the thickness is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0111] (adhesive layer) When the laminate has a substrate and a transparent resin layer, an adhesive layer may be provided between the substrate and the transparent resin layer to improve adhesion between these layers. When a decorative layer is further provided between the substrate and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. Specifically, the decorative layer, adhesive layer, and transparent resin layer may be provided in this order from the side closest to the substrate (see Figure 3), or the adhesive layer, decorative layer, and transparent resin layer may be provided in this order from the side closest to the substrate.

[0112] The adhesive layer can be made of, for example, an adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a rubber adhesive, etc. Among these adhesives, a urethane adhesive is preferred in terms of adhesive strength. Examples of urethane adhesives include adhesives that utilize two-component curing urethane resins containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

[0113] From the viewpoint of efficiently obtaining a desired adhesive strength, the thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0114] [Method for manufacturing laminate] The laminate of the present disclosure has the simplest layer structure, which includes a substrate and a surface layer, as shown in Figure 2, but can also have a layer structure, such as that shown in Figure 3, which includes a substrate, a decorative layer, an adhesive layer, a transparent resin layer, a primer layer, and a surface layer in that order. Below, a method for producing a laminate having the layer structure shown in Figures 2 and 3 will be described.

[0115] The laminate of the present disclosure has a specific surface shape, that is, a wrinkled structure and a contact angle with water of 90.0 degrees or more. For example, when producing a laminate having a substrate and a surface layer, the laminate can be produced by the following method. a coating layer forming step of applying a resin composition for forming a surface layer to one main surface side of the substrate to form a coating layer; a surface layer forming step of curing the coating layer by irradiation with ionizing radiation such as ultraviolet rays to form a surface layer having a surface shape; In addition, when the resin composition for forming the surface layer contains a solvent, a solvent drying step may be carried out after the coating layer forming step.

[0116] (Coating layer forming process) In the coating layer forming step, the resin composition for forming the surface layer is applied by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating to form a coating layer (uncured resin layer).

[0117] The resin composition for forming the surface layer used in the coating layer forming step is the resin composition described in the description of the surface layer above, and is preferably a resin composition containing an ionizing radiation curable resin as a resin and other additives such as a photopolymerization initiator and a weathering agent. In the coating layer forming step, the thickness of the coating layer formed by coating the resin composition is the same as the thickness of the surface layer described above.

[0118] (Surface layer formation process) In the surface layer forming step, the coating layer formed in the coating layer forming step is cured by irradiation with ionizing radiation such as ultraviolet light to form a surface layer having a specific surface shape. The surface shape has a wrinkled structure and a contact angle with water of 90.0 degrees or more. Therefore, this step can form the specific surface shape possessed by the laminate of the present disclosure, and excellent antifouling properties can be obtained.

[0119] As the irradiation treatment, it is preferable to carry out at least the following irradiation treatments (1) and (2) in this order. (1) Irradiation with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beams and light with wavelengths of 200 nm or more and 400 nm or less By carrying out the irradiation treatments (1) and (2) above, the surface tends to have a wrinkled structure and a specific surface shape with a contact angle with water of 90.0 degrees or more, which tends to improve the antifouling properties.

[0120] Although the details of the mechanism by which irradiation by at least the above-mentioned irradiation treatments (1) and (2) facilitates obtaining a surface shape that exhibits excellent antifouling properties are unknown, it is presumed to be due to the following mechanism.

[0121] First, when the irradiation treatment with the short-wavelength (short-wavelength) ultraviolet light described above is performed, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the layers below, so that only the surface portion of the resin composition begins to harden, and it is thought that the wrinkle structure is formed by the cure shrinkage occurring only at the surface. In this way, it is thought that the formation of the wrinkle structure occurs when the surface-forming resin composition is cured only in a certain thickness direction from the surface by the irradiation of the short-wavelength (short-wavelength) ultraviolet light.

[0122] Subsequent irradiation with at least one of the electron beams (2) and longer wavelength (longer wavelength) ultraviolet light (200 nm to 400 nm) can promote curing from the surface-nearby portion, where curing progresses slowly, to deeper portions, while maintaining the wrinkled structure formed on the surface of the coating layer. While the irradiation treatment (1) above can cure the coating layer throughout its entire thickness and form a surface layer, further combining it with the irradiation treatment (2) above improves the curing state. As a result, a wrinkled structure develops on the surface of the surface layer, and the wrinkled structure increases the water contact angle to 90.0 degrees or greater, making it easier to obtain a surface shape that exhibits excellent antifouling properties. Furthermore, by curing the coating layer throughout its entire thickness and improving the curing state, it is believed that surface properties other than antifouling properties, such as scratch resistance, strength, and weather resistance, as well as processability, are also improved.

[0123] The wavelength light of 100 nm or more and less than 200 nm used in the irradiation treatment (1) is preferably "excimer light," which includes light in the ultraviolet wavelength range from excited dimers, i.e., excimers, formed by discharge of rare gases such as Ar, Kr, Xe, and Ne, halides of rare gases such as halogens F, Cl, I, and Br, or mixed gases thereof. Examples of wavelengths and excimers that can be used as excimer light include light with a wavelength of 126 nm radiated from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), and 193 nm (ArF). While spontaneous emission light and highly coherent laser light due to stimulated emission can both be used as excimer light, spontaneous emission light is usually sufficient. Discharge lamps that emit these types of light (ultraviolet rays) are also called "excimer lamps."

[0124] Excimer light has a single wavelength peak and is characterized by a narrower half-width wavelength than ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). The use of such excimer light makes it easier to develop a wrinkled structure, and the wrinkled structure makes the contact angle with water 90.0 degrees or more, making it easier to achieve excellent antifouling properties.

[0125] For the same reason, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more, with the upper limit being less than 200 nm, and particularly preferably 172 nm (Xe2). Thus, in order to facilitate the development of a wrinkled structure and to make the contact angle with water by the wrinkled structure 90.0 degrees or more and to facilitate the achievement of excellent antifouling properties, it is preferable to use light with a shorter wavelength, and it can be said that, among short-wavelength ultraviolet rays (wavelength: 280 nm or less), short-wavelength ultraviolet rays in the region of less than 200 nm are preferred.

[0126] The integrated light amount of wavelength light is preferably 1 mJ / cm 2 More preferably, 2 mJ / cm 2 More preferably, 5 mJ / cm 2 There is no particular upper limit, but in consideration of reducing the number of lamps required for irradiating wavelength light and improving productivity such as improving production efficiency, the upper limit is preferably 1,000 mJ / cm. 2 Less than or equal to 300 mJ / cm 2 More preferably, 100 mJ / cm or less 2 or less, even more preferably 10 mJ / cm 2 The following is the result.

[0127] The ultraviolet irradiance is preferably 1 mW / cm 2 More than 5mW / cm 2 More preferably, 10 mW / cm 2 The upper limit is preferably 10 W / cm 2 Less than 3W / cm, preferably 3W / cm 2Less than 1 W / cm, more preferably 2 In particular, when productivity is taken into consideration, the 2 Less than 300mW / cm is preferable. 2 Less than 150 mW / cm is more preferable. 2 The following is even more preferred: Furthermore, the oxygen concentration during irradiation with light of the above wavelengths is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

[0128] In the surface layer forming step, it is preferable that the above (1) irradiation treatment with light having a wavelength of 100 nm or more and less than 200 nm is followed by the above (2) irradiation treatment with at least one of electron beams and light having a wavelength of 200 nm or more and 400 nm or less.

[0129] The electron beam irradiation conditions used in the irradiation treatment (2) are not particularly limited as long as the resin composition for forming the surface layer is cured, but the electron beam acceleration voltage is preferably 10 kV or more, more preferably 30 kV or more, even more preferably 50 kV or more, and even more preferably 75 kV or more, with the upper limit being preferably 300 kV or less, more preferably 250 kV or less, and even more preferably 200 kV or less. When the electron beam acceleration voltage is within the above range, the cured product tends to retain the shape of the wrinkle structure, and the wrinkle structure makes the contact angle with water 90.0 degrees or more, making it easier to obtain excellent antifouling properties. In addition, surface properties other than antifouling properties, such as scratch resistance, strength, and weather resistance, as well as processability, are improved. For the same reason, the electron beam irradiation dose is preferably 5 kGy or more, more preferably 10 kGy or more, and even more preferably 15 kGy or more, with the upper limit being preferably 150 kGy or less, more preferably 125 kGy or less, and even more preferably 100 kGy or less.

[0130] The electron beam source is not particularly limited as long as it can achieve the above-mentioned irradiation conditions, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used.

[0131] (2) The ultraviolet light of 200 nm or more and 400 nm or less used in the irradiation treatment can be irradiated using an ultraviolet light irradiation device using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, etc. Also, excimer light of 200 nm or more and 400 nm or less, such as 222 nm (KrCl), 247 nm (KrF), or 308 nm (XeCl), may be used.

[0132] (2) The wavelength of the ultraviolet light used in the irradiation treatment is preferably 330 nm or more, with the upper limit preferably being 390 nm or less. When the wavelength of the ultraviolet light is within this range, the wrinkled structure is more likely to be maintained as it is, and the wrinkled structure results in a contact angle with water of 90.0 degrees or more, making it easier to obtain excellent stain resistance. In addition to stain resistance, surface properties such as scratch resistance, strength, and weather resistance, as well as processability, are also improved. For the same reason, the output of the ultraviolet irradiation device that can be used in the irradiation treatment (2) is preferably 50 W / cm or more, more preferably 100 W / cm or more, with the upper limit being preferably 300 W / cm or less, more preferably 200 W / cm or less. The irradiation speed is preferably 1 r / min or more, more preferably 3 r / min or more, with the upper limit being preferably 50 r / min or less, more preferably 10 r / min or less.

[0133] Furthermore, prior to the irradiation treatments (1) and (2), an irradiation treatment for pre-curing (3) may be performed. The resin composition for forming the surface layer is applied to a coating layer having a predetermined thickness, and the coating layer is pre-cured overall by the irradiation treatment for pre-curing (3). This imparts an appropriate viscosity to the resin composition. Therefore, sagging of the wrinkle structure formed by the irradiation treatment (1) above can be suppressed, and the wrinkle structure can be better maintained.

[0134] The ionizing radiation used in the irradiation treatment for pre-curing (3) may have a wavelength of, for example, more than 320 nm, preferably more than 320 nm and up to 400 nm, more preferably 385 nm or more and up to 400 nm (ultraviolet light). By using light (ultraviolet light) with such a wavelength in the irradiation treatment (3), the entire resin composition for forming the surface layer, i.e., the entire coating layer, can be efficiently pre-cured.

[0135] The ultraviolet irradiance in the irradiation treatment of (3) is preferably 0.01 W / cm 2 More than 0.1 W / cm 2 More preferably, 0.3 W / cm 2 The upper limit is preferably 5 W / cm 2 Less than 3W / cm, preferably 3W / cm 2 Less than 2 W / cm, more preferably 2 When the amount of ultraviolet light is within the above range, the coating layer does not completely harden, and the coating layer can be efficiently pre-hardened overall.

[0136] The ultraviolet rays of 200 nm or more and 400 nm or less used in the irradiation treatment (3) can be irradiated using an ultraviolet irradiation device using, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, an LED light, or the like as a light source.

[0137] In this way, a laminate having a specific surface shape, namely, a wrinkled structure and a contact angle with water of 90.0 degrees or more, is obtained. Other properties of the surface shape are as explained above in the description of the surface shape.

[0138] (Formation of other layers) The above has described a manufacturing method for a laminate according to the present disclosure having a layer structure including a substrate and a surface layer. However, the laminate according to the present disclosure may have layers other than the substrate and the surface layer, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc.

[0139] For example, the decorative layer, adhesive layer, and primer layer can be formed by applying a coating liquid containing a composition for forming each layer using the known method described above, and then drying and curing it as necessary. When a transparent resin layer is formed, a resin film for forming the transparent resin layer can be formed by dry lamination or the like.

[0140] (Total light transmittance) The laminate of the present disclosure may employ a substrate, decorative layer, etc., made of a non-transparent material, as described above, and may be used primarily for applications such as exterior components and interior components, as described below. Considering the cases where the above substrates, decorative layers, etc. are employed and the cases where the laminate of the present disclosure is used for the above applications, the total light transmittance of the laminate of the present disclosure, measured in accordance with JIS K7361-1:1997, is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.

[0141] [Decorative materials] Representative uses of the laminate of the present disclosure include using the laminate itself as a so-called decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material. Which use is to be made can be determined as desired. When an adherend is included, the decorative article comprises the laminate of the present disclosure and the adherend, specifically, the surface of the adherend that requires decoration is laminated opposite the surface of the laminate of the present disclosure that has the specific surface shape. Furthermore, when the laminate of the present disclosure is in the form of a sheet, it also has the characteristic of being easily laminated onto the adherend.

[0142] (adherent material) The adherend may be a member made of a material appropriately selected from the materials exemplified above as materials that can be used as the substrate. The adherend may be selected appropriately from the above depending on the application. When the application is for interior building components such as walls, ceilings, and floors; exterior building components such as exterior walls, roofs, eaves ceilings, fences, and gates; or fixtures or fittings such as window frames, doors, handrails, baseboards, moldings, and other fixtures or fittings, it is preferable to use at least one member selected from wood members made of wood-based materials, metal members made of metal, and resin members made of resin. When the application is for exterior building components such as entrance doors, or fixtures such as window frames and doors, it is preferable to use at least one member selected from metal members and resin members.

[0143] The thickness of the adherend may be selected appropriately depending on the application and material, and is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, with the upper limit being preferably 100 mm or less, more preferably 5 mm or less, and even more preferably 3 mm or less.

[0144] (adhesive layer) The laminate of the present disclosure and the adherend are preferably attached via an adhesive layer to obtain excellent adhesion. The adhesive used in the adhesive layer is not particularly limited, and any known adhesive can be used, and may be appropriately selected depending on the application. Preferred examples include moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives.

[0145] Resins used in these adhesives include, for example, acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, and epoxy resins, which can be used alone or in combination. Two-component curing urethane adhesives and ester adhesives that use an isocyanate compound or the like as a curing agent can also be used. The adhesive layer may also contain a pressure-sensitive adhesive, which may be appropriately selected from various pressure-sensitive adhesives such as acrylic, urethane, silicone, and rubber-based pressure-sensitive adhesives.

[0146] The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, and the upper limit is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. When the thickness of the adhesive layer is within the above range, excellent adhesiveness can be efficiently obtained.

[0147] (Manufacturing method for decorative components) The decorative member can be produced through a process of laminating the laminate of the present disclosure and an adherend. This step involves laminating the laminate of the present disclosure onto an adherend, with the surface of the adherend that requires decoration facing the surface of the laminate opposite the surface having the specific surface shape. Examples of methods for laminating the laminate onto the adherend include a lamination method in which the laminate is pressed onto the plate-shaped adherend with a pressure roller via an adhesive layer.

[0148] When a hot melt adhesive (heat-sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160°C or higher and 200°C or lower, although this depends on the type of resin that makes up the adhesive, and for reactive hot melt adhesives, the heating temperature is preferably 100°C or higher and 130°C or lower. Vacuum forming is generally performed while heating, and the temperature is preferably 80°C or higher and 130°C or lower, and more preferably 90°C or higher and 120°C or lower.

[0149] [Application] The laminate of the present disclosure, and decorative members using the laminate, can be cut as desired and the surface or end grain can be decorated with grooves, chamfers, and other processing tools such as a router or cutter. They are suitable for a variety of uses, including interior building components such as walls, ceilings, and floors; exterior building components such as exterior walls, eaves ceilings, roofs, fences, and fences; fixtures and fittings such as window frames, doors, door frames, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets and other appliances and office equipment; and interior or exterior components for vehicles. When in sheet form, the laminate of the present disclosure is suitable for use as a decorative sheet for the various components listed above.

[0150] Considering the characteristics of the laminate of the present disclosure, namely, excellent stain resistance and excellent surface performance other than stain resistance, such as scratch resistance, strength, and weather resistance, the laminate is suitable for use in applications where these surface performances are particularly required, such as interior building materials, such as flooring materials, and frequently used building materials, such as window frames, doors, door frames, and handrails. Furthermore, in addition to the various components described above, the laminate of the present disclosure can be used alone or in a form laminated or combined with other materials as packaging materials, antiglare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various certificates, keys of various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc. [Example]

[0151] Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples in any way.

[0152] (Method for measuring water contact angle) In accordance with the provisions of JIS R3257:1999, the water contact angle of the samples obtained in the Examples and Comparative Examples was measured using a contact angle meter ("DM 500 (model number)" manufactured by Kyowa Interface Science Co., Ltd.). Specifically, for the samples obtained in the Examples and Comparative Examples, 1.5 μL of pure water was dropped onto the surface of the sample having a wrinkled surface, and one second after the drop landed, the contact angle was calculated from the angle of the line connecting the left and right endpoints of the dropped drop to the vertex relative to the solid surface according to the θ / 2 method. The average of five measurements was taken as the contact angle value.

[0153] (surface shape measurement) The Ra (arithmetic mean roughness) and RSm (average length of curved elements) of the laminates obtained in the examples and comparative examples were measured in accordance with JIS B0601:2013, specifically by the following method. Rectangular samples (1024 μm × 768 μm) at 10 random locations were measured using a shape analysis laser microscope ("VK-X150 (controller) / VK-X160 (measurement unit)", manufactured by Keyence Corporation) with an objective lens of 50x, a laser wavelength of 658 nm, measurement mode: surface profile mode, measurement pitch: 0.13 μm, and measurement quality: high-speed mode. The average values ​​of the measurements at 10 random locations were taken as Ra (arithmetic mean roughness) and RSm (average length of curved elements). The cutoff values ​​for Ra (arithmetic mean roughness) and RSm (average length of curved elements) were set to 0.8 mm.

[0154] (Measurement of total light transmittance) The total light transmittance of the laminates obtained in the examples and comparative examples was measured in accordance with JIS K7361-1:1997, specifically, using a haze meter (model number "HM-150", manufactured by Murakami Color Research Laboratory) at 10 random locations, and the average value was taken as the total light transmittance.

[0155] (Evaluation of antifouling properties) The antifouling properties of the laminates obtained in the examples and comparative examples were evaluated based on the water contact angle and the results of the following staining test, according to the following criteria. A: The contact angle of water was 91.0 degrees or more, and the staining test showed that no stain remained on any of the samples, demonstrating extremely excellent stain resistance. B: The water contact angle was 90.0 degrees or more and less than 91.0 degrees, and as a result of the staining test, slight staining remained on at least one surface, but this did not pose any practical problem, and the surface had excellent stain resistance. C: The contact angle of water was less than 90.0 degrees, and as a result of the staining test, stains remained on at least one surface, and it could not be said that the antifouling properties were excellent. (Contamination test) For the laminates obtained in the examples and comparative examples, a test specimen was placed horizontally in accordance with the JAS Special Plywood Staining Test A. Then, a 10 mm wide line was drawn on the surface of the test specimen using commercially available office blue ink, oil-based ink (black) (both of which fall under the category of "marking pen" as specified in JIS S6037:2006), and red crayon (which falls under the category of "crayon and pencil" as specified in JIS S6026:2007 or has equivalent performance), and the test specimen was left for 4 hours, after which the line was wiped off with a cloth soaked in ethanol.

[0156] [Example 1] A corona discharge-treated PET sheet (thickness: 100 μm) was used as the substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by the gravure method to form a colored layer (thickness: 3 μm). A resin composition for forming a surface layer having the following composition was applied to the colored layer by the gravure method (application amount: 5 g / m 2 (When dry)), a coating layer was formed. The coating layer was irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (UV-LED irradiation, wavelength: 395 nm, maximum illuminance: 0.6 W / cm). 2 , Accumulated light intensity: 30~100mJ / cm 2 ) to perform pre-curing, and then irradiate with ultraviolet light using an excimer light irradiation device (excimer irradiation, wavelength: 172 nm (Xe), maximum irradiance: 30 mW / cm 2 , Accumulated light intensity: 6mJ / cm 2 The substrate was then irradiated with an electron beam (acceleration voltage: 100-150 kV, exposure dose: 30-100 KGy) in a nitrogen atmosphere (oxygen concentration 200 ppm or less) to form a surface layer on the substrate, thereby obtaining a laminate having the substrate, colored layer, and surface layer. The resulting laminate was subjected to measurement of water contact angle, measurement of surface shape, and measurement of total light transmittance by the above-mentioned methods, and the antifouling properties were evaluated. The measurement results and evaluation results are shown in Table 1.

[0157] (Resin composition for forming surface layer) Trifunctional urethane (meth)acrylate oligomer: 30 parts by mass Monofunctional acrylate monomer: 40 parts by mass Bifunctional acrylate monomer: 30 parts by mass Photopolymerization initiator (benzophenone type): 0.8 parts by mass Water repellent (silicone-based): 0.5 parts by weight

[0158] [Examples 2 to 4] Laminates of Examples 2 to 4 were obtained in the same manner as in Example 1, except that the irradiation treatment in Example 1 was changed to the treatment shown in Table 1. The resulting laminate was subjected to measurement of water contact angle, measurement of surface shape, and measurement of total light transmittance by the above-mentioned methods, and the antifouling properties were evaluated. The measurement results and evaluation results are shown in Table 1.

[0159] [Examples 5 to 7] Laminates of Examples 5 to 7 were obtained in the same manner as in Example 1, except that the resin composition for forming the surface layer in Example 1 was changed to the composition shown in Table 1. The resulting laminate was subjected to measurement of water contact angle, measurement of surface shape, and measurement of total light transmittance by the above-mentioned methods, and the antifouling properties were evaluated. The measurement results and evaluation results are shown in Table 1.

[0160] [Comparative Examples 1 and 2] Laminates of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the irradiation treatment in Example 1 was changed to the treatment shown in Table 1. The resulting laminate was subjected to measurement of water contact angle, measurement of surface shape, and measurement of total light transmittance by the above-mentioned methods, and the antifouling properties were evaluated. The measurement results and evaluation results are shown in Table 1.

[0161] [Table 1] Note) Multifunctional oligomer A: Trifunctional urethane (meth)acrylate oligomer Multifunctional oligomer B: Trifunctional (meth)acrylate oligomer (having an aromatic group) Monofunctional monomer: Monofunctional acrylate monomer Multifunctional monomer: Difunctional acrylate monomer

[0162] An optical microscope image ( FIG. 4 ) of the laminate of Example 1 confirms that the laminate of the present disclosure has a wrinkled structure on its surface. The water contact angle of the laminate of Example 1 was 91.4 degrees, and the results of the antifouling test showed that no stains remained when using any writing implement, demonstrating excellent antifouling properties. Therefore, it was confirmed that there is a correlation between the wrinkled structure, water contact angle, and antifouling properties of the laminate of the present disclosure. More specifically, the wrinkled structure causes the water contact angle to be 90.0 degrees or more, and the wrinkled structure and a water contact angle of 90.0 degrees or more result in excellent antifouling properties. Therefore, from the results of Example 1 and other examples shown in Table 1, it was confirmed that the laminate of the present disclosure has excellent antifouling properties because it has a wrinkled structure and a surface shape in which the wrinkled structure results in a water contact angle of 90.0 degrees or more. On the other hand, the laminate of Comparative Example 1 had a low water contact angle of 78.8 degrees, and therefore did not have excellent antifouling properties. According to the optical microscope image ( FIG. 5 ) of the laminate of Comparative Example 1, the surface shape did not have a wrinkled structure, which is thought to be the reason for the low water contact angle. Furthermore, according to the optical microscope image ( FIG. 6 ), the laminate of Comparative Example 2 had a wrinkled surface shape, but the water contact angle was low at 87.8 degrees, and therefore did not have excellent antifouling properties. These examples and comparative examples confirmed that the laminate of the present disclosure does not exhibit excellent antifouling properties unless it has a specific surface shape.

[0163] Example 5 is an example in which a polyfunctional oligomer having an aromatic group was used, and it was found that even without using a water repellent, the laminate had a water contact angle equivalent to that of the other examples in which a water repellent was used, and also had excellent stain resistance. Furthermore, a comparison of Example 6 with Example 1 shows that the use of a wrinkle structure formation stabilizer increases the water contact angle, resulting in even better stain resistance. [Industrial Applicability]

[0164] The laminate of the present disclosure is suitable for use in a variety of applications, for example, as various components such as interior building components such as walls, ceilings, and floors; exterior components such as exterior walls, eaves ceilings, roofs, fences, and fences; fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels such as cabinets for home appliances and office equipment; and interior or exterior components for vehicles. Furthermore, in addition to the various components described above, the laminate can be used alone or in a form laminated or combined with other materials as packaging materials, antiglare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various certificates, keys of various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc.

Claims

1. The surface has a wrinkled structure and a water contact angle of 90.0 degrees or more, as measured in accordance with the provisions of JIS R3257:1999; The surface shape has a lateral parameter RSm (average length of curved elements) of a profile curve defined in B0601:2013 of 50.00 μm or less, A laminate having a total light transmittance of 20% or less as measured in accordance with JIS K7361-1:1997.

2. 2. The laminate according to claim 1, wherein the surface shape has an arithmetic mean roughness (Ra), which is a parameter in the height direction of a profile curve defined in JIS B0601:2013, of 2.00 μm or more.

3. The laminate according to claim 1 or 2, wherein the wrinkle structure is constituted by an uneven shape due to irregular wrinkles.

4. 4. The laminate according to claim 3, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.

5. 5. The laminate according to claim 1, further comprising a surface layer, wherein the surface shape is formed by the surface of the surface layer.

6. The laminate according to claim 5 , wherein the surface layer is formed from a cured product of a resin composition.

7. The laminate according to claim 6 , wherein the resin composition contains an ionizing radiation curable resin as a resin component.

8. The laminate according to any one of claims 5 to 7, wherein the surface layer contains a water repellent agent.

9. The laminate according to any one of claims 5 to 8, wherein the surface layer is provided over the entire surface.

10. The laminate according to any one of claims 5 to 9, further comprising a substrate, wherein the surface feature is present on a surface of the surface layer opposite to the substrate.

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