Laminate and decorative material

Abstract

To provide a laminate and a decorative material, which have an excellent print-processing property, and are capable of reducing occurrence of a crack (fracture) that may occur when a decorative sheet is processed into a building material, and have a post-processing property.SOLUTION: There is provided a decorative sheet 10 that is a laminate at least comprising a base layer 7, a picture print layer 6, an adhesive layer 5, and a transparent resin layer 1 in this order. The base layer 7 has an erosion rate E1 measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the range of 0.9 μm / g or more and 5.5 μm / g or less. A thickness of the base layer 7 is in a range of 30 μm or more and 150 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a laminate and a decorative material using the laminate. [Background technology]

[0002] In recent years, many decorative sheets using polyolefin resins have been proposed as alternatives to decorative sheets made of polyvinyl chloride, which are of concern from the viewpoint of environmental protection. These decorative sheets do not use vinyl chloride resin, which reduces the generation of toxic gases when burned. However, polyolefin sheets (e.g., polypropylene sheets) generally have problems such as poor scratch resistance due to their low elastic modulus, and being prone to stretching when tension is applied to the sheets during sheet creation for printing, etc. (e.g., Patent Document 1).

[0003] By attaching a decorative sheet to the surface of a substrate such as a wood substrate, metal substrate, or non-flammable substrate, a decorative board is created, and the decorative sheet imparts a design to the decorative board according to the purpose. Therefore, the decorative sheet must completely conceal the surface of the substrate as needed. In this case, it is necessary to use a decorative sheet that is colored with at least a pigment and has concealing properties. The simplest configuration of a decorative sheet can be said to be a configuration consisting only of a base layer made of a single colored sheet (single layer). In the case of such decorative sheets consisting of only a base layer, the designs that can be imparted are usually limited to a single color without a pattern, but it is possible to impart a sense of brilliance by adding, for example, lustrous materials such as aluminum flakes or pearl pigments as pigments, so it is possible to express the necessary and sufficient design. Furthermore, if an even more sophisticated design is desired, it is also effective to decorate the surface of the base layer by printing or the like.

[0004] On the other hand, as mentioned above, since colored polypropylene film has a low modulus of elasticity, when using a colored polypropylene film as a single-layer decorative sheet, it is necessary to impart excellent scratch resistance to the colored polypropylene film itself and to prevent the colored polypropylene film itself from stretching even when tension is applied during processing such as printing. The stretchability upon tension application can be improved in conventional colored polypropylene films by increasing the layer thickness to about 60 μm or more. Furthermore, the scratch resistance of conventional colored polypropylene films can be improved by providing a transparent resin layer made of polypropylene resin or a top coat layer using a urethane-based thermosetting resin made of polyol and isocyanate, as in Patent Documents 2 and 3.

[0005] In addition, when manufacturing decorative sheets, a pattern printed layer and an adhesive layer are generally formed in this order on a polyolefin film used as a substrate. In this case, if the polyolefin film used as the substrate is prone to stretching, unnatural distortion (misregistration) may occur in the pattern of the pattern printed layer. In other words, in this case, the printability may be reduced. The adhesive layer and the pattern printed layer are often made of polyester resin or polyurethane resin, which has good adhesion to the substrate and transparent resin layer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 3271022 [Patent Document 2] Patent No. 3861472 [Patent Document 3] Patent No. 3772634 [Patent Document 4] Patent No. 4737722 Summary of the Invention [Problem to be solved by the invention]

[0007] To solve the above-mentioned problems, that is, to improve the scratch resistance of the decorative sheet or the printability (resistance to stretching, etc.), the thickness of the polyolefin film substrate can be increased, or the degree of crystallinity can be increased to increase the elastic modulus. However, such decorative sheets can cause problems such as cracks (breaks) when the decorative sheet is processed into a building material (deterioration of post-processability). Therefore, there is a demand for the development of a decorative sheet that is excellent in printability and that can reduce the occurrence of cracks (breaks) that can occur when the decorative sheet is processed into building materials (excellent in post-processability).

[0008] The present disclosure has been made in consideration of the above circumstances, and aims to provide a laminate and decorative material (with excellent post-processability) that has excellent printability and can reduce the occurrence of cracks (fractures) that can occur when a decorative sheet is processed into a building material. [Means for solving the problem]

[0009] In order to solve the above problem, a laminate according to one embodiment of the present disclosure is a laminate including at least a substrate, a picture printed layer, an adhesive layer, and a transparent resin layer in this order, wherein the substrate has an erosion rate E1 measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the range of 0.9 μm / g or more and 5.5 μm / g or less, and the thickness of the substrate is in the range of 30 μm or more and 150 μm or less. A decorative material according to one aspect of the present disclosure is characterized by having the above-described laminate on an adherend. [Effects of the Invention]

[0010] According to one aspect of the present disclosure, it is possible to provide a laminate and decorative material (with excellent post-processability) that has excellent printability and can reduce the occurrence of cracks (fractures) that can occur when a decorative sheet is processed into a building material. [Brief explanation of the drawings]

[0011] [Figure 1]1 is a cross-sectional view showing a schematic configuration of a decorative sheet according to an embodiment of the present disclosure. [Figure 2] FIG. 1 is a cross-sectional view showing a schematic configuration of a decorative sheet according to a first modified example of an embodiment of the present disclosure. [Figure 3] FIG. 10 is a cross-sectional view illustrating a schematic configuration of a decorative material according to a second modified example of an embodiment of the present disclosure. [Figure 4] FIG. 10 is a cross-sectional view illustrating another configuration example of a decorative material according to a second modified example of an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0012] Decorative sheets and decorative materials according to embodiments of the present disclosure will be described below with reference to the drawings. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, and the like differ from reality. The layers do not necessarily need to be stacked in the order shown in the drawings, as long as they fall within the scope of the present disclosure. Layers not shown in the drawings may also be added. Furthermore, the embodiments shown below exemplify configurations that embody the technical ideas of the present disclosure, and the materials, shapes, structures, and the like of the components of the present disclosure are not limited to those described below. The technical ideas of the present disclosure may be modified in various ways within the technical scope defined by the claims. Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left."

[0013] As a result of extensive research, the present inventors have found that in a decorative sheet (laminate), by setting the erosion rate value of the substrate and the thickness of the substrate within specific ranges, it is possible to impart excellent printability and sufficient post-processability to the laminate. This has led the present inventors to invent a decorative sheet (laminate) that is excellent in printability and post-processability, and a decorative material comprising the decorative sheet. A first embodiment of the present disclosure (hereinafter referred to as "the present embodiment") will be described below with reference to the drawings.

[0014] (Measurement of erosion rate E) First, the "erosion rate E" defined in this embodiment will be explained. The erosion rate E in this embodiment is a value measured using, for example, a material surface precision testing machine (micro slurry jet erosion tester, hereinafter referred to as MSE tester, manufactured by Palmeso Co., Ltd. / device name Nano MSE / model N-MSE-A). The specific method for measuring the erosion rate E is as follows. Spherical alumina powder (spherical alumina particles) with an average particle diameter D50 of 3.0 μm was dispersed in water to prepare a slurry containing 3% by mass of spherical alumina powder relative to the total mass of the slurry. A decorative sheet was fixed to a base, and the projection distance between the decorative sheet and the nozzle used to spray the slurry was set to 4 mm. The nozzle diameter was 1 mm x 1 mm. Slurry containing spherical alumina powder was sprayed from the nozzle to gradually cut the decorative sheet fixed to the base, starting with the surface protection layer. The spray strength at this time was determined based on the standard projection force X, which was calculated in advance by cutting an existing hardness standard block, Si wafer, or PMMA substrate under similar experimental conditions and calculating the cut displacement relative to the amount of slurry sprayed (i.e., the depth cut when 1 g of slurry was sprayed).

[0015] In this embodiment using spherical alumina powder, the projection force when 1.000 μm / g was removed from an existing hardness standard block HRC-45 was defined as the standard projection force X. In this embodiment, in the case of spherical alumina powder, X=1 / 1 projection force (projection force when 1.0 μm / g is scraped off from an existing hardness standard block HRC-45). After washing the cut portion with water, the depth of the cut, i.e., the erosion depth Z, is measured. The erosion depth Z is measured, for example, using a stylus surface profiler (manufactured by Kosaka Laboratory Co., Ltd., model PU-EU1, stylus tip R=2 μm, load 150 μN, measurement magnification 10,000, measurement length 6 mm, measurement speed 0.2 mm / sec). In this embodiment, the erosion rate E [μm / g] is calculated using the amount of projected particles X' [g] calculated from the above-mentioned projection force and the erosion depth Z [μm]. It is known that the erosion rate E is not affected by the magnitude of the erosion rate E of the underlying layers present in the depth direction when measuring the erosion rate E. Therefore, when measuring the erosion rate E, the MSE test may be performed starting from the surface protection layer located on the outermost surface.

[0016] In this embodiment, the erosion rate E is measured for each of the substrate, the picture print layer, and the adhesive layer. Therefore, in the measurement method, cutting may be performed sequentially starting from the surface protection layer as described above, or cutting may be performed sequentially as each layer is formed. Hereinafter, the value obtained by measuring the erosion rate E for the base material will be referred to as erosion rate E1, and the average value of the values ​​obtained by measuring each of the picture printed layer and adhesive layer will be referred to as erosion rate E2. Note that in this embodiment, if it is difficult to measure the erosion rate for each of the picture printed layer and adhesive layer, the average value of the values ​​obtained by measuring the intermediate layer composed of the picture printed layer and adhesive layer may be referred to as erosion rate E2.

[0017] (Composition of decorative sheet) The components of the decorative sheet (an example of a laminate) of this embodiment will be described below, assuming that the transparent resin layer is a single layer. The decorative sheet 10 shown in Figure 1 is a laminate comprising multiple layers, and comprises, from the top of the drawing, a surface protective layer 4, a transparent resin layer 1, an adhesive layer 5 (adhesive layer, heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer (primer layer) 8. The base fabric layer 7 is the layer that serves as the base material for the decorative sheet 10, and is also referred to as a base sheet or base material layer.

[0018] The decorative sheet 10 according to this embodiment may be any decorative sheet having at least an adhesive layer 5, a picture printed layer 6, and a base fabric layer 7 provided on one side of a transparent resin layer 1. In other words, the decorative sheet 10 is a laminate, and may be any decorative sheet having at least a base fabric layer 7, a picture printed layer 6, an adhesive layer 5, and a transparent resin layer 1, in this order. In addition, in the decorative sheet 10 according to this embodiment, the laminate consisting of the picture printed layer 6 and the adhesive layer 5 is referred to as an intermediate layer 50. In order to improve the design, an embossed pattern may be appropriately provided on the surface of the transparent resin layer 1 on the surface protection layer 4 side.

[0019] The total thickness of the decorative sheet 10 is preferably in the range of 60 μm to 250 μm. If the total thickness is thinner than 60 μm, there is a concern that the required performance of the decorative sheet, such as hiding ability (ability to hide the underlying surface of the substrate for decorative material) and scratch resistance, may be reduced. Furthermore, if the total thickness is thicker than 250 μm, there is a concern that costs may increase and processability may be reduced when bonding the decorative sheet to the substrate for decorative material. Furthermore, the decorative sheet of this embodiment preferably does not contain vinyl chloride resin. By using a decorative sheet that does not contain vinyl chloride resin, concerns about the generation of toxic gases and the like during incineration are reduced. Hereinafter, each layer constituting the decorative sheet of this embodiment will be described in detail.

[0020] (Original layer) To impart design, scratch resistance, and post-processing resistance to the decorative sheet, the base fabric layer (substrate) 7 may be appropriately selected from the following materials: paper (such as tissue paper, titanium paper, or resin-impregnated paper); synthetic resins (such as polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, or acrylic); foams of these synthetic resins; rubbers (such as ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane); organic or inorganic nonwoven fabrics; synthetic paper; and metal foils (such as aluminum, iron, gold, or silver). The base fabric layer 7 may also be a sheet made of the same resin composition as the transparent resin layer 1. Among these, thermoplastic resins, particularly polyolefin-based materials such as polypropylene and polyethylene, are preferred.

[0021] Examples of the polyolefin resin contained in the raw fabric layer 7 include polypropylene, polyethylene, polybutene, and the like, as well as α-olefins (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl ... Examples of such copolymers include those obtained by homopolymerizing or copolymerizing two or more types of α-olefins (e.g., 1-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) and those obtained by copolymerizing ethylene or α-olefins with other monomers, such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer.

[0022] When a substrate with an inactive surface such as a polyolefin-based material is used as the raw fabric layer 7, it is desirable to perform, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc. on the front and back of the raw fabric layer 7. Furthermore, a primer layer (not shown) may be provided between the raw fabric layer 7 and the picture printed layer 6 to ensure adhesion. If it is desired to impart hiding properties to the decorative sheet, a hiding colored sheet may be used for the base fabric layer 7, or as shown in FIG. 1, a hiding layer 3 may be provided above the base fabric layer 7 and below the picture-printed layer 6. The hiding layer 3 will be described later. When a colored sheet is used as the base fabric layer 7, the resin material constituting the base fabric layer 7 can be colored by adding a colorant. Examples of colorants that can be used include inorganic pigments (titanium oxide, carbon black, etc.) and organic pigments (phthalocyanine blue, etc.), as well as dyes. The colorant used in this embodiment can be one or more types selected from known or commercially available colorants, and the amount added can be adjusted to obtain the desired hiding properties and design.

[0023] If necessary, various additives such as fillers, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, nucleating agents, UV absorbers, light stabilizers, heat stabilizers, colorants, and matting agents may be added to the raw fabric layer 7. The thickness of the raw fabric layer 7 is preferably in the range of 30 μm to 150 μm, more preferably in the range of 50 μm to 150 μm, and even more preferably in the range of 50 μm to 100 μm. When the thickness of the raw fabric layer 7 is within the above range, the printability and post-processability are good. If the thickness of the raw fabric layer 7 is less than 30 μm, the film strength of the raw fabric layer 7 may be insufficient, resulting in poor printability (e.g., stretching during printing, misalignment of prints, etc.). If the thickness of the raw fabric layer 7 is more than 150 μm, cracks may occur during post-processing. The raw fabric layer 7 may have a single layer structure or a multi-layer structure (laminate).

[0024] (Erosion rate E1 of original layer 7) In the decorative sheet 10 according to this embodiment, the erosion rate E1 of the raw fabric layer 7 is preferably in the range of 0.9 μm / g to 5.5 μm / g, more preferably in the range of 1.0 μm / g to 3.5 μm / g. When the erosion rate E1 of the raw fabric layer 7 is within the above range, the printability and post-processability are excellent. If the erosion rate E1 of the raw fabric layer 7 is less than 0.9 μm / g, the hardness of the raw fabric layer 7 increases (the raw fabric layer 7 becomes hard), which may result in cracks during post-processing. If the erosion rate E1 of the raw fabric layer 7 exceeds 5.5 μm / g, the hardness of the raw fabric layer 7 decreases (the raw fabric layer 7 becomes soft), which may result in reduced printability.

[0025] The erosion rate E1 can be controlled, for example, by selecting the material for the raw fabric layer 7 or by the process conditions during formation. Controlling the crystallinity of the crystalline polypropylene resin by the process conditions can be performed by a known method. For example, when the raw fabric layer 7 is formed from a crystalline polypropylene resin, the erosion rate E1 can be increased by increasing the crystallinity through heating control during film formation of the raw fabric layer 7. The erosion rate E1 can also be decreased by decreasing the crystallinity.

[0026] (Picture printing layer) The pattern printed layer 6 can be formed on the base layer 7 or the transparent resin layer 1 by, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like. When ink is used to form the picture print layer 6, the binder contained in the ink may be selected appropriately from, for example, soluble nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., either alone or modified. These may be water-based, solvent-based, or emulsion type, and may be either a one-component type or a two-component type using a hardener. Furthermore, the ink can also be cured by irradiation with ultraviolet light, electron beams, etc. Among these, the preferred method is to use a urethane-based ink and cure it with isocyanate. In other words, in the decorative sheet 10 according to this embodiment, the picture-printed layer 6 preferably contains a urethane-based resin as a binder.

[0027] The urethane-based resin used in the picture-printed layer 6 is not particularly limited, and either a one-component curing type or a two-component curing type can be used. For example, a one-component ester-based polyurethane resin can be suitably used as a one-component curing type urethane-based resin. Furthermore, a two-component curing type urethane-based resin can be used that contains, for example, a polyol component having OH groups as a main component and an isocyanate component as a curing agent component. Examples of polyol components having OH groups include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of isocyanate components include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main component can be suitably used for the picture-printed layer 6.

[0028] In addition to the binder, the picture print layer 6 may contain pigments, colorants such as dyes, extender pigments, solvents, and various additives that are commonly contained in ink. Additives may include, for example, weather resistance agents (UVA, HALS). Particularly commonly used pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. In addition to applying ink, designs can also be applied by vapor deposition or sputtering of various metals.

[0029] The thickness of the picture-printed layer 6 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 2 μm. By making the picture-printed layer 6 sufficiently thick, it may be possible to improve interlayer adhesion in the decorative sheet 10 (for example, adhesion between the base fabric layer 7, the concealing layer 3, and the adhesive layer 5). On the other hand, if the picture-printed layer 6 is too thick, post-processability (for example, bending processability) may be reduced. Therefore, by setting the thickness of the picture printed layer 6 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between layers and the post-processability. It is preferable that the pattern printed layer 6 be in contact with the base fabric layer 7 from the viewpoint of adhesion.

[0030] (hidden layer) The concealing layer 3 can be provided on the base fabric layer 7 or on the pattern-printed layer 6 formed on the transparent resin layer 1 by the same printing method as for the pattern-printed layer 6. The concealing layer 3 may be formed as needed, and can be omitted, for example, when a concealing colored sheet is used for the base fabric layer 7. When applying the concealing layer 3, for example, a comma coater, knife coater, lip coater, metal vapor deposition, sputtering, or the like may be used. The concealing layer 3 is generally provided as an upper layer of the base fabric layer 7 and as a lower layer of the pattern-printed layer 6.

[0031] The material used for the concealing layer 3 can basically be the same as that used for the picture-printed layer 6. Since the purpose of the concealing layer 3 is to provide concealment, it is preferable to use, for example, opaque pigments, titanium oxide, iron oxide, etc. as pigments. Metals such as gold, silver, copper, and aluminum can also be added to improve concealment. Flake-shaped aluminum is commonly added. If the coating thickness, i.e., the thickness of the concealing layer 3, is less than 2 μm, it is difficult to provide concealment, and if it exceeds 10 μm, the cohesive strength of the resin layer tends to be weakened. Therefore, the thickness of the concealing layer 3 is preferably in the range of 2 μm to 10 μm.

[0032] (adhesive layer) Any material can be selected for the adhesive layer 5, and bonding methods using the adhesive layer 5 include, for example, thermal lamination, extrusion lamination, and dry lamination. The adhesive contained in the adhesive layer 5 can be selected from, for example, acrylic, polyester, polyurethane, and phthalic acid (alkyd acid)-based materials. The adhesive contained in the adhesive layer 5 is usually a two-component curing type due to its high cohesive strength, and it is particularly desirable to use a urethane-based material obtained by reacting isocyanate with a polyol due to its workability, cost, and high cohesive strength. In other words, the adhesive layer 5 preferably contains a urethane resin.

[0033] The urethane-based resin used in the adhesive layer 5 is not particularly limited, and either a one-component curing type or a two-component curing type can be used. For example, a one-component ester-based polyurethane resin can be suitably used as a one-component curing type urethane-based resin. Furthermore, a two-component curing type urethane-based resin can be used that contains, for example, a polyol component having an OH group as a main component and an isocyanate component as a curing agent component. Examples of polyol components having an OH group include acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, polycarbonate polyol, and polycaprolactone polyol. Examples of isocyanate components include tolylene diisocyanate, hexamethylene diisocyanate, and metaxylene diisocyanate. In this embodiment, a polyester urethane resin using a polyester polyol as a main component can be suitably used for the adhesive layer 5.

[0034] The thickness of the adhesive layer 5 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 5 μm. By making the adhesive layer 5 sufficiently thick, it may be possible to improve the interlayer adhesion (e.g., adhesion between the base layer 7, the concealing layer 3, and the transparent resin layer 1) in the decorative sheet 10. On the other hand, if the adhesive layer 5 is too thick, post-processability (e.g., bending processability) may be reduced. Therefore, by setting the thickness of the adhesive layer 5 within the range of 1 μm or more and 10 μm or less as described above, it is possible to improve the adhesion between layers and the post-processability. From the viewpoint of improving post-processing properties, the total thickness of the intermediate layer 50 (the total thickness of the picture printed layer 6 and the adhesive layer 5) is preferably less than 20 μm.

[0035] (Erosion rate of the middle layer) In the decorative sheet 10 according to this embodiment, the difference (absolute value) between the erosion rate value E1 of the raw fabric layer 7 and the average erosion rate value E2 of the intermediate layer 50 composed of the picture-printed layer 6 and the adhesive layer 5 is within a specific range (specifically, 3.0 μm / g or less), thereby improving the adhesion between the raw fabric layer 7 and the picture-printed layer 6. Furthermore, the smaller the difference between the erosion rate value E1 of the raw fabric layer 7 and the average erosion rate value E2 of the intermediate layer 50, the better the adhesion between the raw fabric layer 7 and the picture-printed layer 6. Therefore, it is preferable that the difference (absolute value) between the erosion rate value E1 of the raw fabric layer 7 and the average erosion rate E2 of the intermediate layer 50 composed of the picture-printed layer 6 and the adhesive layer 5 be 3.0 μm / g or less, and more preferably 2.5 μm / g or less. If the difference in erosion rate between the raw fabric layer 7 and the intermediate layer 50 exceeds 3.0 μm / g, stress will be concentrated at the interface between the raw fabric layer 7 and the picture printed layer 6, which may lead to a decrease in interlayer adhesion. This makes it possible to provide a decorative sheet (laminate) that has excellent interlayer adhesion and excellent post-processability.

[0036] As described above, in this embodiment, the erosion rate value E1 of the raw fabric layer 7 and the average erosion rate value E2 of the intermediate layer 50 are adjusted so that the difference (absolute value) between the erosion rate value E1 of the raw fabric layer 7 and the average erosion rate value E2 of the intermediate layer 50 is 3.0 μm / g or less. Therefore, the erosion rate value E1 of the raw fabric layer 7 may be larger than the average erosion rate value E2 of the intermediate layer 50, or the average erosion rate value E2 of the intermediate layer 50 may be larger than the erosion rate value E1 of the raw fabric layer 7. The average value E2 of the erosion rate of the intermediate layer 50 in this embodiment will be described in detail below.

[0037] [Calculation of average value E2] Here, an example of a method for calculating the average value E2 of the erosion rate of the intermediate layer 50 constituted by the picture printed layer 6 and the adhesive layer 5 will be described. For example, the average value E2 of the erosion rate of the intermediate layer 50 is obtained by repeating the measurement of the erosion rate [μm / g] of the intermediate layer 50 "n times" and dividing the sum of the erosion rates obtained for the n times by the number of repetitions (n) (average value E2 = sum of the erosion rates for n times / n).

[0038] Specifically, the erosion rate of the intermediate layer 50 is measured. The method for measuring the erosion rate is as described above. When measuring the erosion rate, the measurement of the erosion depth Z (shape measurement) using the shape measuring instrument is repeated a set number of times (N times), and the erosion rate [μm / g] is calculated after obtaining shape measurement data for N times. Because both the picture printed layer 6 and the adhesive layer 5 are thin films, it may be difficult to measure the erosion rate individually. Therefore, in this embodiment, the erosion rate is measured for the intermediate layer 50, which is a laminate composed of the picture printed layer 6 and the adhesive layer 5.

[0039] In this embodiment, the erosion rate of the intermediate layer is measured multiple times to obtain the average value E2. Specifically, a series of erosion rate measurement processes including the above-mentioned N shape measurements is performed n times (n = an integer equal to or greater than 2). The number of erosion rate measurements (n) may be 2 or more, but is typically assumed to be 2 to 4. In other words, the erosion rate of the intermediate layer 50 is measured two to four times. Note that if the measured erosion rate value is an abnormal value (for example, a value significantly different from other measured values), it is preferable not to use it in measuring the average value E2. In other words, it is sufficient to obtain two or more erosion rate measurement values ​​excluding abnormal values.

[0040] After obtaining the erosion rates for n runs, the average value E2 can be calculated by dividing the sum of the erosion rates for n runs obtained as described above by the number of repetitions (n). Note that the above calculation method is an example, and the method for calculating the average value E2 is not limited to this calculation method. For example, if it is possible to measure the erosion rate of the picture-printed layer 6 using spherical alumina particles with an average particle diameter (D50) of 3.0 μm and the erosion rate of the adhesive layer 5 using spherical alumina particles with an average particle diameter (D50) of 3.0 μm separately, the erosion rate of the picture-printed layer 6 and the erosion rate of the adhesive layer 5 may be measured separately, and the average value E2 may be calculated from these measurements.

[0041] The average erosion rate E2 can be controlled by, for example, the material selection and formation conditions (curing method) of the intermediate layer 50, which is composed of the picture-printed layer 6 and the adhesive layer 5. For example, the average erosion rate E2 can be increased by curing the resin material (e.g., urethane-based resin) with ultraviolet light or electron beams. When a two-component curing resin is used, the average erosion rate E2 can be increased by increasing the amount of curing agent added, and can be decreased by inhibiting curing by reducing the amount of curing agent added. The erosion rate can also be increased by using an acrylic resin as the main agent in the intermediate layer 50 (picture-printed layer 6 and adhesive layer 5). The degree of curing of the intermediate layer 50 can also be controlled by the temperature history until the decorative sheet (laminate) is in its final form.

[0042] (Transparent resin layer) The transparent resin layer 1 is formed on the adhesive layer 5. The transparent resin layer 1 may be a sheet formed by film formation, or may be a laminate of already formed sheets. The transparent resin layer 1 is preferably formed using a polyolefin resin. Specifically, it is preferable to use a polyethylene resin or a polypropylene resin as the transparent resin layer 1, and it is particularly preferable to use a polypropylene resin. The transparent resin layer 1 is formed, for example, from a highly crystalline polypropylene resin. Furthermore, one or both surfaces of the transparent resin layer 1 may be activated, if necessary, by, for example, corona treatment, plasma treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, or the like.

[0043] When forming the transparent resin layer 1 as a film-forming sheet, a method using an extruder is typically used. When forming the transparent resin layer 1 by lamination, there are no particular restrictions, and methods using, for example, heat and pressure, extrusion lamination, and dry lamination are commonly used. Furthermore, when forming an embossed pattern 1a, there are methods, for example, where a sheet is first laminated by various methods and then embossed by heat and pressure, or where a pattern is formed on a cooling roll and embossed using the cooling roll simultaneously with extrusion lamination. More specifically, the embossed pattern 1a is directly applied to, for example, a highly crystalline polypropylene sheet, which is the transparent resin layer 1. Methods include applying the embossed pattern to the formed sheet using an embossing plate with a patterned pattern under heat and pressure, or using a cooling roll with a patterned pattern to form an embossed pattern simultaneously with cooling during film formation using an extruder. Here, ink can be embedded in the embossed pattern 1a as an embossed portion to further improve the design. The embossed pattern 1a may be provided if necessary, and may not be provided if unnecessary.

[0044] The thickness of the transparent resin layer 1 is preferably within a range of 40 μm or more and 170 μm or less. If the thickness of the transparent resin layer 1 is less than 40 μm, weather resistance and scratch resistance may decrease. If the thickness of the transparent resin layer 1 exceeds 170 μm, the manufacturing cost may increase and flexibility may decrease. Various additives such as heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, and catalyst scavengers may also be added to the transparent resin layer 1 as needed, provided that the features of this embodiment are not impaired.

[0045] Typically, heat stabilizers include, for example, phenols, sulfur compounds, phosphorus compounds, and hydrazine compounds; flame retardants include, for example, aluminum hydroxide and magnesium hydroxide; UV absorbers include, for example, benzotriazoles, benzoates, benzophenones, and triazines; and light stabilizers include, for example, hindered amines, all of which are added in any combination. Weather resistance must be considered when using the transparent resin layer 1 for this purpose. In this case, a UV absorber and a light stabilizer may be added to the transparent resin layer 1, with the appropriate amounts being 0.1% by mass to 2.0% by mass, based on 100% by mass of the transparent resin layer 1. The transparent resin layer 1 may also contain a nucleating agent (nano-sized nucleating agent) that has been subjected to vesiculation treatment by supercritical reverse-phase evaporation.

[0046] The crystalline polypropylene resin forming the transparent resin layer 1 can be appropriately selected from isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof, each having a different pentad fraction. It is more important that the crystalline polypropylene resin be a highly crystalline homopolypropylene resin, i.e., a homopolymer of propylene, having an isotactic pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Resins other than the crystalline polypropylene forming the transparent resin layer 1 can be appropriately selected depending on the purpose of blending, as long as they do not significantly adversely affect the physical properties of the crystalline polypropylene. However, to maintain suitability for V-groove bending, resins with good compatibility with the crystalline polypropylene resin forming the transparent resin layer 1 are preferred. The material of the transparent resin layer 1 is not limited to this, and a highly flexible polyolefin resin such as a random polypropylene resin containing an ethylene content or a polyolefin thermoplastic elastomer can be used.

[0047] The terms used in the above description of the transparent resin layer 1 will be briefly explained below. Nucleating agents are added to promote the formation of crystal nuclei during resin crystallization or to convert the nucleating agent itself into a crystal nucleus. Nucleating agents include melting agents, which melt into the base resin upon addition and re-precipitate to form crystal nuclei, and non-melting agents, which do not melt and remain as crystal nuclei after addition to the base resin. Examples of nucleating agents for polypropylene resin include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in this embodiment, in order to maximize the effects of nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts, which are non-melting agents that are expected to have good transparency. However, if transparency can be achieved by nano-processing, colored quinacridone, cyanine blue, talc, and the like can also be used. Furthermore, melting benzylidene sorbitol may be appropriately mixed with a non-melting nucleating agent.

[0048] The isotactic pentad fraction (mmmm fraction) is calculated from the electromagnetic wave absorption rate (EMF) obtained by resonating the resin material constituting the transparent resin layer 1 at a predetermined resonance frequency using C-NMR (nuclear magnetic resonance) measurement with a mass number of 13 (C). This value defines the atomic arrangement, electronic structure, and molecular microstructure of the resin material. The isotactic pentad fraction of a polypropylene resin is the ratio of five propylene units arranged in a row as determined by C-NMR and is used as a measure of crystallinity or stereoregularity. This isotactic pentad fraction is one of the important factors that primarily determines the scratch resistance of the surface. Essentially, the higher the isotactic pentad fraction, the higher the crystallinity of the sheet, resulting in improved scratch resistance.

[0049] (Surface protective layer) As shown in Fig. 1, the surface protective layer 4 is formed on the transparent resin layer 1. That is, the decorative sheet 10 has the surface protective layer 4, which serves as the outermost surface layer, laminated on the transparent resin layer 1. The surface protective layer 4 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 10. The surface protective layer 4 may contain various additives, such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as needed.

[0050] A curable resin composition can be used as a material for forming the surface protective layer 4. In this embodiment, the surface protective layer 4 contains a cured product of the curable resin composition. More specifically, the curable resin composition constituting the surface protective layer 4 preferably contains at least one of a resin that cures with heat, i.e., a thermosetting resin, and a resin that cures with ultraviolet light or electron beam irradiation, i.e., an ionizing radiation curable resin. That is, the surface protective layer 4 may be formed containing only a thermosetting resin as the curable resin composition, or may be formed containing only an ionizing radiation curable resin. Furthermore, the surface protective layer 41 may be formed containing both a thermosetting resin and an ionizing radiation curable resin, i.e., a mixed composition of a thermosetting resin and an ionizing radiation curable resin.

[0051] The thermosetting resin used for the surface protective layer 4 can be appropriately selected from, for example, polyurethane, acrylic, acrylic urethane, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, etc. The form can be any of water-based, emulsion, and solvent-based, and the curing can be either a one-component type or a two-component type using a curing agent. Among these, a urethane-based top coat that utilizes an isocyanate reaction is desirable from the viewpoints of workability, cost, and the cohesive strength of the resin itself. Specifically, it is preferable to use an acrylic urethane resin in which an acrylic polyol is combined with an isocyanate curing agent as the thermosetting resin used for the surface protective layer 4. In other words, it is preferable that the thermosetting resin constituting the surface protective layer 4 is composed of an acrylic polyol (acrylic polyol compound) and an isocyanate curing agent.

[0052] The isocyanate can be appropriately selected from curing agents such as adducts, biurets, and isocyanurates, which are derivatives of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), and various prepolymers. However, in consideration of weather resistance, it is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure.

[0053] The ionizing radiation curable resin used in the surface protective layer 4 can be appropriately selected from, for example, polyester acrylates, epoxy acrylates, urethane acrylates, acrylic acrylates, etc., but it is particularly preferable to use urethane acrylates and acrylic acrylates, which have good weather (light) resistance. From the viewpoint of workability, the ionizing radiation curable resin is preferably cured with active energy rays such as ultraviolet rays or electron beams. Examples of electron beam sources that can be used include light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, and metal halide lamps. The wavelength of the ultraviolet light is preferably in the range of 180 nm to 400 nm.

[0054] It is more preferable to use a mixture of a thermosetting resin and an ionizing radiation curable resin used in the surface protective layer 4, for example, a urethane-based resin obtained by reacting an acrylic polyol with an isocyanate as the thermosetting resin, and a urethane acrylate-based resin as the ionizing radiation curable resin. By using a mixture of a thermosetting resin and an ionizing radiation curable resin, it is possible to improve the surface hardness and at least one of the suppression of cure shrinkage and the adhesion of inorganic fine particles (inorganic filler). The ionizing radiation curable resin constituting the surface protective layer 4 is preferably an ultraviolet curable resin that is cured by ultraviolet rays.

[0055] The UV-curable resin constituting the surface protective layer 4 preferably has four or more functional groups and contains one or more components with a mass-average molecular weight of 500 or more. More preferably, it has four or more functional groups and contains one or more components with a mass-average molecular weight in the range of 500 to 5,000. UV-curable resins with fewer than four functional groups are undesirable because the crosslinking density is low and scratch resistance is significantly reduced. UV-curable resins with a mass-average molecular weight of less than 500 are undesirable because the surface condition during coating is significantly deteriorated. UV-curable resins with a mass-average molecular weight of more than 5,000 are undesirable because the viscosity of the coating liquid increases and coating suitability is significantly reduced.

[0056] The amount of the photoinitiator to be added is not particularly limited, but is preferably about 0.1 to 15 parts by mass per 100 parts by mass of the base resin. The type of photoinitiator is not particularly limited. In the case of a resin system having a radically polymerizable unsaturated group, the photoinitiator can be selected from at least one of, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, and isopropyl-N,N dimethylaminobenzoate. It is also desirable to combine multiple types to suit the light source and production environment. In the case of a resin system having a cationically polymerizable functional group, the photoinitiator can be selected from at least one of, for example, aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and furyloxysulfoxonium diallyliodosyl salts.

[0057] The method for forming the surface protection layer 4 is not particularly limited, and the surface protection layer 4 may be formed by applying a coating liquid of the above-mentioned material using a conventional method such as gravure coating, microgravure coating, comma coating, knife coating, or die coating, and then curing the liquid using a method suitable for the resin material, such as thermal curing or ultraviolet curing. This surface protective layer 4 may be provided on the transparent resin layer 1 after bonding the pattern printed layer 6 provided on the original fabric layer 7 to the transparent resin layer 1 via the adhesive layer 5, or it may be provided on the transparent resin layer 1 before bonding the transparent resin layer 1 to the original fabric layer 7.

[0058] To further improve weather resistance, an ultraviolet absorber may be added to the surface protective layer 4. That is, the surface protective layer 4 may contain an ultraviolet absorber. The ultraviolet absorber may be, for example, an ultraviolet absorber selected from a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. In addition to the ultraviolet absorber, a light stabilizer may be added to the surface protective layer 4 as appropriate. Furthermore, in order to improve the scratch resistance of the surface or to adjust the gloss (luster) associated with imparting design properties, it is desirable to add an inorganic filler to the surface protective layer 4 as a gloss adjuster.

[0059] Examples of inorganic fillers that may be added to the surface protective layer 4 include alumina, silica, boehmite, iron oxide, magnesium oxide, aluminosilicate, diamond, silicon nitride, silicon carbide, glass beads, calcium titanate, barium titanate, magnesium pyroporate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, and glass fiber. Inorganic fine particles having an average particle size of 1 μm to 30 μm can be used as the inorganic filler, with inorganic fine particles having an average particle size of 1 μm to 10 μm being particularly preferred. If the average particle size of the inorganic filler is less than 1 μm, it tends to be difficult to achieve a matte finish. This is because, to achieve a matte finish, the inorganic filler should ideally have a particle size equal to or larger than the thickness of the film (layer) to which it is added. If the average particle size of the inorganic filler exceeds 30 μm, or more precisely, 10 μm, the inorganic filler is likely to fall off from the surface protective layer 4 under high load conditions, resulting in a change in gloss and a deterioration in the appearance of the surface.

[0060] For example, when gravure printing is selected as the method for forming the surface protective layer 4, the coating thickness of one layer is appropriate to be in the range of 4 μm to 21 μm. In this case, as described above, it is preferable to select an inorganic filler having an average particle size equal to or smaller than the thickness that can be coated at one time. The content of the inorganic filler in the surface protective layer 4 is preferably in the range of 1 part by mass to 20 parts by mass relative to 100 parts by mass of the resin constituting the surface protective layer 4. If the content of the inorganic filler is less than 1 part by mass, scratch resistance may decrease. On the other hand, if the content of the inorganic filler exceeds 20 parts by mass, the surface gloss may be significantly reduced, which may impair the design and reduce weather resistance and stain resistance.

[0061] It is desirable to perform a surface treatment on the inorganic filler contained in the surface protective layer 4. By performing a surface treatment on the inorganic filler, it is possible to strengthen the bond with the surface protective layer 4. Note that inorganic fillers with untreated surfaces may also be added to the surface protective layer 4. Furthermore, when performing the surface treatment, it is desirable that the inorganic filler surface has a functional group that hydrophobicizes the inorganic filler surface and imparts reactivity with the surface protective layer 4. In other words, it is desirable that the surface treatment agent used to treat the surface of the inorganic filler has a reactive group that reacts with the main resin that constitutes the surface protective layer 4. When the inorganic filler is subjected to the surface treatment, the method is not particularly limited, and any known method can be selected.

[0062] The surface treatment agent used for the surface treatment of the inorganic filler can be at least one of surfactants, fatty acid metal salts, silane coupling agents, silicones, waxes, and modified resins. Examples of the surface treatment agent of this embodiment include silicone oils, alkyl silazanes, trimethylsilylating agents, alkoxysilanes, siloxanes, and silane coupling agents, as well as titanium coupling agents and phosphoric acid- and fatty acid-based surfactants, and may be one type or a combination of multiple types. Examples of silicone oil-based treatment agents that can be selected include straight silicone oils (dimethyl silicone oil, methylphenyl silicone oil, etc.) and modified silicone oils (amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacrylic-modified, mercapto-modified, phenol-modified, one-end reactive-modified, heterofunctional group-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, specially hydrophilic-modified, higher alkoxy-modified, higher fatty acid-containing-modified, and fluorine-modified silicone oils).

[0063] As the alkylsilazane-based treatment agent, for example, hexamethyldisilazane, vinylsilazane, etc. can be selected. Examples of the silane coupling agent include alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-hexyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenylsilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltriethoxysilane, and aminopropyltrimethoxysilane; and chlorosilane compounds such as trimethylchlorosilane and diethyldichlorosilane.

[0064] As the trimethylsilylating agent, an alkoxysilane compound among silane coupling agents can be selected. Furthermore, examples of titanate coupling agents that may be selected include isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, and bis(dioctyl pyrophosphate)oxyacetate titanate. Furthermore, as an aluminate-based coupling agent, for example, acetoalkoxyaluminum diisopropylate may be selected.

[0065] When an embossed pattern 1a is applied to the surface of the transparent resin layer 1 on the surface protective layer 4 side, the ink forming the surface protective layer 4 can be embedded into this embossed pattern by wiping processing to improve the design. From the viewpoint of weather resistance, in order to protect the transparent resin layer 1 as a substrate, one method is to impart weather resistance to the surface protective layer 4 and the transparent resin layer 1 as described above. In addition to this, there is also a method in which an ultraviolet absorber and a light stabilizer are added to the adhesive layer 5 and the picture printed layer 6 themselves, respectively, in order to protect the picture printed layer 6. Although not shown, an embossed pattern similar to the embossed pattern 1a may be provided on the outermost surface of the surface protection layer 4. This can further improve the design.

[0066] Furthermore, although an example in which the surface protective layer 4 is a single layer has been described in FIG. 1, the surface protective layer 4 in the decorative sheet 10 according to this embodiment is not limited to a single layer. The surface protective layer 4 may be a single layer or may have a multi-layer structure. In other words, the surface protective layer 4 may be composed of one or more layers. Therefore, the surface protective layer 4 may have an overall thickness in the range of 4 μm to 21 μm. Furthermore, when the surface protective layer 4 has a multi-layer structure, it may include layers formed from different resins. Furthermore, when the surface protective layer 4 has a multi-layer structure, the gloss control agent may be contained in at least one layer of the multi-layer structure. Furthermore, when the surface protective layer 4 is a multi-layer structure, it is sufficient that at least the uppermost layer contains a cured product of a curable resin composition, and layers formed from different types of resin materials may be included.

[0067] (Easy adhesion layer) The easy-adhesion layer 8 is a layer for bonding the adherend of the decorative sheet 10 (for example, a substrate for a decorative material) and the raw fabric layer 7, and is also called a primer layer. The material used for the easy-adhesion layer 8 may basically be the same as the material for the picture-printed layer 6 and the concealing layer 3. Furthermore, considering that the easy-adhesion layer 8 is applied to the back surface of the decorative sheet and therefore wound up in web form, inorganic fillers such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added to the easy-adhesion layer 8 to avoid blocking and improve adhesion to the adhesive. The coating thickness, i.e., the thickness of the easy-adhesion layer 8 (primer layer), is intended to ensure adhesion to the base fabric layer 7, and therefore is appropriately in the range of 0.1 μm to 10.0 μm, more preferably in the range of 0.1 μm to 3.0 μm. The adhesive layer 8 is necessary when the surface of the raw fabric layer 7 is inactive, such as when it is made of an olefin-based material, but is not particularly necessary when the surface is active.

[0068] <First Modification> A first modified example of the decorative sheet according to the first embodiment will be described with reference to Fig. 2. Fig. 2 is a schematic cross-sectional view illustrating one structural example of a decorative sheet 20 according to the first modified example of the first embodiment. The decorative sheet 20 according to this modified example differs from the decorative sheet 10 according to the first embodiment in that the transparent resin layer is not a single layer but a multi-layer. The decorative sheet shown in Fig. 2 comprises, in order from the top of the drawing, a surface protective layer 4, a transparent resin layer 11, an adhesive layer 5 (adhesive layer, heat-sensitive adhesive layer, anchor coat layer, dry lamination adhesive layer), a picture print layer 6, a concealing layer 3, a base fabric layer 7, and an easy-adhesion layer (primer layer) 8. As will be described in more detail below, the transparent resin layer 11 has a multi-layer structure and includes a transparent resin layer 1 and a transparent resin layer 2.

[0069] More specifically, the decorative sheet 20 according to this modification may be any decorative sheet having a configuration in which at least an adhesive layer 5, a picture printed layer 6, and a base fabric layer 7 are provided on one surface (the transparent resin layer 2 side) of a multi-layer transparent resin layer 11. In other words, the decorative sheet 10 is a laminate, and may be any decorative sheet having at least a base fabric layer 7, a picture printed layer 6, an adhesive layer 5, and a transparent resin layer 11 (transparent resin layers 1 and 2) in this order. Below, we will explain in detail the transparent resin layer 11, which is a configuration of the decorative sheet 20 that differs from the decorative sheet 10. Note that the configuration of the decorative sheet 20 other than the transparent resin layer 11 is the same as that of the decorative sheet 10. For this reason, the same reference numerals as those in the decorative sheet 10 will be used and detailed explanations will be omitted.

[0070] (Transparent resin layer) As shown in Fig. 2, the decorative sheet 20 has a transparent resin layer 11. The transparent resin layer 11 is a multi-layer (two-layer in this example) structure, and is composed of a transparent resin layer 1 and a transparent resin layer 2. More specifically, the transparent resin layer 11 is a multi-layer structure, and has the transparent resin layer 1 which becomes the first transparent resin layer, and the transparent resin layer 2 which becomes the second transparent resin layer located between the transparent resin layer 1 and the adhesive layer 5.

[0071] [First transparent resin layer] 2, transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11 in this modified example, is in contact with surface protective layer 4 and is located above transparent resin layer 2. Transparent resin layer 1, which is the first transparent resin layer of transparent resin layer 11, has the same configuration as transparent resin layer 1 of decorative sheet 10 according to the first embodiment, and therefore is given the same reference numeral and detailed description will be omitted. Note that in this modified example, transparent resin layer 1 is not in contact with intermediate layer 50. [Second transparent resin layer] 2, in the decorative sheet 20 according to this modification, a transparent resin layer 2, which is a second transparent resin layer, is provided between the transparent resin layer 1, which is the first transparent resin layer, and the adhesive layer 5. In other words, the transparent resin layer 2 is located below the transparent resin layer 1, and is adjacent to the intermediate layer 50 (particularly the adhesive layer 5). The transparent resin layer 2 may be provided when further laminate strength is required, particularly when the transparent resin layer is formed by extrusion lamination.

[0072] The transparent resin layer 1 and the transparent resin layer 2 in the transparent resin layer 11 are generally laminated and formed by a co-extrusion method. The resin contained in the transparent resin layer 2 is preferably, for example, an acid-modified resin such as polypropylene, polyethylene, or an acrylic resin. For the purpose of improving adhesive strength, the thickness of the transparent resin layer 2 is desirably 2 μm or more. If the thickness of the transparent resin layer 2 is less than 2 μm, it tends to be difficult to obtain sufficient adhesive strength. The thickness of the transparent resin layer 2 is preferably 20 μm or less. If the thickness of the transparent resin layer 2 exceeds 20 μm, the transparent resin layer 2 tends to deteriorate during long-term use, causing cohesive failure and making the layer more susceptible to peeling. That is, the thickness of the transparent resin layer 2 is preferably within the range of 2 μm to 20 μm. In addition, in the transparent resin layer 11, the sum of the thickness of the transparent resin layer 1 and the thickness of the transparent resin layer 2 is preferably 40 μm or more and 170 μm or less. In other words, the total thickness of the transparent resin layer 11 is preferably 40 μm or more and 170 μm or less. This makes it possible to improve weather resistance and scratch resistance while suppressing an increase in manufacturing costs and a decrease in flexibility.

[0073] <Second Modification> A decorative material according to a second modified example of this embodiment will be described with reference to Fig. 3. The decorative sheet according to this embodiment can be suitably used for producing a decorative material by laminating it with a substrate for a decorative material. Fig. 3 is a cross-sectional view illustrating an example of the configuration of a decorative material 100 according to a second modified example of this embodiment. 3, the decorative material 100 according to this modification is obtained by laminating the decorative sheet 10 according to this embodiment onto a substrate for a decorative material (adherend) 16 so that the surface protective layer 4 of the decorative sheet 10 is the outermost layer. That is, the decorative material 100 differs from the decorative sheet 10 according to the first embodiment in that it includes an adhesive 15 and a substrate for a decorative material 16.

[0074] (decorative materials) 3, in decorative material 100, a concealing layer 3, a pattern printed layer 6, an adhesive layer 5, a transparent resin layer 1, and a surface protective layer 4 are laminated in this order on one side of raw fabric layer 7 in decorative sheet 10, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate (adherend) 16 are provided on the other side of raw fabric layer 7. In other words, decorative material 100 comprises a decorative material substrate 16 and a decorative sheet 10 that is a laminate bonded to the decorative material substrate 16. As a result, the decorative material 100 can provide a decorative material that is highly suitable for printing, has excellent interlayer adhesion, and is also excellent in post-processing properties.

[0075] (Base material for decorative materials) The decorative material substrate 16 can be a wood substrate or a metal substrate. Examples of wood substrates that can be used include wood veneers, wood plywood, laminated lumber, particle board, medium-density fiberboard, hard fiberboard, and chipboard. Examples of metal substrates that can be used include steel plates and aluminum plates. The decorative material substrate 16 can also be made of a resin such as plastic, or a composite material thereof. When the decorative material substrate 16 is a resin substrate, for example, vinyl chloride resin can be used.

[0076] The decorative material substrate 16 may also be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Notification No. 1400 of the Ministry of Construction. The shape of the decorative material substrate 16 is not particularly limited, but it can be, for example, a flat plate. Adhesive 15 can be used to bond the decorative material substrate 16 and the decorative sheet 10. Since adhesive 15 is the same as the adhesive 15 in the second modified example of the first embodiment, it is given the same reference numeral and a description thereof will be omitted. When bonding the decorative material substrate 16 and the decorative sheet 10 together, bonding devices such as a cold press, a hot press, a roll press, a laminator, a wrapping machine, an edge bonding machine, a vacuum press, or the like can be used. After bonding the decorative material substrate 16 and the decorative sheet 10, depending on the characteristics of the final product, it may be cut, tongued using a tenon, V-shaped grooved, or chamfered on all four sides (e.g., C-chamfered).

[0077] The decorative material 100 according to this modification may have grooves and / or chamfers extending from the decorative sheet 10 side to the decorative material substrate 16, and the grooves and chamfers may be painted with a colored paint. The colored paint for coating the grooves and chamfered portions can be, for example, an ink prepared by dissolving or dispersing a colorant (organic pigment or inorganic pigment) that can also be used in the adhesive layer 5 in a vehicle. Specific examples of colorants are the same as those described above. Examples of vehicles include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes composed of isocyanates and polyols, polyacrylics, polyvinyl acetates, polyvinyl chlorides, vinyl chloride-vinyl acetate copolymers, cellulose-based resins, and polyamide-based resins. These vehicles can be used alone or in combination of two or more. As described above, it is preferable to use a colored paint containing a curing agent such as isocyanate that chemically bonds with the silanol groups of the modified resin layer. In addition, solvents, auxiliary agents, etc. can also be added as needed.

[0078] The decorative material 100 according to this modified example has been described above. Note that while FIG. 3 illustrates an example in which the decorative material 100 is constructed using the decorative sheet 10 according to the first embodiment, the present disclosure is not limited to this. The decorative material 100 may also be constructed using the decorative sheet 20 according to the first modified example of this embodiment, as shown in FIG. 4. For example, the decorative material 100 may have a concealing layer 3, a picture print layer 6, an adhesive layer 5, a transparent resin layer 2, a transparent resin layer 11, and a surface protection layer 4 laminated in this order on one side of the raw fabric layer 7 of the decorative sheet 20, and an easy-adhesion layer 8, an adhesive 15, and a decorative material substrate 16 provided on the other side of the raw fabric layer 7. That is, the decorative material 100 may be configured to include a base material 16 for a decorative material and a decorative sheet 20 that is a laminate bonded to the base material 16 for a decorative material. This makes it possible to provide a decorative material with high printability, excellent interlayer adhesion, and excellent post-processability.

[0079] (Effects of the first embodiment) The decorative sheet and decorative material according to this embodiment have the following effects. (1) The decorative sheet (decorative sheets 10, 20) of this embodiment is a laminate including at least a base fabric layer 7, a pattern printed layer 6, an adhesive layer 5, and a transparent resin layer (transparent resin layer 1, transparent resin layer 2) in this order, and the base fabric layer 7 has an erosion rate value E1 measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the range of 0.9 μm / g or more and 5.5 μm / g or less, and the thickness of the base fabric layer 7 is in the range of 30 μm or more and 150 μm or less. This configuration makes it possible to provide a decorative sheet (laminate) that is excellent in suitability for printing and that can reduce the occurrence of cracks (breaks) that can occur when the decorative sheet (decorative sheets 10, 20) is processed into the form of a building material (with excellent post-processability).

[0080] (2) The difference between the erosion rate value E1 of the raw fabric layer 7 in the decorative sheet (decorative sheets 10, 20) and the average erosion rate E2 measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the pattern printed layer 6 and the average erosion rate measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the adhesive layer 5 is 3.0 μm / g or less. In other words, the difference between the erosion rate value E1 of the raw fabric layer 7 in the decorative sheet 10 and the average erosion rate value E2 of the intermediate layer 50 consisting of the pattern printed layer 6 and the adhesive layer 5, measured using spherical alumina particles with an average particle diameter (D50) of 3.0 μm, is 3.0 μm / g or less. This configuration can prevent stress from concentrating between the raw fabric layer 7 and the intermediate layer 50, further improving interlayer adhesion.

[0081] (3) In the decorative sheets (decorative sheets 10 and 20) according to this embodiment, the layer adjacent to the base layer 7 is the pattern printed layer 6. This configuration can prevent stress from concentrating between the raw fabric layer 7 and the intermediate layer 50, further improving interlayer adhesion. (4) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, the raw fabric layer 7 contains a thermoplastic resin. This configuration can further improve printability.

[0082] (5) In the decorative sheets (decorative sheets 10, 20) according to this embodiment, the base fabric layer 7 contains a polyolefin resin. This configuration can further improve printability. (6) In the decorative sheet (decorative sheets 10, 20) according to this embodiment, the surface protective layer 4, which is the outermost layer, is laminated on the transparent resin layer (transparent resin layer 1, 11). This configuration allows the decorative sheet to be endowed with functions such as weather resistance, scratch resistance, stain resistance, and designability.

[0083] (7) The decorative material 100 according to this embodiment includes a base material 16 for a decorative material and a decorative sheet (decorative sheets 10, 20) that is a laminate bonded to the base material 16 for a decorative material. According to this configuration, a decorative material having excellent interlayer adhesion and excellent post-processability can be provided.

[0084] (Example) The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. In this example, the erosion rate value E1 of the raw fabric layer 7 was controlled by selecting the following polypropylene (PP) resin, polyethylene (PE) resin, and polybutylene terephthalate (PBT) resin and by controlling the crystallinity (extrusion temperature, cooling roll water temperature during film formation (cooling roll temperature)) conditions.

[0085] [Polypropylene (PP) resin] As the main component, 78 parts by mass of highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230°C), and a molecular weight distribution MWD (Mw / Mn) of 2.3 was added, and 6 parts by mass of titanium oxide pigment and 16 parts by mass of chromium-antimony composite oxide pigment were added as inorganic pigments. The mixture was extruded using a melt extruder to produce a raw fabric layer 7 consisting of a 55 μm thick colored polypropylene film. [Polyethylene (PE) resin] A raw fabric layer 7 was formed in the same manner as in the case of the PP resin, except that a C6-LLDPE resin "SP2540" (manufactured by Prime Polymer Co., Ltd., MFR 3.8 g / 10 min.) was used as the base resin. [Polybutylene terephthalate (PBT) resin] A base fabric layer 7 was formed in the same manner as in the case of the PP resin, except that a PBT resin "Novaduran 5505S" (manufactured by Mitsubishi Chemical Corporation, MFR 25 g / 10 min) was used as the base resin.

[0086] In this example, the following urethane resins A to C were mainly used as the resin material forming the adhesive layer 5 of the intermediate layer 50. The following urethane resins a to c were also used as the resin forming the picture printed layer 6 of the intermediate layer 50. In this example, the average erosion rate E2 of the intermediate layer 50 was controlled by selecting each resin material of the following urethane resins A to C and a to c and by the curing conditions (curing temperature or amount of curing agent added).

[0087] [Urethane resin A] A polyester urethane resin, specifically a one-component ester polyurethane resin, was used. [Urethane resin B] A two-component curing polyester urethane resin containing caprolactone-based polyester polyol as the base resin and isophorone diisocyanate as the curing agent was used. [Urethane resin C] The two-component curing polyester urethane resin was used, which was based on polyester polyol and contained hexamethylene diisocyanate as a curing agent.

[0088] [Urethane resin a] A one-component ester-based polyurethane resin was used. [Urethane resin b] A two-component curing polyester urethane resin containing caprolactone-based polyester polyol as the base resin and isophorone diisocyanate as the curing agent was used. [Urethane resin c] The two-component curing polyester urethane resin was used, which contained polyester polyol as the base resin and hexamethylene diisocyanate as the curing agent.

[0089] Example 1 A wood grain pattern was gravure printed using urethane ink with urethane resin c as a binder on a polypropylene base fabric (polypropylene (PP) resin with a thickness of 60 μm) having opacity as the base fabric layer 7 to form a pattern printed layer 6 (thickness of 3 μm), and an adhesive layer 5 (thickness of 1 μm) was further formed on the pattern printed layer 6 using urethane resin C to form an intermediate layer 50. Furthermore, a transparent resin layer 1 was dry laminated via the adhesive layer 5. In this example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 1.0 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 1.0 μm / g by controlling the process so that the extrusion temperature of the polypropylene (PP) resin was 220°C and the cooling roll water temperature during film formation was 40°C.

[0090] Furthermore, the hardness of the intermediate layer 50 was adjusted so that the average erosion rate E2 was 4.0 μm / g by heating and curing the urethane resins C and c at 60° C. The method for calculating the average value E2 in this example will be described later. The transparent resin layer 1 was formed from polypropylene (PP) resin A. More specifically, a resin material containing 100 parts by mass of random polypropylene resin "F219DA" (manufactured by Prime Polymer Co., Ltd., MFR 8.0 g / 10 min.), 0.5 parts by mass of a hindered phenol-based antioxidant (Irganox 1010; manufactured by BASF), 0.5 parts by mass of a triazine-based ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM), and 0.5 parts by mass of a NOR-type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) was extruded using a melt extruder to form a 90 μm-thick transparent resin sheet (protective film) to be used as the transparent resin layer 1. Furthermore, as the surface protective layer 4, a two-component cured polyurethane resin layer consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (a nurate form of hexamethylene diisocyanate) was applied (layer thickness 10 μm) onto the transparent resin layer 1 (the above-mentioned protective film), thereby obtaining the decorative sheet 10 of Example 1.

[0091] <Example 2> A polyethylene (PE) resin having a thickness of 55 μm was used for the raw fabric layer 7. The resin used as the binder for the picture-printed layer 6 was urethane resin c, and the resin used for the adhesive layer 5 was urethane resin C. The extrusion temperature of the raw fabric layer 7 was set to 220°C, and the cooling roll water temperature during film formation was set to 40°C, thereby adjusting the hardness so that the erosion rate value E1 of the raw fabric layer 7 was 2.8 μm / g. The amount of curing agent (isophorone diisocyanate) added to the intermediate layer 50 was adjusted to adjust the hardness so that the average erosion rate E2 of the intermediate layer 50 was 4.0 μm / g. Specifically, the amount of curing agent added was 10% by mass relative to 100% by mass of urethane resin C. The curing agent was also added to urethane resin c in the same ratio as that of urethane resin C. Otherwise, the decorative sheet 10 of Example 2 was obtained in the same manner as Example 1.

[0092] Example 3 A 100 μm-thick polybutylene terephthalate (PBT) resin was used for the raw fabric layer 7. The resin used as the binder for the picture-printed layer 6 was urethane resin c, and the resin used for the adhesive layer 5 was urethane resin C. The extrusion temperature of the raw fabric layer 7 was 250°C, and the cooling roll water temperature during film formation was 40°C, thereby adjusting the hardness so that the erosion rate value E1 of the raw fabric layer 7 was 5.4 μm / g. The amount of curing agent (hexamethylene diisocyanate) added to the intermediate layer 50 was adjusted to adjust the hardness so that the average erosion rate E2 of the intermediate layer 50 was 4.0 μm / g. Specifically, the amount of curing agent added was 10% by mass relative to 100% by mass of urethane resin C. The curing agent was also added to urethane resin c in the same ratio as that of urethane resin C. Otherwise, the decorative sheet 10 of Example 3 was obtained in the same manner as Example 1.

[0093] Example 4 The resin used as the binder for the picture printed layer 6 was urethane resin b, and the resin used for the adhesive layer 5 was urethane resin B. Furthermore, by adjusting the amount of curing agent (hexamethylene diisocyanate) added to the intermediate layer 50, the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 2.5 μm / g. Specifically, the amount of curing agent added was 10 mass% relative to 100 mass% of urethane resin B. Furthermore, the curing agent was added to urethane resin b in the same ratio as that of urethane resin B. Otherwise, the decorative sheet 10 of Example 4 was obtained in the same manner as in Example 1.

[0094] <Example 5> As in Example 4, the resin used as the binder for the picture-printed layer 6 was urethane resin b, and the resin used for the adhesive layer 5 was urethane resin B, and the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 2.5 μm / g. Otherwise, the decorative sheet 10 of Example 5 was obtained in the same manner as in Example 2.

[0095] Example 6 As in Example 4, the resin used as the binder for the picture-printed layer 6 was urethane resin b, and the resin used for the adhesive layer 5 was urethane resin B, and the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 2.5 μm / g. Otherwise, the decorative sheet 10 of Example 6 was obtained in the same manner as in Example 3.

[0096] Example 7 The resin used as the binder for the picture printed layer 6 was urethane resin a, and the resin used for the adhesive layer 5 was urethane resin A. Furthermore, by adjusting the amount of curing agent (hexamethylene diisocyanate) added to the intermediate layer 50, the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 1.6 μm / g. Specifically, the amount of curing agent added was 10 mass% relative to 100 mass% of urethane resin A. Furthermore, the curing agent was added to urethane resin a in the same ratio as that of urethane resin A. Otherwise, the decorative sheet 10 of Example 7 was obtained in the same manner as in Example 1.

[0097] Example 8 As in Example 7, the resin used as the binder for the picture-printed layer 6 was urethane resin a, and the resin used for the adhesive layer 5 was urethane resin A, and the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 1.6 μm / g. Otherwise, the decorative sheet 10 of Example 8 was obtained in the same manner as in Example 2.

[0098] Example 9 As in Example 7, the resin used as the binder for the picture-printed layer 6 was urethane resin a, and the resin used for the adhesive layer 5 was urethane resin A, and the hardness was adjusted so that the average erosion rate E2 of the intermediate layer 50 was 1.6 μm / g. Otherwise, the decorative sheet 10 of Example 9 was obtained in the same manner as in Example 3.

[0099] Example 10 A decorative sheet 10 of Example 10 was obtained in the same manner as in Example 1, except that a polypropylene (PP) resin having a thickness of 35 μm was used as the raw fabric layer 7 . In this example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.9 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.9 μm / g by controlling the process so that the extrusion temperature of the polypropylene (PP) resin was 220° C. and the cooling roll water temperature during film formation was 45° C.

[0100] Example 11 A polybutylene terephthalate (PBT) resin having a thickness of 145 μm was used as the raw fabric layer 7. Except for this, the decorative sheet 10 of Example 11 was obtained in the same manner as in Example 3.

[0101] Example 12 The decorative sheet 10 of Example 12 was obtained in the same manner as in Example 1, except that the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0102] Example 13 The decorative sheet 10 of Example 13 was obtained in the same manner as in Example 2, except that the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0103] Example 14 The decorative sheet 10 of Example 14 was obtained in the same manner as in Example 3, except that the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0104] Example 15 The decorative sheet 10 of Example 15 was obtained in the same manner as in Example 1, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B).

[0105] Example 16 The decorative sheet 10 of Example 16 was obtained in the same manner as in Example 2, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B).

[0106] Example 17 The decorative sheet 10 of Example 17 was obtained in the same manner as in Example 3, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B).

[0107] Example 18 The decorative sheet 10 of Example 18 was obtained in the same manner as in Example 1, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B), and the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0108] Example 19 The decorative sheet 10 of Example 19 was obtained in the same manner as in Example 2, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B), and the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0109] Example 20 The decorative sheet 10 of Example 20 was obtained in the same manner as in Example 3, except that the resin component forming the transparent resin layer 1 was polyolefin thermoplastic elastomer "F3740" (manufactured by Prime Polymer Co., Ltd.), MFR 4.5 g / 10 Min.) (polypropylene (PP) resin B), and the resin component forming the surface protective layer 4 was a 4:1 mixture of an ionizing radiation curable resin consisting of a tri- to hexafunctional acrylate compound and a two-component curable polyurethane resin consisting of an acrylic polyol (a copolymer of methyl methacrylate and 2-hydroxy methacrylate) and a curing agent (nurate form of hexamethylene diisocyanate).

[0110] <Comparative Example 1> A decorative sheet 10 of Comparative Example 1 was obtained in the same manner as in Example 7, except that a polypropylene (PP) resin layer 7 having a thickness of 60 μm was used. In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g by controlling the process by setting the extrusion temperature of the polypropylene (PP) resin to 220°C and the cooling roll water temperature during film formation to 50°C.

[0111] <Comparative Example 2> A decorative sheet 10 of Comparative Example 2 was obtained in the same manner as in Example 1, except that a polypropylene (PP) resin having a thickness of 60 μm was used as the raw fabric layer 7 . In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g by controlling the process by setting the extrusion temperature of the polypropylene (PP) resin to 220°C and the cooling roll water temperature during film formation to 50°C.

[0112] <Comparative Example 3> A decorative sheet 10 of Comparative Example 3 was obtained in the same manner as in Example 7, except that a polypropylene (PP) resin having a thickness of 25 μm was used as the raw fabric layer 7 . In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 0.8 μm / g by controlling the process by setting the extrusion temperature of the polypropylene (PP) resin to 220°C and the cooling roll water temperature during film formation to 50°C.

[0113] <Comparative Example 4> A decorative sheet 10 of Comparative Example 4 was obtained in the same manner as in Example 7, except that a polybutylene terephthalate (PBT) resin having a thickness of 100 μm was used as the raw fabric layer 7 . In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 5.8 μm / g. Specifically, the hardness of the raw fabric layer 7 was adjusted so that the erosion rate value E1 of the raw fabric layer 7 was 5.8 μm / g by controlling the process by setting the extrusion temperature of the polybutylene terephthalate (PBT) resin to 250°C and the cooling roll water temperature during film formation to 25°C.

[0114] <Comparative Example 5> A decorative sheet 10 of Comparative Example 5 was obtained in the same manner as in Example 1, except that a polybutylene terephthalate (PBT) resin having a thickness of 100 μm was used as the raw fabric layer 7 . In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the base film layer 7 was 5.8 μm / g. Specifically, as process control for the base film layer 7, the extrusion temperature of the polybutylene terephthalate (PBT) resin was set to 250°C, and the water temperature of the cooling roll during film formation was set to 25°C, thereby adjusting the hardness so that the erosion rate value E1 of the base film layer 7 became 5.8 μm / g.

[0115] <Comparative Example 6> The decorative sheet 10 of Comparative Example 6 was obtained in the same manner as in Example 7, except that a polybutylene terephthalate (PBT) resin with a thickness of 155 μm was used as the base film layer 7. In this comparative example, the hardness was adjusted so that the erosion rate value E1 of the base film layer 7 was 5.8 μm / g. Specifically, as process control for the base film layer 7, the extrusion temperature of the polybutylene terephthalate (PBT) resin was set to 250°C, and the water temperature of the cooling roll during film formation was set to 25°C, thereby adjusting the hardness so that the erosion rate value E1 of the base film layer 7 became 5.8 μm / g.

[0116] <MSE test erosion rate measurement> The measurement method for the erosion rate (erosion rates E1, E2) of each decorative sheet obtained in Examples 1 to 20 and Comparative Examples 1 to 6 will be described below. Spherical alumina powder with an average particle diameter D50 = 3.0 μm was dispersed in water to prepare a slurry containing 3% by mass of spherical alumina powder with respect to the total mass of the slurry. Each decorative sheet was fixed to a table, and the projection distance between the decorative sheet and the nozzle for injecting the above slurry was set to 4 mm. The nozzle diameter of the nozzle was 1 mm × 1 mm. A slurry containing spherical alumina powder was injected from the nozzle, and the decorative sheet fixed to the table was sequentially cut from the surface protective layer. At this time, the injection intensity was determined based on the value obtained by previously cutting an existing hardness reference piece under the same experimental conditions and obtaining the standard projection force X from the cut displacement with respect to the injection amount of the slurry (that is, the depth cut when 1 g of the slurry was sprayed). In the measurement method of this example using spherical alumina powder, the projection force when the existing hardness reference piece HRC-45 was cut by 1.0 μm / g was defined as the standard projection force X.

[0117] In this example, the erosion treatment and the shape measurement using the shape measuring instrument were repeated a set number of times (twice), and shape measurement data for two runs was obtained. In addition, in this example, the erosion rate E [μm / g] was calculated using the amount of projected particles X' [g] calculated from the above-mentioned projection force and the erosion depth Z [μm]. In this example, X = 1 projection force (the projection force required to remove 1.0 μm / g of the existing hardness standard HRC-45). After the cut portion was washed with water, the depth of the cut, i.e., erosion depth Z, was measured. Erosion depth Z was measured using a stylus surface profiler (Kosaka Laboratory Co., Ltd., Model PU-EU1, stylus tip R = 2 μm, load 200 μN, measurement magnification 10,000, measurement length 5 mm, measurement speed 0.2 mm / sec). More specifically, slope correction was performed using reference areas A and B at both ends of the measurement length that were not worn. Next, the step from the reference regression line to the center C of the wear scar (average value of a 50 μm width) was measured. Next, the difference between the step data at 0 g projection and the step data at each projection amount was calculated to obtain the erosion depth Z. An erosion progress graph and an erosion rate distribution graph were created from the obtained projection amount vs. erosion depth Z data. In this way, the erosion depth Z was determined.

[0118] <Calculation of average value E2> The erosion rate of the intermediate layer was measured twice using the MSE test described above, and the sum of the two erosion rates obtained was divided by the number of repetitions (2) to obtain the average value E2 (average value E2 = sum of the two erosion rates / 2).

[0119] (evaluation) The decorative sheets of Examples 1 to 20 and Comparative Examples 1 to 6 obtained by the above methods were evaluated for defects during printing (printing processability), post-processability, and interlayer adhesion as follows.

[0120] <Problems during printing (printing suitability)> The picture print layer 6 was formed by gravure printing using a gravure printing machine, and the raw fabric layer 7 was stretched by tension during the process, resulting in misregistration during lamination of each color, which was evaluated as a printing defect. The evaluation was carried out according to the following evaluation criteria and is shown in Table 1. If the evaluation was "Good" or "Good", it was evaluated as not causing any problems in practical use (passed). ○: No register adjustment is required, or automatic register adjustment is possible △: Caution is required in register adjustment ×: Register adjustment is impossible and printing cannot be continued, or the film breaks frequently during printing, causing problems with mass production

[0121] <Evaluation of post-processing properties> The post-processability was evaluated by the following method. The surface of the 3mm thick MDF (hardwood) used as the base material for the fixture was coated with 100g / m2 of a two-component water-based emulsion adhesive (Rikabond manufactured by Chuo Rika Kogyo Co., Ltd., weight ratio BA-10L / BA-11B = 100:2.5) in a wet state. 2 After coating, the decorative sheets of Examples 1 to 20 and Comparative Examples 1 to 6 were attached to the decorative materials, respectively, and cured for 24 hours to produce the decorative materials of Examples 1 to 20 and Comparative Examples 1 to 6. These decorative materials were subjected to V-cut processing, and the appearance was confirmed by visually inspecting the top of the folded portion. The V-cut processing involved creating a V-shaped groove from the side of the decorative material for doors and windows to which the decorative sheet was not attached to the boundary where the base material for doors and windows and the decorative sheet were attached, to prevent scratches on the decorative sheet. Next, the base material for the decorative material was folded 90 degrees along the V-shaped groove, with the side to which the decorative sheet of Examples 1 to 20 and Comparative Examples 1 to 6 was attached forming a mountain fold. The folded portion of the decorative sheet was then visually inspected and evaluated for whitening, cracks, etc., using an optical microscope to evaluate the superiority or inferiority of post-processability. The evaluation was carried out according to the following evaluation criteria and is shown in Table 1. Note that if the evaluation is "Good", it is evaluated as having no problem in actual use (passed). ○: No cracks or whitening of the surface protection layer were observed at the top of the bent part. ×: Significant cracking and whitening of the surface protection layer was observed at the top of the bent portion, even by visual inspection.

[0122] <Evaluation of interlayer adhesion> The adhesion between the base layer and the picture printed layer was evaluated as follows. Specifically, after being kept under conditions of 25°C and 50% RH for 2 days, the decorative sheets of each Example and Comparative Example were subjected to an adhesion test using the cross-cut method in accordance with JIS K5600-5-6. The surface of the decorative sheet was then visually observed to determine whether or not there was interlayer delamination (here, peeling between the base layer and the picture printed layer adjacent to the base layer) after the adhesion test, i.e., the interlayer adhesion, was evaluated according to the following criteria: The evaluation was carried out according to the following evaluation criteria and is shown in Table 1. Note that if the evaluation is "Good", it is evaluated as having no problem in actual use (passed). ◯: No peeling occurred between the original layer of the decorative sheet and the adjacent printed pattern layer ×: Peeling occurred between the original layer of the decorative sheet and the adjacent printed pattern layer

[0123] [Table 1]

[0124] <Evaluation results> As shown in Table 1, the evaluation results for both printability and post-processability were pass (◯) for Examples 1 to 20. In other words, decorative sheets in which the erosion rate value E1 of the original sheet layer (substrate) measured using spherical alumina particles with an average particle size (D50) of 3.0 μm was in the range of 0.9 μm / g or more and 5.5 μm / g or less, and the thickness of the original sheet layer (substrate) was in the range of 30 μm or more and 150 μm or less, were found to have excellent printability and also excellent post-processability. Furthermore, in Examples 1 to 20, the evaluation results for interlayer adhesion as well as printability and post-processability were also acceptable.

[0125] On the other hand, Comparative Examples 1 to 6 failed (evaluated as "x") in at least one of printability and post-processability. In Comparative Examples 1 to 3, the erosion rate E1 of the raw sheet layer was 0.8 μm / g, less than 0.9 μm / g, making it hard and brittle, and it is thought that the brittleness of the resin material caused cracks in the picture printed layer, making post-processing difficult to use.In addition, in Comparative Example 3, the thickness of the raw sheet layer was 25 μm, which increased flexibility and caused the decorative sheet to stretch during printing processing, which is thought to have reduced suitability for printing processing. In Comparative Examples 4 to 6, the erosion rate E1 of the raw sheet layer was 5.8 μm / g, exceeding 5.5 μm / g, which increased flexibility, which is thought to have caused the decorative sheet to elongate more during printing processing and reduced printability. In Comparative Example 6, the thickness of the raw sheet layer was 155 μm, which increased the curvature during post-processing, which is thought to have caused cracks.

[0126] As is clear from Table 1, the decorative sheets according to Examples 1 to 20 of the present disclosure were "passed" in all evaluation items, resulting in a well-balanced and excellent printability and post-processability. In other words, it was demonstrated that the decorative sheets and decorative materials according to the above embodiments of the present disclosure have excellent printability and post-processability.

[0127] Furthermore, for example, this embodiment can have the following configuration. (1) A laminate including at least a substrate, a picture print layer, an adhesive layer, and a transparent resin layer in this order, The substrate has an erosion rate E1 measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the range of 0.9 μm / g or more and 5.5 μm / g or less, A laminate characterized in that the thickness of the substrate is in the range of 30 μm or more and 150 μm or less. (2) The laminate described in (1) above, characterized in that the difference between the value E1 of the substrate and the average value E2 of the erosion rate measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the pattern printed layer and the erosion rate measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the adhesive layer is 3.0 μm / g or less. (3) The laminate according to (1) or (2) above, wherein the layer adjacent to the substrate is the picture-printed layer. (4) The laminate according to any one of (1) to (3) above, wherein the substrate contains a thermoplastic resin. (5) The laminate according to any one of (1) to (4) above, wherein the substrate contains a polyolefin resin. (6) The laminate according to any one of (1) to (5) above, wherein a surface protective layer is laminated on the transparent resin layer. (7) A decorative material having the laminate according to any one of (1) to (6) above on an adherend. [Explanation of symbols]

[0128] 1, 2 Transparent resin layer 1a Embossed pattern 3 Hidden Layer 4 Surface protective layer 5 Adhesive layer 6. Picture printing layer 7. Original layer 8 Easy adhesive layer 10, 20 decorative sheet 100 Cosmetic Materials

Claims

1. A laminate including at least a substrate, a picture print layer, an adhesive layer, and a transparent resin layer in this order, The substrate has an erosion rate E measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm. １ is in the range of 0.9 μm / g or more and 5.5 μm / g or less, A laminate characterized in that the thickness of the substrate is in the range of 30 μm or more and 150 μm or less.

2. The value E of the substrate １ and the average value E of the erosion rate measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the picture printed layer and the erosion rate measured using spherical alumina particles having an average particle diameter (D50) of 3.0 μm in the adhesive layer. ２ 2. The laminate according to claim 1, wherein the difference between the thickness and the thickness is 3.0 μm / g or less.

3. 3. The laminate according to claim 2, wherein the layer adjacent to the substrate is the picture printed layer.

4. The laminate according to claim 1 , wherein the substrate comprises a thermoplastic resin.

5. The laminate according to claim 1 , wherein the substrate comprises a polyolefin resin.

6. 2. The laminate according to claim 1, further comprising a surface protective layer laminated on the transparent resin layer.

7. A decorative material having the laminate according to any one of claims 1 to 6 on an adherend.

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