Decorative sheet

Abstract

To provide a decorative sheet which is low gloss and has an excellent balance among designability, concealability and durability.SOLUTION: There is provided a decorative sheet 1 which comprises an original fabric layer 2 and a surface protective layer 5 provided on one surface of the original fabric layer, wherein an uneven structure including a plurality of ridge-shaped portions each protruding in a ridged shape is provided on the surface of the surface protective layer 5, and in the reflection chromaticity measured under D50 light source, expressed in the Lab color system, L* is in the range of 10 or more and less than 90, a* is in the range of -2.0 or more and +16.0 or less and b* is in the range of -2.0 or more and +38.0 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet. The decorative sheet can be used, for example, for the interior and exterior decoration of buildings, and for the surface decoration of fixtures, furniture, fixtures, flooring materials, and the like. [Background technology]

[0002] In recent years, as shown in Patent Document 1, many decorative sheets using olefin resins (e.g., polypropylene sheets) have been proposed as an alternative to decorative sheets made of polyvinyl chloride, which are of concern in terms of environmental protection. The widespread use of decorative sheets that do not contain vinyl chloride resins reduces the generation of toxic gases and the like during incineration.

[0003] Decorative sheets are used to impart design and durability to the surfaces of, for example, buildings, fittings, furniture, fixtures, flooring materials, etc., and are generally widely used by laminating them to the surfaces of wood, wood boards, metal plates, non-flammable boards, paper substrates, resin substrates, etc. to form decorative sheets. Therefore, decorative sheets are required to have concealing properties that completely conceal the surface of the substrate as needed. In such cases, a large amount of pigment may be added to impart sufficient concealing properties to the decorative sheet. However, adding a large amount of pigment causes the entire decorative sheet to become hard and prone to tearing. Various technologies have been proposed to address this issue (see, for example, Patent Document 2).

[0004] When it comes to adding design, a wide variety of decorative sheets are available to choose from depending on the requirements and application, from decorative sheets printed with patterns such as wood grain or stone grain to decorative sheets without any pattern. In addition to patterns, fingerprint resistance and glossiness of the surface are also important design features required of decorative sheets. A wide variety of decorative sheets are available to choose from depending on the requirements and application, from decorative sheets with excellent fingerprint resistance and mirror-like high gloss to low gloss decorative sheets with no reflections at all. Low gloss decorative sheets are generally preferred as they are considered to have a luxurious feel.

[0005] To impart durability, a surface protective layer is typically formed on the outermost surface of a decorative sheet. Furthermore, with regard to the aforementioned glossiness, it is common to add a gloss adjuster (matt agent) to the surface protective layer, particularly to achieve a low gloss. Patent Document 3 discloses a decorative sheet that has improved design and durability (particularly scratch resistance and stain resistance) by including two gloss-adjusting layers as surface protective layers, each containing a gloss adjuster and having an adjusted gloss level.

[0006] On the other hand, Patent Documents 4 to 9 propose a method for producing a low-gloss decorative sheet by forming wrinkles on the surface of a surface protective layer using excimer light with a wavelength of less than 200 nm. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 3271022 [Patent Document 2] Patent No. 6622468 [Patent Document 3] Patent No. 7003667 [Patent Document 4] Japanese Patent Publication No. 2022-132678 [Patent Document 5] Patent No. 7060155 [Patent Document 6] Patent No. 7088431 [Patent Document 7] Patent No. 7196968 [Patent Document 8] Patent No. 7215514 [Patent Document 9] Patent No. 7294482 Summary of the Invention [Problem to be solved by the invention]

[0008] In recent years, the applications of decorative sheets have expanded, and consumers have become increasingly conscious of quality. As a result, the requirements for the design, hiding power, and durability of decorative sheets have become more diverse and sophisticated, and advanced performance is required in various properties such as low gloss, design, hiding power, fingerprint resistance, scratch resistance, stain resistance, and bending processability.

[0009] The technology of adding a gloss adjuster (matting agent) to the surface protective layer to achieve low gloss has the problem of reducing the oil repellency of the surface protective layer, making it more susceptible to fingerprints. In response to this problem, by adopting the above-mentioned technology of forming wrinkles on the surface of the surface protective layer using light of a specific wavelength instead of adding a gloss adjuster (matting agent), it is possible to achieve both low gloss and fingerprint resistance in the decorative sheet. However, the present inventors have discovered a new problem: the entire decorative sheet may appear whitish. If the decorative sheet appears whitish, the clarity of the pattern and the sense of depth or luxury that comes with low gloss are lost, thereby deteriorating the design. Furthermore, if the hiding power of the decorative sheet is insufficient, good design cannot be imparted.

[0010] An object of the present invention is to provide a decorative sheet that has low gloss and an excellent balance of design, hiding power, and durability. [Means for solving the problem]

[0011] According to one aspect of the present invention, there is provided a substrate layer and a surface protective layer provided on one surface of the substrate layer, wherein the surface protective layer has a concavo-convex structure including a plurality of ridge-like portions each protruding in a ridge-like shape, and the reflected chromaticity measured with a D50 light source is L in the Lab color system. * is in the range of 10 or more and less than 90, and a * is between -2.0 and +16.0, and b * is in the range of -2.0 or more and +38.0 or less.

[0012] According to another aspect of the present invention, the above-mentioned L * is within the range of 75 or more and less than 90, and* is in the range of -1.5 to +2.5, and the above b * is in the range of -1.5 or more and +8.5 or less.

[0013] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the gloss of the surface protective layer is 20.0 or less.

[0014] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the gloss of the surface protective layer is 10.0 or less.

[0015] According to yet another aspect of the present invention, there is provided a decorative sheet relating to any of the above aspects, wherein the raw fabric layer contains an inorganic pigment, and the content of the inorganic pigment in the raw fabric layer is in the range of 15 parts by mass or more and 45 parts by mass or less per 100 parts by mass of the raw fabric layer.

[0016] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the base layer contains a white pigment and a colored pigment as the inorganic pigment, and the mass ratio (P1 / P2) of the white pigment (P1) to the colored pigment (P2) is within the range of 98 / 2 to 2 / 98.

[0017] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, which contains at least titanium oxide as the white pigment and one or more selected from iron-zinc composite oxide, chromium-antimony composite oxide, and iron-aluminum composite oxide as the coloring pigment.

[0018] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the base layer contains a white pigment and a colored pigment as inorganic pigments, and the colored pigment contains at least a blue pigment.

[0019] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the base layer further contains a fatty acid metal salt.

[0020] According to yet another aspect of the present invention, there is provided a decorative sheet according to any one of the above aspects, wherein the surface protective layer contains an ionizing radiation curable resin formed from a cured product of an ionizing radiation curable compound.

[0021] According to yet another aspect of the present invention, there is provided a decorative sheet according to the above aspect, wherein the ionizing radiation curable compound includes either or both of an acrylate oligomer and an acrylate monomer.

[0022] According to yet another aspect of the present invention, there is provided a decorative sheet according to any of the above aspects, wherein the surface protective layer further contains particles, and the ratio of the particles to the ionizing radiation curable resin is within the range of 2 to 13 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

[0023] According to yet another aspect of the present invention, there is provided a decorative material comprising a decorative sheet according to any one of the above aspects and a substrate to which the decorative sheet is attached.

[0024] According to yet another aspect of the present invention, a method for producing a film-forming material for a substrate includes forming a coating film containing a composition containing an ionizing radiation curable compound on one surface of a substrate layer; Irradiating the coating film with light having a wavelength of 200 nm or less; After the irradiation, irradiating with ionizing radiation or ultraviolet light having a wavelength longer than that of the light, The reflected chromaticity measured with a D50 light source is L in the Lab color system. * is in the range of 10 to 90, and a * is between -2.0 and +16.0, and b * is in the range of -2.0 or more and +38.0 or less.

[0025] According to yet another aspect of the present invention, there is provided a method for producing a decorative sheet according to the above aspect, wherein the light has a wavelength of 172 nm. [Effects of the Invention]

[0026] According to the present invention, a decorative sheet is provided which has low gloss and an excellent balance of design, hiding power and durability. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view of a decorative material including a decorative sheet according to another embodiment of the present invention. [Figure 3] FIG. 3 is a cross-sectional view of the surface protection layer of the decorative sheet of FIGS. [Figure 4] FIG. 4 is a microscope image of the surface protective layer of a decorative sheet according to one example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0028] The configuration of a decorative sheet according to an embodiment of the present invention will be described below with reference to the drawings. The embodiments described below are more specific embodiments of any of the above aspects. The following features can be incorporated into each of the above aspects, either singly or in combination.

[0029] In the drawings referred to below, elements having the same or similar functions are denoted by the same reference numerals, and redundant explanations will be omitted. Furthermore, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. may differ from the actual ones.

[0030] Furthermore, the embodiments shown below are merely examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention does not limit the materials, shapes, structures, etc. of the components to those described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims.

[0031] <1> Decorative materials and decorative sheets Fig. 1 is a cross-sectional view of a decorative material including a decorative sheet according to one embodiment of the present invention. Fig. 2 is a cross-sectional view of a decorative material including a decorative sheet according to another embodiment of the present invention. Fig. 3 is a cross-sectional view of the surface protective layer of the decorative sheet of Figs. 1 and 2. Fig. 4 is a microscope image of the surface protective layer of a decorative sheet according to one example of the present invention.

[0032] The cross section shown in Fig. 3 is a cross section taken along the thickness direction of the surface protection layer. The microscope image in Fig. 4 is a planar image obtained by a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0033] The decorative material 11 shown in Figures 1 and 2 includes a substrate B and a decorative sheet 1 attached thereto. Here, the decorative material 11 is a decorative board. The decorative board may be a flat board, or may be curved or folded. The decorative board 11 may have a shape other than a board.

[0034] Here, the substrate B is a plate material. The plate material is, for example, a wood board, an inorganic board, a metal plate, or a composite board made of multiple materials. The substrate B may have a shape other than a plate.

[0035] The decorative sheet 1 shown in Fig. 1 has a printed layer 3 and a surface protective layer 5 provided in this order from the raw fabric layer 2 side on one surface, i.e., the front side, of the raw fabric layer 2, and a primer layer 6 provided on the other surface (i.e., the surface facing the substrate B) of the raw fabric layer 2. In Fig. 1, one or more of the printed layer 3 and the primer layer 6 may be omitted.

[0036] In addition, the decorative sheet 1 shown in Figure 2 has a printing layer 3, an adhesive resin layer 4b, a transparent resin layer 4, and a surface protection layer 5 provided in this order from the raw fabric layer 2 side on one surface (the front side) of the raw fabric layer 2, and a primer layer 6 provided on the other surface of the raw fabric layer 2 (i.e., the surface facing the substrate B). Here, an embossed uneven pattern (embossed pattern 4a) is provided on the transparent resin layer 4. In Figure 2, one or more of the printing layer 3, adhesive resin layer 4b, transparent resin layer 4, and primer layer 6 may be omitted. Also, the embossed pattern 4a does not have to be provided.

[0037] Furthermore, if scratch resistance or other requirements are required, at least one of the transparent resin layer 4 and the surface protective layer 5 may be laminated in multiple layers. Also, in consideration of the adhesion between the layers, other known layers may be arranged. Furthermore, a concealing layer (not shown) or the like may be provided between the base layer 2 and the primer layer 6 as appropriate.

[0038] The decorative sheet 1 has a surface protective layer 5 on the surface of which an uneven structure including a plurality of ridge-like portions each protruding in a ridge shape is provided, and the reflected chromaticity measured with a D50 light source is L in the Lab color system. * Between 10 and 90, a * is between -2.0 and +16.0, and b * is in the range of -2.0 or more and +38.0 or less. As a result, as will be explained below, it is possible to provide a decorative sheet that is low in gloss and has an excellent balance of design, hiding power, and durability.

[0039] Next, each layer that constitutes the decorative sheet 1 will be described. <1.1> Raw fabric layer The raw fabric layer 2 can be made of any material selected from paper, synthetic resin, synthetic resin foam, rubber, nonwoven fabric, synthetic paper, metal foil, etc. Examples of paper include tissue paper, titanium paper, and resin-impregnated paper. Examples of synthetic resins include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic. Examples of rubber include ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane. Examples of nonwoven fabrics include organic and inorganic nonwoven fabrics. Examples of metals for the metal foil include aluminum, iron, gold, and silver. The raw fabric layer 2 may also be a sheet made of the same resin composition as the transparent resin layer 4. In this case, the raw fabric layer 2 is obtained by molding a resin material or resin composition into a film. Examples of methods for forming the raw fabric layer 2 include calendar molding and extrusion molding.

[0040] In one embodiment, the base layer 2 is preferably a colored layer formed by mixing an inorganic pigment with a resin, etc. When the reflective chromaticity of the decorative sheet 1 is measured from the surface protective layer 5 side using a D50 light source, as described above, the reflective chromaticity is measured using a D50 light source from the surface protective layer 5 side. * is in the range of 10 or more and less than 90, and a * is between -2.0 and +16.0, and b * is in the range of -2.0 to +38.0. In the following, each value of the reflection chromaticity in this Lab color system (L * , a * , b * The above range of the reflected chromaticity (L * , a * , b * ) can be within the first suitability range.

[0041] Here, the Lab color system is a system of three values ​​(L * , a * , b * ) is a color system expressed in coordinates using L * indicates brightness, and the larger the value, from 0 to 100, the brighter it becomes. * , b * and a * , b * If both are 0, the color will be achromatic. * The more positive the value, the stronger the redness, and the more negative the value, the stronger the greenness. * The more positive the value, the stronger the yellowness, and the more negative the value, the stronger the blueness. In this embodiment, the reflected chromaticity of the decorative sheet 1 was measured using a fluorescence spectrodensitometer (FD-7) manufactured by Konica Minolta, Inc., with a D50 light source and a viewing angle of 10 degrees, by measuring the reflected chromaticity on a white background of an opacity test paper (byko-chart high brightness 2A) manufactured by BYK-GARDNER.

[0042] In the decorative sheet 1 provided with the surface protective layer 5 described later, the values ​​of reflected chromaticity (L * , a * , b * ) within the first suitable range makes it possible to effectively improve design and hiding power while achieving both low gloss and durability. * , a * , b * ), especially L * If L is less than 10, the decorative sheet will be black overall and will have good hiding power, but the light diffused by the ridges on the surface of the surface protective layer 5 will be noticeable, making the decorative sheet look whitish overall. If the decorative sheet looks whitish, the clarity of the pattern and the sense of depth or luxury due to low gloss will be lost, resulting in a deterioration in design. *If the value is 90 or more, the decorative sheet becomes white, and is perceived as the sum of the light diffused by the ridges and the light reflected. This prevents the decorative sheet from appearing whitish overall, but the hiding power deteriorates. If the hiding power is insufficient, the base fabric layer 2 cannot fulfill its role of hiding the pattern of the substrate B. If the printing layer 3 is a pattern layer, the pattern of the printing layer 3 and the pattern of the substrate B will be mixed together, which is not desirable. From the viewpoint of achieving both design and hiding power, the above L in the Lab color system * is preferably in the range of 60 or more and 85 or less.

[0043] (inorganic pigments) Examples of inorganic pigments include natural inorganic pigments and synthetic inorganic pigments. Examples of natural inorganic pigments include earth pigments, calcined earth, and mineral pigments. Examples of synthetic inorganic pigments include oxide pigments, hydroxide pigments, sulfide pigments, silicate pigments, phosphate pigments, carbonate pigments, metal powder pigments, and carbon pigments. Furthermore, as synthetic inorganic pigments, mixed pigments containing one or more natural and / or synthetic inorganic pigments may be used. Furthermore, as synthetic inorganic pigments, organic pigments such as carbon black may be used.

[0044] The raw fabric layer 2 preferably contains a white pigment and a colored pigment (an inorganic pigment other than a white pigment) as inorganic pigments. When the raw fabric layer 2 contains a white pigment and a colored pigment, the values ​​of the reflected chromaticity of the decorative sheet 1 (L * , a * , b * ) can be easily set within the first suitable range. Examples of the white pigment include titanium oxide and zinc oxide.

[0045] As inorganic pigments, composite oxides, which are combinations of two or more oxides, are preferably used. Composite oxides form an even ion lattice with each metal ion occupying the gaps of the closest-packed O2, creating an extremely stable structure. Due to their structural stability, composite oxides are characterized by excellent heat resistance, chemical resistance, weather resistance, and safety. They are also useful as pigments and have long been used in a wide range of applications. A wide range of hues can be created by combining metals, and iron-zinc, chromium-antimony, and iron-aluminum composite oxides are preferably used. These composite oxide pigments are preferably used in combination with white pigments, such as titanium oxide, as coloring pigments. They are also preferably used in combination with black pigments, such as carbon black.

[0046] L in the Lab color system * is within the range of 75 or more and less than 90, and a * is between -1.5 and +2.5, and b * It is preferable that the decorative sheet in which L is in the range of -1.5 or more and +8.5 or less contains a blue pigment in the raw fabric layer 2. * In the decorative sheet 1 in the high region, by adding a blue pigment, it is possible to improve the hiding power while maintaining excellent design. In the following, each value of the reflected chromaticity (L * , a * , b * ) is referred to as the "second suitable range."

[0047] In ancient times, powdered lapis lazuli was used as a blue pigment to create a beautiful blue-purple color. This was called ultramarine because it was brought from far across the ocean. Nowadays, it can be synthesized and is known as ultramarine. Ultramarine can be synthesized, for example, by mixing the clay mineral kaolin, sulfur, activated carbon, etc., and firing the mixture. The three-dimensional aluminosilicate lattice that makes up ultramarine contains three sulfur atoms that are bonded to form an ion. The blue color of the pigment is due to a radical anion with an unpaired electron, and its drawback is that it is vulnerable to acids. Ultramarine can also be synthesized by mixing, for example, a sulfur-containing sodium silicate complex (Na8-10 Al6Si6O 24 S 2-4 ) is available.

[0048] Prussian blue (Mirrory blue) is the first synthetic pigment developed in Germany and is also known as Prussian blue. Cobalt blue is another bright blue pigment. Other inorganic pigments (colored pigments) that can be used include cerulean blue and gosu (underglaze). Prussian blue (Mirrory blue) is a pigment with the formula Fe4[Fe(CN)6]3, for example. Cobalt blue is a pigment with the formula CoAl2O4 or CoOAl2O3, for example. Cerulean blue is a pigment with the formula CoO·nSnO2·mMgO (n = 1.5-3.5, m = 2-6). Gosu is made of, for example, quartz, halloysite, and lithiopholite.

[0049] The content of the inorganic pigment contained in the raw fabric layer 2 is preferably in the range of 15 to 45 parts by mass, more preferably in the range of 18 to 30 parts by mass, per 100 parts by mass of the raw fabric layer 2. A low content of the inorganic pigment results in poor hiding power, while a high content undesirably causes embrittlement of the raw fabric layer 2.

[0050] As mentioned above, the base layer 2 preferably contains a white pigment and a colored pigment (an inorganic pigment other than a white pigment) as inorganic pigments. In this case, the mass ratio (P1 / P2) of the white pigment (P1) to the colored pigment (P2) is preferably within the range of 99.9 / 0.1 to 0.1 / 99.9, and more preferably within the range of 98 / 2 to 2 / 98. By adjusting the blending ratio of the white pigment and the colored pigment within a suitable range, the values ​​of the reflected chromaticity (L * , a * , b * ) can be easily adjusted to fall within the first suitable range or the second suitable range, thereby improving both the design and hiding power.

[0051] When the raw fabric layer 2 contains a blue pigment as an inorganic pigment, the content thereof is preferably in the range of 0.5 parts by mass to 5.0 parts by mass per 100 parts by mass of the raw fabric layer 2 . In particular, the values ​​of reflected chromaticity (L * , a * , b * ) is within the second aptitude range, and the above L * When the chromaticity is in the high region of 75 or more, the content of the blue pigment contained in the raw fabric layer 2 is preferably in the range of 0.5 parts by mass to 3.0 parts by mass, more preferably in the range of 1 part by mass to 2 parts by mass, per 100 parts by mass of the raw fabric layer 2. If the content of the blue pigment is low, it is difficult to obtain the effect of improving hiding power while maintaining excellent design. If the content of the blue pigment is high, the blue tinge becomes strong, and the desired color may not be obtained.

[0052] (resin) From the viewpoint of environmental protection, the resin to be mixed with the inorganic pigment is preferably an olefin resin. Examples of the olefin resin include olefin homopolymers such as ethylene, propylene, and butene, ethylene-propylene block copolymers, random copolymers, copolymers of at least one of ethylene and propylene with at least one other olefin such as butene, pentene, and hexene, and copolymers of at least one of ethylene and propylene with at least one other monomer such as vinyl acetate and vinyl alcohol. Among these, polyethylene and polypropylene are preferred from the viewpoint of obtaining excellent scratch resistance and good bending processability.

[0053] [Polyethylene resin] The polyethylene may be a homopolymer of ethylene, or a copolymer of ethylene and another comonomer copolymerizable with ethylene (e.g., α-olefins such as propylene, 1-butene, 1-hexene, and 1-octene, vinyl acetate, vinyl alcohol, etc.). Examples of polyethylene resins include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHMWPE), and cross-linked polyethylene (PEX). These polyethylenes may be used alone or in combination of two or more.

[0054] [Polypropylene resin] The polypropylene resin is preferably a highly crystalline polypropylene. In particular, it is preferable to use a highly crystalline homopolypropylene resin, which is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more, in an amount of 50% by mass to 100% by mass of the total polypropylene resin. For example, a random polypropylene resin or a known amorphous polypropylene resin having an ethylene content within a predetermined range can be mixed with the highly crystalline homopolypropylene.

[0055] Furthermore, additives such as fatty acid metal salts may be added to the resin to improve dispersibility and extrusion suitability.

[0056] When a substrate with an inactive surface such as an olefin-based material is used as the raw fabric layer 2, it is desirable to subject the front and back of the raw fabric layer 2 to corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc.

[0057] In another embodiment, the raw fabric layer 2 preferably has a colored layer formed by mixing an inorganic pigment with a resin or the like, and a skin layer that does not contain an inorganic pigment. The thickness of the skin layer is preferably 3 μm to 20 μm, and the thickness ratio of the skin layer to the colored layer (skin layer:colored layer) is preferably within the range of 1:6 to 1:50. When the raw fabric layer 2 is formed by co-extrusion, if the colored layer is the outermost layer, the pigment components contained in the colored layer will bleed and contaminate the T-die of the extruder and the rolls during transport, so it is desirable that the outermost layer be a skin layer that does not contain a pigment. It is desirable to provide skin layers on both sides of the colored layer. Increasing the thickness of the skin layer and increasing its ratio to the colored layer is undesirable because it reduces the ratio of the colored layer and reduces hiding power.

[0058] It is also important that the thickness of the raw fabric layer 2 is 50 μm or more and 150 μm or less. If the thickness of the raw fabric layer 2 is less than 50 μm, the performance of covering the unevenness of the base (unevenness) will decrease. On the other hand, if the thickness of the raw fabric layer 2 exceeds 150 μm, problems such as whitening and cracking may occur during bending.

[0059] <1.2>Printing layer A printed layer 3 can be provided on the surface of the base fabric layer 2. The printed layer 3 may be a patterned layer or a solid ink layer. When the printed layer 3 is a patterned layer, a pattern can be added to the decorative sheet 1. Patterns that can be used include wood grain, pebble grain, sand grain, tiled, brickwork, fabric grain, leather-grained, and geometric shapes. When the printed layer 3 is a solid ink layer, the solid ink layer is provided so as to cover the entire surface of the base fabric layer 2.

[0060] Furthermore, a base solid ink layer (not shown) may be provided between the base fabric layer 2 and the printing layer 3 depending on the level of the desired design. The base solid ink layer is provided so as to cover the entire surface of the base fabric layer 2. The base solid ink layer may also be multi-layered, with two or more layers, as needed for hiding properties, etc. Furthermore, the printing layer 3 may be formed by laminating the same number of plates as necessary to express the desired design. In this way, the printing layer 3 and the base solid ink layer can be combined in various ways depending on the desired design, i.e., the design to be expressed, but there are no particular limitations.

[0061] The constituent materials of the base solid ink layer and the printed layer 3 are not particularly limited. Examples of materials that can be used for the base solid ink layer and the printed layer 3 include printing inks and coating agents prepared by dissolving or dispersing a matrix and a colorant, such as a dye or pigment, in a solvent. Examples of the matrix include various synthetic resins, such as oil-based nitrocellulose resins, two-component urethane resins, acrylic resins, styrene resins, polyester resins, urethane resins, polyvinyl resins, alkyd resins, epoxy resins, melamine resins, fluorine-containing resins, silicone resins, and rubber resins, as well as mixtures and copolymers thereof. Examples of colorants that can be used include inorganic pigments, such as carbon black, titanium white, zinc white, red iron oxide, yellow lead, iron blue, and cadmium red; organic pigments, such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; and mixtures thereof. As the solvent, toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, or a mixture thereof can be used.

[0062] In the decorative sheet 1, the presence or absence of the printing layer 3 depends on the respective values ​​of the above-mentioned reflected chromaticity (L * , a * , b * Therefore, the decorative sheet 1, depending on the combination of the base layer 2 and the printed layer 3, has the effect of controlling the above-mentioned reflected chromaticity values ​​(L * , a* , b * ) is formed so as to be within the first suitability range.

[0063] That is, when the printed layer 3 is, for example, a pattern layer having openings, the surface of the surface protection layer 5 to be inspected, where the reflected chromaticity is measured, has an area (1) directly below which the printed layer 3 is formed, and an area (2) directly below which the printed layer 3 is not formed. In this case, for example, the values ​​of the reflected chromaticity measured with a D50 light source (L * , a * , b * ) is within the first suitable range, the respective values ​​of the reflected chromaticity (L * , a * , b * ) is within the first suitability range.

[0064] Functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the base solid ink layer and the printing layer 3 to impart various functions.

[0065] Here, the base solid ink layer and the printed layer 3 can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. Furthermore, since the base solid ink layer covers the entire surface of the base layer 2, it can also be formed by various coating methods such as roll coating, knife coating, microgravure coating, and die coating. These printing and coating methods may be selected separately depending on the layer to be formed, but it is more efficient to select the same method and process them all at once.

[0066] The thickness of the printed layer 3 is preferably 3 μm or more and 20 μm or less. When the thickness of the printed layer 3 is within this range, the printing can be made clear, the printing workability when producing the decorative sheet 1 is improved, and production costs can be reduced.

[0067] <1.3>Transparent resin layer The resin material used as the main component of the transparent resin layer 4 is preferably made of an olefin-based resin, and in addition to polypropylene, polyethylene, polybutene, etc., α-olefins (for example, 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-pent ... Examples of such copolymers include homopolymers or copolymers of two or more types of α-olefins (e.g., ethylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.), as well as copolymers of 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.

[0068] Furthermore, when attempting to improve the surface strength of the decorative sheet 1, it is preferable to use a highly crystalline polypropylene as the olefin resin. For example, the highly crystalline polypropylene preferably has a pentad fraction (mmmm fraction) of 96% or more, a melt flow rate (MFR) of 5 g / 10 min (230°C) to 40 g / 10 min (230°C), and a molecular weight distribution (MWD; Mw / Mn) of 4 or less. In this case, the surface strength is good, and the bending processability of the decorative sheet 1 is also good.

[0069] Here, the olefin resin contained as the main component in the transparent resin layer 4 preferably exists in the transparent resin layer 4 at a ratio of 90% by mass or more of the materials contained in the transparent resin layer 4.

[0070] When a transparent resin layer 4 is provided, the thickness of the transparent resin layer 4 is preferably 50 μm or more and 100 μm or less. If it is less than 50 μm, the effect of improving the scratch resistance of the surface of the transparent resin layer 4 is low, and the purpose of providing the transparent resin layer 4 is diminished. If the thickness of the transparent resin layer 4 exceeds 100 μm, the rigidity of the decorative sheet 1 may be too high, which may cause problems such as whitening and cracking during bending. However, when a surface protective layer 5 is provided on the transparent resin layer 4, the thickness of the transparent resin layer 4 may be less than 50 μm.

[0071] The resin composition constituting the transparent resin layer 4 may contain various functional additives, such as a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as needed. These various functional additives can be appropriately selected from well-known additives.

[0072] Additionally, the adhesive used to bond the printed layer 3 and the transparent resin layer 4 can be any material selected depending on the bonding method. Examples of bonding methods include lamination methods such as thermal lamination, extrusion lamination, and dry lamination, and the adhesive can be selected from acrylic, polyester, polyurethane, and other materials. Due to their cohesive strength, two-component curing urethane materials that utilize the reaction between isocyanate and polyol are typically preferred. There are no particular restrictions on the lamination method for the transparent resin layer 4, but methods that apply heat and pressure, extrusion lamination, and dry lamination are commonly used.

[0073] The transparent resin layer 4 may also be provided with an embossed pattern (embossed pattern 4a). Ink can be embedded in the embossed pattern 4a to further improve the design. The embossed pattern 4a can be provided by a method in which a sheet that has been laminated by various methods is embossed later by heat and pressure, or by a method in which a pattern is provided on a cooling roll and embossed simultaneously with extrusion lamination.

[0074] Alternatively, a method can be used in which the printed layer 3, which has been embossed simultaneously with extrusion, and the transparent resin layer 4 are bonded together by heat or dry lamination.

[0075] Furthermore, to improve adhesion between the printed layer 3 and the transparent resin layer 4, an adhesive resin layer 4b may be provided between the printed layer 3 and the transparent resin layer 4. Specifically, when further lamination strength is required in the extrusion lamination method, an adhesive resin layer 4b may be provided between the transparent resin layer 4 and the adhesive. When the adhesive resin layer 4b is provided, lamination can be performed by co-extrusion of the transparent resin layer 4 and the adhesive resin layer 4b. The adhesive resin layer 4b can be an acid-modified resin such as polypropylene, polyethylene, or acrylic resin. The thickness of the adhesive resin layer 4b is preferably 2 μm or more to improve adhesive strength.

[0076] <1.4>Surface protective layer As shown in FIG. 3 , the surface protective layer 5 has a core portion 5A and a ridge portion 5B that protrudes in a ridge-like manner from one surface of the core portion 5A. This forms an uneven shape in the surface protective layer 5. Here, in the decorative sheet 1 according to one embodiment of the present invention, the term "ridge-like" refers to a long, raised, linear shape in a planar view. The ridge portion 5B may be curved or linear in a planar view, but is preferably curved from the viewpoint of the fingerprint resistance of the decorative sheet 1. Furthermore, in this embodiment, the ridge portion 5B refers to, for example, the portion from the lowest to the highest point of the uneven shape of the surface protective layer 5, and the core portion 5A refers to the portion of the surface protective layer 5 excluding the ridge portion 5B. The cross-sectional shape of the ridge portion 5B in the thickness direction of the surface protective layer 5 may be sinusoidal. Here, the sinusoidal shape refers to a shape in which the line from the lowest point to the highest point of the ridge portion 5B can be expressed as a sine wave.

[0077] Fig. 3 is a cross-sectional view schematically showing a cross section of the ridge portion 5B of the surface protective layer 5 (a cross section in the thickness direction of the surface protective layer 5), and Fig. 4 is a planar image showing the surface configuration of the surface protective layer 5. Here, Fig. 4 is a planar image obtained by a laser microscope (OLS-4000 manufactured by Olympus Corporation).

[0078] The ridge portions 5B are elongated raised portions that are connected linearly in plan view, as shown in the planar image of Fig. 4. As will be described later, the ridge portions 5B are formed by irradiating the surface of a coating film of a composition containing an ionizing radiation-curable compound (coating liquid for surface protective layer) with light of a specific wavelength, causing buckling of a cured film containing an ionizing radiation-curable resin that is a cured product of the ionizing radiation-curable compound.

[0079] The shape of the ridge portions 5B can be expressed by the ratio RSm / Ra of the surface roughness index RSm (μm) in the horizontal direction (the planar direction of the surface protective layer 5, i.e., the left-right direction in FIG. 3 ) to the surface roughness index Ra (μm) in the vertical direction (the depth direction of the ridge portions 5B, i.e., the thickness direction of the surface protective layer 5, i.e., the up-down direction in FIG. 3 ). RSm / Ra is preferably in the range of 10 to 300, more preferably 10 to 250. As the ratio RSm / Ra decreases, the shape of the ridge portions 5B becomes finer, making it difficult to wipe off dirt and reducing contamination resistance. As the ratio RSm / Ra increases, the spacing between the ridges becomes wider, resulting in higher gloss. Here, the surface roughness indexes Ra and RSm are measured using a line roughness meter in accordance with JIS B0601.

[0080] The thickness t of the surface protective layer 5 is preferably in the range of 2 μm to 20 μm, more preferably in the range of 3 μm to 10 μm. If the surface protective layer 5 is too thin, it becomes difficult to achieve a low gloss, and if it is too thick, processability decreases and whitening occurs when the layer is bent.

[0081] Here, the thickness of the surface protective layer 5 refers to the thickness of a layer having the same apparent area and volume as the surface protective layer 5 and a flat surface. The thickness of the surface protective layer 5 can be determined, for example, by the following method. First, a cross section parallel to the thickness direction of the surface protective layer 5 and perpendicular to the length direction of the ridge portions 5B is imaged. Next, the dimension of the surface protective layer 5 in the width direction of the ridge portions 5B and the area of ​​the cross section of the surface protective layer 5 are determined from this cross-sectional image. The thickness of the surface protective layer 5 is obtained by dividing this area by the above dimension. The thickness of the surface protective layer 5 is also determined by observing the cross section with a scanning electron microscope and averaging the values ​​at 25 points. Specifically, the thickness of the surface protective layer 5 can be determined as described in the Examples below. Note that when the coating liquid for the surface protective layer described below does not contain a solvent, the thickness of the coating film made of the coating liquid for the surface protective layer is equal to the thickness of the surface protective layer 5.

[0082] Here, the surface protective layer 5 can be formed by various printing methods such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. Furthermore, since the surface protective layer 5 covers the entire surface of the front side of the raw fabric layer 2, it can also be formed by various coating methods such as roll coating, knife coating, microgravure coating, and die coating. These printing or coating methods may be selected separately for each layer to be formed, or the same method may be selected and used for batch processing.

[0083] The printing layer 3 and the surface protective layer 5 may be synchronized from the viewpoint of design. In such a case, it is necessary to form the surface protective layer 5 after forming the printing layer 3, and therefore it is preferable to use a gravure printing method. Furthermore, the gravure printing method allows for relatively high speed processing, which is advantageous in terms of cost and is therefore preferable. Here, synchronization means that 50% or more, preferably 70% or more, and most preferably 90% or more of the area where the surface protective layer 5 is formed overlaps with the pattern portion of the printing layer 3 in a planar view.

[0084] The thickness of the surface protective layer 5 can be adjusted by adjusting the amount of coating in the printing method and coating method described above. The amount of coating can be calculated from the mass difference between a substrate (raw fabric layer) with a surface protective layer formed thereon and one without, prepared using various printing and coating methods.

[0085] The surface protective layer 5 contains, as a main component, an ionizing radiation curable resin, which is a cured product of an ionizing radiation curable compound. Specifically, the ionizing radiation curable resin is contained in an amount of preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and most preferably 80 parts by mass or more per 100 parts by mass of the surface protective layer 5. In the present disclosure, "ionizing radiation" refers to charged particle beams such as electron beams (EB). The ionizing radiation curable compound is cured by irradiation with ionizing radiation. The ionizing radiation curable compound can also be cured by ultraviolet irradiation. The ionizing radiation curable compound used here is cured by irradiation with light having a wavelength of 200 nm or less, and has a high absorption coefficient for this light.

[0086] In this disclosure, the term "functional group number" refers to the number of acryloyl groups or methacryloyl groups contained in one molecule of an ionizing radiation-curable compound. Furthermore, in this disclosure, the term "acrylic" generally refers to acrylic and / or methacrylic. Similarly, the term "acryloyl" generally refers to acryloyl and / or methacryloyl, and the term "acrylate" generally refers to acrylate and / or methacrylate.

[0087] The surface protective layer 5 is a cured film of a coating film formed using a composition containing an ionizing radiation-curable compound (hereinafter referred to as "ionizing radiation-curable composition"), and as described above, contains, as a main component, an ionizing radiation-curable resin, which is a cured product of the ionizing radiation-curable compound. The ionizing radiation-curable compound is, for example, an acrylate oligomer, which contains one or more acrylate oligomers selected from acrylic acrylate oligomers and urethane acrylate oligomers having 2 to 15 functional groups. The ionizing radiation-curable compound may further contain an acrylate monomer, which will be described later. The proportion of the acrylate oligomer in the ionizing radiation-curable compound is in the range of more than 60 parts by mass to 100 parts by mass, and preferably in the range of more than 60 parts by mass to 80 parts by mass.

[0088] By including the acrylate oligomer having a mass-average molecular weight of 700 to 20,000 in the ionizing radiation-curable composition, the shaping properties are improved, improving the formability of the ridge-containing uneven structure in the surface protective layer 5, thereby contributing to low gloss and fingerprint resistance. Furthermore, a high mass-average molecular weight of the acrylate oligomer results in a high viscosity. High viscosity tends to result in a problem of gloss not decreasing when the line speed is increased in the first irradiation step described below. In contrast, when the mass-average molecular weight of the acrylate oligomer is 20,000 or less, such a problem can be suppressed even when the line speed is increased, thereby achieving low gloss while improving production efficiency. The mass-average molecular weight of the acrylate oligomer is preferably within the range of 700 to 7,000. Here, the mass-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0089] Furthermore, in the acrylate oligomer contained in the ionizing radiation-curable composition, the number of functional groups possessed by the urethane acrylate oligomer is within the range of 2 to 15, which contributes to further improvement in formability. In the acrylate oligomer contained in the ionizing radiation-curable composition, the number of functional groups possessed by the acrylic acrylate oligomer may be, for example, the same range as that of the urethane acrylate oligomer, that is, 2 to 15. Inclusion of the acrylate oligomer in the ionizing radiation-curable composition increases the crosslink density in the ionizing radiation-curable resin that is the cured product, improving scratch resistance and stain resistance.

[0090] As the acrylate oligomer, commercially available products may be used, for example, EBECRYL (registered trademark) 9270, KRM9465, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8409, EBECRYL9270, KRM2000 (all bifunctional urethane acrylates, manufactured by Daicel-Allnex Co., Ltd.), UN-2601, UN-6200, UN-6304, UN- 6306 (all bifunctional urethane acrylates, manufactured by Negami Chemical Industrial Co., Ltd.), UA-4200, UA-4400, UA-1100H (all bifunctional urethane acrylates, manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL4513, EBECRYL4738, EBECRYL4740, EBECRYL4820, EBECRYL9260, EBECRYL8701, EBECRYL4265 (all trifunctional urethane acrylates, manufactured by Daicel Allnex Co., Ltd.), SMT-001 (trifunctional urethane acrylate, Negami Chemical Industrial Co., Ltd.), EBECRYL4666, EBECRYL4680, EBECRYL8210, KRM8528 (tetrafunctional urethane acrylate, Daicel Allnex Co., Ltd.), EBECRYL1290, EBECRYL5129, EBECRYL8254, KRM8200, KRM8452 (hexafunctional urethane acrylate, Examples of such urethane acrylates include acrylate, manufactured by Daicel-Allnex Co., Ltd.), UN-3320HA (hexafunctional urethane acrylate), UN-3320HC (hexafunctional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.), UN-904 (10-functional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.), UN-3320HS (15-functional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.), OAP-5000, and OAP-2531 (acrylic acrylates, manufactured by Negami Chemical Industrial Co., Ltd.). These all have a mass average molecular weight in the range of 700 to 20,000.

[0091] Among the above, for example, UA-4400 (bifunctional urethane acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) has a mass average molecular weight of 1400 and a viscosity of 3000 Pa·s / 25°C, EBECRYL8701 (trifunctional urethane acrylate, manufactured by Daicel-Allnex Co., Ltd.) has a mass average molecular weight of 2000 and a viscosity of 4500 Pa·s / 60°C, SMT-001 (trifunctional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.) has a mass average molecular weight of 1700 and a viscosity of 1000 Pa·s / 25°C, and EBECRYL4666 (tetrafunctional urethane acrylate, manufactured by Daicel-Allnex Co., Ltd.) has a mass average molecular weight of 1700 and a viscosity of 1000 Pa·s / 25°C. EBECRYL5129 (hexafunctional urethane acrylate, manufactured by Daicel-Allnex Corporation) has a mass average molecular weight of 800 and a viscosity of 700 Pa·s / 60°C. UN-904 (10-functional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.) has a mass average molecular weight of 4900 and a viscosity of 500,000 Pa·s / 25°C. UN-3320HS (15-functional urethane acrylate, manufactured by Negami Chemical Industrial Co., Ltd.) has a mass average molecular weight of 5,000 and a viscosity of 185,000 Pa·s / 25°C. The acrylate oligomers may be used alone or in combination of two or more.

[0092] Preferably, the ionizing radiation-curable compound further contains an acrylate monomer. When the ionizing radiation-curable composition further contains an acrylate monomer in addition to the acrylate oligomer described above as the ionizing radiation-curable compound, the viscosity of the composition is reduced, thereby achieving the effect of, for example, shortening the time it takes for the coating film to buckle due to light irradiation. This effect is particularly significant when the acrylate oligomer has a large number of functional groups. When the ionizing radiation-curable compound contains an acrylate monomer, the proportion of the acrylate monomer in the ionizing radiation-curable compound is less than 40% by mass, for example, preferably in the range of 10% by mass or more but less than 40% by mass, and more preferably in the range of 20% by mass or more but less than 40% by mass.

[0093] The number of functional groups possessed by the acrylate monomer is preferably 1 to 4. The molecular weight of the acrylate monomer is preferably within a range of 100 to 2,000, and more preferably within a range of 200 to 1,500.

[0094] Specific examples of acrylate monomers include tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, PO-modified neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, glycerin propoxy triacrylate, pentaerythritol, pentaerythritol ethoxy tetraacrylate, pentaerythritol (tri / tetra)acrylate, etc. The monomers may be used alone or in combination of two or more.

[0095] As described later in this specification, the surface protective layer 5 is formed by a first irradiation step and a second irradiation step, in which a crosslinking reaction of the ionizing radiation curable resin occurs only on the surface of the coating film in the first irradiation step, and in which curing of the entire coating film occurs in the second irradiation step.

[0096] When gravure printing is used as the coating method, the viscosity of the ionizing radiation-curable composition is preferably in the range of 10 to 500 mPa·s, and more preferably in the range of 20 to 500 mPa·s. Here, the viscosity is measured at room temperature, 25°C. To adjust the viscosity, an organic solvent can be used or a low-viscosity acrylate monomer can be added, but from the perspective of environmental impact, it is preferable not to use organic solvents.

[0097] The surface protection layer 5 may contain particles. By incorporating particles of an optimal particle size and content into the surface protection layer 5, a uniform surface can be formed. Examples of particles that can be used include organic materials such as polyethylene (PE) wax, polypropylene (PP) wax, and resin beads, as well as inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate. It is desirable for the particles to have an average particle size (D50) of 3 μm or more. The average particle size (D50) of the particles is preferably 3 μm or more and 11 μm or less, and more preferably 4 μm or more and 10 μm or less.

[0098] When the surface protective layer 5 contains particles having a preferred particle size, wrinkles can be more uniformly formed on the coating surface in the first irradiation step described below. Therefore, if the average particle size (D50) is too small or too large, wrinkles on the coating surface will be non-uniform. Furthermore, if large particles are used, the particles are likely to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance. If the particles are small, the effect of forming wrinkles uniformly will be small.

[0099] Here, the "average particle size (D50)" refers to the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. If the coating liquid for the surface protective layer contains particles, the surface protective layer 5 obtained from this coating liquid will also contain particles. The average particle size of the particles contained in the surface protective layer 5 can be determined by observing the cross section of the layer and averaging the particle sizes of multiple particles. The value obtained in this manner is essentially the same as the median size (D50) measured using a laser diffraction / scattering particle size distribution analyzer. Therefore, the above-mentioned range of average particle size can also be interpreted as the range of average particle sizes of the particles contained in the surface protective layer 5.

[0100] The particles are preferably contained in the surface protection layer 5 in a proportion of 2 to 13 parts by mass relative to 100 parts by mass of the ionizing radiation curable resin.

[0101] When the amount of particles added is within the above range, the effect of generating wrinkles uniformly is particularly large. When the amount of particles added is large, the particles tend to fall off from the surface protective layer 5, making it difficult to achieve high scratch resistance. When the amount of particles added is small, the effect of generating wrinkles uniformly is small.

[0102] When the entire surface protective layer 5 is cured by ultraviolet light, it is necessary to add a photopolymerization initiator to the surface protective layer 5. The photopolymerization initiator is not particularly limited, but examples thereof include benzophenone-based, acetophenone-based, benzoin ether-based, and thioxanthone-based initiators.

[0103] When a photopolymerization initiator is added, it is preferably added in an amount ranging from 0.2 to 5 parts by mass per 100 parts by mass of the ionizing radiation-curable compound. If the amount of photopolymerization initiator added is small, the surface will tend to be insufficiently cured when cured with ultraviolet light, resulting in poor scratch resistance and contamination resistance. On the other hand, if the amount of photopolymerization initiator added is large, the gloss will tend to remain constant when the line speed is increased in the first irradiation step described below. When considering production efficiency, it is more desirable to add the photopolymerization initiator in an amount of 3 parts by mass or less.

[0104] The surface protective layer 5 may further contain additives such as antibacterial agents and antifungal agents. Furthermore, as other additives, the surface protective layer 5 may further contain ultraviolet absorbers and light stabilizers as necessary. Generally, ultraviolet absorbers such as benzotriazoles, benzoates, benzophenones, and triazines are added as ultraviolet absorbers, and light stabilizers such as hindered amines are added as light stabilizers in any combination.

[0105] Examples of hindered amine light stabilizers that can be used include bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate (a representative example is BASF's product name "Tinuvin 144"), BASF's product name "Tinuvin 123", and a reaction product of decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester (1,1-dimethylethyl hydroperoxide) and octane.

[0106] When a hindered amine light stabilizer is added to the surface protective layer 5, it is preferably added in an amount ranging from 0.05 to 5 parts by mass relative to 100 parts by mass of the ionizing radiation-curable resin. The amount of hindered amine light stabilizer added is more preferably from 0.2 to 3 parts by mass. Adding an amount of hindered amine light stabilizer less than 0.05 parts by mass may reduce the resin's resistance to ultraviolet light. Adding an amount greater than 5 parts by mass increases the likelihood of bleed-out. The surface protective layer 5 can be formed by irradiating the surface with light of 200 nm or less to cause curing and shrinkage near the surface, forming a fine irregularity. In this case, adding more than 3 parts by mass of hindered amine light stabilizer may inhibit curing near the surface. To achieve both low gloss and weather resistance, it is desirable to add the hindered amine light stabilizer in an amount ranging from 3 parts by mass or less.

[0107] The glossiness of the surface protective layer 5 is preferably 20.0 or less, and more preferably 10.0 or less. Here, the "glossiness" is a value measured at an incident angle of 60 degrees using a glossmeter conforming to JIS Z8741:1997.

[0108] <1.5> Primer layer The primer layer 6 can basically be made of the same material as the printed layer 3. Considering that the primer layer 6 is applied to the back surface of the decorative sheet 1 and will be wound up in web form, inorganic fillers such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added to prevent blocking and improve adhesion with the adhesive. The coating thickness of the primer layer 6 is preferably 0.1 μm or more and 3.0 μm or less, as its purpose is to ensure adhesion with the substrate B. The primer layer 6 is necessary when the base layer 2 has an inactive surface, such as an olefin-based material, but is not particularly necessary when the surface is active.

[0109] <2> Manufacturing method of decorative sheet The decorative sheet 1 is produced, for example, by the following method: Here, for the sake of brevity, explanations regarding the print layer 3, transparent resin layer 4, adhesive resin layer 4b, and primer layer 6 will be omitted.

[0110] First, a coating film made of a coating liquid for a surface protective layer is formed on one surface of the base layer 2. As described in the section <1.4> Surface protective layer, the ionizing radiation curable composition contains an ionizing radiation curable compound and, if necessary, particles and additives. The coating film made of the ionizing radiation curable composition can be formed, for example, by printing.

[0111] After forming a coating film made from the coating liquid for a surface protective layer, a first irradiation step is carried out. In the first irradiation step, the coating film is irradiated with light having a wavelength of 200 nm or less (hereinafter referred to as first radiation). The ionizing radiation-curable compound contained in the ionizing radiation-curable composition has a large absorption coefficient for the first radiation. Therefore, the first radiation incident on the coating film can only reach a position several tens to several hundreds of nm away from the outermost surface. Therefore, in the first irradiation step, a crosslinking reaction proceeds in the surface region of the coating film, forming an extremely thin cured film, while the crosslinking reaction does not proceed in other regions, leaving the other regions uncured.

[0112] The coating film after the first irradiation step has wrinkles on its surface that correspond to the ridge portions 5 B. The present inventors believe that the reason why wrinkles are formed on the coating film surface by the first irradiation step is as follows.

[0113] As described above, the first radiation can only reach a position tens to hundreds of nanometers from the outermost surface of the coating film. That is, the crosslinking reaction of the ionizing radiation-curable compound occurs only on the surface of the coating film, and regions more than tens to hundreds of nanometers from the outermost surface are uncured and contain highly fluid molecules. These highly fluid molecules swell the cured film, thereby increasing its volume. The increase in volume in the in-plane direction generates in-plane compressive stress, which causes the cured film to buckle, resulting in wrinkles on the surface of the coating film.

[0114] The first radiation can be extracted from excimer VUV light. Excimer VUV light can be produced from a lamp that uses a rare gas or a rare gas halide compound. When high-energy electrons are externally applied to a lamp that contains a rare gas or a rare gas halide compound, a large number of discharge plasmas (dielectric barrier discharges) are generated. This plasma discharge excites the atoms of the discharge gas (rare gas), which momentarily enters an excimer state. When returning from this excimer state to the ground state, light is emitted in a wavelength range specific to that excimer.

[0115] The gas used in the excimer lamp may be any conventional gas that emits light of 200 nm or less. Examples of gases that can be used include rare gases such as Xe, Ar, and Kr, and mixtures of rare gases such as ArBr and ArF with halogen gases. The center wavelength of excimer lamps varies depending on the gas used, with wavelengths ranging from approximately 172 nm (Xe), approximately 126 nm (Ar), approximately 146 nm (Kr), approximately 165 nm (ArBr), and approximately 193 nm (ArF).

[0116] Considering the magnitude of photon energy and the difference between wavelength and bond energy of organic matter, it is preferable to use a xenon lamp that emits excimer light with a central wavelength of 172 nm as the light source. Also, considering the cost of maintaining the equipment and the availability of materials, it is preferable to use a xenon lamp as the light source.

[0117] The first irradiation step is carried out in an atmosphere with a low oxygen concentration. Oxygen has a high absorption coefficient for light of 200 nm or less. Therefore, the first irradiation step is preferably carried out in, for example, a nitrogen gas atmosphere. The oxygen concentration in the gas phase in the first irradiation step, i.e., the residual oxygen concentration in the reaction atmosphere, is preferably 2000 ppm or less, and more preferably 1000 ppm or less.

[0118] Furthermore, oxygen in the atmosphere inhibits radical polymerization. Therefore, the residual oxygen concentration in the reaction atmosphere affects the formation of wrinkles on the coating surface. Therefore, changing the residual oxygen concentration in the reaction atmosphere can also change the surface properties of the surface protective layer 5.

[0119] The cumulative light intensity of the first radiation is 0.5 mJ / cm 2 More than 200mJ / cm 2 It is preferable that the dose is 1 mJ / cm or less. 2 More than 100mJ / cm 2 More preferably, it is 3 mJ / cm or less. 2 More than 50mJ / cm 2 It is more preferable that the dose is 5 mJ / cm or less, and 2 More than 30mJ / cm 2 It is most preferable to set the integrated light dose as follows: If the integrated light dose is small, the expansion of the cured film in the in-plane direction will be small; if the integrated light dose is large, the surface condition of the coating film will deteriorate.

[0120] After the first irradiation step is completed, the second irradiation step is carried out. In the second irradiation step, the coating film is irradiated with a second radiation to cure the entire coating film. In this way, the surface protective layer 5 is obtained.

[0121] The second radiation is ionizing radiation such as an electron beam, or ultraviolet radiation having a longer wavelength than the first radiation. When ultraviolet radiation is used as the second radiation, the ultraviolet radiation has a wavelength at which the ionizing radiation curable resin exhibits a smaller absorption coefficient.

[0122] The cumulative light intensity of the second radiation is 10 mJ / cm 2 More than 500mJ / cm 2 It is preferable that the dose is 50 mJ / cm or less. 2 More than 400mJ / cm 2 It is more preferable that the dose is 100 mJ / cm or less, and 2 More than 300mJ / cm 2 It is more preferable that:

[0123] <3> Actions and other The decorative sheet 1 described with reference to FIGS. 1 to 4 has a reflection chromaticity measured with a D50 light source of L in the Lab color system. * is in the range of 10 to 90, and a * is between -2.0 and +16.0, and b * The surface protective layer 5 has an uneven surface formed with a plurality of ridges, each of which protrudes in a ridge-like shape, within a range of -2.0 to +38.0. This configuration allows for a decorative sheet to be obtained that has low gloss and a good balance of design, hiding power, and durability. Here, durability refers to fingerprint resistance, contamination resistance, scratch resistance, and process resistance, among others. That is, the gloss (gloss level) of the surface protective layer can be adjusted even without the inclusion of a gloss adjuster (matt additive) in the surface protective layer. Because gloss adjusters reduce the oil repellency of layers formed from resin materials, surface protective layers 5 containing gloss adjusters are prone to fingerprints. Surface protective layers 5 that do not contain large amounts of gloss adjusters are less likely to absorb oil and therefore less prone to fingerprints. Furthermore, surface protective layers 5 with excellent oil repellency are less likely to develop oil stains or adsorb contaminants. Furthermore, when the surface of a surface protective layer 5 that does not contain a gloss adjusting agent is scratched, the gloss adjusting agent particles do not fall off, and therefore a decorative sheet 1 that includes such a surface protective layer 5 is less likely to suffer from gloss changes or scratches.

[0124] In this embodiment, the surface protective layer 5 is formed as a single layer, but is not limited to this configuration. For example, the surface protective layer 5 may be formed as a multi-layer. That is, the surface protective layer 5 may be formed by laminating multiple layers of the same ionizing radiation curable resin or multiple layers of different ionizing radiation curable resins, thereby forming an uneven shape on the surface. When multiple layers of different ionizing radiation curable resins are laminated, the layer located on the raw sheet layer 2 side of the surface protective layer 5 (i.e., the layer located below the outermost layer of the surface protective layer 5) is not particularly limited. [Example]

[0125] The following describes tests carried out in connection with the present invention. <Example 1> The raw material for the base layer 2 was a mixture of 60.0 parts by mass of polypropylene resin and 38.0 parts by mass of titanium oxide and 2.0 parts by mass of chromium-antimony composite oxide as inorganic pigments. The resulting mixture was melt-extruded using a melt extruder to form a base layer 2 with a thickness of 140 μm. One side of the base layer 2 was subjected to corona treatment, and then solid printing was performed on that side to form a printed layer 3. The printed layer 3 was formed using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) to which 0.5 parts by mass of a hindered amine light stabilizer (Chimasorb 944; manufactured by BASF) was added per 100 parts by mass of the binder resin of the ink.

[0126] Next, a primer layer 6 was formed on the back surface of the raw fabric layer 2. The primer layer 6 was formed by printing the same two-component urethane ink as used for the printed layer 3.

[0127] Next, a coating liquid for a surface protective layer was applied onto the printed layer 3. The thickness of the coating liquid for a surface protective layer was 5 μm. The coating liquid for a surface protective layer was prepared by blending the following ionizing radiation curable compound with the following photopolymerization initiator.

[0128] ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 100 parts by mass Photopolymerization initiator Product name: Omnirad184 (manufactured by IGM Resins) Blend: 1 part by mass

[0129] Thereafter, the first irradiation step was carried out. Specifically, under atmospheric pressure in a nitrogen gas atmosphere with an oxygen concentration of 100 ppm, ultraviolet rays having a wavelength of 172 nm were irradiated onto the surface of the coating film made of the coating liquid for the surface protective layer by using a Xe excimer lamp at an integrated light intensity of 30 mJ / cm. 2 This caused wrinkles to form on the surface of the coating film.

[0130] Subsequently, the second irradiation step was carried out. Specifically, the coating film was irradiated with 200 mJ / cm using a high-pressure mercury lamp. 2 The entire sheet was cured by irradiating it with ultraviolet light so that the surface was protected by the ultraviolet light, thereby forming a surface protective layer 5. In this manner, a decorative sheet 1 having a total thickness of 145 μm and shown in FIG.

[0131] <Example 2> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 70.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 10.0 parts by mass Type: Iron-aluminum composite oxide Blend: 6.0 parts by mass Type: Iron-zinc composite oxide Blend: 14.0 parts by mass

[0132] <Example 3> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 75.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 2.0 parts by mass Type: Iron-aluminum composite oxide Blend: 22.0 parts by mass Type: Carbon black Blend: 1.0 parts by mass

[0133] <Example 4> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 75.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 16.0 parts by mass Type: Iron-aluminum composite oxide Blend: 5.0 parts by mass Type: Cobalt Blue Blend: 3.0 parts by mass Type: Carbon black Blend: 1.0 parts by mass

[0134] <Example 5> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 75.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 14.0 parts by mass Type: Iron-aluminum composite oxide Blend: 2.0 parts by mass Type: Cobalt Blue Blend: 3.0 parts by mass Type: Carbon black Blend: 6.0 parts by mass

[0135] <Example 6> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 60.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 37.6 parts by mass Type: Chromium-antimony composite oxide Blend: 1.4 parts by mass Type: Cobalt Blue Blend: 1.0 parts by mass

[0136] <Example 7> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material of the raw sheet layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 60.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 37.2 parts by mass Type: Chromium-antimony composite oxide Blend: 0.8 parts by mass Type: Cobalt Blue Blend: 2.0 parts by mass

[0137] <Example 8> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the ionizing radiation curable compound in Example 1 was replaced with the following. ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 50 parts by mass Type: Acrylate monomer Product name: Viscoat #310HP (tripropylene glycol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) Blend: 50 parts by mass

[0138] <Example 9> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the ionizing radiation curable compound in Example 1 was replaced with the following. ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 80 parts by mass Type: Acrylate monomer Product name: A-DPH (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 20 parts by mass

[0139] <Example 10> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the ionizing radiation curable compound in Example 1 was replaced with the following. ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 60 parts by mass Type: Acrylate monomer Product name: A-DPH (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 40 parts by mass

[0140] <Example 11> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the ionizing radiation curable compound in Example 1 was replaced with the following. ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 40 parts by mass Type: Acrylate monomer Product name: A-DPH (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 60 parts by mass

[0141] <Example 12> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the ionizing radiation curable compound in Example 1 was replaced with the following. ·Ionizing radiation-curable compounds Type: Difunctional urethane acrylate oligomer Product name: UA-4400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 20 parts by mass Type: Acrylate monomer Product name: A-DPH (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Blend: 80 parts by mass

[0142] <Example 13> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the following particles were added to the ionizing radiation curable compound of Example 1 (100 parts by mass). ·particle Type: Silica particles Product name: Silysia (registered trademark) 250N (manufactured by Fuji Silysia Chemical Ltd.) Particle size: 5μm Blend: 2 parts by mass

[0143] <Example 14> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the following particles were added to the ionizing radiation curable compound of Example 1 (100 parts by mass). ·particle Type: Silica particles Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 3 parts by mass

[0144] <Example 15> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the following particles were added to the ionizing radiation curable compound of Example 1 (100 parts by mass). ·particle Type: Silica particles Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 5 parts by mass

[0145] <Example 16> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the following particles were added to the ionizing radiation curable compound of Example 1 (100 parts by mass). ·particle Type: Silica particles Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 11 parts by mass

[0146] <Example 17> A decorative sheet 1 having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the following particles were added to the ionizing radiation curable compound of Example 1 (100 parts by mass). ·particle Type: Silica particles Product name: Silysia 250N (Fuji Silysia Chemical) Particle size: 5μm Blend: 13 parts by mass

[0147] <Example 18> No photopolymerization initiator was added to the ionizing radiation-curable compound of Example 15. In addition, in the second irradiation step, the coating film was irradiated with an electron beam to cure the entire film, thereby forming a surface protective layer 5. Other than that, the same procedures as in Example 15 were followed to obtain a decorative sheet 1 having a total thickness of 145 μm.

[0148] <Comparative Example 1> A decorative sheet having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material for raw fabric layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 60.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 40.0 parts by mass

[0149] <Comparative Example 2> A decorative sheet having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material for raw fabric layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 60.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 39.0 parts by mass Type: Iron-aluminum composite oxide Blend: 1.0 parts by mass

[0150] <Comparative Example 3> A decorative sheet having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the raw material for raw fabric layer 2 in Example 1 was replaced with the following. Polypropylene resin Blend: 80.0 parts by mass Inorganic pigments Type: Titanium oxide Blend: 5.0 parts by mass Type: Carbon black Blend: 15.0 parts by mass

[0151] <Comparative Example 4> A decorative sheet having a total thickness of 145 μm was obtained in the same manner as in Example 1, except that the first irradiation step in Example 1 was not carried out and the second irradiation step was carried out.

[0152] <Evaluation> (1) Thickness of the surface protection layer and total thickness of the decorative sheet The thickness of the surface protective layer 5 was measured as follows. The decorative sheet 1 was embedded in a resin such as a cold-curing epoxy resin or a UV-curable resin, and the resin was allowed to fully cure. The decorative sheet was then cut to reveal its cross section, and mechanically polished to obtain a measurement surface. A cross-sectional image of the decorative sheet 1 was then captured using a SIGMA 500 scanning electron microscope manufactured by Carl Zeiss Microscopy. The imaging was performed at an acceleration voltage of 0.5 keV (low acceleration voltage), in the SE2 mode, and at a magnification of 2000x. No sputtering was performed on the measurement sample. Next, the dimensions of the surface protective layer 5 in the width direction of the ridge-shaped portion and the cross-sectional area of ​​the surface protective layer 5 were determined from the cross-sectional image. The thickness of the surface protective layer 5 was calculated by dividing this area by the above dimensions. Measurements were performed at 25 random points, and the average value of the 25 points was defined as the "thickness t of the surface protective layer." The "thickness t of the surface protective layer" was equal to the thickness of the coating film made of the coating liquid for the surface protective layer.

[0153] Next, the total thickness of the decorative sheet 1 was measured from the cross-sectional image obtained above. Measurements were taken at 25 random points, and the average value of the 25 points was defined as the "total thickness of the decorative sheet." The total thickness of the decorative sheet 1 in Examples 1 to 18 and Comparative Examples 1 to 4 was equal to the sum of the thicknesses of the surface protective layer 5 and the base fabric layer 2.

[0154] (2) Surface condition The surface condition was evaluated visually for uniformity of the surface of the surface protection layer 5. The evaluation criteria were as follows: In all examples and comparative examples given an "A" rating, there were only a few uneven areas, and there was no problem in practical use. AA: Uniform surface condition A: There are some uneven areas. B: Uneven surface condition

[0155] (3) Hue The hue was evaluated by measuring the chromaticity using a Konica Minolta fluorescent spectrodensitometer (FD-7) under a D50 light source on a white background using BYK-GARDNER's opacity test paper (byko-chart high brightness 2A).

[0156] (4) Concealment The opacity was evaluated by measuring the color difference between a white and black background on an opacity test paper (byko-chart high brightness 2A) manufactured by BYK-GARDNER using a fluorescent spectrodensitometer (FD-7) manufactured by Konica Minolta, Inc. The smaller the color difference, the better the opacity. The evaluation criteria were as follows: A rating of "B" or higher was deemed to be satisfactory for practical use. AA: 0.5 or less A: More than 0.5 but less than 0.7 B: More than 0.7 but less than 1.0 C: over 1.0

[0157] (5) Design The design was evaluated by placing the decorative sheet horizontally directly under a fluorescent lamp and looking at it at a 45-degree angle, and determining whether the decorative sheet appeared whitish or not. The evaluation criteria were as follows: AA: The decorative sheet does not appear whitish. A: The decorative sheet has a slight whitish tint, but this is acceptable. B: The decorative sheet has a whitish appearance and is unacceptable.

[0158] (6) Glossiness The glossiness was measured at 60 degrees using a Rhopoint IQ (manufactured by Konica Minolta, Inc.) The "60° glossiness" in Table 1 below represents this 60° glossiness.

[0159] (7) Fingerprint resistance To evaluate fingerprint resistance, an evaluation of fingerprint wiping ability was carried out. The 60° gloss of the surface of each decorative sheet was measured and designated as "initial gloss." Next, a fingerprint-resistant evaluation liquid was applied to the outermost layer, and then the fingerprint-resistant evaluation liquid that had adhered to the surface of the decorative sheet was wiped off. Thereafter, the 60° gloss of the area from which the fingerprint-resistant evaluation liquid had been wiped off was measured and designated as "gloss after wiping." Here, a higher fatty acid was used as the fingerprint-resistant evaluation liquid.

[0160] The fingerprint removal rate was calculated using the following formula: Fingerprint removal rate (%) = (glossiness after wiping / initial glossiness) x 100 The evaluation criteria were as follows: AA: 70% or more but less than 250% A: 50% or more but less than 70%, or 250% or more but less than 300% B: Less than 50% or more than 300%.

[0161] (8) Stain resistance To evaluate stain resistance, the Staining A Test specified in the Japanese Agricultural Standards (JAS) was conducted. Specifically, 10 mm wide lines were drawn on the surface protective layer of each decorative sheet using blue ink, black quick-drying ink, and red crayon, and the sheets were left for 4 hours. The blue ink, black quick-drying ink, and red crayon lines were then wiped off with a cloth soaked in ethanol, and stain resistance by ink was evaluated.

[0162] The evaluation criteria were as follows: AA: Lines of each color could be easily wiped off. A: Some of the lines of each color could be wiped away, but some stains remained. B: I couldn't wipe off the lines of each color.

[0163] (9) Scratch resistance: Steel wool rubbing test The resulting decorative sheet was attached to wood substrate B using a urethane adhesive, and then a steel wool rubbing test was carried out to evaluate scratch resistance. Specifically, a 100g load was applied to the steel wool and the sheet was rubbed back and forth 20 times, and the surface of the decorative sheet was visually inspected for scratches and changes in gloss.

[0164] The evaluation criteria were as follows: AA: No scratches or changes in gloss occurred on the surface. A: Minor scratches or changes in gloss have occurred on the surface. B: Significant scratches or changes in gloss occurred on the surface.

[0165] (10) Bending suitability To evaluate workability, a bending workability test was conducted. First, each decorative sheet was attached to a wood substrate, and a V-shaped groove was made on the other side of the substrate up to the boundary where the substrate and decorative sheet were attached, so as not to scratch the decorative sheet on the other side. Next, the substrate was bent 90 degrees along the V-shaped groove so that the surface of the decorative sheet was folded in a mountain fold, and the bent part of the surface of the decorative sheet was observed using an optical microscope to see if there was any whitening or cracking.

[0166] The evaluation criteria were as follows: A rating of "A" or higher was deemed to be satisfactory for practical use. AA: No whitening or cracks were observed. A: Some bleaching was observed. B: Whitening is visible on the entire surface or cracks are visible in some areas.

[0167] The evaluation results are shown in Table 1.

[0168] [Table 1-1]

[0169] [Table 1-2]

[0170] [Table 1-3]

[0171] As shown in Table 1, the decorative sheets 1 of Examples 1 to 18 had excellent design properties, without appearing whitish overall. Furthermore, the decorative sheets 1 of Examples 1 to 18 had low gloss and were excellent in hiding power, fingerprint resistance, stain resistance, scratch resistance, processability, and surface condition.

[0172] Examples 1 to 5 and Comparative Examples 1 to 3 have different hues due to differences in the mass ratio (P1 / P2) of the white pigment (P1) and the color pigment (P2) contained in the raw fabric layer 2. * Comparative Examples 1 and 2, in which L is more than 90, have poor hiding power. * In Comparative Example 3, where the value was less than 10, the overall appearance was whitish, resulting in an unacceptable design. * Examples 1 to 5 where L is between 10 and less than 90 * In Example 1, where L is more than 85, the hiding power is slightly lowered, but this is at a level that does not cause any problems in practical use. * Examples 2 to 5, in which L was 85 or less, had particularly excellent hiding power. * In Examples 3 and 5, where the L was less than 60, a slight whitish appearance was observed, but both were at an acceptable level. * Examples 1, 2 and 4, in which the value was 60 or more, had particularly excellent design properties.

[0173] In Examples 1, 6, and 7, the mass ratio (P1 / P2) of the white pigment (P1) to the color pigment (P2) contained in the base layer 2 was high, and all of them were L * The main difference between them is that the raw layer 2 of Examples 6 and 7 further contains a blue pigment. Examples 6 and 7 have better hiding power than Example 1, and therefore the addition of the blue pigment improves the L * It can be seen that the hiding power is improved in the region where

[0174] Example 1 and Examples 8 to 12 differ from each other in the raw materials of the ionizing radiation curable resin contained in the surface protective layer 5. While Example 1 uses only an acrylate oligomer, Examples 8 to 12 use mixtures of acrylate oligomer and acrylate monomer, each with a different blend ratio. These evaluation results show that the addition of acrylate monomer and the blend ratio of acrylate oligomer to acrylate monomer affect gloss, stain resistance, and processability. Therefore, the raw materials of the ionizing radiation curable resin contained in the surface protective layer 5 can be selected depending on the desired performance and application.

[0175] In Examples 13 to 17, particles were added to the surface protective layer 5 in comparison with Example 1, but the amounts added were different. It was found that the addition of particles improved the surface condition of the surface protective layer 5. It was also found that the amount of particles added affected the gloss, fingerprint resistance, and scratch resistance. Therefore, the addition of particles to the surface protective layer 5 and the amount of particles added can be selected depending on the desired performance and application.

[0176] The only difference between Examples 15 and 18 is that the second irradiation step was carried out with ultraviolet light in the former and ionizing radiation in the latter. There was no difference in the evaluation results between the two, and both were good results.

[0177] Comparative Example 4 is an example in which the irradiation with excimer VUV light in the first irradiation step was omitted compared to Example 15. The surface of the surface protection layer 5 of Comparative Example 4 had unevenness caused by particles. Since the unevenness caused by these particles was larger than the unevenness caused by excimer VUV light, fingerprint resistance deteriorated and gloss increased. Furthermore, contamination resistance and scratch resistance also deteriorated. [Explanation of symbols]

[0178] 1...decorative sheet, 2...raw material layer, 3...printed layer, 4...transparent resin layer, 4a...embossed pattern, 4b...adhesive resin layer, 5...surface protection layer, 5A...core portion, 5B...ridged portion, 6...primer layer, 11...decorative material, B...base material.

Claims

1. A substrate layer and a surface protective layer provided on one surface of the substrate layer, a surface of the surface protection layer having an uneven structure including a plurality of ridge-like portions each protruding in a ridge shape; The reflected chromaticity measured with a D50 light source is L in the Lab color system. ＊ is in the range of 10 or more and less than 90, ＊ is in the range of -2.0 or more and +16.0 or less, and b ＊ A decorative sheet in which the value is within the range of -2.0 or more and +38.0 or less.

2. Said L ＊ is in the range of 75 or more and less than 90, ＊ is in the range of -1.5 or more and +2.5 or less, and ＊ The decorative sheet according to claim 1, wherein the value of the σ is in the range of -1.5 or more and +8.5 or less.

3. 2. The decorative sheet according to claim 1, wherein the gloss of said surface protective layer is 20.0 or less.

4. 2. The decorative sheet according to claim 1, wherein the glossiness of said surface protective layer is 10.0 or less.

5. The decorative sheet according to claim 1, wherein the raw fabric layer contains an inorganic pigment, and the content of the inorganic pigment in the raw fabric layer is in the range of 15 parts by mass or more and 45 parts by mass or less per 100 parts by mass of the raw fabric layer.

6. The decorative sheet according to claim 5, wherein the base layer contains a white pigment and a colored pigment as the inorganic pigment, and the mass ratio (P1 / P2) of the white pigment (P1) to the colored pigment (P2) is in the range of 98 / 2 to 2 / 98.

7. 7. The decorative sheet according to claim 6, wherein the white pigment comprises at least titanium oxide, and the coloring pigment comprises one or more selected from the group consisting of iron-zinc composite oxide, chromium-antimony composite oxide, and iron-aluminum composite oxide.

8. 3. The decorative sheet according to claim 2, wherein said base layer contains a white pigment and a colored pigment as inorganic pigments, and said colored pigment contains at least a blue pigment.

9. 6. The decorative sheet according to claim 5, wherein said base layer further contains a fatty acid metal salt.

10. 2. The decorative sheet according to claim 1, wherein said surface protective layer contains an ionizing radiation curable resin formed from a cured product of an ionizing radiation curable compound.

11. 11. The decorative sheet according to claim 10, wherein said ionizing radiation curable compound contains either an acrylate oligomer or an acrylate monomer, or both.

12. 11. The decorative sheet according to claim 10, wherein the surface protective layer further contains particles, and the ratio of the particles to the ionizing radiation curable resin is within the range of 2 to 13 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

13. A decorative material comprising the decorative sheet according to any one of claims 1 to 12 and a substrate to which the decorative sheet is attached.

14. forming a coating film containing a composition containing an ionizing radiation curable compound on one surface of a raw film layer; irradiating the coating film with light having a wavelength of 200 nm or less; After the irradiation, irradiating with ionizing radiation or ultraviolet light having a wavelength longer than that of the light, The reflected chromaticity measured with a D50 light source is L in the Lab color system. ＊ is in the range of 10 or more and 90 or less, and a ＊ is in the range of -2.0 or more and +16.0 or less, and b ＊ is in the range of -2.0 or more and +38.0 or less.

15. The method for producing a decorative sheet according to claim 14, wherein the light has a wavelength of 172 nm.

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