Decorative sheets and decorative materials

Abstract

Provided are a decorative sheet and a decorative material that are black when formed of an olefin-based material, have heat insulation properties, and can suppress deformation due to absorption of solar radiation. 【Solution means】In the decorative sheet 1 according to this embodiment, the colored original layer 2 is formed using a colored polyolefin-based thermoplastic resin, the transparent resin layer 4 is formed using a transparent polyolefin-based thermoplastic resin, contains an ultraviolet absorber, and the pattern layer 3 contains any one or two or more of an azomethine azo-based pigment, a perylene-based pigment, a titanium-based black pigment, a black iron oxide pigment, or a black composite oxide pigment as a black pigment. When the decorative sheet is colorimetrically measured from the outermost surface side of the sheet, the CIE1976 L * a * b * value in the color space is 15 or more and 35 or less, and when the colored original layer is colorimetrically measured alone, the CIE1976 L * value * a * b * value in the color space is 85 or more. * ​

Description

[Technical Field]

[0001] This disclosure relates to decorative sheets and decorative materials. [Background technology]

[0002] Due to the problem of gases during combustion, decorative sheets have recently been made primarily from olefin-based materials (see Patent Documents 1-3). To protect the design from surface abrasion, a multi-layered decorative sheet is widely used, in which a transparent olefin sheet is laminated onto a colored olefin sheet that has been printed on top (see paragraph

[0034] and Figure 1 of Patent Document 2, and paragraph

[0059] and Figure 1 of Patent Document 3). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2006-110929 [Patent Document 2] Japanese Patent Publication No. 2015-199313 [Patent Document 3] Japanese Patent Publication No. 2016-101663 [Overview of the project] [Problems that the invention aims to solve]

[0004] When using decorative sheets made from olefin-based materials as exterior materials, they are required to have physical properties suitable for long-term outdoor use. For example, if a pattern is printed in black or a dark color close to black, in environments exposed to sunlight, it tends to absorb solar radiation and accumulate heat, which could cause deformation of the colored olefin sheet on which the pattern is formed, or the resin sash or window frame used as its base material. Therefore, when using decorative sheets made of olefin material as exterior materials, properties that do not easily absorb solar radiation (= heat shielding properties) are also required.

[0005] This disclosure is made in view of the above circumstances and aims to provide decorative sheets and decorative materials that, even when formed from olefin-based materials, are black in color, have heat-shielding properties, and can suppress deformation due to solar radiation absorption. [Means for solving the problem]

[0006] To solve the above problems, a decorative sheet according to one aspect of the present disclosure is a decorative sheet in which at least a colored base layer, a pattern layer, and a transparent resin layer are laminated in this order, wherein the colored base layer is formed using a colored polyolefin thermoplastic resin, the transparent resin layer is formed using a transparent polyolefin thermoplastic resin and contains an ultraviolet absorber, and the pattern layer contains one or more of the following as a black pigment: azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, or black composite oxide pigment, and when the decorative sheet is colored from the outermost surface side of the sheet, CIE1976L * a * b * L in color space * The value is between 15 and 35, and when the colored raw material layer is measured individually, it is CIE1976L * a * b * L in color space * The value is 85 or higher.

[0007] Furthermore, a decorative material according to another aspect of the present disclosure comprises a base material for decorative materials and a decorative sheet laminated to the base material for decorative materials. [Effects of the Invention]

[0008] According to one aspect of this disclosure, it is possible to provide a decorative sheet and decorative material that, even when formed from an olefin-based material, is black in color, yet possesses heat-shielding properties and can suppress deformation due to the absorption of solar radiation. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view showing a decorative material according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0010] Hereinafter, decorative sheets and decorative members according to embodiments of this disclosure will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Furthermore, the embodiments shown below are illustrative examples of configurations for realizing the technical concept of this disclosure, and the technical concept of this disclosure is not limited to the materials, shapes, structures, etc. of the components described below. The technical concept of this disclosure can be modified in various ways within the technical scope defined by the claims described in the patent claims. Furthermore, the terms "left / right" and "up / down" in the following explanation are merely definitions for the sake of explanation and do not limit the technical concept of this disclosure. Therefore, for example, if the page is rotated 90 degrees, "left / right" and "up / down" will be swapped when read, and if the page is rotated 180 degrees, "left" will become "right" and "right" will become "left".

[0011] The composition of the decorative material 10 will be described below with reference to Figure 1. As shown in Figure 1, the decorative material 10 comprises a decorative sheet 1 and a base material 8 which is a base material for the decorative material and is the base material to which the decorative sheet 1 is attached. In this example, the base material 8 has a decorative sheet 1 laminated on one side (the upper side in Figure 1). That is, the decorative material 10 comprises the base material 8 and the decorative sheet 1 laminated on one side of the base material 8. The specific configuration of the decorative sheet 1 and the base material 8 will be described later.

[0012] (Composition of decorative sheet) As shown in Figure 1, the decorative sheet 1 comprises a colored base layer 2, a pattern layer 3, a transparent resin layer 4, a surface protection layer 5, and an embossed portion 6. Specifically, in the decorative sheet 1, the pattern layer 3, the transparent resin layer 4, and the surface protection layer 5 are laminated in this order on the colored raw material layer 2 (on one side of the colored raw material layer 2). In addition, an embossed portion 6 is formed on the surface of the surface protection layer 5, which is the outermost layer of the decorative sheet 1 (the side opposite to the transparent resin layer 4).

[0013] In this embodiment, the decorative sheet 1 does not require the surface protective layer 5, but can be provided as needed. In other words, the decorative sheet 1 only needs to have a structure in which at least a colored raw material layer 2, a pattern layer 3, and a transparent resin layer 4 are laminated in this order.

[0014] <Colored original fabric layer> The colored base layer 2 is configured to serve as a support for the decorative sheet 1. In this embodiment, the colored base layer 2 is opaquely colored and has opacity. As a result, when forming a decorative member by bonding the decorative sheet 1 to a predetermined substrate, for example, the colored base layer 2 can conceal color variations and defects on the substrate surface.

[0015] Furthermore, the base sheet that forms the colored raw material layer 2 is composed of paper, resin sheets, foil, etc. Examples of paper include tissue paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabrics, synthetic paper, etc. Thermoplastic resin films are preferably used as the resin sheet. Various materials other than polyvinyl chloride resin are possible as thermoplastic resins, and examples include synthetic resins such as polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, rubbers such as 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, as well as polyolefin-based thermoplastic elastomers. For example, considering non-pollution properties, cost, performance, and ease of coloring, polyolefin-based resins with added fillers and coloring pigments are preferably used. Examples of the foil include metal foils such as aluminum, iron, gold, and silver foils.

[0016] In the decorative sheet 1 according to the present embodiment, for example, the colored original layer 2 is formed using a colored polyolefin-based thermoplastic resin. Further, the colored original layer 2 as a colored sheet (colored film) of an opaque colored polyolefin-based thermoplastic resin can appropriately select the hue as the base color of the pattern layer 3. Also, when taking advantage of the texture of the surface of the base material 8 which is a base material for decorative materials, the colored original layer 2 is preferably a polyolefin-based thermoplastic resin layer having transparency such that the surface of the base material 8 can be seen through.

[0017] The colored original layer 2 can appropriately select the hue so as to conceal the base material 6 to which the decorative sheet 1 is adhered and to serve as the base color of the pattern layer 3. For example, the colored original layer 2 can be colored by mixing and kneading a colorant such as a pigment into the resin material (polyolefin-based thermoplastic resin) constituting the colored original layer 2. As the colorant, organic and inorganic pigments can be used, but it is preferable to use an inorganic pigment. That is, the colored original layer 2 preferably contains an inorganic substance as the colorant. For example, the colored original layer 2 preferably contains any one or more of inorganic substances such as calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0018] Also, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss modifiers may be added to the colored original layer 2 as necessary.

[0019] Also, when the colored original layer 2 in the decorative sheet 1 according to the present embodiment is colorimetrically measured alone, the L value in the CIE1976L * a * b * color space is 85 or more (L *(≥85). Here, the color measurement of the decorative sheet 1 may be, for example, a measurement of the reflected chromaticity using a D65 light source. Here, CIE1976L * a * b * A color space is a set of three values ​​(L) recommended by the CIE (International Commission on Illumination). * a * b * This is a color space represented by coordinates using ). * " indicates brightness (luminosity), with the higher the number from 0 to 100, the brighter it is. More details can be found in "L * " is the brightness of achromatic colors, and "L * =0" is black, L * "=100" represents the diffuse color of white, while the reflective color of white is even higher. CIE1976L * a * b * The color space is defined in JIS Z 8781-4 (2013). In the decorative sheet 1 according to this embodiment, the colored base layer 2 has a relatively high brightness (L * By setting the L value to ≥85, the material is given reflectivity of visible light and near-infrared rays, which are the main components of solar radiation, resulting in a heat-shielding effect. For example, even if the pattern layer 3 is a dark color, the absorption of infrared light is suppressed, reducing the heat storage effect and suppressing deformation caused by heat storage. The L value in the colored base material layer 2 can be controlled by the coloring agent (type, amount added, etc.).

[0020] When the color of the colored raw material layer 2 is measured individually, the L value is within the above range (L * If the value is ≥85, a decorative sheet can be obtained that is black, yet has excellent solar reflectivity, is less prone to heat accumulation, and is less susceptible to deformation.

[0021] <Pattern Layer 3> The pattern layer 3 is laminated on one side of the colored base material layer 2 (the upper side in Figure 1) and is a layer for adding a pattern to the decorative sheet 1 to enhance its aesthetic appeal.

[0022] Furthermore, the pattern layer 3 is formed using printing ink or paint. The printing ink or paint that forms the pattern layer 3 is formed, for example, by dissolving or dispersing a coloring agent such as a dye or pigment together with a suitable binder resin in a suitable diluent solvent. The pattern layer 3 contains an azomethine azo-based or perylene-based organic black pigment as the black pigment. A typical perylene-based black pigment is, for example, perylene black. These organic black pigments are infrared non-absorbent. In other words, the inclusion of these organic black pigments in the pattern layer 3 provides a heat-shielding effect. Therefore, by using these organic black pigments as colorants, even when a pattern in black or a dark color close to black is printed on the colored polyolefin thermoplastic resin sheet, the absorption of infrared light can be suppressed. Although some infrared light passes through the pattern layer 3, as mentioned above, it is reflected by the colored resin sheet 2, thus suppressing the absorption of infrared light for the decorative sheet 1 as a whole. This contributes to suppressing deformation of the decorative sheet 1 or decorative material 10 caused by heat accumulation due to the absorption of infrared light.

[0023] The decorative sheet 1 according to this embodiment contains the above-mentioned organic black pigment in the pattern layer 3, so that the color measured from the outermost surface of the sheet is CIE1976L * a * b * The L value in the color space is between 15 and 35 (15 ≤ L * The value is set to ≤35). This allows for sufficient solar reflectance and a deep design using dark colors to be given to the decorative sheet 1. Here, the color measurement of the decorative sheet 1 may be the same as the color measurement of the colored raw material layer 2, for example, by measuring the reflected chromaticity using a D65 light source. In other words, the color measurement from the outermost surface of the sheet may be the color measurement of the reflected chromaticity from the surface protection layer 5 (or the transparent resin layer 4 if the surface protection layer 5 is omitted) side.

[0024] In the decorative sheet 1 according to this embodiment, as described above, the colored raw material layer 2 has a relatively high brightness (L * (≧85) Therefore, it provides a heat-shielding effect, and even with a pattern layer 3 that allows for patterns with low brightness and dark colors, 15≦L measured from the outermost surface side* If the condition ≤35 is met, the absorption of infrared light can be suppressed and the heat storage effect can be reduced. Furthermore, by using the above-mentioned organic black pigment in the pattern layer 3, the lightness L can be reduced while avoiding the near-infrared absorption of the decorative sheet 1. * This makes it possible to lower the temperature. In other words, the decorative sheet 1 according to this embodiment contains the above-mentioned organic black pigment in the pattern layer 3, and CIE1976L in the outermost surface of the sheet and the colored raw material layer 2. * a * b * By controlling the L value in the color space, even when formed using polyolefin-based thermoplastic resin, heat shielding properties can be achieved, and deformation of the decorative sheet 1 or decorative material 10 caused by heat accumulation due to the absorption of infrared light can be suppressed. Furthermore, the design can be improved by creating a deep design using dark-colored patterns. The L value from the outermost surface of the sheet can be controlled by the organic black pigment in the pattern layer 3, as well as other pigments (amount added, etc.) including other black pigments described later.

[0025] Furthermore, when solar reflectance measurements are performed on a decorative sheet 1 having a pattern layer 3 formed on a colored base layer 2 using the above-mentioned organic black pigment, using a spectrophotometer conforming to JIS K 5602, it is preferable that the solar reflectance in the entire wavelength range from 300 nm to 2500 nm is 30% or more. Here, the solar reflectance measurement may be performed from the outermost surface of the sheet (surface protective layer or transparent resin layer 4). This reliably provides heat shielding by suppressing the solar radiation absorbed by the decorative sheet 1 and decorative material 10, and greatly contributes to suppressing deformation of the decorative sheet 1 or decorative material 10 caused by heat accumulation due to absorption of external light.

[0026] Furthermore, the decorative sheet 1 according to this embodiment does not use carbon black as the black pigment in the pattern layer 3, which is commonly used in existing decorative sheets. Carbon black has a high absorption rate in the near-infrared light region (0.781 μm to 2.5 μm), and therefore cannot improve the problem of heat accumulation due to heat absorption from infrared light. In other words, by not using carbon black as a coloring agent in the pattern layer 3, the absorption of infrared light can be suppressed more reliably.

[0027] Furthermore, the pattern layer 3 may contain pigments other than the organic black pigment mentioned above. For example, other black pigments include titanium-based black pigment, black iron oxide pigment, and black composite oxide pigment. The pattern layer 3 contains, as a black pigment, one or more of the above organic black pigment and other black pigments, namely azomethine azo pigment, perylene pigment, titanium-based black pigment, black iron oxide pigment, or black composite oxide pigment. Further other pigments include, for example, isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium dioxide. It is preferable that the pattern layer 3 contains at least one of these pigments. This makes it possible to express a wider range of hues compared to using only black pigment, and can impart a deeper design to the decorative sheet 1.

[0028] The printing ink or coating that forms the pattern layer 3 is applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. If the colored base material layer 2 is available in a rolled state, printing for the formation of the pattern layer 3 can be performed using a roll-to-roll printing device. The binder resin contained in the pattern layer 3 is not particularly limited, but examples include polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, butyral, acrylic, urethane, polyester, epoxy, alkyd, and polyamide resins. The binder may be water-based, solvent-based, or emulsion type, and the curing method is not particularly limited, including one-component type, two-component type consisting of a main component and a hardener, or type that cures with ultraviolet light or electron beam. The most common method is the two-component type, which uses a urethane-based main component and a hardener consisting of isocyanate. In addition, designs may be applied by vapor deposition or sputtering of various metals.

[0029] The pattern formed by pattern layer 3 can be any pattern, such as wood grain, stone pattern, fabric pattern, abstract pattern, geometric pattern, letters, symbols, solid color, or a combination thereof.

[0030] Furthermore, in order to improve the aesthetic appeal of the decorative sheet 1, the pattern layer 3 may be made into a multi-layer structure. For example, in order to better conceal the color and pattern of the material to which the decorative sheet 1 is attached, the structure may include a solid pattern layer that is solidly applied on the colored base layer 2 (surface) and a pattern layer provided on the solid layer to add a pattern to give the decorative sheet 1 a high level of aesthetic appeal. In this case, the solid pattern layer contains the above-mentioned organic black pigment (azomethine azo type or perylene type), and when the color is measured from the outermost surface of the sheet, the L value in the Lab color space is 15 or higher (L * It is acceptable to set it to ≥15). Furthermore, the pattern layer may have a higher brightness than the solid pattern layer, that is, a higher L value in the Lab color space than that of the solid pattern layer. In other words, the pattern layer 3 may consist of a dark solid pattern layer and a pattern layer that forms a pattern (for example, a light-colored pattern) on the solid pattern layer that has a higher brightness than the solid pattern layer. Note that the pattern layer may contain the above-mentioned organic black pigment, but in this case, the amount of organic black pigment added to the pattern layer shall be less than the amount of organic black pigment added to the solid pattern layer.

[0031] The thickness of the pattern layer 3 is preferably within the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, it is possible to make the printing clearer. Also, when the thickness of the pattern layer 3 is 10 μm or less, the printability when manufacturing the decorative sheet 1 is improved and manufacturing costs can be reduced.

[0032] Furthermore, 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 pattern layer 3 to impart various functions.

[0033] <Transparent resin layer 4> The transparent resin layer 4 is, for example, a single-layer sheet. The transparent resin layer 4 is manufactured and laminated as a transparent resin sheet made of, for example, a transparent thermoplastic resin, so that the pattern of the pattern layer 3 is visible through it. The thermoplastic resin contained in the transparent resin layer 4 only needs to be transparent, and may be various resins other than polyvinyl chloride resin, for example.

[0034] Examples of transparent thermoplastic resins used in the transparent resin layer 4 include polyolefin resins such as low-density polyethylene resin (LDPE), high-density polyethylene resin (HDPE), linear low-density polyethylene resin (LLDPE), polypropylene resin (PP), polyolefin elastomers, polyester resins such as polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), and polyethylene naphthalate resin (PEN), polymethyl methacrylate resin (PMMA), ethylene-vinyl acetate copolymer resin (EVA), ionomer resin, polybutene resin, polyacrylonitrile resin, polyamide resins such as nylon-6 and nylon-66, polystyrene resin (PS), polyvinylidene chloride resin (PVDC), polycarbonate resin (PC), fluororesin, and urethane resin. In particular, considering environmental compatibility, processability, and cost, it is preferable to use polyolefin-based thermoplastic resins. In other words, the transparent resin layer is formed using a transparent polyolefin-based thermoplastic resin.

[0035] The transparent resin layer 4 may also be formed using a resin composition containing multiple types of polypropylene resins. Specifically, the resin composition forming the transparent resin layer 4 may include multiple types of polypropylene resins, such as highly crystalline polypropylene resin, low-crystalline polypropylene resin, and random polypropylene resin. To improve post-processability (bending properties) in transparent resin layers containing highly crystalline PP resin and low-crystalline PP resin, it is necessary to increase the proportion of low-crystalline PP resin added to the highly crystalline PP resin. However, increasing the proportion of low-crystalline PP resin can lead to increased flexibility, potentially resulting in reduced scratch resistance and film-forming properties. In the decorative sheet 1 according to this embodiment, by using random PP resin in addition to highly crystalline PP resin and low crystalline PP resin as described above, it is possible to improve the bending processability of the bender while suppressing a reduction in scratch resistance and film-forming properties. The details of each polypropylene resin will be described below.

[0036] [Highly crystalline polypropylene resin] The highly crystalline polypropylene resin contained in the transparent resin layer 4 can be appropriately selected and designed from, for example, isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof with different pentad fractions. In this embodiment, it is preferable that the highly crystalline polypropylene resin is a highly crystalline homopolypropylene resin, which is a homopolymer of propylene with a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Furthermore, considering film-forming properties and scratch resistance, the MFR of the highly crystalline polypropylene resin at 230°C can be designed to be within the range of 0.5 g / 10 min to 30 g / 10 min (more preferably within the range of 10 g / 10 min to 25 g / 10 min).

[0037] The above pentad fraction (mmmm fraction) is based on carbon (C) with a mass number of 13. 13 This value (electromagnetic wave absorption rate) is calculated from the numerical value obtained by resonating the resin composition constituting the transparent resin layer 4 at a predetermined resonance frequency using the 1C-NMR (nuclear magnetic resonance) measurement method. This pentad fraction (mmmm fraction) defines the atomic arrangement, electronic structure, and molecular microstructure within the resin composition. The pentad fraction of polypropylene resin is as follows: 13 This refers to the ratio of five propylene units arranged in a row, as determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. This pentad fraction is one of the important factors that primarily determine the scratch resistance of a surface; generally, the higher the pentad fraction, the higher the crystallinity of the sheet, and therefore the better the scratch resistance. Furthermore, by making highly crystalline polypropylene resin the main component of the transparent resin layer 4, the surface strength (scratch resistance) of the decorative sheet is increased.

[0038] [Low-crystalline polypropylene resin] The low-crystallinity polypropylene resin added to the transparent resin layer 4 is preferably a polypropylene resin that satisfies at least one of the following characteristics. • Mesopentad fraction: 20% to 60% (More preferably, 40% to 55%) • MFR at 230℃ is between 30g / 10min and 100g / 10min. (More preferably, 30g / 10min to 60g / 10min) • Mass-average molecular weight (Mw) is between 10,000 and 500,000. (More preferably, between 50,000 and 200,000) • Molecular weight distribution (Mw / Mn) is less than 4 The melting point is defined as the peak top of the highest temperature peak observed in the melting endothermic curve obtained by holding the endothermic curve at -10°C for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC) and then increasing the temperature at 10°C / min, and is between 0°C and 120°C. (More preferably, 40°C to 100°C)

[0039] Low-crystallinity polypropylene resins tend to have properties such as low crystallinity, flexibility, low melting point, and high solubility in solvents. By using such low-crystallinity polypropylene resins, when added to high-crystallinity polypropylene resins, they can have high compatibility and slow crystallization rates while either not affecting the crystallinity of the high-crystallinity polypropylene resin or significantly reducing its impact on crystallinity.

[0040] [Random polypropylene resin] The random polypropylene resin added to the transparent resin layer 4 preferably has a melting frame rate (MFR) of 10 g / 10 min to 50 g / 10 min at 230°C (more preferably, a melting frame rate (MFR) of 10 g / 10 min to 30 g / 10 min at 230°C). By setting the MFR of the random polypropylene resin between the MFR of the high-crystalline polypropylene resin and the MFR of the low-crystalline polypropylene resin, the compatibility of the three types of PP resins in the molten state can be improved, and the film-forming properties of the transparent resin layer 4 can be further improved. Furthermore, in this embodiment, the random PP resin used for the transparent resin layer 4 preferably has a tensile modulus of 300 MPa to 1000 MPa (more preferably 500 MPa to 800 MPa) as defined in JIS K 7161.

[0041] Next, we will explain the blending ratio MR1 of the highly crystalline PP resin, the blending ratio MR2 of the low-crystalline PP resin, and the blending ratio MR3 of the random PP resin, based on the mass of the resin composition forming the transparent resin layer 4.

[0042] In this embodiment, the proportion of random PP resin MR3 in the transparent resin layer 4 is less than both the proportion of PP resin MR1 and the proportion of low-crystallinity PP resin MR2 (MR1 > MR3 and MR2 > MR3). In other words, random PP resin has the lowest proportion among the multiple types (three types in this example) of PP resin in the resin composition forming the transparent resin layer 4. Therefore, in the resin composition forming the transparent resin layer 4, the amount of random PP resin added is the smallest, while the amounts of highly crystalline PP resin and low crystalline PP resin added are greater than those of random PP resin.

[0043] More specifically, the blending ratios of the three types of polypropylene resins in the transparent resin layer 4 are preferably such that, based on the mass of the resin composition forming the transparent resin layer 4, the blending ratio MR1 of the highly crystalline PP resin is within the range of 30% to 60% by mass, the blending ratio MR2 of the low crystalline PP resin is within the range of 30% to 50% by mass, and the blending ratio MR3 of the random PP resin is within the range of 10% to 20% by mass. More preferably, the blending ratio MR1 of the highly crystalline PP resin is within the range of 40% to 50% by mass, the blending ratio MR2 of the low crystalline PP resin is within the range of 35% to 45% by mass, and the blending ratio MR3 of the random PP resin is within the range of 10% to 20% by mass. By setting the blending ratios of the three types of PP resin in the transparent resin layer 4 as described above, it is possible to provide the transparent resin layer 4 with excellent bending properties (post-processing properties) while maintaining the scratch resistance, film-forming properties, and transparency required in actual use. Therefore, it is possible to provide a decorative sheet 1 having a transparent resin layer 4 that has excellent bending properties (post-processing properties) while maintaining the scratch resistance, film-forming properties, and transparency required in actual use.

[0044] On the other hand, if the blending ratio MR1 of highly crystalline PP resin is less than 30% by mass, the influence of the softness of the low-crystalline PP resin and random PP resin becomes greater, which may reduce scratch resistance (surface hardness of decorative sheet 1). Furthermore, if the blending ratio MR1 of highly crystalline PP resin exceeds 60% by mass, the appropriate softness provided by the low-crystalline PP resin and random PP resin, which is sufficient to ensure good post-processability, may not be achieved, which may reduce the post-processability (bending flexibility in this example) of decorative sheet 1. Furthermore, if the blending ratio MR2 of the low-crystallinity PP resin is less than 30% by mass, the appropriate flexibility necessary for good post-processing is not imparted, and the post-processing properties (bending properties) of the decorative sheet 1 may be reduced. Moreover, if the blending ratio MR2 of the low-crystallinity PP resin exceeds 50% by mass, the softness increases excessively, which may cause neck-in or film breakage during film formation, reducing the film-forming properties of the transparent resin layer 4. Here, film-forming properties refer to the ability to form a film without problems during melt extrusion of the transparent resin layer 4. Furthermore, if the random PP resin blending ratio MR3 is less than 10% by mass, neck-in or film breakage may occur during film formation, reducing the film-forming properties of the transparent resin layer 4. Also, if the random PP resin blending ratio MR3 exceeds 20% by mass, the compatibility between the highly crystalline PP resin and the low-crystalline PP resin may be inhibited, causing clouding in the transparent resin layer and reducing the transparency of the transparent resin layer 4.

[0045] In this way, by setting the blending ratios MR1, MR2, and MR3 of the three types of polypropylene resin as described above, it is possible to provide a decorative sheet 1 having a transparent resin layer 4 that reliably maintains high scratch resistance, film-forming properties, and transparency, while also reliably exhibiting excellent bending properties (post-processing properties).

[0046] In addition, in the present embodiment, the magnitude relationship between the blending ratio MR1 of the highly crystalline PP resin and the blending ratio MR2 of the low crystalline PP resin is not particularly limited. That is, in the transparent resin layer 4, the blending ratio MR1 of the highly crystalline PP resin may be greater than the blending ratio MR2 of the low crystalline PP resin (MR1>MR2). Also, the blending ratio MR2 of the low crystalline PP resin may be greater than the blending ratio MR1 of the highly crystalline PP resin (MR1<MR2). Further, the blending ratio MR1 of the highly crystalline PP resin and the blending ratio MR2 of the low crystalline PP resin may be equal (MR1=MR2). In addition, when the blending ratio MR2 of the low crystalline PP resin is greater than the blending ratio MR1 of the highly crystalline PP resin (MR1<MR2), it is preferable that the difference between the blending ratio MR2 of the low crystalline PP resin and the blending ratio MR1 of the highly crystalline PP resin is less than 20% by mass (MR2-MR1<20% by mass). Thereby, even when the blending ratio of the low crystalline PP resin is the highest in the transparent resin layer, the softness can be suitably controlled, and the scratch resistance and film-forming property can be improved together with the bending processability of the bender.

[0047] Also, in the cosmetic sheet 1 according to the present embodiment, the transparent resin layer 4 is not limited to the above configuration. In the transparent resin layer 4 of the present embodiment, the tensile elastic modulus of the low crystalline PP resin contained in the above resin composition may be 25 MPa or more and 500 MPa or less, more preferably 50 MPa or more and 120 MPa or less. Also, in this case, the low crystalline PP resin may be added in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the highly crystalline PP resin. By making the blending ratio of the highly crystalline polypropylene resin the highest in the transparent resin layer 4, the surface strength (scratch resistance) of the cosmetic sheet can be further improved. In addition, since the low crystalline polypropylene resin exhibits high compatibility with the highly crystalline polypropylene resin, by adding a low crystalline polypropylene resin having a tensile elastic modulus within the above range, high transparency can be imparted to the transparent resin layer 4 while improving the post-processing property. Further, by setting the addition amount of the low crystalline polypropylene resin within the above range, the scratch resistance and post-processing property of the cosmetic sheet can be made better.

[0048] [Ultraviolet absorber] Furthermore, in this embodiment, the transparent resin layer 4 contains an ultraviolet absorber. In other words, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is formed of a transparent polyolefin thermoplastic resin and contains an ultraviolet absorber. This provides the transparent resin layer 4 with excellent weather resistance. More specifically, it is preferable that the transparent resin layer 4 contains at least one of the following ultraviolet absorbers: a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. This provides excellent weather resistance to the transparent polyolefin-based thermoplastic resin forming the transparent resin layer 4, thereby improving the weather resistance of the decorative sheet 1. The amount of UV absorber added to the transparent resin layer 4 should be adjusted according to the desired weather resistance, but it is preferable that it be 0.5 parts by mass or more per 100 parts by mass of the transparent polyolefin thermoplastic resin constituting the transparent resin layer 4. This ensures that the weather resistance of the decorative sheet 1 is reliably improved.

[0049] (Benzotriazole-based UV absorbers) Examples of "benzotriazole-based" UV absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and mixtures, modified products, polymers, and derivatives thereof.

[0050] (Triazine-based UV absorber) Examples of "triazine-based" UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0051] The thickness of the transparent resin layer 4 is preferably in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 is reliably improved, and the unevenness of the substrate to which it is adhered (in this example, the substrate 8) can be absorbed, resulting in a good finish when the decorative sheet 1 is applied. Furthermore, when the thickness of the transparent resin layer 4 is 150 μm or less, the transparent resin layer 4 does not need to be formed to be unnecessarily thick, improving the workability (e.g., bendability) and reducing the manufacturing cost of the decorative sheet 1.

[0052] (Surface protective layer) The surface protection layer 5 of the decorative sheet 1 according to this embodiment is provided on the transparent resin layer 4 (on the side opposite to the pattern layer 3). This layer is provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1. The material constituting the surface protection layer 5 is not particularly limited, and can be appropriately selected and used from resin materials such as urethane, acrylic, acrylic silicone, fluorine, and epoxy resins. The surface protective layer 5 may contain various additives as needed, such as ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and gloss modifiers. An example of the surface protective layer 5 according to this embodiment will be described below with specific examples.

[0053] In this embodiment, the surface protective layer 5 may mainly consist of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component. In this embodiment, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl (meth)acrylate as a monomer component, the affinity for water can be reduced, and degradation due to hydrolysis and other factors can be suppressed.

[0054] Regarding the cyclohexyl (meth)acrylate content, it is desirable that the cyclohexyl (meth)acrylate content be within the range of 5% by mass or more and 50% by mass or less among the monomer components of all acrylic resin compositions, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protection layer 5. By setting the cyclohexyl (meth)acrylate content to 5% by mass or more, a sufficient degradation suppression effect can be obtained. Furthermore, by setting the cyclohexyl (meth)acrylate content to 50% by mass or less, it becomes possible to impart high weather resistance over time without significantly changing the various properties of the surface protection layer 5 of the decorative sheet, such as improved surface hardness maintenance, improved stain resistance, and adjustment of surface gloss. Here, the "main component" mentioned above means that the content of the acrylic resin composition constituting the surface protection layer 5 is 50% by mass or more of the total mass of the surface protection layer 5.

[0055] In addition to cyclohexyl (meth)acrylate, examples of monomer components of the acrylic resin composition that can be used in the surface protective layer 5 according to this embodiment include cyclohexylmethyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylpropyl (meth)acrylate, cyclohexylbutyl (meth)acrylate, dimethylcyclohexane mono (meth)acrylate, dimethylcyclohexane di (meth)acrylate, trimethylcyclohexane mono (meth)acrylate, trimethylcyclohexane di (meth)acrylate, trimethylcyclohexane tri (meth)acrylate, tetramethylcyclohexane mono (meth)acrylate, tetramethylcyclohexane di (meth)acrylate, tetramethylcyclohexane tri (meth)acrylate, tetramethylcyclohexane tetra (meth)acrylate, dicyclohexylmethyl (meth)acrylate, dicyclohexylmethyl (meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, methoxycyclohexylmethyl (meth)acrylate, and methoxycyclohexylmethyl (meth)acrylate. Among these, those containing isomers may be each isomer individually and / or a mixture of each isomer.

[0056] Furthermore, in this embodiment, the surface protection layer 5 may be formed by coating the outermost surface of the decorative sheet with a coating liquid containing an acrylic resin composition containing the above-mentioned cyclohexyl (meth)acrylate as a monomer component and a weather-resistant agent such as an ultraviolet absorber, which will be described later. As will be described in detail later, for example, the coating liquid containing the above-mentioned acrylic resin composition and weather-resistant agent may be coated onto a transparent resin layer 4 on which an embossed portion 6 has been formed, and then wiped to embed the coating liquid into the embossed portion 6 and form the surface protection layer 5. As for the curing method of the coating liquid for forming the surface protective layer 5, any of the following can be used: a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type cured by irradiation with ultraviolet light or ionizing radiation. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable, and if post-processing after bonding to various substrates to become decorative components is considered, the two-component curing type that is crosslinked by isocyanate curing is desirable.

[0057] As a two-component curing type acrylic resin composition, a composition containing, for example, an acrylic resin having two or more functional groups selected from hydroxyl groups, amino groups, and carboxyl groups in one molecule, and a polyisocyanate compound having two or more isocyanate groups that can react with the functional groups in one molecule is preferred. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0058] As acrylic polyols having two or more hydroxyl groups in one molecule, in addition to the cyclohexyl (meth)acrylate mentioned above, for example, (meth)acrylic acid ester copolymers containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as polyisocyanate compounds having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, and burette types synthesized by known techniques from one or more compounds selected from these. Furthermore, compositions by mixing one or more of these different types of polyisocyanates can be used. Among these, HDI, or the trimer type, TMP adduct type, and burette type of HDI are preferred from the viewpoint of weather resistance. The content of the isocyanate compound relative to the resin component described above can be set arbitrarily, but it is desirable to set it so that the hydroxyl group / isocyanate group equivalent ratio is about 1 / 1 to 1 / 3. In particular, if the equivalent amount of hydroxyl groups is greater than the equivalent amount of isocyanate groups, crosslinking may not proceed sufficiently, and the desired performance may not be added to the surface protective layer 5, which is undesirable.

[0059] When the curing method for the coating solution used to form the surface protective layer 5 is active energy ray curing, known monomers, oligomers, etc. having (meth)acryloyl groups can be used as the active energy ray curing type acrylic resin composition, and in addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth)acrylate may be added.

[0060] In order to further improve the weather resistance of the decorative sheet 1, in this embodiment, a UV absorber and a light stabilizer are added to the surface protective layer 5 as weather-resistant agents. In other words, the surface protective layer 5 contains a UV absorber and a light stabilizer.

[0061] <UV absorber> As UV absorbers, known types such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), and benzophenone-based UV absorbers can be used. Among these, selecting a hydroxyphenyltriazine-based UV absorber allows for long-term UV absorption performance because the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically more stable than the skeletons of benzotriazole-based and benzophenone-based UV absorbers. In other words, it is preferable that the surface protective layer 5 contains a triazine-based UV absorber as the UV absorber.

[0062] Examples of hydroxyphenyltriazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl) Examples include -3-hydroxyphenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl)-3-hydroxyphenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine. In this embodiment, the surface protective layer 5 may contain 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter referred to as "ultraviolet absorber A" for convenience). Note that 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is used as ultraviolet absorber A, is generally known as the main component of "Tinuvin 479: manufactured by BASF Japan Ltd."

[0063] In the surface protection layer 5 of this embodiment, the amount of the above-mentioned triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber added is preferably within the range of 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the resin composition (e.g., acrylic resin composition) forming the surface protection layer 5. By adding 1 part by mass or more of the above-mentioned ultraviolet absorber, a weather resistance improvement effect is achieved, and by adding 30 parts by mass or less, the influence on physical properties other than weather resistance of the surface protection layer 5 can be suppressed to a level that does not pose a practical problem. In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber added to the surface protective layer 5, the amount added is preferably in the range of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the acrylic resin composition, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and even more preferably in the range of 8 parts by mass or more and 12 parts by mass or less. By adding 1 part by mass or more of ultraviolet absorber A, a weather resistance improvement effect is achieved, and by adding 20 parts by mass or less, the influence on physical properties other than weather resistance of the surface protective layer 5 can be suppressed to a level that does not pose a practical problem.

[0064] Furthermore, in this embodiment, by using both UV absorber A and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "UV absorber B" for convenience) as triazine-based (hydroxyphenyltriazine-based) UV absorbers in the surface protective layer 5, even better weather resistance is provided. This is because UV absorber B has a high UV absorption capacity in the short-wavelength region, which is relatively high energy among UV rays, and is chemically stable compared to other UV absorbers that absorb in almost the same wavelength region, so the wavelength region over which UV rays are absorbed is broadened when used in combination. Note that 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is used as UV absorber B, is generally known as the main component of "ADEKA Stab LA-46: manufactured by ADEKA Corporation".

[0065] In this embodiment, the amount of ultraviolet absorber A added to the surface protective layer 5 is preferably within the range of 10 parts by mass to 200 parts by mass, more preferably within the range of 20 parts by mass to 100 parts by mass, and even more preferably within the range of 40 parts by mass to 80 parts by mass, relative to 100 parts by mass of ultraviolet absorber B. By setting the amount of ultraviolet absorber A within the above numerical range, even better weather resistance can be provided.

[0066] <Light stabilizer> In this embodiment, the surface protective layer 5 contains a light stabilizer in addition to an ultraviolet absorber as a weather-resistant agent. This improves the weather resistance of the decorative sheet 1.

[0067] As a light stabilizer added to the surface protective layer 5, for example, a radical scavenger can be used. In other words, the surface protective layer 5 may contain a triazine-based ultraviolet absorber and a light stabilizer. By using the above-mentioned triazine-based ultraviolet absorber and the radical scavenger in combination, the weather resistance of the decorative sheet 1 can be further improved. Examples of hindered amine-based radical scavengers that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl- 4-Piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bi Su(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-diter-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) Hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino Examples include, but are not limited to, the reaction products of )-s-triazine-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatecyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro1,3,5-triazine and 2-aminoethanol.

[0068] In this embodiment, the amount of light stabilizer (e.g., hindered amine-based radical scavenger) added to the surface protective layer 5 is preferably within the range of 1 part by mass to 30 parts by mass per 100 parts by mass of the resin composition (e.g., acrylic resin composition) forming the surface protective layer 5. Adding 1 part by mass or more of the light stabilizer allows for the desired weather resistance to be obtained, while adding 30 parts by mass or less suppresses the bleed-out of the weather stabilizer and minimizes its influence on other physical properties of the surface protective layer 5.

[0069] <Application amount> The amount of surface protective layer 5 applied, that is, the amount of material for the surface protective layer 5 applied on the transparent resin layer 4, is 3 g / m². 2 More than 10g / m 2 A range of less than 3 g / m² is preferable. 2 If the amount is less than 10g / m², good weather resistance cannot be obtained. 2If the coating amount exceeds this range, it may hinder recyclability. By keeping the coating amount within this range, it is possible to achieve both good weather resistance and recyclability. Furthermore, keeping the coating amount within this range improves productivity and processability (e.g., bendability).

[0070] In this embodiment, the surface protection layer 5 includes an ultraviolet absorber and a light stabilizer, but the disclosure is not limited thereto. The surface protection layer 5 may be provided with the desired weather resistance according to the application, and the surface protection layer 5 may be configured to include at least one of the ultraviolet absorber and the light stabilizer.

[0071] In this embodiment, various known coating methods can be used to provide the surface protection layer 5, such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating. Furthermore, various additives such as anti-friction agents, anti-blocking agents, and antistatic agents may be added to the surface protection layer 5 in this embodiment as needed.

[0072] (Embossed area) As shown in Figure 1, an embossed portion 6 is provided on the outermost surface of the decorative sheet 1 according to this embodiment. By providing an embossed portion 6 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte finish of the decorative sheet 1 surface. Furthermore, the embossed portion 6 can be made into various uneven shapes, such as wood grain grooves, stone slab surface irregularities (granite cleavage surfaces, etc.), fabric surface textures, pearlescent, sandy, hairline, or fine-line grooves, thereby imparting a given design to the surface of the decorative sheet 1. The embossed portion 6 can be made into various uneven shapes, for example, according to the design of the pattern layer 3 or according to the desired design. The embossed portion 6 is formed on the surface (outermost surface) side of the surface protection layer 5, which is the outermost layer of the decorative sheet 1, and constitutes an uneven pattern. In this embodiment, the aforementioned surface protection layer 5 is embedded in the embossed portion 6 that constitutes this uneven pattern. This point will be explained below.

[0073] In the decorative sheet 1 according to this embodiment, the embossed portion 6 is provided on the transparent resin layer 4. That is, the transparent resin layer 4 is the layer on which the embossed portion 6 is formed. The shape of the uneven pattern provided on the surface of the transparent resin layer 4 is not particularly limited, but it is preferable that the shape of the embossed portion 6 constituting the uneven pattern is such that the opening diameter increases from the back side (pattern layer 3 in this example) to the front side (surface protection layer 5) of the transparent resin layer 4. With such a shape, it is easier to embed the surface protection layer composition (coating liquid) into the embossed portion 6 by wiping.

[0074] Furthermore, it is preferable that the side surface forming the embossed portion 6 is an inclined surface. If the side surface forming the embossed portion 6 is an inclined surface, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 6 by wiping. Furthermore, all sides forming the embossed portion 6 may be covered with the surface protective layer 5. Furthermore, the depth of the embossed portion 6 is preferably within the range of 1 μm to 50 μm in the thickness direction of the transparent resin layer 4. If the depth of the embossed portion 6 is within the above numerical range, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 6 by wiping, and peeling of the surface protective layer can be prevented.

[0075] Furthermore, the width of the embossed portion 6 is preferably within the range of 1 μm to 20 μm. If the width of the embossed portion 6 is within the above numerical range, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 6 by wiping, and it is possible to prevent the surface protective layer embedded in the embossed portion 6 from peeling off.

[0076] Furthermore, it is preferable that the embossed portion 6 is completely filled with the surface protective layer composition (coating liquid), but it is preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 be 10% or more. If the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 is 10% or more, the weather resistance of the embossed portion 6 can be improved. That is, if the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 is 10% or more, the occurrence of whitening and breakage in the conduit portion can be reduced. Also, as mentioned above, it is preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 be 100%, but it is more preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 be 80% or less, and it is even more preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 be 60% or less. If the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 6 is 80% or less, a sufficient tactile feel can be obtained in the embossed portion 6. Alternatively, by making the filling rate of the surface protective layer 5 with respect to the volume of the embossed portion 6 100%, the surface of the surface protective layer 5 filled in the embossed portion 6 and the surface of the transparent resin layer 4 in the area without the embossed portion 6 may be made flush.

[0077] (Total sheet thickness) The overall thickness (total thickness) of the decorative sheet 1 according to this embodiment is preferably in the range of 100 μm to 300 μm, and more preferably in the range of 120 μm to 200 μm. This makes it possible to form a decorative sheet 1 that, for example, has opacity and good processability. In this example, the total thickness of the decorative sheet 1 is the sum of the thicknesses of the two layers, the colored raw material layer 2 and the transparent resin layer 4.

[0078] As described above, the decorative sheet 1 according to this embodiment has at least a colored base layer 2, a pattern layer 3, and a transparent resin layer 4 laminated in this order, the colored base layer 2 is made of a colored polyolefin thermoplastic resin, the transparent resin layer 4 is made of a transparent polyolefin thermoplastic resin and contains an ultraviolet absorber, and the pattern layer 3 contains an azomethine azo pigment or a perylene pigment as a black pigment, and when the decorative sheet 1 is colored from the outermost surface side of the sheet, CIE1976L* a * b * L in color space * The value is 18 or higher, and when the colored raw material layer 2 is measured individually, CIE1976L * a * b * L in color space * The value is 50 or higher. This makes it possible to obtain a decorative sheet that, even when formed from olefin-based materials, has heat-shielding properties, suppresses deformation due to the absorption of infrared light, and has excellent weather resistance.

[0079] <Decorative materials> In this embodiment, the decorative sheet 1 described above may be bonded to a base material 8, which is a base material for decorative materials, to form a decorative material 10.

[0080] <Adhesive layer> The adhesive layer 7 is formed to improve adhesion with the substrate 8. When the substrate 8 is a wood-based substrate, the adhesive layer 7 can be made of, for example, ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, etc. These resins can be used individually or in combination to form an adhesive composition, which can then be formed using appropriate coating methods such as roll coating or gravure printing. In this case, a urethane-acrylate resin is preferred as the resin constituting the adhesive layer 7, and it is particularly preferred to form it with a resin consisting of a copolymer of an acrylic resin and a urethane resin and an isocyanate. When laminating the decorative sheet 1 onto the base material 8, an adhesive layer 7 may be provided by laminating via an appropriately selected adhesive as needed, or the sheets may be laminated directly without using an adhesive.

[0081] <Base material> In this embodiment, the decorative sheet 1 described above may be laminated to the base material 8 to form a decorative material 10. The decorative material 10 according to this embodiment comprises a base material 8 which is a base material for decorative materials, and a decorative sheet 1 laminated to the base material 8. In the decorative material 10, the decorative sheet 1 only needs to be provided on at least one side of the base material 8. The base material 8 in the decorative material 10 can be, for example, a wood-based base material such as MDF (Medium-density fiberboard), particleboard, or plywood. Alternatively, the base material 8 may be a metal-based base material such as steel plate or aluminum plate, or a resin-based base material such as PET, PVC, or ABS. By laminating the decorative sheet 1 onto the base material 8, even when formed from an olefin-based material, it is possible to obtain a decorative material 10 that has heat-shielding properties and suppresses deformation of the decorative material 10 due to absorption of sunlight. Furthermore, even when formed from an olefin-based material, a decorative material 10 with excellent weather resistance can be obtained. In addition, when a resin composition containing the above-mentioned multiple types of polypropylene resin is used for the transparent resin layer 4 in the decorative sheet 1, a decorative material 10 can be obtained that has a transparent resin layer with excellent bending properties (post-processing properties) while maintaining the scratch resistance, film-forming properties, and transparency required in actual use.

[0082] <Method for manufacturing decorative sheets and decorative materials> Below, an example of a method for manufacturing the decorative sheet 1 according to this embodiment will be briefly described. The pattern layer 3 is printed on the colored base layer 2 described above. Next, a transparent resin layer 4 is formed on the colored raw material layer 2 on which the pattern layer 3 is formed by heat lamination. At the same time, an embossed pattern is created on the surface of the transparent resin layer 4 opposite to the colored raw material layer 2 by embossing, thereby forming an embossed portion 6. Next, a coating liquid is applied to the surface of the transparent resin layer 4, which has an embossed pattern (embossed portion 6), to form a surface protective layer 5. Finally, the coating liquid is wiped into the embossed areas 6 that make up the uneven pattern, and the coating liquid is cured to form a surface protective layer 5 on the transparent resin layer 4. In this way, the decorative sheet 1 according to this embodiment is formed. Below, an example of a method for manufacturing the cosmetic material 10 according to this embodiment will be briefly described. The decorative sheet 1 and the base material 8 described above are bonded together to form the decorative material 10.

[0083] <Variation> While hydroxyphenyltriazine-based ultraviolet absorbers that can be added to the surface protective layer 5 have been described, the hydroxyphenyltriazine-based ultraviolet absorbers that can be used in this embodiment are not limited to these. The surface protective layer 5 according to this embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1). Alternatively, the surface protective layer 5 may contain an ultraviolet absorber having a structure represented by the following general formula (2). Specifically, it may contain 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl)]-6-(4-methoxyphenyl)-s-triazine shown in the following formula (3), or it may contain a hydroxyphenyltriazine-based ultraviolet absorber shown in the following formula (4).

[0084] [ka]

[0085] In general formula (1), R1 to R3 each independently represent a hydrogen atom, a methyl group, a phenyl group, or an alkoxy group, and at least two of them are alkoxy groups having 8 to 18 carbon atoms that do not contain a carbonyl group; R4 and R5 each independently represent a hydroxyl group, a methyl group, or a hydrogen atom; and R6 to R8 each independently represent a methyl group or a hydrogen atom.

[0086] [ka]

[0087] In general formula (2), R1 and R2 represent alkoxy groups having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent hydrogen atoms.

[0088] [ka]

[0089] [ka]

[0090] Furthermore, by using both hydroxyphenyltriazine and benzotriazole UV absorbers in combination, even better weather resistance can be imparted due to their interaction. This is because benzotriazole UV absorbers have an absorption peak at longer wavelengths than hydroxyphenyltriazine UV absorbers, thus broadening the wavelength range over which ultraviolet light is absorbed when used in combination. The amount of benzotriazole UV absorber to be added is preferably in the range of 1 to 30 parts by mass per 100 parts by mass of the acrylic resin composition. Adding 1 part by mass or more will yield the desired effect, while adding 30 parts by mass or less will suppress the bleed-out of the weather-resistant agent. However, because benzotriazole UV absorbers have an absorption peak at longer wavelengths, they may have a yellowish tint. If color is a concern, the amount added should be reduced.

[0091] Examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-diter-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-ter-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-ter-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-ter-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-ter-butyl-5'-carboxyphenyl)benzotriazole.

[0092] <Effects of this embodiment> (1) The decorative sheet 1 is a decorative sheet in which at least a colored base layer 2, a pattern layer 3, and a transparent resin layer 4 are laminated in this order, the colored base layer 2 is formed using a colored polyolefin thermoplastic resin, the transparent resin layer 4 is formed using a transparent polyolefin thermoplastic resin and contains an ultraviolet absorber, and the pattern layer 3 contains one or more of the following as a black pigment: azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, or black composite oxide pigment, and when the decorative sheet 1 is colored from the outermost surface side of the sheet, it conforms to CIE1976L * L in the a*b* color space * The value is between 15 and 35, and when the colored base layer 2 is measured individually, the L value in the CIE1976L*a*b* color space is * The value is 85 or higher. According to this configuration, the colored base layer 2 has a relatively high brightness (L * By setting it to ≥85, the reflectivity of visible light and near-infrared rays, which are the main components of solar radiation, is imparted, resulting in a heat-shielding effect. Therefore, even if the pattern layer 3 is a dark color, 15 ≤ L is measured from the outermost surface. * If the condition ≤ 35 is met, the absorption of infrared light can be suppressed and the heat storage effect can be reduced. Therefore, even when formed from olefin-based materials, the decorative sheet 1 has heat-shielding properties and can suppress deformation of the decorative sheet 1 or decorative material 10 caused by heat storage due to absorption of solar radiation. (2) The decorative sheet 1 may have a solar reflectance of 30% or more in the entire wavelength range from 300 nm to 2500 nm when solar reflectance measurements are taken on the outermost surface of the sheet using a spectrophotometer in accordance with JIS K 5602. This configuration ensures reliable heat shielding by suppressing solar radiation absorbed by the decorative sheet 1 and decorative material 10, and greatly contributes to suppressing deformation of the decorative sheet 1 or decorative material 10 caused by heat accumulation due to absorption of external light. (3) In the decorative sheet 1, carbon black is not used as the black pigment in the pattern layer 3. This configuration allows for more reliable suppression of infrared light absorption. (4) In the decorative sheet 1, the pattern layer may contain at least one pigment from among isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium dioxide. This configuration allows for a wider range of color expression compared to using only black pigment, and can impart a deeper, more sophisticated design to the decorative sheet 1. (5) In the decorative sheet 1, the colored raw material layer 2 may contain one or more inorganic substances from among calcium carbonate, titanium dioxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. This configuration allows for the colored base layer 2 to be suitably colored and given opacity. (6) In the decorative sheet 1, the transparent resin layer 4 may contain at least one of a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber as an ultraviolet absorber. This configuration provides excellent weather resistance to the transparent polyolefin-based thermoplastic resin forming the transparent resin layer 4, thereby improving the weather resistance of the decorative sheet 1. (7) In the decorative sheet 1, the transparent resin layer 4 is formed from a resin composition containing multiple types of polypropylene resins, and the resin composition includes highly crystalline polypropylene, low-crystalline polypropylene, and random polypropylene as the multiple types of polypropylene resins. The blending ratios of each of the multiple types of polypropylene resins, based on the mass of the resin composition, may be in the range of 30% to 60% by mass for the highly crystalline polypropylene, in the range of 30% to 50% by mass for the low crystalline polypropylene, and in the range of 10% to 20% by mass for the random polypropylene. This configuration allows for the transparent resin layer 4 to be given excellent bending properties (post-processing properties) while maintaining the scratch resistance, film-forming properties, and transparency required in actual use. (8) In the decorative sheet 1, a surface protection layer 5 is laminated on a transparent resin layer 4, and the surface protection layer 5 may contain a triazine-based ultraviolet absorber and a light stabilizer. This configuration allows for further improvement of the weather resistance of the decorative sheet 1. (9) The decorative sheet 1 may have an embossed portion 6 formed on the surface side of the surface protective layer 5. This configuration allows for improved fingerprint resistance while maintaining the matte finish of the decorative sheet 1 surface, and also provides a design element to the surface. (10) The decorative sheet 1 may have a sheet temperature of less than 70°C after 60 minutes of illumination from the sheet surface at an illuminance of 100,000 lux using an artificial sunlight lamp. This configuration ensures a reduction in heat storage and effectively suppresses deformation caused by solar radiation. (11) The decorative sheet 1 may have a sheet temperature of less than 70°C after 30 minutes of illumination from the sheet surface at an illuminance of 100,000 lux using an artificial sunlight lamp. This configuration significantly reduces heat storage in practical applications and effectively suppresses deformation caused by solar radiation. (12) The decorative material 10 comprises a base material 8, which is a base material for decorative materials, and a decorative sheet 1 that is bonded to the base material 8. With this configuration, even when formed from olefin-based materials, the decorative material 10 has heat-shielding properties, which can suppress deformation due to the absorption of solar radiation.

[0093] <Examples> The present disclosure will be described in detail below with reference to examples and comparative examples, but the present disclosure is not limited to the examples below.

[0094] (Example 1) A pattern layer was created by gravure printing printing ink onto a colored polyolefin thermoplastic resin sheet, which served as the colored base layer. Subsequently, a highly weather-resistant transparent polyolefin thermoplastic resin sheet was heat-laminated onto the colored base layer with the pattern layer, forming a surface protective layer mainly composed of an acrylic resin composition on the transparent resin layer. This resulted in obtaining the decorative sheet according to Example 1. [Colored original fabric layer] Material: Polyolefin thermoplastic resin, Thickness: 80 μm Coloring agent: Titanium dioxide [Picture layer] A wood grain pattern was printed onto a colored substrate layer using gravure printing with a printing ink containing 3 parts by mass of four pigments—isoindolinone, polyazo, phthalocyanine, and an organic black pigment (perylene black)—as colorants, added to a binder resin. [Transparent resin layer] Material: Polyolefin thermoplastic resin, Thickness: 80 μm Additives: Triazine-based UV absorber (0.5 parts by mass per 100 parts by mass of thermoplastic resin) [Surface protective layer] • Main ingredient (methyl methacrylate / 2-hydroxyethyl methacrylate = 95 / 5 copolymer) ... 90 parts by mass • UV absorber (Tinuvin 479; manufactured by BASF Japan Ltd.) ... 9 parts by mass • Light stabilizer (Tinuvin 123; manufactured by BASF Japan Ltd.) ... 1 part by mass • Hardening agent (Takenate D170; manufactured by Mitsui Chemicals, Inc.) ·· 10 parts by mass • Solvent (ethyl acetate) ... 240 parts by mass ·Amount of application: 3g / m 2 [Total sheet thickness] 160 μm (= thickness of colored base material layer: 80 μm + thickness of transparent resin layer: 80 μm) [L value in the Lab color space] CIE1976L color measured from the sheet surface * a * b * L value in color space: 20 CIE1976L color measured on the colored raw material layer * a * b * L value in color space: 85 The L value on the sheet surface was controlled by the black pigment added to the pattern layer. Furthermore, the L value in the colored base layer was controlled by the coloring agent (titanium dioxide) added to the colored base layer.

[0095] (Example 2) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 15, and the color was measured on the colored substrate layer using CIE1976L. * a * b * The L value in the color space was set to 85. Otherwise, the decorative sheet of Example 2 was obtained in the same manner as in Example 1. (Example 3) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 25, and the color was measured on the colored raw material layer using CIE1976L. * a * b * The L value in the color space was set to 85. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1. (Example 4) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 35, and the color was measured on the colored substrate layer using CIE1976L. * a * b * The L value in the color space was set to 85. Otherwise, the decorative sheet of Example 4 was obtained in the same manner as in Example 1. (Example 5) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 20, and the color was measured on the colored raw material layer using CIE1976L. * a * b *The L value in the color space was set to 90. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 5 was obtained. (Example 6) CIE1976L measured from the sheet surface * a * b * The L value in the color space was 25, and CIE1976L measured for the coloring original layer * a * b * The L value in the color space was set to 90. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 6 was obtained. (Example 7) In the printing ink used for printing the pattern layer, instead of perylene black, an azomethine azo-based organic black pigment was used. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 7 was obtained. (Example 8) In the printing ink used for printing the pattern layer, instead of perylene black, a titanium-based organic black pigment was used. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 8 was obtained. (Example 9) In the printing ink used for printing the pattern layer, instead of perylene black, an iron oxide-based organic black pigment was used. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 9 was obtained. (Example 10) In the printing ink used for printing the pattern layer, instead of perylene black, a composite oxide-based organic black pigment was used. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Example 10 was obtained.

[0096] (Comparative Example 1) In the printing ink used for printing the pattern layer, instead of perylene black, carbon black was used. Otherwise, in the same manner as in Example 6, a cosmetic sheet of Comparative Example 1 was obtained. (Comparative Example 2) CIE1976L measured from the sheet surface * a * b * The L value in the color space was 10, and CIE1976L measured for the coloring original layer * a * b *The L value in the color space was set to 85. Otherwise, the decorative sheet for Comparative Example 2 was obtained in the same manner as in Example 1. (Comparative Example 3) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 20, and the color was measured on the colored raw material layer using CIE1976L. * a * b * The L value in the color space was set to 80. Otherwise, the decorative sheet for Comparative Example 3 was obtained in the same manner as in Example 1. (Comparative Example 4) CIE1976L color measured from the sheet surface * a * b * The L value in the color space is 40, and the color was measured on the colored raw material layer using CIE1976L. * a * b * The L value in the color space was set to 85. Otherwise, the decorative sheet for Comparative Example 4 was obtained in the same manner as in Example 1.

[0097] <Color measurement> CIE1976L * a * b * The L value in the color space was measured. For each example and comparative example of the decorative sheet, the reflective chromaticity was measured from the surface protective layer side of the entire sheet using a D65 light source to obtain the L value from the outermost surface of the sheet. In addition, the reflective chromaticity was measured on the colored base layer before printing of the pattern layer to obtain the L value of the colored base layer alone. Specifically, using an X-rite spectrophotometer (530JP / LP), the above-mentioned reflectivity was measured on a white background of BYK-GARDNER opacity test paper (byko-chart high brightness 2A) under the D65 light source, which is a standard light source defined by the International Commission on Illumination (CIE), and CIE1976L * a * b * The L value in the color space was obtained.

[0098] <Rating> The decorative sheets obtained in the above examples and comparative examples were evaluated for solar reflectance (heat shielding performance), weather resistance, heat storage capacity (reduction of heat storage effect), design, and presence or absence of deformation using the following method. The evaluation results are shown in Table 1.

[0099] (Solar reflectance) The solar reflectance of the decorative sheets in each example and comparative example was measured using the solar reflectance measurement method for coating films specified in JIS K5602 to evaluate their heat shielding performance. Measurements were performed on decorative sheets obtained by laminating a PVC substrate to the side of the colored base material layer (colored polyolefin thermoplastic resin sheet) opposite to the patterned layer. The measurement was performed using a Hitachi High-Technologies Corporation U-4100 spectrophotometer. Specifically, the reflectance of each example and comparative decorative material for light in the wavelength range of 780 nm to 2500 nm was measured to evaluate its heat-shielding properties. The evaluation criteria are as follows. ○: The measured reflectance is 30% or higher, indicating good heat shielding properties. ×: The measured reflectance is less than 30%, indicating insufficient heat shielding. In this embodiment, "〇" was considered a passing grade.

[0100] (Weather resistance test) The appearance of the decorative sheets in each example and comparative example after the accelerated weathering test was visually evaluated according to the following criteria. The accelerated weathering test was conducted using a metal weather tester (KU-R5DCI-A) manufactured by Daipla Wintes Co., Ltd., with a black panel temperature of 63°C and an illuminance of 65 mW / cm². 2 The experiment was conducted in 21 cycles (504 hours), with each cycle consisting of 20 hours of UV irradiation and 4 hours of condensation. The evaluation criteria are shown below. ◎: The color difference before and after the weather resistance test is less than △E=2. ○: The color difference before and after the weather resistance test is △E = 2 or more and 4 or less. △: In some areas, the color difference before and after the weather resistance test is △E=4 or greater. ×: Overall, the color difference before and after the weather resistance test is △E=4 or greater. In this embodiment, a score of "△" or higher was considered acceptable.

[0101] (Heat storage performance evaluation) Each example and comparative example's decorative sheet (size: 100mm x 100mm) was laminated onto a 2mm thick white PVC board (size: 100mm x 100mm, manufactured by Takiron CI Co., Ltd., ES-9700A) using a urethane resin adhesive (manufactured by No Tape Industry Co., Ltd., No. 5211). The laminated white PVC sheet was attached to a 6.5mm thick foam (size: 100mm x 100mm, manufactured by Sanfuku Kogyo Co., Ltd., 3F-10, thermal conductivity: 0.052 W / mK) using double-sided tape, and the resulting laminate was used to create the test specimen. At that time, a thermocouple was placed between the double-sided tape in the center of the white PVC sheet, allowing the temperature of the back of the white PVC sheet (test specimen temperature) to be measured with a data logger. An artificial sunlight lamp (XC-100EFSS, manufactured by Seric Co., Ltd.) was installed while measuring the illuminance of the test specimen surface (decorative sheet surface) with an illuminance meter (FT3424, manufactured by HIOKI E.E. CORPORATION) to 100,000 lux, and then the lamp was turned off. At this time, the optical axis of the artificial sunlight lamp was positioned so that it struck the center of the test specimen and was perpendicular to the surface of the test specimen. The test was started by irradiating the test specimen with artificial sunlight from a room temperature and a test specimen temperature of 23°C. The evaluation criteria (overall evaluation) are shown below. ◎: The temperature of the test specimen is below 70°C (〇) 30 minutes and 60 minutes after the start of the test. ○: The temperature of the test specimen 30 minutes after the start of the test is less than 70°C (○), and the temperature of the test specimen 60 minutes after the start of the test is 70°C or higher (×). ×: The test specimen temperature is 70°C or higher 30 minutes after the start of the test (×). In this embodiment, an overall evaluation of "〇" or higher was considered a passing grade.

[0102] (Design) The perceived blackness of the decorative sheets in each example and comparative example was subjectively evaluated by 10 people, and the evaluation was as follows for each number of people who judged them to be sufficiently black. The evaluation criteria are as follows. ◎◎◎: 10 people judged it to be sufficiently black. ◎◎: 9 people judged it to be sufficiently black. ◎: 7-8 people judged it to be sufficiently black. ○: 5-6 people judged it to be sufficiently black. △: 1 to 4 people judged it to be sufficiently black. ×: 0 people judged it to be sufficiently black. In this example, a score of "△" or higher was considered a passing grade.

[0103] (Deformation evaluation) Each of the decorative sheets (size: 100mm x 100mm) for each example and comparative example was laminated onto a 2mm thick white PVC board (size: 100mm x 100mm, manufactured by Takiron CI Co., Ltd., ES-9700A) using a urethane resin adhesive (manufactured by No Tape Industry Co., Ltd., No. 5211) to prepare a test specimen. The white PVC board side was placed face down on a 6.5mm thick foam (size: 100mm x 100mm, manufactured by Sanfuku Kogyo Co., Ltd., 3F-10, thermal conductivity: 0.052 W / mK). An artificial sunlight lamp (XC-100EFSS, manufactured by Seric Co., Ltd.) was installed while measuring the illuminance on the surface of the test specimen with an illuminance meter (FT3424, manufactured by HIOKI E.E. CORPORATION) to 100,000 lux, and then the lamp was turned off. At this time, the optical axis of the artificial sunlight lamp was positioned so that it struck the center of the test specimen and was perpendicular to the surface of the test specimen. The test was started by irradiating the test specimen with artificial sunlight from a room temperature of 23°C. The evaluation criteria are as follows. ○: No deformation was observed visually 60 minutes after the start of the test. △: Slight deformation was observed visually 60 minutes after the start of the test. ×: Significant deformation was observed visually 60 minutes after the start of the test. In this example, a score of "△" or higher was considered a passing grade.

[0104] The evaluation results for each of the above, along with the composition of the decorative sheet, are shown in Table 1. Note that in Table 1, CIE1976L * a * b *The color space is simply referred to as "Lab color space."

[0105] [Table 1]

[0106] As can be seen from Table 1, in the decorative sheets of Examples 1 to 10, the pattern layer contains azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, or black composite oxide pigment as a black pigment, and when the decorative sheet is colored from the outermost surface side, CIE1976L * a * b * L in color space * The value is between 15 and 35, and when the colored raw material layer is measured individually, it is CIE1976L * a * b * L in color space * The value was 85 or higher. As a result, the solar reflectance (heat shielding) of the decorative sheets in Examples 1 to 10 all passed the test ("○"). Furthermore, because the transparent resin layer contains an ultraviolet absorber, the weather resistance also passed the test ("○"). In addition, the evaluation of heat storage (reduction of heat storage effect) and design (black color) also passed, and the deformation evaluation also passed. In other words, it was found that the decorative sheets in Examples 1 to 10 were excellent in all evaluation items. Therefore, even when formed from olefin-based materials, they can have heat shielding properties while being black, and can suppress deformation due to solar radiation absorption.

[0107] On the other hand, in Comparative Example 1, carbon black, which has low reflectivity in the near-infrared light region, was used as the black pigment, resulting in a reduction in solar reflectance (heat shielding) and an increase in heat storage, leading to a failure in evaluation. Furthermore, deformation was observed as a result, resulting in a failure in deformation evaluation. In addition, in Comparative Example 2, the color measured from the sheet surface using CIE1976L * a * b *The L value in the color space was less than 15, resulting in very low brightness and high infrared absorption, which led to a failure in the heat storage evaluation. Therefore, the deformation evaluation also failed, similar to Comparative Example 1. Furthermore, in the decorative sheet of Comparative Example 3, the L value in the CIE1976L*a*b* color space of the colored raw material layer alone was less than 85, indicating insufficient brightness and low near-infrared reflectivity, resulting in a failure in the heat storage evaluation. Therefore, the deformation evaluation also failed, similar to Comparative Example 1. In the decorative sheet of Comparative Example 4, the CIE1976L color measured from the sheet surface... * a * b * The L value in the color space exceeded 35, resulting in high brightness, which meant that the aesthetic appeal (black) was not adequately evaluated.

[0108] Furthermore, the decorative sheets and decorative materials of this disclosure are not limited to the embodiments and examples described above, and various modifications are possible as long as they do not impair the features of the invention.

[0109] Furthermore, for example, this disclosure can take the following configuration. (1) A decorative sheet in which at least a colored base layer, a pattern layer, and a transparent resin layer are laminated in this order, The aforementioned colored base layer is formed using a colored polyolefin-based thermoplastic resin. The transparent resin layer is formed using a transparent polyolefin-based thermoplastic resin and contains an ultraviolet absorber. The aforementioned pattern layer contains one or more of the following as black pigments: azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, or black composite oxide pigment. When the color of the decorative sheet is measured from the outermost surface side of the sheet, CIE1976L * a * b * L in color space * The value is between 15 and 35. When the aforementioned colored raw material layer was measured individually, CIE1976L * a * b * L in color space *The value is 85 or higher. A decorative sheet characterized by the following features. (2) The decorative sheet according to (1) above, characterized in that, when solar reflectance measurement is performed on the outermost surface of the sheet using a spectrophotometer in accordance with JIS K 5602, the solar reflectance in the entire wavelength range from 300 nm to 2500 nm is 30% or more. (3) The decorative sheet according to either (1) or (2) above, characterized in that the pattern layer does not use carbon black as a black pigment. (4) The decorative sheet according to any one of (1) to (3) above, characterized in that the pattern layer contains at least one pigment from among isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium dioxide. (5) The decorative sheet according to any one of (1) to (4) above, characterized in that the colored base layer contains one or more inorganic substances selected from calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. (6) The decorative sheet according to any one of (1) to (5) above, characterized in that the transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber as the ultraviolet absorber. (7) The transparent resin layer is formed from a resin composition containing multiple types of polypropylene resins. The resin composition includes, as the plurality of types of polypropylene resins, highly crystalline polypropylene, low crystalline polypropylene, and random polypropylene. The decorative sheet according to any one of (1) to (6) above, characterized in that the blending ratio of each of the multiple types of polypropylene resins, based on the mass of the resin composition, is in the range of 30% to 60% by mass for the highly crystalline polypropylene, in the range of 30% to 50% by mass for the low crystalline polypropylene, and in the range of 10% to 20% by mass for the random polypropylene. (8) A surface protective layer is laminated on the transparent resin layer. The decorative sheet according to any one of (1) to (7) above, characterized in that the surface protective layer contains a triazine-based ultraviolet absorber and a light stabilizer. (9) The decorative sheet according to (8) above, characterized in that an embossed portion is formed on the surface side of the surface protective layer. (10) A decorative sheet according to any one of the above items (1) to (9), characterized in that the sheet temperature after 60 minutes of irradiation with an illuminance of 100,000 lux from the sheet surface using an artificial sunlight lamp is less than 70°C. (11) A decorative sheet according to any one of the above items (1) to (9), characterized in that the sheet temperature after 30 minutes of irradiation with an illuminance of 100,000 lux from the sheet surface using an artificial sunlight lamp is less than 70°C. (12) Base material for decorative materials, A decorative material comprising a decorative sheet according to any one of the above items (1) to (11) bonded to the aforementioned decorative material substrate. [Industrial applicability]

[0110] This disclosure is a technology suitable for building exteriors and semi-exterior building materials, such as entrance doors, their frames, window frames, and bay window counters. [Explanation of Symbols]

[0111] 1 Decorative sheet 2 Colored original fabric layer 3 Pattern Layers 4 Transparent resin layer 5 Surface protective layer 6 Embossed area 7 Adhesive layer

Claims

1. A decorative sheet in which at least a colored base layer, a pattern layer, and a transparent resin layer are laminated in this order, The aforementioned colored base layer is formed using a colored polyolefin-based thermoplastic resin. The transparent resin layer is formed using a transparent polyolefin-based thermoplastic resin and contains an ultraviolet absorber. The aforementioned pattern layer contains one or more of the following as black pigments: azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, or black composite oxide pigment. When the decorative sheet is colored from the outermost surface side of the sheet, CIE1976L ＊ a ＊ b ＊ L in color space ＊ The value is between 15 and 35. When the aforementioned colored raw material layer was measured individually, CIE1976L ＊ a ＊ b ＊ L in color space ＊ The value is 85 or higher. A decorative sheet characterized by the following features.

2. When solar reflectance measurements are performed on the outermost surface of the sheet using a spectrophotometer compliant with JIS K 5602, the solar reflectance is 30% or more across the entire wavelength range from 300 nm to 2500 nm. The decorative sheet according to feature 1.

3. The aforementioned pattern layer does not use carbon black as the black pigment. The decorative sheet according to feature 2.

4. The aforementioned pattern layer contains at least one pigment from among isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium dioxide. The decorative sheet according to feature 3.

5. The aforementioned colored raw material layer contains one or more inorganic substances from among calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides. The decorative sheet according to feature 4.

6. The transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber as the ultraviolet absorber. The decorative sheet according to feature 5.

7. The transparent resin layer is formed from a resin composition containing multiple types of polypropylene resins. The resin composition includes, as the plurality of types of polypropylene resins, highly crystalline polypropylene, low crystalline polypropylene, and random polypropylene. Based on the mass of the resin composition, the respective blending ratios of the multiple types of polypropylene resins are as follows: the highly crystalline polypropylene is within the range of 30% to 60% by mass, the low crystalline polypropylene is within the range of 30% to 50% by mass, and the random polypropylene is within the range of 10% to 20% by mass. The decorative sheet according to feature 6.

8. A surface protective layer is laminated on the transparent resin layer. The aforementioned surface protective layer contains a triazine-based ultraviolet absorber and a light stabilizer. The decorative sheet according to feature 7.

9. An embossed portion is formed on the surface side of the aforementioned surface protective layer. The decorative sheet according to feature 8.

10. The sheet temperature after 60 minutes of illumination at an intensity of 100,000 lux from the sheet surface using an artificial sunlight lamp is less than 70°C. The decorative sheet according to feature 9.

11. The sheet temperature after 30 minutes of illumination at an intensity of 100,000 lux from the sheet surface using an artificial sunlight lamp is less than 70°C. The decorative sheet according to feature 9.

12. Base material for decorative materials, A decorative sheet according to any one of claims 1 to 11, which is bonded to the aforementioned decorative material substrate, A decorative material characterized by having the following features.

Images