JP2017202674A - Decorative sheet and decorative member having decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of constantly exhibiting a black color even when used outdoors, and exerting a heat shielding performance, or to provide a decorative member.SOLUTION: A decorative sheet (10) includes: a base material sheet (11); a printed layer (12) including an organic black pigment and an inorganic black pigment; a transparent resin layer (13); and a surface protective layer (14). In the decorative sheet (10), an Lvalue, an avalue and a bvalue of an Labcolorimetric system are 30 or less, 0 to 2.5, and -2.5 to 0 respectively, when measured by irradiating a surface of a surface protective layer side of the decorative sheet (10) with light. An average spectral reflectance of wavelength region 780 to 2500 nm is at least 35% when measured by irradiating the surface of the surface protective layer side of the decorative sheet (10) with light of wavelength region 780 to 2500 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet and a decorative member including the decorative sheet.

  In addition to the interior and exterior components of buildings such as walls, ceilings and floors, window frames, doors, handrails, skirting boards, edges, malls and other fittings, surface decoration boards for cabinets such as kitchens, furniture or light electrical appliances, OA equipment, As a vehicle interior / exterior member, a decorative member is generally used in which a metal member such as a steel plate, a resin member, and a wooden member are used as adherends and a decorative sheet is bonded thereto.

  In recent years, the demand for dark-colored decorative sheets or decorative members has increased, and as a dark-colored decorative sheet or decorative member, any layer (for example, an adherend or a base material) constituting the decorative sheet or decorative member is used. A decorative sheet or decorative member containing carbon black as a black pigment in the decorative layer) is known. However, when a decorative sheet or decorative member containing carbon black is used in an environment where it is exposed to direct sunlight, the carbon black absorbs heat (infrared rays), resulting in a temperature difference between the layers constituting the decorative sheet or decorative member. There is a problem that the decorative sheet or the decorative member is warped. There is also a problem that the heat absorbed by the carbon black propagates inside the building and the temperature inside the building rises.

  On the other hand, Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-168176) describes a laminate in which heat storage properties are reduced by using an inorganic pigment having infrared reflection characteristics. However, the inorganic pigment used in Patent Document 1 shows sufficient infrared reflection characteristics if it is a high brightness product such as white, but if it is a dark color low brightness product such as black, sufficient infrared reflection is achieved. Does not show properties. Therefore, it is difficult to realize a decorative sheet or decorative member that exhibits black color and exhibits heat shielding performance according to Patent Document 1.

  Further, Patent Document 2 (Japanese Patent Laid-Open No. 2014-43066) and Patent Document 3 (Japanese Patent Laid-Open No. 2013-237248) describe organic pigments having high infrared transmittance (low infrared absorption) (in Patent Document 2, azomethineazo). A decorative sheet having improved heat shielding performance by use of a pigment (perylene pigment in Patent Document 3) is described. However, the organic pigment described in Patent Document 2 or 3 has low weather resistance as compared with the inorganic pigment. Therefore, it is difficult to realize a decorative sheet or decorative member that exhibits a black color continuously and exhibits thermal insulation performance even when used outdoors.

JP 2007-168176 A JP, 2014-043066, A JP 2013-237248 A

  Accordingly, an object of the present invention is to provide a decorative sheet or a decorative member that continuously exhibits black color even when used outdoors, and that exhibits thermal insulation performance.

In order to solve the above problems, the present invention provides the following inventions.
(1) A decorative sheet having a base sheet, a printing layer containing an organic black pigment and an inorganic black pigment, a transparent resin layer, and a surface protective layer in this order,
The L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value measured by irradiating light on the surface of the decorative sheet on the surface protective layer side are L ^* values: 30 or less, a ^* Value: 0 or more and 2.5 or less, and b ^* Value: -2.5 or more and 0 or less,
The said decorative sheet whose average spectral reflectance of the wavelength range 780-2500 nm measured by irradiating the light of the wavelength range 780-2500 nm to the surface protective layer side surface of the said decorative sheet is 35% or more.
(2) The decorative sheet according to (1), wherein the printed layer includes a first printed layer containing the organic black pigment and a second printed layer containing the inorganic black pigment.
(3) The decorative sheet according to (2), wherein the second printed layer does not contain the organic black pigment.
(4) The decorative sheet according to (2), wherein the second printed layer contains the organic black pigment.
(5) The decorative sheet according to any one of (1) to (4), wherein the organic black pigment is an azomethine azo black pigment.
(6) The decorative sheet according to any one of (1) to (5), wherein the inorganic black pigment is a complex oxide containing a manganese element.
(7) L ^* a ^* b ^* L ^* value, a ^* value and b ^* value of the color system after the weather resistance test are L ^* value: 30 or less, a ^* value: 0 or more and 2.5 or less, and , B ^* value: The decorative sheet according to any one of (1) to (6), which is −2.5 or more and 0 or less.
(8) The spectral reflectance at a wavelength of 800 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light having a wavelength of 800 nm is 20% or more, and is described in any one of (1) to (7). Makeup sheet.
(9) The average spectral reflectance in the wavelength region 300 to 650 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength region 300 to 650 nm is 6% or less (1) to ( The decorative sheet according to any one of 8).
(10) In the state where the transparent resin layer is present alone, the a ^* value and b ^* value of the L ^* a ^* b ^* color system measured by irradiating the surface of the transparent resin layer with a ^* Value: -1 or more and 0 or less, and b ^* value: -3 or more and -2 or less The decorative sheet according to any one of (1) to (9).
(11) The decorative sheet according to any one of (1) to (10), wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.
(12) The decorative sheet according to any one of (1) to (11), wherein the base sheet is a colored resin sheet.
(13) The decorative sheet according to any one of (1) to (12), wherein the decorative sheet does not contain carbon black.
(14) A decorative member comprising an adherend and the decorative sheet according to any one of (1) to (13) so that the adherend and the base sheet of the decorative sheet face each other.
(15) The decorative member according to (14), wherein the adherend is at least one member selected from a wooden member, a metal member, and a resin member.

  ADVANTAGE OF THE INVENTION According to this invention, even when it uses outdoors, while providing black continuously, the decorative sheet or decorative member which exhibits heat-shielding performance is provided.

FIG. 1 is a side view schematically showing a configuration of a decorative sheet according to an embodiment of the present invention. FIG. 2 is a side view schematically showing the configuration of the decorative member according to the embodiment of the present invention. FIG. 3 is a diagram showing a spectral reflectance curve in a wavelength range of 300 to 2500 nm in the base sheet used in the examples.

[Definition]
The parameters used in the present invention are defined as follows.
“L ^* a ^* b ^* color system” means a color system standardized by CIE (International Lighting Commission) and adopted in JIS Z 8781-4: 2013. In the L ^* a ^* b ^* color system, lightness is represented by L ^* , and chromaticity indicating hue and saturation is represented by a ^* and b ^* .

“L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value” in the decorative sheet is measured using a spectrocolorimeter (CM-3700d manufactured by Konica Minolta Holdings, Inc.) The surface protective layer side surface is irradiated with light at an incident angle of 8 degrees (the normal direction of the surface of the decorative sheet is 0 degree), and measurement is performed based on total light reflected light (specular reflection light + diffuse reflection light).

  The “average spectral reflectance (%) in the wavelength range of 780 to 2500 nm” in the decorative sheet is obtained by changing each wavelength by 1 nm from a wavelength of 780 nm to a wavelength of 2500 nm (ie, wavelengths of 780 nm, 781 nm, 782 nm,... (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of 1721 spectral reflectances measured is divided by 1721. “Spectral reflectance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) based on JIS K 0115: 2004, and the incident angle is 5 on the surface protective layer side surface of the decorative sheet. The light of each wavelength is irradiated at a degree (the normal direction of the surface of the decorative sheet is 0 degree) and measured as a ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectivity). The measuring method of the total light reflectance is based on JIS K 7375: 2008.

  The spectrophotometer (V-670 manufactured by JASCO Corporation) conforming to JIS K 0115: 2004 is used for “spectral reflectance (%) at a wavelength of 800 nm” in the decorative sheet, and the surface protective layer side surface of the decorative sheet is used. Light with a wavelength of 800 nm is irradiated at an incident angle of 5 degrees (the normal direction of the surface of the decorative sheet is 0 degree), and the ratio is measured as the ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectance). The measuring method of the total light reflectance is based on JIS K 7375: 2008.

  The “average spectral reflectance (%) in the wavelength range of 300 to 650 nm” in the decorative sheet is the wavelength of each wavelength (that is, 300 nm, 301 nm, 302 nm,...) While changing the wavelength from 300 nm to 650 nm. 648 nm, 649 nm, and 650 nm), and the sum of the measured 351 spectral reflectances is divided by 351. “Spectral reflectance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) based on JIS K 0115: 2004, and the incident angle is 5 on the surface protective layer side surface of the decorative sheet. The light of each wavelength is irradiated at a degree (the normal direction of the surface of the decorative sheet is 0 degree) and measured as a ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectivity). The measuring method of the total light reflectance is based on JIS K 7375: 2008.

  “Average spectral reflectance (%) in wavelength range 300 to 2500 nm”, “Spectral reflectance in wavelength range 800 nm (%)” and “Average spectral reflectance (%) in wavelength range 300 to 650 nm” in the base sheet are The spectral reflectance on the surface side (surface protective layer side) of the base material sheet is measured in a state where the material sheet exists alone (that is, in a state where no layers are laminated on both surfaces of the base material sheet). Therefore, when measuring the spectral reflectance of the base sheet from the form of the decorative sheet in which the printed layer, the transparent resin layer, and the surface protective layer are laminated on the base sheet, the surface side of the base sheet from the decorative sheet ( Spectral reflection of the base sheet with all the layers (printing layer, transparent resin layer, and surface protective layer) laminated on the surface protective layer side removed by cutting or peeling and exposing the surface of the base sheet Measure the rate. However, when the spectral reflectances of the front and back surfaces of the base sheet are the same, the spectral reflectance of the back surface (the surface opposite to the surface protective layer) of the decorative sheet is measured, and this is measured in the base sheet. Spectral reflectance. The “average spectral reflectance (%) in the wavelength range of 300 to 2500 nm” in the base sheet is the wavelength (ie, wavelengths of 300 nm, 301 nm, 302 nm,...) While changing the wavelength by 1 nm from the wavelength of 300 nm to the wavelength of 2500 nm. The spectral reflectance (%) of 2498 nm, 2499 nm, and 2500 nm is measured, and the sum of the measured 2201 spectral reflectances is divided by 2201. “Spectral reflectance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) conforming to JIS K 0115: 2004, and an incident angle of 5 degrees (base) on the surface of the base sheet. The light of each wavelength is irradiated at a normal direction of the surface of the material sheet of 0 degree) and measured as a ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectivity). The measuring method of the total light reflectance is based on JIS K 7375: 2008. The measurement method of “spectral reflectance (%) at a wavelength of 800 nm” and “average spectral reflectance (%) at a wavelength range of 300 to 650 nm” in a base sheet is “spectral reflectance (%) at a wavelength of 800 nm” in a decorative sheet. And “average spectral reflectance (%) in wavelength range 300 to 650 nm”.

The “a ^* value and b ^* value of the L ^* a ^* b ^* color system” in the transparent resin layer is a state in which the transparent resin layer exists alone (that is, no layers are formed on both sides of the transparent resin layer). Measure with no condition. The measuring method is the same as “L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value” in the decorative sheet.

The weather resistance test for the decorative sheet includes a UV lamp (M04-L21WB / SUV manufactured by Iwasaki Electric Co., Ltd.), a lamp jacket (WJ50-SUV manufactured by Iwasaki Electric Co., Ltd.), and an illuminance meter (UVD-365PD manufactured by Iwasaki Electric Co., Ltd.). The surface protection layer side surface of the decorative sheet for 20 hours under the conditions of a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm ² using an ultra-accelerated weather resistance test apparatus (Isuper UV Tester SUV-W131 manufactured by Iwasaki Electric Co., Ltd.) After irradiating light, the cycle of condensation for 4 hours is repeated 33 times. In addition, when mentioning the characteristics of the decorative sheet after the weather resistance test (for example, L ^* value, a ^* value and b ^* value of the L ^* a ^* b ^* color system), the characteristics of the decorative sheet after the weather resistance test However, when referring to the characteristics of the decorative sheet before the weather resistance test (initial state), the fact that it is the characteristics of the decorative sheet before the weather resistance test is not specified. Therefore, when it is not specified that the properties of the decorative sheet after the weather resistance test are specified, the properties mean the properties of the decorative sheet before the weather resistance test (initial state).

[Decorative sheet]
Hereinafter, a decorative sheet according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a side view schematically showing a configuration of a decorative sheet 10 according to an embodiment of the present invention.

  As shown in FIG. 1, a decorative sheet 10 according to an embodiment of the present invention includes a base sheet 11, a printed layer 12, a transparent resin layer 13, and a surface protective layer 14 in this order.

The L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value measured by irradiating light on the surface of the decorative sheet 10 on the surface protective layer side are L ^* values: 30 or less, a ^* Value: 0 or more and 2.5 or less, and b ^* value: -2.5 or more and 0 or less. Thereby, the decorative sheet 10 can exhibit black that is recognized as a pure black (black) or a color close thereto by human eyes. The L ^* value is not particularly limited as long as it is 30 or less, but is preferably 29 or less. The lower limit value of the L ^* value is not particularly limited, but is usually 20 and preferably 23. The a ^* value is not particularly limited as long as it is 0 or more and 2.5 or less, but is preferably 0.1 or more and 1.5 or less, and more preferably 0.2 or more and 1 or less. Although b ^* value is not specifically limited as long as it is -2.5 or more and 0 or less, Preferably it is -2.3 or more and -0.5 or less, More preferably, it is -2.0 or more and -0.7 or less.

A color whose a ^* value and b ^* value are close to 0 exhibits a color close to pure black. In the decorative sheet 10, an organic black pigment having low infrared absorptivity (high infrared transmittance) is used, and the a ^* value is adjusted to 0 to 2.5 and the b ^* value is adjusted to −2.5 to 0. Therefore, it is possible to exhibit a black color that is recognized as a pure black or a color close thereto by human eyes, and to exhibit a heat shielding performance.

L ^* a ^* b ^* L ^* value of the color system measured by irradiating light on the surface of the decorative sheet 10 after the weather resistance test after the weather resistance test is performed on the decorative sheet 10 , A ^* value and b ^* value are preferably L ^* value: 30 or less, a ^* value: 0 or more and 2.5 or less, and b ^* value: -2.5 or more and 0 or less. Thereby, even when used outdoors, the decorative sheet 10 can continuously exhibit black that is recognized as pure black (black) or a color close thereto by human eyes. The L ^* value of the decorative sheet 10 after the weather resistance test is preferably 29.5 or less. The lower limit of the L ^* value of the decorative sheet 10 after the weather resistance test is not particularly limited, but is usually 20, preferably 23. The a ^* value of the decorative sheet 10 after the weather resistance test is preferably 0.5 or more and 2.3 or less, more preferably 0.8 or more and 2.3 or less. The b ^* value of the decorative sheet 10 after the weather resistance test is preferably −2.3 to −0.5, and more preferably −2.1 to −1.

  The average spectral reflectance in the wavelength region 780 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10 with light in the wavelength region 780 to 2500 nm is 35% or more. Thereby, the decorative sheet 10 can exhibit the heat shielding performance based on near-infrared reflective performance. The average spectral reflectance in the wavelength range of 780 to 2500 nm in the decorative sheet 10 is not particularly limited as long as it is 35% or more, but is preferably 38% or more, more preferably 40% or more, still more preferably 43% or more, and even more preferably. Is 45% or more. In addition, although the upper limit of the average spectral reflectance of the wavelength region 780 to 2500 nm in the decorative sheet 10 is not particularly limited, it is usually 100%.

  The spectral reflectance at a wavelength of 800 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10 with light having a wavelength of 800 nm is preferably 20% or more. Thereby, the decorative sheet 10 can exhibit the heat shielding performance based on near-infrared reflective performance. The spectral reflectance at a wavelength of 800 nm in the decorative sheet 10 is preferably 23% or more, more preferably 25% or more, still more preferably 28% or more, and still more preferably 30% or more. The upper limit of the spectral reflectance at a wavelength of 800 nm in the decorative sheet 10 is not particularly limited, but is usually 100%, preferably 95%, and more preferably 90%.

  The average spectral reflectance in the wavelength region 300 to 650 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10 with light in the wavelength region 300 to 650 nm is preferably 6% or less. Thereby, the decorative sheet 10 can exhibit black that is recognized as a pure black (black) or a color close thereto by human eyes. The average spectral reflectance in the wavelength region 300 to 650 nm in the decorative sheet 10 is preferably 5.9% or less, more preferably 5.8% or less, and even more preferably 5.7% or less. The lower limit value of the average spectral reflectance in the wavelength region 300 to 650 nm in the decorative sheet 10 is not particularly limited.

  The decorative sheet 10 has a feature that the spectral reflectance at a wavelength of 800 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10 with a wavelength of 800 nm is 20% or more, and the surface protective layer side of the decorative sheet 10 It is preferable to combine the characteristics that the average spectral reflectance in the wavelength region of 300 to 650 nm measured by irradiating the surface with light in the wavelength region of 300 to 650 nm is 6% or less. As a result, the spectral reflectance of the decorative sheet 10 has a sharp rise in the wavelength range of 650 to 800 nm, and the decorative sheet 10 has a black color that is recognized as pure black (black) or a color close thereto. It is possible to effectively achieve both the color and the performance of the heat shielding performance.

(Substrate sheet)
The spectral reflectance of the base sheet 11 affects the spectral reflectance of the decorative sheet 10. Therefore, by adjusting the spectral reflectance of the base sheet 11, the average spectral reflectance in the wavelength region 300 to 2500 nm in the decorative sheet 10 can be adjusted.

  The average spectral reflectance in the wavelength region 300 to 2500 nm in the substrate sheet 11 is usually 50% or more, preferably 53% or more, and more preferably 55% or more. In addition, the upper limit of the average spectral reflectance in the wavelength region 300 to 2500 nm in the substrate sheet 11 is not particularly limited, but is usually 100%, preferably 90%, and more preferably 80%.

  The spectral reflectance at a wavelength of 750 nm in the substrate sheet 11 is usually 70% or more, preferably 75% or more, and more preferably 80% or more. The upper limit value of the spectral reflectance at a wavelength of 750 nm in the base sheet 11 is not particularly limited, but is usually 100%, preferably 95%.

  The spectral reflectance at a wavelength of 800 nm in the substrate sheet 11 is usually 70% or more, preferably 75% or more, and more preferably 80% or more. The upper limit of the spectral reflectance at a wavelength of 800 nm in the substrate sheet 11 is not particularly limited, but is usually 100%, preferably 95%.

  The average spectral reflectance in the wavelength region 300 to 650 nm in the substrate sheet 11 is usually 50% or more, preferably 55% or more, and more preferably 60% or more. The upper limit value of the average spectral reflectance in the wavelength region 300 to 650 nm in the substrate sheet 11 is not particularly limited, but is usually 90%, preferably 85%, and more preferably 80%.

  The spectral reflectance of the base sheet 11 is determined by appropriately selecting the type of resin constituting the base sheet 11, the thickness of the base sheet 11, and the type and amount of the colorant when the base sheet 11 contains the colorant. It can be adjusted by selecting.

  As resin which comprises the base material sheet 11, a polyester resin, polyolefin resin, etc. are mentioned, for example. The resin constituting the base sheet 11 may be a single type or a combination of two or more types.

  Examples of the polyester resin constituting the base sheet 11 include polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer, Examples thereof include polyarylate, and among these, polyethylene terephthalate and polybutylene terephthalate are preferable, and polyethylene terephthalate is more preferable.

  Examples of the polyolefin resin constituting the base sheet 11 include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and the like. Of these, polyethylene and polypropylene are preferred.

  The thickness of the base sheet 11 is usually 20 to 200 μm, preferably 40 to 150 μm, more preferably 60 to 100 μm, from the viewpoint of realizing a desired spectral reflectance in the base sheet 11.

  The base sheet 11 is preferably a colored resin sheet composed of a colored resin. By using a colored resin sheet as the base sheet 11, the surface hue of the adherend can be well concealed even when the surface hue of the adherend to which the decorative sheet 10 is adhered varies. Excellent design properties can be obtained. Moreover, the stability of the color tone of the printing layer 12 provided on the base material sheet 11 can be ensured. From the viewpoint of realizing the excellent heat shielding performance of the decorative sheet 10, the colored resin sheet is preferably colored white (that is, contains a white pigment).

  The colorant may be appropriately selected depending on the application. For example, the base sheet 11 can be colored transparent or colored opaque. In general, from the viewpoint of concealing the surface of the adherend, it is preferable to make it colored and opaque.

  Examples of the colorant include inorganic pigments such as iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine blue, and cobalt blue; organics such as quinacridone red, isoindolinone yellow, and phthalocyanine blue Examples thereof include pigments or dyes; metal pigments composed of scaly foil pieces such as aluminum and brass; pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate.

  In the case where the base sheet 11 contains carbon black (black) as a colorant, from the viewpoint of realizing the excellent heat shielding performance of the decorative sheet 10, the content of the carbon black is 100 mass of the resin forming the base sheet 11. The amount is preferably 5.0 parts by mass or less, more preferably 1.0 part by mass or less, and most preferably 0 (no carbon black added). This is because carbon black has a characteristic that it easily absorbs heat, and therefore, the use of carbon black for the decorative sheet 10 makes the decorative sheet 10 easy to absorb heat and the heat shielding performance decreases.

  When the base sheet 11 contains titanium oxide as a white pigment, the crystal form of titanium oxide is not particularly limited and can be appropriately selected from known crystal forms such as a rutile type, anatase type, and brookite type. From the viewpoint of having excellent whiteness, weather resistance, heat shielding performance and the like, the rutile type is preferable. Further, since titanium oxide may deteriorate the resin by photocatalytic action, it is preferably surface-treated with a surface coating agent for the purpose of stabilizing the photocatalytic action, and the composition of the surface coating agent is limited. For example, inorganic oxides such as silicon oxide, alumina, or zinc oxide can be used. The coating method of the surface coating agent is not particularly limited, and titanium oxide obtained by a known method can be used.

  The amount of the colorant contained in the base sheet 11 is usually 1 to 70 masses with respect to 100 parts by mass of the resin constituting the base sheet 11 from the viewpoint of realizing a desired spectral reflectance in the base sheet 11. Part, preferably 1 to 50 parts by weight.

  The base material sheet 11 has physical properties such as an oxidation method and a concavo-convex method on one side or both sides for the purpose of enhancing the adhesion between the base material sheet 11 and other layers, and the adhesion to various adherends. Or chemical surface treatment can be applied. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method. These surface treatments are appropriately selected according to the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, you may perform processes, such as forming a primer layer and a back surface primer layer, for the purpose of reinforcement | strengthening of the interlayer adhesiveness of the base material sheet 11 and each layer.

  The base sheet 11 may contain an inorganic filler as necessary. Examples of the inorganic filler include powders of calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide), and the like. The amount of the inorganic filler contained in the substrate sheet 11 is usually 1 to 50 parts by mass with respect to 100 parts by mass of the resin that forms the substrate sheet 11. The base sheet 11 may contain other various additives as necessary, for example, a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like.

(Print layer)
The printing layer 12 contains an organic black pigment and an inorganic black pigment. Thereby, even when used outdoors, the decorative sheet 10 can continuously exhibit black that is recognized as pure black (black) or a color close thereto by human eyes. The printed layer 12 has the effect of concealing the base sheet 11 in addition to the effect of imparting black color to the decorative sheet 10 and improving the design properties of the decorative sheet 10. The printed layer 12 may be partially formed on one surface of the base sheet 11 so as to be recognized as a pattern. However, the printed sheet 12 is formed so that the entire surface of the decorative sheet 10 is recognized as black. It is preferable that it is formed on the whole of one surface. Examples of the printing method for forming the printing layer 12 include gravure printing, flexographic printing, silk screen printing, and the like.

  Examples of the organic black pigment contained in the printing layer 12 include azomethine azo black pigment, perylene black pigment, azo black pigment, aniline black, acetylene black, carbon black, lamp black, benzimidazolone pigment brown 25 (brown ) And phthalocyanine blue (blue). Among them, azomethine azo black pigments and perylene black pigments are preferable. The organic black pigment contained in the printing layer 12 may be a single type or a combination of two or more types.

  The azomethine azo black pigment is not particularly limited as long as it has a methine group and an azomethine group. For example, Japanese Patent Application Laid-Open Nos. 62-30202 and 62-32149 (Japanese Patent Publication No. 4-15265). ), Azomethine azo black pigments described in JP-A No. 2002-256165 (Patent No. 4084022), JP-A No. 2002-348491 (Patent No. 4084023), and the like.

Examples of the azomethine azo black pigment include compounds represented by the following formula.

を表し、
ｎが２を表す場合、メチル基、エチル基、メトキシ基及びアニリノカルボニル基からなる群より選択される１又は２以上の置換基を有していてもよいフェニレン基、ナフチレン基又はビフェニレン基を表す。 In the above formula,
X represents a hydrogen atom or a halogen atom,
m represents an integer of 1 to 4,
R ₁ represents a phenylene group, a naphthylene group, or a biphenylene group that may have one or more substituents selected from the group consisting of a halogen atom, a methyl group, a methoxy group, and a nitro group,
n represents 1 or 2,
when n represents 1, R ₂ is a phenyl group optionally having one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group and an anilinocarbonyl group;

Represents
When n represents 2, a phenylene group, a naphthylene group or a biphenylene group which may have one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group and an anilinocarbonyl group Represent.

Examples of the azomethine azo black pigment include compounds represented by the following formula.

In the above formula,
R represents a group selected from the group consisting of a lower alkyl group having 1 to 3 carbon atoms and a lower alkoxy group having 1 to 3 carbon atoms,
n represents an integer of 1 to 5;
When n represents an integer greater than or equal to 2, R may be the same or different.

  Specific examples of the azomethine azo black pigment include 1-[[4-[(4,5,6,7-tetrachloro-3-oxo-isoindoline-1-ylidene) amino] phenyl] azo] -2-hydroxy. -N- (4-methoxy-2-methylphenyl) -11H-benzo [a] carbazole-3-carboxamide, (2-hydroxy-N- (2'-methyl-4'-methoxyphenyl) -1- { [4-[(4,5,6,7-tetrachloro-1-oxo-2,3-dihydro-1H-isoindole-3-ylidene) amino] phenyl] azo} -11H-benzo [a] -carbazole -3-carboxamide) and the like.

As a perylene type black pigment, the compound represented by a following formula is mentioned, for example.

を表す。 In the above formula,
R is the same or different, and — (CH ₂ ) ₂ —OH, —CH ₂ —CH ₂ —Y (Y represents a phenyl group, a methyl group or a hydroxymethyl group), or

Represents.

Specific examples of the perylene black pigment include perylene-3,4,9,10-tetracarboxylic acid diimide represented by the following formula.

  Examples of the inorganic black pigment contained in the printing layer 12 include composite oxide, iron black, and titanium black. Of these, composite oxide is preferable. The inorganic black pigment contained in the printing layer 12 may be one kind alone or a combination of two or more kinds.

  The composite oxide is an oxide containing at least two kinds of metal elements. The composite oxide is preferably a composite oxide containing at least a manganese element, that is, an oxide containing a manganese element and at least one metal element other than the manganese element. The metal element other than the manganese element contained in the composite oxide is not particularly limited, and can be appropriately selected from the viewpoint of obtaining a calm design with lower brightness, the viewpoint of obtaining the heat shielding performance, and the like. One kind of metal element other than the manganese element contained in the composite oxide may be used alone, or two or more kinds may be used in combination. Examples of metal elements other than manganese elements contained in the composite oxide include group 2 elements such as calcium elements and barium elements; yttrium elements, lanthanum elements, praseodymium elements; group 3 elements such as neodymium elements, titanium elements, Examples include Group 4 elements such as zirconium elements; Group 13 elements such as boron elements, aluminum elements, gallium elements, and indium elements; and metal elements such as Group 15 elements such as antimony elements and bismuth elements. Of these, Group 2 elements, Group 4 elements, and Group 15 elements are preferable, calcium elements, titanium elements, and bismuth elements are more preferable, and calcium elements and titanium elements are more preferable. As a particularly preferable specific example of the composite oxide, a composite oxide containing a manganese element, a calcium element, and a titanium element can be given.

  The structure of the complex oxide is not particularly limited, but from the viewpoint of being stable as a structure, obtaining excellent heat shielding performance and design, etc., a perovskite structure, an orthorhombic structure, a hexagonal structure, etc. And a perovskite structure is more preferable.

  The printing layer 12 may be composed only of an organic black pigment and an inorganic black pigment, or may contain components other than the organic black pigment and the inorganic black pigment. Examples of components other than the organic black pigment and the inorganic black pigment include a binder. The binder is not particularly limited, and examples thereof include curable resins such as thermoplastic resins, one-part curable resins, and two-part curable resins. Specifically, urethane resin, acrylic urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin A binder selected from polystyrene resin, nitrocellulose resin (nitrified cotton), cellulose acetate resin and the like can be used alone or in combination of two or more. Examples of components other than the binder include colorants, stabilizers, plasticizers, catalysts, and curing agents other than organic black pigments and inorganic black pigments. Specific examples of the colorant are the same as the specific examples described above with respect to the colorant contained in the base sheet 11. The printing layer 12 preferably does not contain carbon black (black). This is because carbon black has a characteristic that it easily absorbs heat, and therefore, the use of carbon black for the decorative sheet 10 makes the decorative sheet 10 easy to absorb heat and the heat shielding performance decreases.

The amount of the organic black pigment and inorganic black pigment contained in the printing layer 12, the thickness of the printing layer 12, and the like of the L ^* a ^* b ^* color system of the decorative sheet 10 before the weather resistance test and after the weather resistance test are determined. Affects L ^* value, a ^* value and b ^* value. Therefore, L ^* a ^* in the decorative sheet 10 before the weather resistance test and after the weather resistance test is adjusted by adjusting the amount of the organic black pigment and inorganic black pigment contained in the print layer 12, the thickness of the print layer 12, and the like ^. b ^* color system of ^{L *} value, it is possible to adjust the ^{a *} and ^{b *} values.

The amount of the organic black pigment contained in the printing layer 12 is a desired L ^* value, a ^* value and b ^* value in the decorative sheet 10 before and after the weather resistance test and a desired wavelength range of 780 to 2500 nm. From the viewpoint of realizing the average spectral reflectance, it is usually 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably 5 to 35% by mass with respect to the total solid content contained in the printing layer 12.

The amount of the inorganic black pigment contained in the printing layer 12 is a desired L ^* value, a ^* value and b ^* value in the decorative sheet 10 before and after the weather resistance test and a desired wavelength range of 780 to 2500 nm. From the viewpoint of realizing the average spectral reflectance, it is usually 1 to 29% by mass, preferably 1 to 25% by mass, and more preferably 3 to 20% by mass with respect to the total solid content contained in the printing layer 12.

The mass ratio of the inorganic black pigment and the organic black pigment contained in the printing layer 12 (the mass of the inorganic black pigment: the mass of the organic black pigment) is the desired L in the decorative sheet 10 before the weather resistance test and after the weather resistance test. ^* values, from the viewpoint of realizing the average spectral reflectance of ^{a *} and ^{b *} values and the desired wavelength range 780～2500Nm, usually 0.1: 1 to 1: 1, preferably 0.1: 1-0. 8: 1.

The thickness of the printing layer 12 realizes a desired L ^* value, a ^* value and b ^* value and an average spectral reflectance in a desired wavelength range of 780 to 2500 nm in the decorative sheet 10 before and after the weather resistance test. From the viewpoint of, it is usually 0.5 to 15 μm, preferably 1 to 10 μm, and more preferably 3 to 7 μm.

  As printing ink used in order to form printing layer 12, what mixed organic black pigment and inorganic black pigment in a binder is mentioned, for example. The printing ink may contain colorants other than organic black pigments and inorganic black pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, and the like. Specific examples of the colorant contained in the printing ink are the same as the specific examples described above with respect to the colorant contained in the substrate sheet 11. The printing ink preferably does not contain carbon black (black). This is because carbon black has a characteristic that it easily absorbs heat, and therefore, the use of carbon black for the decorative sheet 10 makes the decorative sheet 10 easy to absorb heat and the heat shielding performance decreases. The amounts of organic black pigment, inorganic black pigment, and binder contained in the printing ink (solid content standard) are the amounts of organic black pigment, inorganic black pigment, and binder contained in the printing layer 12, respectively (solid content standard). ).

When forming the printing layer 12, the amount of printing ink applied per unit area of the surface to which the printing ink is applied (for example, one surface of the base sheet 11) (based on solid content) is the value before the weather resistance test. From the viewpoint of realizing the desired L ^* value, a ^* value and b ^* value and the average spectral reflectance in the desired wavelength range of 780 to 2500 nm in the decorative sheet 10 after the weather resistance test, usually 0.5 to 15 g / m. ² , preferably 1 to 10 g / m ² , more preferably 3 to 7 g / m ² .

  The print layer 12 may be composed of a single print layer or a plurality of print layers, but the uniformity of the distribution of the organic black pigment and inorganic black pigment in the print layer 12 is improved. It is preferable that it is comprised by the some printing layer from a viewpoint made to make it.

  In the present embodiment, the print layer 12 includes a first print layer 121 containing an organic black pigment and a second print layer 122 containing an inorganic black pigment. Note that the boundary between the first print layer 121 and the second print layer 122 is not always clear. For example, a region in which the components constituting the first print layer 121 and the components constituting the second print layer 122 are mixed may be formed at the boundary between the first print layer 121 and the second print layer 122. .

  The order in which the first printed layer 121 and the second printed layer 122 are formed is not particularly limited, and the printed layer 12 may include the first printed layer 121 and the second printed layer 122 in order from the base sheet 11 side. And you may have the 2nd printing layer 122 and the 1st printing layer 121 in order from the base material sheet 11 side. In this embodiment, the printing layer 12 has the 1st printing layer 121 and the 2nd printing layer 122 in order from the base material sheet 11 side. When the printing layer 12 has the 1st printing layer 121 and the 2nd printing layer 122 in order from the base material sheet 11 side, the printing layer 12 has the 2nd printing layer 122 and the 1st printing layer 121 in order from the base material sheet 11 side. The weather resistance of the decorative sheet 10 can be improved as compared with the case where the decorative sheet 10 is provided.

  The organic black pigment contained in the first printing layer 121 may be a part of the organic black pigment contained in the printing layer 12 or may be all of the organic black pigment contained in the printing layer 12. Good. When the organic black pigment contained in the first printed layer 121 is a part of the organic black pigment contained in the printed layer 12, from the viewpoint of imparting a desired black color to the decorative sheet 10 by the first printed layer 121, The amount of the organic black pigment contained in the first printing layer 121 is usually 20% by mass or more, preferably 30% by mass or more, more preferably 35% by mass with respect to the total amount of the organic black pigment contained in the printing layer 12. % Or more. Even when the decorative sheet 10 is used outdoors, from the viewpoint of continuously imparting a desired black color to the decorative sheet 10 by the first printed layer 121, the amount of the organic black pigment contained in the first printed layer 121 is The amount of the organic black pigment contained in the printing layer 12 is usually 80% by mass or less, preferably 70% by mass or less, and more preferably 68% by mass or less.

  From the viewpoint of imparting a desired black color to the decorative sheet 10 by the first printed layer 121, the amount of the organic black pigment contained in the first printed layer 121 is based on the total solid content contained in the first printed layer 121. , Preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Even when the decorative sheet 10 is used outdoors, the first printed layer 121 improves the adhesiveness between the first printed layer 121 and other layers from the viewpoint of continuously imparting a desired black color to the decorative sheet 10. From the viewpoint, the amount of the organic black pigment contained in the first printing layer 121 is preferably 60% by mass or less, more preferably 50% by mass or less, based on the total solid content contained in the first printing layer 121. Still more preferably, it is 40 mass% or less.

  The first printed layer 121 may contain an inorganic black pigment. The inorganic black pigment contained in the first print layer 121 is a part of the inorganic black pigment contained in the print layer 12. When the 1st printing layer 121 contains an inorganic black pigment, the quantity of the inorganic black pigment contained in the 1st printing layer 121 is 5-50 normally with respect to the total amount of the inorganic black pigment contained in the printing layer 12. It is 10 mass%, Preferably it is 10-45 mass%, More preferably, it is 15-40 mass%. When the first printed layer 121 contains an inorganic black pigment, the mass ratio of inorganic black pigment to organic black pigment contained in the first printed layer 121 (mass of inorganic black pigment: mass of organic black pigment) is usually 0.5: 1 to 2: 1, preferably 1: 1: 1.5: 1.

  The thickness of the 1st printing layer 121 is 0.1-5 micrometers normally, Preferably it is 0.5-4 micrometers, More preferably, it is 0.5-3 micrometers.

When forming the 1st printing layer 121, the quantity (based on solid content) of printing ink applied per unit area of the surface (for example, one side of substrate sheet 11) to which printing ink is applied is weather resistance. From the viewpoint of realizing the desired L ^* value, a ^* value and b ^* value in the decorative sheet 10 before the test and after the weather resistance test, usually 0.1 to 5 g / m ² , preferably 0.5 to 4 g / m. ² and more preferably 0.5 to 3 g / m ² .

  The inorganic black pigment contained in the second printing layer 122 may be a part of the inorganic black pigment contained in the printing layer 12 or may be all of the inorganic black pigment contained in the printing layer 12. Good. When the inorganic black pigment contained in the second printing layer 122 is a part of the inorganic black pigment contained in the printing layer 12, the amount of the inorganic black pigment contained in the second printing layer 122 is the printing layer 12. The amount is usually 5 to 60% by mass, preferably 10 to 55% by mass, and more preferably 15 to 50% by mass with respect to the total amount of the inorganic black pigment contained. The amount of the inorganic black pigment contained in the second printed layer 122 is usually 1 to 65% by mass, preferably 5 to 60% by mass, more preferably 5%, based on the total solid content contained in the second printed layer 122. -50 mass%.

  The second printed layer 122 may or may not contain an organic black pigment. The organic black pigment contained in the second printed layer 122 is a part of the organic black pigment contained in the printed layer 12. In the case where the second printed layer 122 contains an organic black pigment, the amount of the organic black pigment contained in the second printed layer 122 is printed from the viewpoint of imparting a desired black color to the decorative sheet 10 by the second printed layer 122. Preferably it is 20 mass% or more with respect to the total amount of the organic black pigment contained in the layer 12, More preferably, it is 30 mass% or more, More preferably, it is 35 mass% or more. Even when the decorative sheet 10 is used outdoors, from the viewpoint of continuously imparting a desired black color to the decorative sheet 10 by the second printed layer 122, the amount of the organic black pigment contained in the second printed layer 122 is The amount of the organic black pigment contained in the printing layer 12 is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 68% by mass or less.

  When the second printed layer 122 contains an organic black pigment, the mass ratio of the inorganic black pigment to the organic black pigment contained in the second printed layer 122 (mass of inorganic black pigment: mass of organic black pigment) is usually The ratio is 0.1: 1 to 3: 1, preferably 0.1: 1 to 2.5: 1.

  The thickness of the 2nd printing layer 122 is 0.1-5 micrometers normally, Preferably it is 0.5-4 micrometers, More preferably, it is 0.5-3 micrometers.

  Regarding the ratio of the amount of inorganic black pigment contained in the first printed layer 121 and the second printed layer 122 to the total amount of inorganic black pigment contained in the printed layer 12, even when the decorative sheet 10 is used outdoors, makeup From the viewpoint of continuously imparting a desired black color to the sheet 10, the ratio of the second print layer 122 located on the surface protective layer side of the first print layer 121 may be larger than the ratio of the first print layer 121. preferable.

  Regarding the ratio of the amount of the organic black pigment contained in the first printed layer 121 and the second printed layer 122 to the total amount of the organic black pigment contained in the printed layer 12, a viewpoint of imparting glossiness peculiar to the organic pigment to the decorative sheet 10 Therefore, it is preferable that the ratio in the second print layer 122 located on the surface protective layer side of the first print layer 121 is larger than the ratio in the first print layer 121.

When forming the 2nd printing layer 122, the quantity (solid content basis) of printing ink applied per unit area of the surface (for example, one side of substrate sheet 11) to which printing ink is applied is weather resistance. From the viewpoint of realizing the desired L ^* value, a ^* value and b ^* value in the decorative sheet 10 before the test and after the weather resistance test, usually 0.1 to 5 g / m ² , preferably 0.5 to 4 g / m. ² and more preferably 0.5 to 3 g / m ² .

  The print layer 12 may include one or more other print layers in addition to the first print layer 121 and the second print layer 122. One or more other print layers can be configured similarly to the first print layer 121 or the second print layer 122. One or two or more other print layers include, for example, between the first print layer 121 and the base sheet 11, between the first print layer 121 and the second print layer 122, and the second print layer 122 and the transparent resin. It can be provided between the layer 13 and the like.

(Transparent resin layer)
The transparent resin layer 13 is provided between the printing layer 12 and the surface protective layer 14. The transparent resin layer 13 may have a function as a color correction layer that corrects the L ^* value, a ^* value, and b ^* value of the L ^* a ^* b ^* color system in the decorative sheet 10. Accordingly, ^{the L} * ^a * ^{b *} color system of ^{L *} value in the transparent resin layer 13, ^{a *} by adjusting the value and ^{b *} value, the ^L * ^a * ^{b *} color system in the decorative sheet 10 ^{L *} The value, a ^* value and b ^* value can be adjusted. The transparent resin layer 13 also has an effect of protecting the printed layer 12 and improving scratch resistance.

  As long as the transparent resin layer 13 is provided between the printing layer 12 and the surface protective layer 14, between the printing layer 12 and the transparent resin layer 13 and / or between the transparent resin layer 13 and the surface protective layer 14. Other layers may be provided.

The a ^* value and b ^* value of the L ^* a ^* b ^* color system in the transparent resin layer 13 are a ^* values: −1 to 0 and b ^* values: −3 to −2 preferable. In addition, it is preferable that the L ^* value of the L ^* a ^* b ^* color system in the transparent resin layer 13 is 30-50.

The L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value in the transparent resin layer 13 are the type of resin constituting the transparent resin layer 13, the thickness of the transparent resin layer 13, and the transparent resin layer 13. Can be adjusted by appropriately selecting the type and amount of the colorant.

  The transparent resin layer 13 can be composed of, for example, a thermoplastic resin. As the resin constituting the transparent resin layer 13, in addition to the specific examples (polyester resin, polyolefin resin) described above with respect to the resin constituting the base sheet 11, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, vinyl chloride resin, Examples include vinyl acetate resin. From the viewpoint of improvement of molding processability and scratch resistance, polyester resins and polyolefin resins are preferable, and polyolefin resins are more preferable. Further, from the same viewpoint, it is preferable that both the base sheet 11 and the resin constituting the transparent resin layer 13 are polyolefin resins.

  The transparent resin layer 13 only needs to have transparency to the extent that the printing layer 12 can be visually recognized, and may be colored transparent or translucent in addition to being colorless and transparent. When the resin layer constituting the transparent resin layer 13 is colored, specific examples of the colorant contained in the resin layer are the same as the specific examples described above with respect to the colorant contained in the base sheet 11. The resin layer constituting the transparent resin layer 13 preferably does not contain carbon black (black). This is because carbon black has a characteristic that it easily absorbs heat, and therefore, the use of carbon black for the decorative sheet 10 makes the decorative sheet 10 easy to absorb heat and the heat shielding performance decreases.

The thickness of the transparent resin layer 13 is usually 20 to 130 μm, preferably 30 to 100 μm, more preferably 40 to 90 μm, from the viewpoint of realizing desired L ^* values, a ^* values, and b ^* values in the decorative sheet 10. is there. When the thickness of the transparent resin layer 13 is within the above range, an improvement in the protective function and scratch resistance of the printing layer 12 can be expected.

  The transparent resin layer 13 can be subjected to a physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides from the viewpoint of improving the adhesion with each layer. Examples of these physical or chemical surface treatments include the same methods as the surface treatment of the base sheet 11. Moreover, the transparent resin layer 13 can also perform processes, such as forming a primer layer and a back surface primer layer, from a viewpoint of improving adhesiveness with each layer.

(Surface protective layer)
The surface protective layer 14 is provided on the transparent resin layer 13. The surface protective layer 14 is a layer located on the outermost surface of the decorative sheet 10, and is a layer that imparts surface characteristics such as scratch resistance, wear resistance, and chemical resistance to the decorative sheet 10. The surface protective layer 14 is preferably composed of a cured product of a resin composition containing a curable resin. By being comprised with the hardened | cured material of curable resin composition, the surface characteristic of the decorative sheet 10 can be improved.

  Examples of the curable resin used for forming the surface protective layer 14 include a thermosetting resin such as a two-component curable resin, and an ionizing radiation curable resin. For example, ionizing radiation using a plurality of these resins. A so-called hybrid type may be used in which a curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination.

  From the viewpoint of increasing the crosslink density of the resin forming the surface protective layer 14 and improving the scratch resistance and abrasion resistance of the surface, ionizing radiation curable resins are preferred, and can be applied without solvent. From the viewpoint of easy handling, an electron beam curable resin is more preferable.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is a resin having an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. is there. Specifically, it can be used by appropriately selecting from a polymerizable monomer, a polymerizable oligomer or a prepolymer conventionally used as an ionizing radiation curable resin.

  Typically, as the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And the like. Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  Along with the polyfunctional (meth) acrylate and the like, a monofunctional (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired for the purpose of reducing the viscosity. These monofunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thickness of the surface protective layer 14 is preferably from 2 to 25 μm, more preferably from 2 to 15 μm, from the viewpoint of obtaining excellent scratch resistance and its durability, as well as surface properties such as wear resistance and chemical resistance. 10 μm is more preferable.

  Various additives other than the above can be contained in the resin composition forming the surface protective layer 14 as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.

(Adhesive layer)
The decorative sheet 10 can have an adhesive layer as necessary. For example, an adhesive layer can be provided between the printing layer 12 and the transparent resin layer 13 in order to improve the adhesion between the printing layer 12 and the transparent resin layer 13. As an adhesive constituting the adhesive layer, an adhesive generally used in decorative sheets can be appropriately selected and used, and its thickness is about 0.1 to 50 μm, and sufficient adhesiveness Is preferably in the range of 1 to 30 μm.

  The adhesive is not particularly limited, and examples thereof include urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives, etc. Among them, urethane adhesives have adhesive strength. This is preferable. In addition, as such a urethane type adhesive agent, for example, a two-component curable type containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate. An adhesive using a urethane resin may be mentioned. Acrylic-polyester-vinyl acetate resins and the like are also suitable adhesives that can easily exhibit adhesiveness by heating and maintain adhesive strength even when used at high temperatures. The adhesive layer can be formed by a known layer forming method such as a coating method using an adhesive composition comprising these resins.

(Primer layer)
The decorative sheet 10 can have a primer layer and a back surface primer layer in any of the respective layers as required in order to improve the adhesion between the respective layers. For example, a decorative member having excellent interlayer adhesion can be obtained by providing a primer layer as a back primer layer on the substrate sheet 11 side between the adherend and the substrate sheet 11. In addition, by providing a primer layer between the transparent resin layer 13 and the surface protective layer 14, excellent scratch resistance of the decorative member can be obtained.

  The primer layer is a transparent or translucent layer and can be formed using, for example, a resin exemplified as a binder resin for printing ink. The thickness of the primer layer is usually about 0.5 to 20 μm, preferably 0.5 to 5 μm, more preferably 0.5 to 3 μm.

(Concave shape)
The decorative sheet 10 preferably has a concave shape in at least the surface protective layer 14. Since the decorative sheet 10 has a concave shape, the texture (tactile feeling) is particularly excellent. The concave shape only needs to exist in at least the surface protective layer 14, and there may be a concave shape that reaches the base material sheet 11. From the viewpoint of obtaining an excellent texture (tactile sensation), not only those that remain in the surface protective layer 14, but also those that reach the transparent resin layer 13, those that reach the printing layer 12, and those that reach the base sheet 11 are combined. It is preferable. In addition, in this specification, when the surface protective layer 14 grade | etc., Has the said concave shape, the thickness of the surface protective layer 14 grade | etc., Means the thickness measured in the location which does not have the said concave shape.

  The maximum depth of the concave shape is preferably 15% or more and less than 100% with respect to the total thickness of the decorative sheet 10, more preferably 15 to 80%, and even more preferably 25 to 80%. Further, the maximum depth of the concave shape is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. By having such a maximum depth, the decorative sheet 10 is not broken during concave processing, for example, embossing, and is not finished as if the concave shape was crushed. A good texture (tactile sensation) is obtained, and as a result, excellent design properties are obtained.

  Here, the measurement of the maximum depth of the concave shape is performed on the height from the lowest point of the concave shape to the surface of the surface protective layer 14 for any 30 concave shapes using a surface roughness shape measuring machine. Then, the cut-off value: 2.50 mm, the cut-off filter type: 2RC, the inclination correction method: measured under a linear measurement condition, and the deepest one was defined as the maximum depth.

  There is no restriction | limiting in particular about the method of giving concave shape to the surface protective layer 14, For example, when the ease of work is considered, it is preferable to employ | adopt embossing. The embossing may be performed by a normal method using a known single-wafer or rotary embossing machine.

(Manufacturing method of decorative sheet)
About the manufacturing method of the decorative sheet of this invention, the manufacturing method is demonstrated taking the decorative sheet 10 which concerns on one Embodiment of this invention as an example. The decorative sheet 10 includes, for example, (a) a step of providing the printing layer 12 on the base material sheet 11, (b) a step of providing the transparent resin layer 13 on the printing layer 12, and (c) curable on the transparent resin layer 13. It can manufacture by passing through the process of apply | coating a resin composition, making it harden | cure, forming the surface protective layer 14, and producing the decorative sheet 10 in order.

  Step (a) is a step of providing the printing layer 12 on the base sheet 11. The printing layer 12 is formed by applying and drying printing ink used for forming the printing layer 12 on the base sheet 11. The printing ink is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.

  The printing layer 12 having the first printing layer 121 and the second printing layer 122 in order from the substrate sheet 11 side is coated with printing ink for forming the first printing layer 121 and dried. The first printing layer 121 is formed, and then the printing ink for forming the second printing layer 122 is applied on the first printing layer 121 and dried to form the second printing layer 122. The

  When surface treatment is performed on the base material sheet 11, the surface treatment may be performed before applying the printing ink used for forming the printing layer 12. Even when a primer layer is provided between the substrate sheet 11 and the printing layer 12, it may be provided before applying the printing ink used for forming the printing layer 12, and the printing layer 12 of the substrate sheet 11 may be provided. When the back primer layer is provided on the surface opposite to the surface to be provided (back surface), it may be provided when the printing ink used for forming the printing layer 12 is applied. The primer layer is formed by applying a resin composition forming the primer layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. Can do.

  Step (b) is a step of providing the transparent resin layer 13 on the printing layer 12. The transparent resin layer 13 uses a resin composition that forms the transparent resin layer 13 after applying an adhesive to the base sheet 11 having the printed layer 12 as necessary to form an adhesive layer. The layer 13 can be formed by adhering and press-bonding by a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination, or the like.

  Step (c) is a step of forming the surface protective layer 14 by applying a curable resin composition on the transparent resin layer 13 and curing it. The surface protective layer 14 is formed by applying an ionizing radiation curable resin composition containing an ionizing radiation curable resin onto the transparent resin layer 13 or a primer layer provided on the transparent resin layer 13 as desired. Can be obtained.

  Application of the resin composition for forming the surface protective layer 14 is preferably gravure coating, bar coating, roll coating, reverse roll coating, comma coating so that the thickness after curing is usually about 1 to 20 μm. Etc., and more preferably by gravure coating.

  When using an ionizing radiation resin composition for forming the surface protective layer 14, the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as electron beams and ultraviolet rays to form a cured product. The surface protective layer 14 is formed. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. It is preferable.

  The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited. For example, various electron beam accelerators such as cockroft walton type, van de graft type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type are used. can do. When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp etc. are used.

  When a thermosetting resin composition is used for forming the surface protective layer 14, the surface protective layer 14 may be formed by applying a heat treatment according to the resin composition to be used and curing it.

  Since the decorative sheet obtained as described above can exhibit pure black (black) or black recognized as a color close to human eyes and can exhibit heat shielding performance, for example, Stacked with dressing materials, interior and exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, baseboards, edges, malls, and other furniture, kitchens, furniture or light electrical appliances, OA equipment It can be suitably used as a decorative member for various uses such as a surface decorative plate of a cabinet, an interior of a vehicle, and an exterior.

[Decorative material]
Hereinafter, a decorative member according to an embodiment of the present invention will be described with reference to FIG. FIG. 2 is a side view schematically showing the configuration of the decorative member 20 according to the embodiment of the present invention.

  As shown in FIG. 2, the decorative member 20 according to the embodiment of the present invention is configured so that the adherend 21 and the decorative sheet 10 are opposed to each other so that the adherent 21 and the base sheet 11 of the decorative sheet 10 face each other. Prepare.

(Substrate)
Examples of the adherend 21 include plate materials of various materials, plate materials such as curved plates, three-dimensional articles, sheets (or films), and the like. Specifically, wood members used as plate materials such as wood fiber boards such as wood veneer, wood plywood, particle board, MDF (medium density fiber board), and three-dimensional shaped articles; plate materials such as iron and aluminum and steel plates , Metal members used as three-dimensional articles or sheets; glass materials, ceramics such as ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates and three-dimensional materials Ceramic materials used as shaped articles, etc .; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, Resin members used as plates such as rubber, three-dimensional shaped articles, or sheets It is below. Moreover, these members can be used individually by 1 type or in combination of 2 or more types.

  The adherend 21 may be appropriately selected from the above according to the application, such as a wall, ceiling, floor or other building interior / exterior member, window frame, door, handrail, skirting board, surrounding edge, mall, etc. When using a joinery, a wood member, a metal member, a resin member, or a combination of these is preferable.

  What is necessary is just to select the thickness of the adherend 21 suitably according to a use and material, and 0.1-5 mm is preferable normally, and 0.1-3 mm is more preferable.

(Adhesive layer)
The decorative member 20 has an adhesive layer 22 between the adherend 21 and the decorative sheet 10. The adhesive layer 22 can be omitted, but it is preferable to bond the adherend 21 and the decorative sheet 10 via the adhesive layer 22 in order to obtain excellent adhesiveness.

  Although it does not specifically limit as an adhesive agent contained in the adhesive bond layer 22, For example, adhesive agents, such as a heat sensitive adhesive and a pressure sensitive adhesive, are mentioned. Examples of the resin constituting the adhesive include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, and polyester resins. And polyamide resins. A two-component curable polyurethane adhesive or polyester adhesive using isocyanate or the like as a curing agent can also be applied. An adhesive can be used for the adhesive layer 22. Examples of the adhesive include acrylic, urethane, silicone, and rubber adhesives.

  The adhesive layer 22 is formed by applying and drying the resin in a form that can be applied, such as a solution or emulsion, by means of a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate. be able to. Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, Usually, it is the range of 1-100 micrometers. By setting it within this range, excellent adhesiveness can be obtained.

(Method for manufacturing decorative member)
About the manufacturing method of the decorative member of invention, the manufacturing method is demonstrated taking the decorative member 20 which concerns on one Embodiment of this invention as an example. The decorative member 20 can be manufactured through a step of laminating the decorative sheet 10 and the adherend 21 with (d) the base sheet 11 and the adherend 21 of the decorative sheet 10 facing each other.

  Examples of the method of laminating the adherend 21 and the decorative sheet 10 include, for example, a laminating method in which the decorative sheet 10 is pressed onto a plate-shaped adherend by a pressure roller with an adhesive interposed therebetween, and an adhesive. Wrapping processing in which the decorative sheet 10 is sequentially pressed and adhered to a plurality of side surfaces constituting the adherend 21 with a plurality of rollers having different directions while the decorative sheet 10 is supplied therebetween. The decorative sheet 10 fixed to the fixed frame is heated with a heater through a silicone rubber sheet until a predetermined temperature at which the decorative sheet 10 is softened, and the vacuum molding die is pressed against the heated and softened decorative sheet 10 at the same time. Preferable examples include a vacuum forming process in which air is sucked with a vacuum pump or the like to firmly attach the decorative sheet 10 to the vacuum forming mold.

  When a hot melt adhesive (heat sensitive adhesive) is used in laminating or wrapping, the heating temperature is usually 160 to 200 ° C., a reactive hot melt adhesive, depending on the type of resin constituting the adhesive. Then, it is about 100-130 degreeC normally. Moreover, in the case of a vacuum forming process, it is common to carry out with heating, and it is normally performed at about 80 to 130 ° C, preferably about 90 to 120 ° C.

  The decorative member obtained as described above can be arbitrarily cut and subjected to optional decoration such as grooving and chamfering on the surface and the end of the mouth using a cutting machine such as a router or a cutter. And various uses, for example, interior decoration members of buildings such as walls, ceilings, floors, balconies, verandas, etc .; decorative panels for exterior members; window frames, doors, handrails, skirting boards, edges, and moldings Surface decorative panels for cabinets such as kitchens, furniture, light electrical appliances, office automation equipment, etc .; surface decorative panels for interior and exterior of vehicles; surface decorative panels for communication devices such as mobile phones; paving roadways, sidewalks, etc. It can be used for a surface decorative board for a road (surface decorative board for providing a color, a pattern or the like by being laminated on a paved surface of a paved road).

  Hereinafter, the present invention will be described in more detail based on examples.

[Example 1] Production and evaluation of decorative sheet Preparation of base sheet A polypropylene (PP) resin sheet having both sides subjected to corona discharge treatment was prepared as a base sheet. This PP resin sheet is a colored resin sheet (thickness: 60 μm) colored white, containing 10 parts by mass of titanium oxide as a pigment with respect to 100 parts by mass of PP resin.

  The average spectral reflectance (%) in the wavelength region of 300 to 2500 nm in the base sheet was measured in a state where the base sheet was present alone (that is, in a state where no layers were laminated on both sides of the base sheet). . The average spectral reflectance (%) in the wavelength range of 300 to 2500 nm is obtained by changing the wavelength by 1 nm from the wavelength of 300 nm to the wavelength of 2500 nm while changing each wavelength (that is, wavelengths of 300 nm, 301 nm, 302 nm,..., 2498 nm, 2499 nm, 2500 nm). ) Was measured, and the sum of the measured 2201 spectral reflectances (%) was divided by 2201. Spectral reflectance (%) of each wavelength was measured using a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, and the light of each wavelength was incident on the surface of the base sheet at an incident angle of 5 degrees (base). The normal direction of the surface of the material sheet was set to 0 degree), and the ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectance) was measured. The method for measuring the total light reflectance was based on JIS K 7375: 2008.

A spectral reflectance curve in the wavelength region 300 to 2500 nm in the base material sheet is shown in FIG.
The average spectral reflectance in the wavelength range 300 to 2500 nm of the substrate sheet is 58.2%, the spectral reflectance at the wavelength 750 nm is 83.9%, the spectral reflectance at the wavelength 800 nm is 82.6%, and the wavelength range is 300 to 650 nm. The average spectral reflectance was 65.8%.

2. Formation of first printing layer As a first printing ink, an azomethine azo black pigment (chromofine black A- manufactured by Dainichi Seika Kogyo Co., Ltd.) having a two-component curable acrylic-urethane resin as a binder and having an average particle size of 0.2 μm A printing ink containing 35% by mass of 1103) based on solid content was prepared. The P / V ratio (mass of azomethine azo black pigment / mass of binder resin) in this printing ink is 0.53.
The first printing ink is applied to one surface of the base sheet by a gravure printing method (coating amount: about 3 g / m ² on a solid basis), cured, and the first printed layer (thickness after curing: 3 μm) Formed.

3. Formation of the second printed layer As the second printing ink, an azomethine azo black pigment having an average particle size of 0.2 μm (chromofine black A-1103 manufactured by Dainichi Seika Kogyo Co., Ltd.), manganese element, calcium element and titanium element is included. A complex oxide black pigment (MPT-370 manufactured by Ishihara Sangyo Co., Ltd.) and a two-component curable acrylic-urethane resin that is a binder, an azomethine azo-based black pigment: a complex oxide-based black pigment: an acrylic-urethane resin = 1. : Printing ink containing 1.18: 2.32 mass ratio was prepared. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in this printing ink is 0.94.
The second printing ink is applied to the upper surface of the first printing layer by a gravure printing method (coating amount: about 3 g / m ² on a solid basis) and cured to form a second printing layer (thickness after curing: 3 μm). Formed.

4). Formation of Backside Primer Layer A two-component curable urethane / nitrified cotton mixed resin composition was applied to the other side of the base sheet and cured to form a backside primer layer (thickness after curing: 2 μm).

5. Formation of Adhesive Layer A transparent polyurethane resin adhesive was applied on the second printed layer and dried to form an adhesive layer (thickness after drying: 3 μm).

6). Formation of Transparent Resin Layer A transparent polypropylene resin was heated and melt-extruded with a T-die extruder on the adhesive layer to form a transparent resin layer (thickness: 80 μm) as a transparent resin layer.

In the same manner as described above, the transparent resin layer is formed alone, and in the state where the transparent resin layer is present alone (that is, in a state where no layers are laminated on both sides of the transparent resin layer), L ^* a ^* The L ^* value, a ^* value and b ^* value in the b ^* color system were measured. L ^* a ^* b ^* L ^* value, a ^* value, and b ^* value in the color system are measured using a spectrocolorimeter (CM-3700d manufactured by Konica Minolta Holdings, Inc.) and the incident angle on the surface of the transparent resin layer Light was irradiated at 8 degrees (the normal direction of the surface of the transparent resin layer was 0 degree), and measurement was performed based on total light reflected light (specular reflection light + diffuse reflection light). The measurement was performed at three locations on the surface of the transparent resin layer. The measurement results are shown in Table 1.

7). Formation of primer layer After the corona discharge treatment is applied to the surface of the transparent resin layer, a two-part curable acrylic-urethane resin composition is applied to the surface of the corona discharge treatment by a gravure printing method and cured to obtain a primer layer (after curing) (Thickness: 1 μm) was formed.

8). Formation of surface protective layer A transparent electron beam curable resin composition (electron beam curable resin: trifunctional urethane acrylate) is applied to the surface of the primer layer by a gravure coating method (solid content: 3 g / m ² ) and dried. Then, an uncured resin layer is formed, and an electron beam (pressurized voltage: 125 KeV, 5 Mrad) is irradiated in an environment with an oxygen concentration of 200 ppm to cure the uncured resin layer, and a surface protective layer (thickness: 3 μm) Formed.

9. Embossing Embossing was performed from the surface protective layer side to form a concavo-convex pattern of a wood grain conduit pattern having a concave shape with a maximum depth of 30 μm, and a decorative sheet of Example 1 was obtained.
Table 2 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 1.

10. Evaluation of decorative sheet The decorative sheet of Example 1 was evaluated as follows. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.
(1) Evaluation of black exhibited by decorative sheet The decorative sheet was visually observed from the surface protective layer side, and the black exhibited by the decorative sheet was evaluated according to the following criteria.
A: The black color exhibited by the decorative sheet is recognized as pure black (black) or a black color close thereto.
B: The black color exhibited by the decorative sheet is not recognized as pure black (black) or black close thereto.

The black color of the decorative sheet was evaluated for the decorative sheet before the weather resistance test and the decorative sheet after the weather resistance test. The weather resistance test was super-accelerated with a UV lamp (Iwasaki Electric Co., Ltd. M04-L21WB / SUV), a lamp jacket (Iwasaki Electric Co., Ltd. WJ50-SUV) and an illuminance meter (Iwasaki Electric Co., Ltd. UVD-365PD). Using a weather resistance test device (Iwasaki Electric Co., Ltd. Eye Super UV Tester SUV-W131), a cycle in which condensation is performed for 4 hours after irradiation for 20 hours under conditions of a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm ² Was repeated 33 times.

In order to consider the relationship with visual evaluation of black, L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value in the decorative sheet before and after the weather resistance test, And the average spectral reflectance (%) of the wavelength range 300-650 nm in the decorative sheet before a weather resistance test was measured.

The L ^* a ^* b ^* color system L ^* , a ^* and b ^* values are measured using a spectrocolorimeter (CM-3700d manufactured by Konica Minolta Holdings, Inc.) The sample was irradiated with light at an incident angle of 8 degrees (the normal direction of the surface of the decorative sheet was 0 degree) and measured based on total light reflected light (specular reflection light + diffuse reflection light).

  The average spectral reflectance (%) in the wavelength range of 300 to 650 nm is obtained by changing the wavelength by 1 nm from the wavelength of 300 nm to the wavelength of 650 nm while changing each wavelength (that is, wavelengths of 300 nm, 301 nm, 302 nm,... 648 nm, 649 nm, 650 nm). ) Was measured, and the sum of the measured 351 spectral reflectances was divided by 351. The spectrophotometer (V-670 manufactured by JASCO Corporation) conforming to JIS K 0115: 2004 is used for the spectral reflectance of each wavelength, and the incident angle is 5 on the surface protective layer side surface of the decorative sheet. Was irradiated at a degree (the normal direction of the surface of the decorative sheet was 0 degree) and measured as the ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectance). The method for measuring the total light reflectance was based on JIS K 7375: 2008. In addition, the spectral reflectance (%) of each wavelength was measured in a state where no layers were laminated on both sides of the decorative sheet.

(2) Evaluation of thermal insulation performance of decorative sheet In order to evaluate the thermal insulation performance of the decorative sheet, the average spectral reflectance (%) in the wavelength region 780 to 2500 nm in the decorative sheet before the weather resistance test was measured.

  The average spectral reflectance (%) in the wavelength range of 780 to 2500 nm in the decorative sheet is obtained by changing the wavelength by 1 nm from a wavelength of 780 nm to a wavelength of 2500 nm while changing each wavelength (that is, wavelengths of 780 nm, 781 nm, 782 nm,..., 2498 nm, (2499 nm, 2500 nm) was measured, and the sum of 1721 spectral reflectances measured was divided by 1721. Spectral reflectance (%) of each wavelength was measured using a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, with an incident angle of 5 degrees on the surface protective layer side surface of the decorative sheet ( The light of each wavelength was irradiated with the normal direction of the surface of the decorative sheet being 0 degree), and the ratio was measured as the ratio of the total reflected light beam to the parallel incident light beam (that is, the total light reflectivity). The method for measuring the total light reflectance was based on JIS K 7375: 2008. In addition, the spectral reflectance (%) of each wavelength was measured in a state where no layers were laminated on both sides of the decorative sheet.

[Example 2]
The decorative sheet of Example 2 was obtained by performing the same operation as in Example 1 except that the formation order of the first printed layer and the second printed layer was reversed. Table 3 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 2.
The decorative sheet of Example 2 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 3
As the second printing ink, an azomethine azo black pigment, a composite oxide black pigment, and a two-component curable acrylic-urethane resin, an azomethine azo black pigment: a composite oxide black pigment: an acrylic-urethane resin = 1. The decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the printing ink contained at a mass ratio of 0.24: 1.92 was used. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in the second printing ink used in Example 3 is 0.64. Table 4 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 3.
The decorative sheet of Example 3 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 4
As the second printing ink, azomethine azo black pigment, composite oxide black pigment, and two-component curable acrylic-urethane resin, azomethine azo black pigment: composite oxide black pigment: acrylic-urethane resin = 1: The decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the printing ink contained at a mass ratio of 2.13: 2.64 was used. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in the second printing ink used in Example 4 is 1.18. Table 5 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 4.
The decorative sheet of Example 4 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 5
The point after changing the thickness of the first printing layer after curing to 4 μm, the point after changing the thickness of the second printing layer after curing to 2 μm, and the second printing ink does not contain an azomethine azo black pigment, Except for using a printing ink containing a composite oxide black pigment and a two-part curable acrylic-urethane resin in a mass ratio of composite oxide black pigment: acryl-urethane resin = 0.494: 1, Operation similar to Example 1 was performed and the decorative sheet of Example 5 was obtained. The P / V ratio (mass of composite oxide black pigment / mass of binder resin) in the second printing ink used in Example 5 is 0.494. Table 6 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 5.
The decorative sheet of Example 5 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 6
A decorative sheet of Example 6 was obtained by performing the same operation as in Example 5 except that the formation order of the first printed layer and the second printed layer was reversed. Table 7 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 6.
The decorative sheet of Example 6 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 7
The point after changing the thickness of the first printed layer to 4 μm, the point after changing the thickness of the second printed layer to 4 μm, and the second printing ink does not contain an azomethine azo black pigment, Except for using a printing ink containing a composite oxide black pigment and a two-part curable acrylic-urethane resin in a mass ratio of composite oxide black pigment: acryl-urethane resin = 0.125: 1, Operation similar to Example 1 was performed and the decorative sheet of Example 7 was obtained. The P / V ratio (mass of composite oxide black pigment / mass of binder resin) in the second printing ink used in Example 7 is 0.125. Table 8 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 7.
The decorative sheet of Example 7 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 8
The point after changing the thickness of the first printed layer after curing to 4 μm, the point after changing the thickness of the second printed layer after curing to 1 μm, and the second printing ink does not contain an azomethine azo black pigment, Except for using a printing ink containing a composite oxide black pigment and a two-component curable acrylic-urethane resin in a mass ratio of composite oxide black pigment: acryl-urethane resin = 0.636: 1, Operation similar to Example 1 was performed and the decorative sheet of Example 8 was obtained. The P / V ratio (mass of composite oxide black pigment / mass of binder resin) in the second printing ink used in Example 8 is 0.736. Table 9 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 8.
The decorative sheet of Example 8 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 9
A decorative sheet of Example 9 was obtained in the same manner as in Example 8, except that a perylene-based black pigment (manufacturer: Palogen Black FK4280 manufactured by BASF) was used instead of the azomethine azo-based black pigment. Table 10 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 9.
The decorative sheet of Example 9 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 10
A decorative sheet of Example 10 was obtained in the same manner as in Example 8 except that a Ni-Fe black pigment (ARCTIC manufactured by Shepherd) was used instead of the complex oxide black pigment. Table 11 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 10.
The decorative sheet of Example 10 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

Example 11
A decorative sheet of Example 11 is obtained by performing the same operation as in Example 8 except that a Bi-Mn black pigment (IRR Pigment manufactured by Asahi Kasei Kogyo Co., Ltd.) is used instead of the composite oxide black pigment. It was. Table 12 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Example 11.
The decorative sheet of Example 11 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 1]
A decorative sheet of Comparative Example 1 was obtained by performing the same operation as in Example 1 except that the first printing ink was used as the second printing ink. Table 13 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 1.
The decorative sheet of Comparative Example 1 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 2]
As a 1st printing ink and a 2nd printing ink, an azomethine azo type black pigment is not included, a complex oxide type black pigment and a two-component curable acrylic-urethane resin, a complex oxide type black pigment: acrylic-urethane resin = 2. A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the printing ink contained at a mass ratio of 28: 1 was used. The P / V ratio (mass of composite oxide black pigment / mass of binder resin) in the first printing ink and the second printing ink used in Comparative Example 2 is 2.28. Table 14 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 2.
The decorative sheet of Comparative Example 2 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 3]
As the second printing ink, an azomethine azo black pigment is not included, and a composite oxide black pigment and a two-component curable acrylic-urethane resin are mixed oxide black pigment: acryl-urethane resin = 2.28: 1. A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the printing ink contained in a mass ratio was used. The P / V ratio (mass of composite oxide black pigment / mass of binder resin) in the second printing ink used in Comparative Example 3 is 2.28. Table 15 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 3.
The decorative sheet of Comparative Example 3 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 4]
As the second printing ink, azomethine azo black pigment, composite oxide black pigment, and two-component curable acrylic-urethane resin, azomethine azo black pigment: composite oxide black pigment: acrylic-urethane resin = 1: A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the printing ink contained at a mass ratio of 3.56: 3.28 was used. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in the second printing ink used in Comparative Example 4 is 1.4. Table 16 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 4.
The decorative sheet of Comparative Example 4 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 5]
As the second printing ink, azomethine azo black pigment, composite oxide black pigment, and two-component curable acrylic-urethane resin, azomethine azo black pigment: composite oxide black pigment: acrylic-urethane resin = 1: A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the printing ink contained at a mass ratio of 10.7: 6.24 was used. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in the second printing ink used in Comparative Example 5 is 1.87. Table 17 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 5.
The decorative sheet of Comparative Example 5 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

[Comparative Example 6]
As the first printing ink and the second printing ink, azomethine azo black pigment, composite oxide black pigment, and two-component curable acrylic-urethane resin, azomethine azo black pigment: composite oxide black pigment: acrylic A decorative sheet of Comparative Example 5 was obtained by performing the same operation as in Example 1 except that the printing ink containing urethane resin = 1: 10.7: 6.24 was used. The P / V ratio ((mass of azomethine azo black pigment + mass of composite oxide black pigment) / mass of binder resin) in the first printing ink and the second printing ink used in Comparative Example 6 is 1.87. is there. Table 18 shows the characteristics of the first printed layer and the second printed layer of the decorative sheet of Comparative Example 6.
The decorative sheet of Comparative Example 6 was evaluated in the same manner as the decorative sheet of Example 1. Table 19 shows the evaluation results for the decorative sheet before the weather resistance test, and Table 20 shows the evaluation results for the decorative sheet after the weather resistance test.

As shown in Table 19 and Table 20, a decorative sheet whose visual black evaluation is A (the black color of the decorative sheet is recognized as pure black (black) or close black) is L ^* a ^* b ^* L ^* value, a ^* value and b ^* value of the color system are L ^* value: 30 or less, a ^* value: 0 to 2.5 and b ^* value: -2.5 to 0 On the other hand, the decorative sheet whose visual black evaluation is B (the black color of the decorative sheet is not recognized as pure black (black) or close black) is L ^* value: 30 or less, a ^* value: 0 or more 2.5 or less and b ^* value: 1 or more of −2.5 or more and 0 or less is not satisfied. Therefore, the L ^* value, a ^* value, and b ^* value of the L ^* a ^* b ^* color system are set to L ^* value: 30 or less, a ^* value: 0 to 2.5, and b ^* value: − By adjusting to 2.5 or more and 0 or less, it turned out that the black color which a decorative sheet exhibits is recognized as pure black (black) or black close to it.

  As shown in Table 19, the decorative sheets of Examples 1 to 11 and Comparative Example 1 have an average spectral reflectance of 35% or more in a wavelength range of 780 to 2500 nm, and are considered to have sufficient heat shielding performance. On the other hand, the decorative sheets of Comparative Examples 2 to 6 have an average spectral reflectance of less than 35% in the wavelength range of 780 to 2500 nm, and are considered not to have sufficient heat shielding performance.

As shown in Table 20, the decorative sheets of Examples 1 to 11 and Comparative Examples 2 to 6 have a black evaluation by visual inspection after the weather resistance test of A (the black color of the decorative sheet is pure black (black) or it. L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value after the weather resistance test are L ^* value: 30 or less, a ^* value: It is 0 or more and 2.5 or less, and b ^* value: -2.5 or more and 0 or less. On the other hand, the decorative sheet of Comparative Example 1 has a black evaluation by visual inspection after the weather resistance test of B (black which the decorative sheet exhibits is not recognized as pure black (black) or black close thereto) and an L ^* value. : 30 or less, a ^* value: 0 or more and 2.5 or less, and b ^* value: 1 or more of −2.5 or more and 0 or less are not satisfied.

  From the results shown in Table 19 and Table 20, it was found that the decorative sheets of Examples 1 to 11 exhibited a black color continuously and exhibited heat shielding performance even when used outdoors.

DESCRIPTION OF SYMBOLS 10 ... Cosmetic sheet 11 ... Base material sheet 12 ... Print layer 121 ... 1st print layer 122 ... 2nd print layer 13 ... Transparent resin layer 14 ... Surface protective layer 20 ... Cosmetic material 21 ... Adhering material 22 ... Adhesive layer

Claims (14)

A decorative sheet having a base sheet, a printing layer containing an organic black pigment and an inorganic black pigment, a transparent resin layer, and a surface protective layer in order,
The L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value measured by irradiating light on the surface of the decorative sheet on the surface protective layer side are L ^* values: 30 or less, a ^* Value: 0 or more and 2.5 or less, and b ^* Value: -2.5 or more and 0 or less,
The said decorative sheet whose average spectral reflectance of the wavelength range 780-2500 nm measured by irradiating the light of the wavelength range 780-2500 nm to the surface protective layer side surface of the said decorative sheet is 35% or more.   The decorative sheet according to claim 1, wherein the printed layer has a first printed layer containing the organic black pigment and a second printed layer containing the inorganic black pigment.   The decorative sheet according to claim 2, wherein the second printed layer does not contain the organic black pigment.   The decorative sheet according to claim 2, wherein the second printed layer contains the organic black pigment.   The decorative sheet according to any one of claims 1 to 4, wherein the organic black pigment is an azomethine azo black pigment.   The decorative sheet according to any one of claims 1 to 5, wherein the inorganic black pigment is a complex oxide containing a manganese element. L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value after the weather resistance test are L ^* value: 30 or less, a ^* value: 0 or more and 2.5 or less, and b ^* Value: The decorative sheet according to any one of claims 1 to 6, which is -2.5 or more and 0 or less.   The decorative sheet according to any one of claims 1 to 7, wherein a spectral reflectance at a wavelength of 800 nm, which is measured by irradiating light having a wavelength of 800 nm on the surface of the decorative sheet, is 20% or more.   The average spectral reflectance in the wavelength region of 300 to 650 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength region of 300 to 650 nm is 6% or less. The decorative sheet according to item.   The decorative sheet according to any one of claims 1 to 9, wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.   The decorative sheet according to any one of claims 1 to 10, wherein the base sheet is a colored resin sheet.   The decorative sheet according to any one of claims 1 to 11, wherein the decorative sheet does not contain carbon black.   A decorative member comprising an adherend and the decorative sheet according to any one of claims 1 to 12 so that the adherend and the base sheet of the decorative sheet face each other.   The decorative member according to claim 13, wherein the adherend is at least one member selected from a wooden member, a metal member, and a resin member.

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