JP2017185782A - Decorative sheet and decorative member with the decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of exhibiting dark color and heat shielding performance and a decorative member.SOLUTION: There are provided a decorative sheet having a substrate sheet (11A), a printing layer (12) containing an azomethine azo-based black pigment, a transparent resin layer (13) and a surface protective layer (14), and having Lvalue of 30 or less, avalue of 0 to 2.5 and bvalue of -3 to 0.5 of a Labcolorimetric system measured by irradiating light to a surface protective layer side surface of the decorative sheet (10A) and average spectral absorptivity of a wavelength range of 360 to 2500 nm measured by irradiating a light with wave length range of 360 to 2500 nm to a surface protective layer side surface of the decorative sheet (10A) of 33% or less, and a decorative member having the decorative sheet (10A).SELECTED DRAWING: Figure 1

Description

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

  Interior and exterior members of buildings such as walls, ceilings, floors, fittings such as window frames, doors and door frames, handrails, baseboards, edges, moldings such as malls, fences, fences, kitchen equipment, furniture or Makeup with a decorative sheet attached to a metal decorative member such as a steel plate, a resin member, or a wooden member, as a surface decorative plate for cabinets of light electrical appliances, office automation equipment, etc. Members are used.

  In recent years, there has been an increasing demand for dark-colored decorative sheets or decorative members such as brown and black, and as dark-colored decorative sheets or decorative members, any layer constituting the decorative sheet or decorative member (for example, an adherend) , A decorative sheet or a decorative member containing carbon black as a black pigment in the base material and decorative layer). 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 Laid-Open No. 2007-168176) contains an inorganic pigment made of a compound containing at least one element selected from Fe, Cr, Mn, Cu, Co and Ni having infrared reflection characteristics. A laminated body having a grain-like appearance with reduced heat storage by use of a thermoplastic resin is described. However, the inorganic pigment used in Patent Document 1 shows a high infrared reflection characteristic if it is a high brightness product such as white, but a dark infrared low brightness product such as black has a sufficient infrared reflection property. Not shown. Therefore, it is difficult to realize a decorative sheet or decorative member that can exhibit a dark color and can exhibit heat shielding performance according to Patent Document 1.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2014-43066) discloses that an azomethine azo pigment having high infrared transmittance is used as a black pigment in a pattern layer for forming a conduit portion in a wood grain pattern. A decorative sheet with improved thermal performance is described. However, azomethine azo pigments exhibit a reddish black color. In Patent Document 2, the proportion of the surface area of the decorative sheet occupied by the area of the pattern pattern layer forming the conduit portion is small, and as disclosed in the examples, the base of the pattern layer is disclosed. The azomethine azo pigment in the pattern layer is offset by adding blue phthalocyanine blue in addition to white titanium oxide, which is an infrared reflective pigment, to the colored film used as a material to offset the redness of the pattern layer. However, even if it exhibits reddish black, the degree of freedom that the decorative sheet exhibits a desired dark color such as black or brown with less redness may not be hindered. However, the greater the proportion of the surface area of the decorative sheet occupied by the area where the pattern layer is provided, the stronger the redness of the azomethine azo pigment in the pattern layer becomes, and the darkness of the decorative sheet is realized. The degree of freedom of selection is narrowed. Therefore, as such a decorative sheet, the area occupancy rate of the pattern pattern occupying the surface such as a wood grain pattern in which the dark color is the base color over the entire surface, a solid surface of the dark color (monochromatic layer over the entire surface), etc. Large design patterns are often selected. In addition to reddish brown, rosy, etc., colors such as black, dark gray, amber, dark green, and tan are often selected as dark colors. Furthermore, by adding a color pigment such as blue into an infrared reflective colored film containing titanium oxide, the infrared reflectance, that is, the heat shielding performance, is somewhat lowered. Therefore, even in a pattern with a large area of the pattern pattern layer, it is not limited to a specific dark color with a reddish color tone, and the degree of freedom in selecting a pattern pattern and a dark color is high, and heat shielding performance can be exhibited. It is difficult to realize a decorative sheet or decorative member that can be produced by Patent Document 2.

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

  Therefore, an object of the present invention is to provide a decorative sheet and a decorative member that can exhibit a dark color and can exhibit heat shielding 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 azomethine azo-based 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: -3 or more and 0.5 or less,
The decorative sheet, wherein an average spectral absorptivity in a wavelength range of 360 to 2500 nm measured by irradiating light in a wavelength range of 360 to 2500 nm on the surface of the decorative sheet on the surface protective layer side is 33% or less.
[2] The average spectral reflectance in the wavelength region 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength region 360 to 2500 nm is 25% or more. Makeup sheet.
[3] The average spectral reflectance in the wavelength range 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength range 831 to 2500 nm is 30% or more. Makeup sheet.
[4] The spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet with a wavelength of 750 nm is 50% or more, and the surface protective layer side surface of the decorative sheet has a wavelength of 800 nm. The decorative sheet according to [2] or [3], wherein the spectral reflectance at a wavelength of 800 nm measured by irradiation with light is 60% or more.
[5] The average spectral reflectance in the wavelength range 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength range 360 to 600 nm is 10% or less. [2] to [4] ] The decorative sheet in any one of.
[6] In the state where the substrate sheet exists alone, the average spectral reflectance of the wavelength region 360 to 2500 nm measured by irradiating the surface of the substrate sheet with light in the wavelength region 360 to 2500 nm is 55% or more. The decorative sheet according to any one of [2] to [5].
[7] The average spectral transmittance in the wavelength region 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength region 360 to 2500 nm is 60% or more. Makeup sheet.
[8] The average spectral transmittance in the wavelength range 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength range 831 to 2500 nm is 75% or more. Makeup sheet.
[9] The spectral transmittance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light having a wavelength of 750 nm is 60% or more, and the surface protective layer side surface of the decorative sheet has a wavelength of 800 nm. The decorative sheet according to [7] or [8], wherein the spectral transmittance at a wavelength of 800 nm measured by irradiation with light is 70% or more.
[10] The average spectral transmittance in the wavelength range 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength range 360 to 600 nm is 8% or less. [7] to [9 ] The decorative sheet in any one of.
[11] In the state where the base sheet is present alone, the average spectral transmittance in the wavelength range 360 to 2500 nm measured by irradiating the surface of the base sheet with light in the wavelength range 360 to 2500 nm is 70% or more. The decorative sheet according to any one of [7] to [10].
[12] 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 [11].
[13] The decorative sheet according to any one of [1] to [12], wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.
[14] The decorative sheet according to any one of [1] to [13], wherein the base sheet is a colored resin sheet.
[15] The decorative sheet according to any one of [1] to [14], wherein the decorative sheet does not contain carbon black.
[16] The makeup according to any one of [1] to [15], wherein the ratio of the area of the region where the printed layer is formed to the surface area of one surface of the base sheet is 50% or more. Sheet.
[17] A decorative member comprising an adherend and the decorative sheet according to any one of [1] to [16] so that the adherend and the base sheet of the decorative sheet face each other.
[18] The decorative member according to [17], wherein the adherend is at least one member selected from a wooden member, a metal member, and a resin member.
[19] The average spectral reflectance in the wavelength range 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative member with light in the wavelength range 360 to 2500 nm is 40% or more. [17] or [18 ] The decorative member as described in.
[20] The average spectral reflectance in the wavelength range 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative member with light in the wavelength range 831 to 2500 nm is 50% or more. Cosmetic material.
[21] The spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative member with a wavelength of 750 nm is 55% or more, and the surface protective layer side surface of the decorative member has a wavelength of 800 nm. The cosmetic member according to [19] or [20], wherein the spectral reflectance at a wavelength of 800 nm measured by irradiation with light is 70% or more.
[22] The average spectral reflectance in the wavelength region 360 to 600 nm measured by irradiating light in the wavelength region 360 to 600 nm on the surface of the decorative member on the surface protective layer side is 10% or less. [19] to [21 ] The decorative member in any one of.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to exhibit a dark color, the decorative sheet and decorative member which can exhibit heat-shielding performance are provided.

FIG. 1 is a side view schematically showing a configuration of a decorative sheet according to the first embodiment of the present invention. FIG. 2 is a side view schematically showing the configuration of the decorative sheet according to the second embodiment of the present invention. FIG. 3 is a conceptual diagram illustrating an example of a spectral reflectance curve, a spectral transmittance curve, and a spectral absorptance curve in a wavelength range of 360 to 2500 nm in the printed layer. FIG. 4 shows a wavelength range 360 to 600 in the base sheet when a base sheet having a high average spectral reflectance in the wavelength range 360 to 2500 nm or a high average spectral reflectance in the wavelength range 831 to 2500 nm is used as the base sheet. It is a conceptual diagram which shows an example of a 2500 nm spectral reflectance curve, a spectral transmittance curve, and a spectral absorptance curve. FIG. 5 shows a case where a base sheet having a high average spectral reflectance in the wavelength region 360 to 2500 nm or a high average spectral reflectance in the wavelength region 831 to 2500 nm is used as the base sheet. It is a conceptual diagram which shows an example of the spectral absorptivity curve of the wavelength range 360-2500nm in a combination. FIG. 6 shows a wavelength range 360 to 600 in the base sheet when a base sheet having a high average spectral transmittance in the wavelength range 360 to 2500 nm or a high average spectral transmittance in the wavelength range 831 to 2500 nm is used as the base sheet. It is a conceptual diagram which shows an example of a 2500 nm spectral reflectance curve, a spectral transmittance curve, and a spectral absorptance curve. FIG. 7 shows a case where a base sheet having a high average spectral transmittance in the wavelength region of 360 to 2500 nm or a high average spectral transmittance in the wavelength range of 831 to 2500 nm is used as the base sheet. It is a conceptual diagram which shows an example of the spectral absorptivity curve of the wavelength range 360-2500nm in a combination. FIG. 8 is a side view schematically showing the configuration of the decorative member according to the first embodiment of the present invention. FIG. 9 is a side view schematically showing the configuration of the decorative member according to the second embodiment of the present invention. FIG. 10 is a diagram illustrating a spectral reflectance curve and a spectral transmittance curve in a wavelength range of 360 to 2500 nm in the base material sheet S1 used in the examples. FIG. 11 is a diagram showing a spectral reflectance curve and a spectral transmittance curve in a wavelength range of 360 to 2500 nm in the base material sheet S2 used in the examples. FIG. 12 is a diagram showing spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 1. FIG. 13 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 2. FIG. 14 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 3. FIG. 15 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 4. FIG. 16 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 5. FIG. 17 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Example 6. FIG. 18 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Comparative Example 1. FIG. 19 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Comparative Example 2. FIG. 20 is a diagram illustrating spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Comparative Example 3. FIG. 21 is a diagram showing spectral reflectance and spectral transmittance in a wavelength range of 360 to 2500 nm in the decorative sheet of Comparative Example 4.

[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 ^* .

The “L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value” in the decorative sheet is measured using a spectrocolorimeter (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.). The protective layer side surface is irradiated with light (D65 light source) at an incident angle of 10 degrees (the normal direction of the surface of the decorative sheet is 0 degree), and based on total light reflected light (specular reflection light + diffuse reflection light) taking measurement.

The “average spectral absorption rate (%) in the wavelength range of 360 to 2500 nm” in the decorative sheet is calculated based on the following formula.
Average spectral absorptance (%) in the wavelength region 360 to 2500 nm = 100 (%) − Average spectral reflectance (%) in the wavelength region 360 to 2500 nm−Average spectral transmittance (%) in the wavelength region 360 to 2500 nm

  The “average spectral reflectance (%) in the wavelength region 360 to 2500 nm” in the decorative sheet or the decorative member is obtained by changing the wavelength by 1 nm from the wavelength 360 nm to the wavelength 2500 nm while changing the wavelength (that is, the wavelength 360 nm, 361 nm, 362 nm,. (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 2141 spectral reflectances is divided by 2141. “Spectral reflectance (%) of each wavelength” is obtained by using a spectrophotometer (V-670, manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, on the surface protective layer side surface of the decorative sheet or decorative member. Irradiate light of each wavelength at an incident angle of 5 degrees (the normal direction of the surface of the decorative sheet or decorative member is 0 degree), and measure 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 transmittance (%) in the wavelength region 360 to 2500 nm” in the decorative sheet is the wavelength (ie, wavelengths 360 nm, 361 nm, 362 nm,...) While changing the wavelength by 1 nm from the wavelength 360 nm to the wavelength 2500 nm. (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 2141 spectral transmittances is divided by 2141. “Spectral transmittance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) based on JIS K 0115: 2004, and the incident angle is 0 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 the ratio of the total transmitted light beam to the parallel incident light beam (that is, the total light transmittance). The measuring method of the total light transmittance is based on JIS K 7375: 2008.

  The “average spectral reflectance (%) in the wavelength region 831 to 2500 nm” in the decorative sheet or the decorative member is obtained by changing each wavelength from 183 nm to 2500 nm while changing the wavelength by 1 nm (that is, wavelengths 831 nm, 832 nm, 833 nm,. ... (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 1670 spectral reflectances is divided by 1670. The measuring method of “spectral reflectance (%) of each wavelength” is as described above.

  The “average spectral transmittance (%) in the wavelength range 831 to 2500 nm” in the decorative sheet is obtained by changing each wavelength by 1 nm from the wavelength 831 nm to the wavelength 2500 nm (ie, wavelengths 831 nm, 832 nm, 833 nm,...). (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 1670 spectral transmittances is divided by 1670. The measuring method of “spectral transmittance (%) of each wavelength” is as described above.

  “Spectral reflectance (%) at a wavelength of 750 nm” or “Spectral reflectance at a wavelength of 800 nm (%)” in a decorative sheet or a decorative member is a spectrophotometer (V-manufactured by JASCO Corporation) according to JIS K 0115: 2004. 670) and irradiating the surface of the decorative sheet or decorative member with light having a wavelength of 750 nm or 800 nm at an incident angle of 5 degrees (the normal direction of the surface of the decorative sheet or decorative member is 0 degree). Then, it 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 “spectral transmittance (%) at a wavelength of 750 nm” or “spectral transmittance (%) at a wavelength of 800 nm” in the decorative sheet is a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004. The decorative sheet surface protective layer side surface is irradiated with light having a wavelength of 750 nm or a wavelength of 800 nm at an incident angle of 0 degree (the normal direction of the decorative sheet surface is 0 degree), and a total transmitted light beam with respect to a parallel incident light beam. As a percentage (ie total light transmittance). The measuring method of the total light transmittance is based on JIS K 7375: 2008.

  The “average spectral reflectance (%) in the wavelength range of 360 to 600 nm” in the decorative sheet or decorative member is the wavelength of each wavelength (that is, 360 nm, 361 nm, 362 nm,. ... (598 nm, 599 nm, 600 nm) is measured, and the sum of the measured 241 spectral reflectances is divided by 241. The measuring method of “spectral reflectance (%) of each wavelength” is as described above.

  The “average spectral transmittance (%) in the wavelength range of 360 to 600 nm” in the decorative sheet is obtained by changing each wavelength by 1 nm from a wavelength of 360 nm to a wavelength of 600 nm (that is, wavelengths of 360 nm, 361 nm, 362 nm,... 598 nm, 599 nm, and 600 nm) are measured, and the sum of the measured 241 spectral transmittances is divided by 241. The measuring method of “spectral transmittance (%) of each wavelength” is as described above.

  “Average spectral reflectance (%) in wavelength range 360 to 2500 nm”, “Average spectral reflectance (%) in wavelength range 831 to 2500 nm”, “Spectral reflectance (%) at wavelength 750 nm”, “Wavelength” “Spectral reflectance (%) at 800 nm” and “Average spectral reflectance (%) in the wavelength range of 360 to 600 nm” indicate that the base sheet is present alone (that is, any layer is laminated on both sides of the base sheet). In the state of not being measured), it is measured as the reflectance on the surface side (surface protective layer side) of the base sheet. Therefore, when measuring the reflectance of a base sheet from the form of a decorative sheet in which a printed layer, a transparent resin layer, and a surface protective layer are laminated on the base sheet, the surface side (surface of the base sheet from the decorative sheet) All layers (print layer, transparent resin layer and surface protective layer) laminated on the protective layer side are removed by cutting or peeling, and the reflectance of the base sheet is measured with the surface of the base sheet exposed. To do. However, when the reflectance of the front and back surfaces of the base sheet is the same, the reflectance of the back surface (the surface opposite to the surface protective layer) of the decorative sheet is measured, and this is reflected on the base sheet. And

  The “average spectral reflectance (%) in the wavelength region 360 to 2500 nm” in the base sheet is the wavelength (ie, wavelengths 360 nm, 361 nm, 362 nm,...) While changing the wavelength by 1 nm from the wavelength 360 nm to the wavelength 2500 nm. (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 2141 spectral reflectances is divided by 2141. “Spectral reflectance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) based on JIS K 0115: 2004, and the incident angle on the surface protective layer side surface of the base sheet. The light of each wavelength is irradiated at 5 degrees (the normal direction of the surface of the substrate 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 region 831 to 2500 nm” in the base material sheet is obtained by changing each wavelength by 1 nm from the wavelength 831 nm to the wavelength 2500 nm (ie, wavelengths 831 nm, 832 nm, 833 nm,... The spectral reflectance (%) of 2498 nm, 2499 nm, and 2500 nm) is measured, and the sum of the measured 1670 spectral reflectances is divided by 1670. The measuring method of “spectral reflectance (%) of each wavelength” is as described above.

  The “spectral reflectance (%) at a wavelength of 750 nm” and “spectral reflectance (%) at a wavelength of 800 nm” in the base sheet are measured by the “spectral reflectance (%) at a wavelength of 750 nm” and “wavelength 800 nm” in the decorative sheet. The spectral reflectance (%) "is the same.

  The “average spectral reflectance (%) in the wavelength range of 360 to 600 nm” in the base sheet is the wavelength (ie, wavelengths of 360 nm, 361 nm, 362 nm,...) While changing the wavelength by 1 nm from the wavelength of 360 nm to the wavelength of 600 nm. The spectral reflectance (%) at 598 nm, 599 nm, and 600 nm is measured, and the sum of the measured 241 spectral reflectances is divided by 241. The measuring method of “spectral reflectance (%) of each wavelength” is as described above.

  “Average spectral transmittance (%) in wavelength range 360 to 2500 nm”, “Average spectral transmittance (%) in wavelength range 831 to 2500 nm”, “Spectral transmittance (%) at wavelength 750 nm”, “Wavelength” The “800 nm spectral transmittance (%)” and “average spectral transmittance (%) in the wavelength range of 360 to 600 nm” indicate that the base sheet is present alone (that is, any layer is laminated on both sides of the base sheet). In a state where it is not carried out, the transmittance is measured as the transmittance from the front surface side (surface protective layer side) to the back surface side of the base sheet. Therefore, when measuring the transmittance of a base sheet from the form of a decorative sheet in which a printed layer, a transparent resin layer, and a surface protective layer are laminated on the base sheet, the surface side (surface of the base sheet from the decorative sheet) All layers (printing layer, transparent resin layer and surface protective layer) laminated on the protective layer side are removed by cutting or peeling, and the transmittance of the base sheet is measured with the surface of the base sheet exposed. To do.

  The “average spectral transmittance (%) in the wavelength region 360 to 2500 nm” in the base sheet is the wavelength (ie, wavelengths 360 nm, 361 nm, 362 nm,...) While changing the wavelength by 1 nm from the wavelength 360 nm to the wavelength 2500 nm. (2498 nm, 2499 nm, 2500 nm) is measured, and the sum of the measured 2141 spectral transmittances is divided by 2141. “Spectral transmittance (%) of each wavelength” is a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, and the incident angle on the surface protective layer side surface of the base sheet. Light of each wavelength is irradiated at 0 degree (the normal direction of the surface of the base sheet is 0 degree), and the ratio is measured as the ratio of the total transmitted light beam to the parallel incident light beam (that is, the total light transmittance). The measuring method of the total light transmittance is based on JIS K 7375: 2008.

  The “average spectral transmittance (%) in the wavelength range 831 to 2500 nm” in the base material sheet is obtained by changing each wavelength from 831 nm to 2500 nm while changing the wavelength by 1 nm (that is, wavelengths 831 nm, 832 nm, 833 nm,... The spectral transmittance (%) of 2498 nm, 2499 nm, and 2500 nm) is measured, and the sum of the measured 1670 spectral transmittances is divided by 1670. The measuring method of “spectral transmittance (%) of each wavelength” is as described above.

  The measurement method of “spectral transmittance (%) at wavelength 750 nm” and “spectral transmittance (%) at wavelength 800 nm” in the base sheet is “spectral transmittance (%) at wavelength 750 nm” and “wavelength 800 nm” in the decorative sheet. Is the same as “Spectral transmittance (%)”.

  The “average spectral transmittance (%) in the wavelength range of 360 to 600 nm” in the base material sheet is obtained by changing each wavelength by 1 nm from a wavelength of 360 nm to a wavelength of 600 nm (that is, wavelengths of 360 nm, 361 nm, 362 nm,... The spectral transmittance (%) of 598 nm, 599 nm, and 600 nm is measured, and the sum of the measured 241 spectral transmittances is divided by 241. The measuring method of “spectral transmittance (%) of each wavelength” is as described above.

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). A ^* value and b ^* value on the surface side (surface protective layer side) of the transparent resin layer. Therefore, when measuring the a ^* value and b ^* value of the transparent resin layer 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 transparent resin layer from the decorative sheet is used. All the layers (base sheet, print layer and surface protective layer) laminated on the front surface side (surface protective layer side) and back surface side (print layer side) are cut or removed to remove the surface of the transparent resin layer. In the exposed state, the a ^* value and b ^* value of the transparent resin layer are measured. The measuring method is the same as “L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value” in the decorative sheet.

[Decorative sheet]
Hereinafter, the decorative sheets according to the first and second embodiments of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a side view schematically showing the configuration of a decorative sheet 10A according to the first embodiment of the present invention, and FIG. 2 schematically shows the configuration of a decorative sheet 10B according to the second embodiment of the present invention. FIG. 1 and 2, the same reference numerals are given to the same parts or members.

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

  As shown in FIG. 2, the decorative sheet 10 </ b> B according to the second embodiment of the present invention includes a base sheet 11 </ b> B, a printed layer 12, a transparent resin layer 13, and a surface protective layer 14 in order.

The L ^* a ^* b ^* color system L ^* value, a ^* value, and b ^* value measured by irradiating the surface of the decorative sheet 10A or 10B with light is L ^* value: 30 or less, a ^* value: 0 to 2.5 and b ^* value: -3 to 0.5. Thereby, the decorative sheet 10A or 10B can exhibit a dark color. “Dark color” means that the color tone is a chromatic or achromatic color with low brightness. For example, achromatic colors such as black and dark gray, and chromatic colors such as amber, brown, yellowish brown, dark green, dark purple, and rosy correspond to dark colors. The L ^* value is not particularly limited as long as it is 30 or less, but is preferably 29 or less. The lower limit of the L ^* value is not particularly limited, but is usually 20, preferably 22, and more preferably 23. The a ^* value is not particularly limited as long as it is from 0 to 2.5, but is preferably from 0.5 to 1.8, more preferably from 0.5 to 1.5, and even more preferably from 0.7 to 1. .3 or less, more preferably 0.7 or more and 1.2 or less. The b ^* value is not particularly limited as long as it is -3 or more and 0.5 or less, preferably -2.8 or more and 0 or less, more preferably -2.3 or more and -0.5 or less, and still more preferably -2 or more. -1 or less.

  The average spectral absorptance in the wavelength region 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10 </ b> A with light in the wavelength region 360 to 2500 nm is 33% or less. Thereby, 10 A of decorative sheets can exhibit a dark color, and can exhibit thermal-insulation performance. The average spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10A is not particularly limited as long as it is 33% or less, but is preferably 30% or less, more preferably 28% or less, and even more preferably 25% or less. The lower limit value of the average spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10A is not particularly limited, but is preferably 5%, more preferably 8%, and still more preferably 10%.

  The average spectral reflectance at a wavelength of 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light of a wavelength of 360 to 2500 nm is preferably 25% or more, more preferably 28% or more, and even more preferably. Is 30% or more. Thereby, the average spectral absorptance of the wavelength region 360 to 2500 nm in the decorative sheet 10A can be adjusted to 33% or less, and the decorative sheet 10A more effectively exhibits the heat shielding performance based on the near infrared reflection performance. be able to. The upper limit of the average spectral reflectance at a wavelength of 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light of a wavelength of 360 to 2500 nm is not particularly limited, but is preferably 90%, more preferably Is 85%, still more preferably 80%.

  The average spectral reflectance at a wavelength of 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light of a wavelength of 831 to 2500 nm is preferably 30% or more, more preferably 33% or more, and even more preferably Is 35% or more. Thereby, 10 A of decorative sheets can exhibit more effectively the heat insulation performance based on near-infrared reflective performance. The upper limit value of the average spectral reflectance at a wavelength of 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light of a wavelength of 831 to 2500 nm is not particularly limited, but is preferably 90%, more preferably Is 85%, still more preferably 80%.

  The spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with a wavelength of 750 nm is 50% or more, and the surface protective layer side surface of the decorative sheet 10A is irradiated with light having a wavelength of 800 nm. Thus, the spectral reflectance at a wavelength of 800 nm measured is preferably 60% or more. Thereby, 10 A of decorative sheets can exhibit more effectively the heat insulation performance based on near-infrared reflective performance. The spectral reflectance at a wavelength of 750 nm in the decorative sheet 10A is preferably 53% or more, more preferably 55% or more, and even more preferably 60% or more. The upper limit of the spectral reflectance at a wavelength of 750 nm in the decorative sheet 10A is not particularly limited, but is preferably 75%, and more preferably 70%. The spectral reflectance at a wavelength of 800 nm in the decorative sheet 10A is preferably 63% or more, more preferably 65% or more, and still more preferably 70% or more. The upper limit of the spectral reflectance at a wavelength of 800 nm in the decorative sheet 10A is not particularly limited, but is preferably 100%, more preferably 95%, and still more preferably 90%.

  The average spectral reflectance in the wavelength range 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light in the wavelength range 360 to 600 nm is preferably 10% or less. Thereby, 10 A of decorative sheets can exhibit dark color more effectively. The average spectral reflectance in the wavelength region 360 to 600 nm in the decorative sheet 10A is preferably 8% or less, more preferably 6% or less, and still more preferably 4% or less. The lower limit value of the average spectral reflectance in the wavelength region 360 to 600 nm in the decorative sheet 10A is not particularly limited.

  The decorative sheet 10A has a feature that the average spectral reflectance in the wavelength region 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light in the wavelength region 360 to 600 nm is 10% or less, The spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the sheet 10A with a wavelength of 750 nm is 50% or more, and the surface protective layer side surface of the decorative sheet 10A is irradiated with light having a wavelength of 800 nm. The spectral reflectance measured at a wavelength of 800 nm is 60% or more, and the average of the wavelength range 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light having a wavelength of 831 to 2500 nm It is preferable to combine the feature that the spectral reflectance is 30% or more. As a result, the spectral reflectance of the decorative sheet 10A has a sharp rise in the wavelength range of 600 to 800 nm, and the decorative sheet 10A has a dark coloration based on a low spectral reflectance in the visible light region and a near infrared region ( It is possible to more effectively achieve the heat shielding performance based on the high spectral reflectance in the wavelength range of more than 830 to 2500 nm.

  Hereinafter, the decorative sheet 10A has a dark color because the average spectral absorptance in the wavelength range 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light in the wavelength range 360 to 2500 nm is 33% or less. The reason why the heat shielding performance can be exhibited will be described with reference to FIGS. FIG. 3 is a conceptual diagram illustrating an example of a spectral reflectance curve, a spectral transmittance curve, and a spectral absorptance curve in the wavelength region 360 to 2500 nm in the printed layer 12, and FIG. 4 illustrates the wavelength region 360 as the base sheet 11A. When a base sheet having a high average spectral reflectance of ˜2500 nm or a high average spectral reflectance of wavelength range 831 to 2500 nm is used, the spectral reflectance curve and spectral transmittance curve of wavelength range 360 to 2500 nm in the base sheet 11A FIG. 5 is a conceptual diagram showing an example of a spectral absorptance curve, and FIG. 5 shows a base sheet having a high average spectral reflectance in a wavelength range of 360 to 2500 nm or a high average spectral reflectance in a wavelength range of 831 to 2500 nm as the base sheet 11A. An example of a spectral absorptance curve in a wavelength range of 360 to 2500 nm in a combination of the base sheet 11A and the printed layer 12 It is a be conceptual diagram.

  Part of the light in the wavelength region 360 to 2500 nm irradiated on the surface protective layer side surface of the decorative sheet 10 </ b> A is reflected by the surface of the surface protective layer 14, and the rest is hardly absorbed by the surface protective layer 14. The surface protective layer 14 is transmitted. Of the light having a wavelength range of 360 to 2500 nm transmitted through the surface protective layer 14, a part of the light is reflected by the surface of the transparent resin layer 13, and the remaining part is hardly absorbed by the transparent resin layer 13, and the transparent resin layer 13 is reflected. To Penetrate. Therefore, the spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10A greatly depends on the spectral absorptivity in the wavelength region 360 to 2500 nm in the combination of the base sheet 11A and the printing layer 12.

  Since the printing layer 12 contains an azomethine azo-based black pigment, as shown in FIG. 3, the spectral absorption A in the visible light region (wavelength region 360 to 830 nm) in the printing layer 12 is high, but the spectral reflectance in the visible light region. R and spectral transmittance T are low. Therefore, the spectral absorptance in the visible light region in the combination of the base sheet 11 </ b> A and the printing layer 12 greatly depends on the spectral absorptance A in the visible light region in the printing layer 12.

  Since the printing layer 12 contains an azomethine azo-based black pigment, as shown in FIG. 3, the spectral transmittance T in the near-infrared region (wavelength region exceeding 830 to 2500 nm) in the printing layer 12 is high, but the spectral absorption in the near-infrared region. The rate A and the spectral reflectance R are low. Therefore, the spectral absorptance in the near infrared region in the combination of the base sheet 11A and the printing layer 12 greatly depends on the spectral absorptance in the near infrared region in the base sheet 11A.

  When a base sheet having a high average spectral reflectance in the wavelength region of 360 to 2500 nm or a high average spectral reflectance in the near-infrared region (wavelength range of 830 to 2500 nm) is used as the base sheet 11A, as shown in FIG. In the base sheet 11A, the spectral reflectance R in the near infrared region is high, but the spectral transmittance T and the spectral absorption rate A in the near infrared region are low.

  As described above, the spectral absorptance A in the visible light region in the combination of the base material sheet 11A and the printing layer 12 greatly depends on the spectral absorptance A in the visible light region in the printing layer 12, and the base material sheet 11A and the printing layer Since the spectral absorption rate A in the near infrared region in combination with 12 greatly depends on the spectral absorption rate A in the near infrared region in the substrate sheet 11A, as shown in FIG. In the combination, the spectral absorption factor A in the visible light region (wavelength region 360 to 830 nm) is high, but the spectral absorption factor A in the near infrared region (wavelength region 830 to 2500 nm) is low.

  As described above, the spectral absorption rate in the wavelength region 360 to 2500 nm in the decorative sheet 10A greatly depends on the spectral absorption rate in the wavelength range 360 to 2500 nm in the combination of the base sheet 11A and the printing layer 12, and thus the decorative sheet 10A When the average spectral absorptance of the wavelength region 360 to 2500 nm measured by irradiating the surface protective layer side surface with light of the wavelength region 360 to 2500 nm is 33% or less, in the combination of the base sheet 11A and the printing layer 12 The average spectral absorptance in the visible light region (wavelength region 360 to 830 nm) is higher than 33%, and the average spectral absorptance in the near-infrared region (wavelength region 830 to 2500 nm) is lower than 33%. When the average spectral absorptance in the visible light region in the combination of the base sheet 11A and the print layer 12 is higher than 33%, the decorative sheet 10A can exhibit a dark color, and the base sheet 11A and the print layer 12 When the average spectral absorption rate in the near infrared region in the combination is lower than 33%, the decorative sheet 10A can exhibit heat shielding performance.

  Wavelength measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light in the wavelength region of 360 to 600 nm in order to make the average spectral absorption rate in the visible light region (wavelength region of 360 to 830 nm) higher than 33%. The average spectral transmittance in the region 360 to 600 nm is preferably 10% or less, more preferably 8% or less, and still more preferably 5% or less. The lower limit value of the average spectral transmittance in the wavelength region 360 to 600 nm in the decorative sheet 10A is not particularly limited, but the amount of material that can be actually obtained and the amount that can be added to the actual manufacturing process conditions, and the actual visual observation. In consideration of the desired dark color reproducibility, it is preferably 2%, more preferably 3.5%.

  Spectroscopy at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light at a wavelength of 750 nm in order to make the average spectral absorptance in the visible light region (wavelength region of 360 to 830 nm) higher than 33%. The transmittance is preferably 47% or less, and the spectral transmittance at a wavelength of 800 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light having a wavelength of 800 nm is preferably 37% or less. The spectral transmittance at a wavelength of 750 nm in the decorative sheet 10A is preferably 47% or less, more preferably 45% or less, and still more preferably 40% or less. The lower limit of the spectral transmittance at a wavelength of 750 nm in the decorative sheet 10A is not particularly limited, but is preferably 30%, and more preferably 35%. The spectral transmittance at a wavelength of 800 nm in the decorative sheet 10A is preferably 37% or less, more preferably 35% or less, and still more preferably 30% or less. In addition, the lower limit value of the spectral transmittance at a wavelength of 800 nm in the decorative sheet 10A is not particularly limited, but the amount of material that can be actually obtained and the addition amount that can be adapted to the actual manufacturing process conditions, as well as the actual visual observation Considering the desired dark color reproducibility, it is preferably 20%, more preferably 25%.

  Wavelength measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light having a wavelength of 831 to 2500 nm in order to make the average spectral absorptance in the near infrared region (wavelength range of 830 to 2500 nm) lower than 33% The average spectral transmittance at 831 to 2500 nm is preferably 30% or more, more preferably 33% or more, and still more preferably 36% or more. The upper limit value of the average spectral transmittance of the wavelength 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light of the wavelength 831 to 2500 nm is not particularly limited. In consideration of the amount of addition that can be adapted to the actual manufacturing process conditions and the tolerance of the desired heat shielding property when actually exposed to sunlight, it is preferably 50%, more preferably 40%.

  The average spectral absorptance in the wavelength range 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light in the wavelength range 360 to 2500 nm is 33% or less. Thereby, the decorative sheet 10 </ b> B can exhibit a dark color and can exhibit heat shielding performance. The average spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10B is not particularly limited as long as it is 33% or less, but is preferably 30% or less, more preferably 28% or less, and even more preferably 25% or less. The lower limit value of the average spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10B is not particularly limited, but is preferably 5%, more preferably 8%, and still more preferably 10%.

  The average spectral transmittance at a wavelength of 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light of a wavelength of 360 to 2500 nm is preferably 60% or more, more preferably 65% or more, and even more preferably. Is 70% or more. Thereby, the average spectral absorptance of the wavelength region 360 to 2500 nm in the decorative sheet 10B can be adjusted to 33% or less, and the decorative sheet 10B more effectively exhibits the heat shielding performance based on the near infrared transmission performance. be able to. The upper limit of the average spectral transmittance at a wavelength of 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light having a wavelength of 360 to 2500 nm is not particularly limited, but is preferably 90%, more preferably Is 85%, still more preferably 80%.

  The average spectral transmittance at a wavelength of 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light of a wavelength of 831 to 2500 nm is preferably 75% or more, more preferably 80% or more, and even more preferably. Is 85% or more. Thereby, the decorative sheet 10B can exhibit the thermal insulation performance based on near-infrared transmission performance more effectively. The upper limit value of the average spectral transmittance of wavelengths 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light of wavelengths 831 to 2500 nm is not particularly limited. In consideration of the amount of addition that can be adapted to the actual manufacturing process conditions, as well as the acceptable degree of heat shielding when actually exposed to sunlight, it is preferably 90%.

  The spectral transmittance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with a wavelength of 750 nm is 60% or more, and the surface of the decorative sheet 10B is irradiated with light having a wavelength of 800 nm. The spectral transmittance measured at 800 nm is preferably 70% or more. Thereby, the decorative sheet 10B can exhibit the thermal insulation performance based on near-infrared transmission performance more effectively. The spectral transmittance at a wavelength of 750 nm in the decorative sheet 10B is preferably 60% or more, more preferably 63% or more, and still more preferably 66% or more. The upper limit of the spectral transmittance at a wavelength of 750 nm in the decorative sheet 10B is not particularly limited, but is preferably 90%, more preferably 85%, and still more preferably 80%. The spectral transmittance at a wavelength of 800 nm in the decorative sheet 10B is preferably 70% or more, more preferably 73% or more, and still more preferably 76% or more. The upper limit of the spectral transmittance at a wavelength of 800 nm in the decorative sheet 10B is not particularly limited, but is preferably 90%, more preferably 85%, and still more preferably 80%.

  The average spectral transmittance in the wavelength range 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light in the wavelength range 360 to 600 nm is preferably 8% or less. Thereby, the decorative sheet 10B can exhibit a dark color more effectively. The average spectral transmittance in the wavelength region 360 to 600 nm in the decorative sheet 10B is preferably 8% or less, more preferably 6.5% or less, and still more preferably 5% or less. The lower limit value of the average spectral transmittance in the wavelength region 360 to 600 nm in the decorative sheet 10B is not particularly limited.

  The decorative sheet 10B has a feature that the average spectral transmittance in the wavelength region 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light in the wavelength region 360 to 600 nm is 8% or less, The spectral transmittance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the sheet 10B with a wavelength of 750 nm is 60% or more, and the surface protective layer side surface of the decorative sheet 10B is irradiated with light having a wavelength of 800 nm. The spectral transmittance measured at a wavelength of 800 nm is 70% or more, and the average spectrum of wavelengths from 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light having a wavelength of 831 to 2500 nm. It is preferable to combine the characteristic that the transmittance is 75% or more. Thereby, the decorative sheet 10B can effectively achieve both a dark coloration based on a low spectral transmittance in the visible light region and a heat shielding performance based on a high spectral transmittance in the near infrared region.

  Hereinafter, the decorative sheet 10B is dark when the average spectral absorptance in the wavelength range 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light in the wavelength range 360 to 2500 nm is 33% or less. The reason why the heat shielding performance can be exhibited will be described based on FIG. 3, FIG. 6, and FIG. FIG. 3 is a conceptual diagram illustrating an example of a spectral reflectance curve, a spectral transmittance curve, and a spectral absorptance curve in the wavelength region 360 to 2500 nm in the printed layer 12, and FIG. 6 illustrates the wavelength region 360 as the base sheet 11B. When a base sheet having a high average spectral transmittance of ˜2500 nm or a high average spectral transmittance of wavelength range 831 to 2500 nm is used, a spectral reflectance curve and a spectral transmittance curve in a wavelength range of 360 to 2500 nm in the base sheet 11B FIG. 7 is a conceptual diagram showing an example of a spectral absorptance curve, and FIG. 7 shows a base sheet having a high average spectral transmittance in the wavelength range 360 to 2500 nm or a high average spectral transmittance in the wavelength range 831 to 2500 nm as the base sheet 11B. An example of a spectral absorptance curve in the wavelength range 360 to 2500 nm in the combination of the base sheet 11B and the printed layer 12 when It is a be conceptual diagram.

  Of the light in the wavelength region 360 to 2500 nm irradiated on the surface of the decorative sheet 10B, a part of the light is reflected on the surface of the surface protective layer 14, and the rest is hardly absorbed by the surface protective layer 14. The surface protective layer 14 is transmitted. Of the light having a wavelength range of 360 to 2500 nm transmitted through the surface protective layer 14, a part of the light is reflected by the surface of the transparent resin layer 13, and the remaining part is hardly absorbed by the transparent resin layer 13, and the transparent resin layer 13 is reflected. To Penetrate. Therefore, the spectral absorptance in the wavelength region 360 to 2500 nm in the decorative sheet 10B greatly depends on the spectral absorptance in the wavelength region 360 to 2500 nm in the combination of the base sheet 11B and the printing layer 12.

  Since the printing layer 12 contains an azomethine azo-based black pigment, as shown in FIG. 3, the spectral absorption A in the visible light region (wavelength region 360 to 830 nm) in the printing layer 12 is high, but the spectral reflectance in the visible light region. R and spectral transmittance T are low. Therefore, the spectral absorptance in the visible light region in the combination of the base sheet 11 </ b> B and the printing layer 12 greatly depends on the spectral absorptance A in the visible light region in the printing layer 12.

  Since the printing layer 12 contains an azomethine azo-based black pigment, as shown in FIG. 3, the spectral transmittance T in the near-infrared region (wavelength region exceeding 830 to 2500 nm) in the printing layer 12 is high, but the spectral absorption in the near-infrared region. The rate A and the spectral reflectance R are low. Therefore, the spectral absorptance in the near infrared region in the combination of the base sheet 11B and the printing layer 12 greatly depends on the spectral absorptance in the near infrared region in the base sheet 11B.

  When a base sheet having a high average spectral transmittance in the wavelength region of 360 to 2500 nm or a high average spectral transmittance in the near-infrared region (wavelength range of 830 to 2500 nm) is used as the base sheet 11B, as shown in FIG. In the base sheet 11B, the spectral transmittance T in the near infrared region is high, but the spectral reflectance R and the spectral absorption factor A in the near infrared region are low.

  As described above, the spectral absorptance A in the visible light region in the combination of the base sheet 11B and the printing layer 12 is largely dependent on the spectral absorptance A in the visible light region in the printing layer 12, and the base sheet 11B and the printing layer. The spectral absorptance A in the near infrared region in combination with 12 greatly depends on the spectral absorptivity A in the near infrared region in the base sheet 11B, so that as shown in FIG. In the combination, the spectral absorption factor A in the visible light region (wavelength region 360 to 830 nm) is high, but the spectral absorption factor A in the near infrared region (wavelength region 830 to 2500 nm) is low.

  As described above, the spectral absorption rate in the wavelength region 360 to 2500 nm in the decorative sheet 10B largely depends on the spectral absorption rate in the wavelength range 360 to 2500 nm in the combination of the base sheet 11B and the printing layer 12, and thus the decorative sheet 10B When the average spectral absorptance of the wavelength region 360 to 2500 nm measured by irradiating the surface protective layer side surface with light of the wavelength region 360 to 2500 nm is 33% or less, in the combination of the base sheet 11B and the printing layer 12 The average spectral absorptance in the visible light region (wavelength region 360 to 830 nm) is higher than 33%, and the average spectral absorptance in the near-infrared region (wavelength region 830 to 2500 nm) is lower than 33%. When the average spectral absorption rate in the visible light region in the combination of the base sheet 11B and the print layer 12 is higher than 33%, the decorative sheet 10B can exhibit a dark color, and the base sheet 11B and the print layer 12 When the average spectral absorptance in the near-infrared region in the combination is lower than 33%, the decorative sheet 10B can exhibit heat shielding performance.

  Wavelength measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light in the wavelength range of 360 to 600 nm in order to make the average spectral absorption rate in the visible light range (wavelength range of 360 to 830 nm) higher than 33% The average spectral reflectance in the region 360 to 600 nm is preferably 8% or less, more preferably 6.5% or less, and still more preferably 5% or less. The lower limit value of the average spectral reflectance in the wavelength range 360 to 600 nm in the decorative sheet 10B is not particularly limited, but the amount of material that can be actually obtained and the amount that can be added to the actual manufacturing process conditions, and the actual visual observation was observed. In consideration of the desired dark color reproducibility, it is preferably 3%, more preferably 4%.

  In order to make the average spectral absorptance in the visible light region (wavelength region 360 to 830 nm) higher than 33%, the spectrum of wavelength 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light of wavelength 750 nm The reflectance is preferably 40% or less, and the spectral reflectance at a wavelength of 800 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10A with light having a wavelength of 800 nm is preferably 30% or less. The spectral reflectance at a wavelength of 750 nm in the decorative sheet 10B is preferably 40% or less, more preferably 35% or less, and still more preferably 30% or less. In addition, the lower limit value of the spectral reflectance at a wavelength of 750 nm in the decorative sheet 10B is not particularly limited, but the amount of material that can be actually obtained and the addition amount that can be adapted to the actual manufacturing process conditions, as well as the actual visual observation Considering the desired dark color reproducibility, it is preferably 20%, more preferably 25%. The spectral reflectance at a wavelength of 800 nm in the decorative sheet 10B is preferably 30% or less, more preferably 28% or less, and even more preferably 25% or less. In addition, the lower limit value of the spectral reflectance at a wavelength of 800 nm in the decorative sheet 10B is not particularly limited, but the amount of material that can be actually obtained and the addition amount that can be adapted to the actual manufacturing process conditions, as well as the actual visual observation Considering the desired dark color reproducibility, it is preferably 15%, more preferably 20%.

  Wavelength measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light having a wavelength of 831 to 2500 nm in order to make the average spectral absorptance in the near infrared region (wavelength range of 830 to 2500 nm) lower than 33% The average spectral reflectance at 831 to 2500 nm is preferably 5% or more, more preferably 8% or more, and even more preferably 10% or more. In addition, the upper limit of the average spectral reflectance of the wavelength 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative sheet 10B with light of the wavelength 831 to 2500 nm is not particularly limited. In consideration of the amount of addition that can be adapted to the actual manufacturing process conditions and the tolerance of the desired heat shielding property when actually exposed to sunlight, it is preferably 20%, more preferably 15%.

(Substrate sheet)
The spectral reflectance and spectral transmittance of the base sheet 11A affect the spectral reflectance and spectral transmittance of the decorative sheet 10A, respectively, and consequently affect the spectral absorption rate of the decorative sheet 10A. Therefore, by adjusting the spectral reflectance and / or spectral transmittance of the substrate sheet 11A, the average spectral absorptance in the wavelength region 360 to 2500 nm, the average spectral reflectance in the wavelength region 360 to 2500 nm, and the wavelength region in the decorative sheet 10A. An average spectral reflectance of 360 to 600 nm, a spectral reflectance of a wavelength of 750 nm, a spectral reflectance of a wavelength of 800 nm, and an average spectral reflectance of a wavelength of 831 to 2500 nm can be adjusted.

  The average spectral reflectance in the wavelength region 360 to 2500 nm in the base sheet 11A is preferably 55% or more, more preferably 58% or more, and even more preferably 60% or more. The upper limit of the average spectral reflectance in the wavelength region 360 to 2500 nm in the base sheet 11A is not particularly limited, but is preferably 100%, more preferably 90%, and still more preferably 80%.

  The average spectral reflectance in the wavelength region 360 to 600 nm in the base sheet 11A is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more. The upper limit value of the average spectral reflectance in the wavelength region 360 to 600 nm in the base sheet 11A is not particularly limited, but is preferably 90%, more preferably 85%, and still more preferably 80%.

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

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

  The average spectral reflectance at a wavelength of 831 to 2500 nm in the base sheet 11A is preferably 50% or more, more preferably 53% or more, and even more preferably 55% or more. The upper limit value of the average spectral reflectance at a wavelength of 831 to 2500 nm in the base sheet 11A is not particularly limited, but is preferably 95%, more preferably 93%, and still more preferably 90%.

  The average spectral transmittance in the wavelength region 360 to 2500 nm in the base sheet 11A is preferably 50% or less, more preferably 45% or less, and still more preferably 35% or less. In addition, the lower limit value of the average spectral transmittance in the wavelength region 360 to 2500 nm in the base sheet 11A is not particularly limited, but is preferably 10%, more preferably 15%, and still more preferably 20%.

  The average spectral transmittance in the wavelength region 360 to 600 nm in the base sheet 11A is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. In addition, the lower limit value of the average spectral transmittance in the wavelength region 360 to 600 nm in the base sheet 11A is not particularly limited, but the material that can be actually obtained and the addition amount that can be adapted to the actual manufacturing process conditions, and actually In consideration of the reproducibility of a desired dark color when visually observed, it is preferably 5%, more preferably 8%.

  The spectral transmittance at a wavelength of 750 nm in the base sheet 11A is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The lower limit value of the spectral transmittance at a wavelength of 750 nm in the base sheet 11A is not particularly limited, but is preferably 5%, more preferably 10%.

  The spectral transmittance at a wavelength of 800 nm in the base sheet 11A is preferably 35% or less, more preferably 27.5% or less, and still more preferably 20% or less. The lower limit value of the spectral transmittance at a wavelength of 800 nm in the base sheet 11A is not particularly limited, but is preferably 5%, more preferably 10%.

  The average spectral transmittance at a wavelength of 831 to 2500 nm in the base sheet 11A is preferably 60% or less, more preferably 50% or less, and even more preferably 40% or less. In addition, the lower limit value of the average spectral transmittance at a wavelength of 831 to 2500 nm in the base sheet 11A is not particularly limited, but is preferably 10%, more preferably 20%, and still more preferably 30%.

  The spectral reflectance and spectral transmittance of the base sheet 11A are the type of resin constituting the base sheet 11A, the thickness of the base sheet 11A, and the type of colorant when the base sheet 11A contains a colorant. It can be adjusted by appropriately selecting the amount and the like.

  Examples of the resin constituting the base sheet 11A include a polyester resin, a polyolefin resin, and a vinyl chloride resin. 1 type of resin which comprises the base material sheet 11A may be single, and 2 or more types of combinations may be sufficient as it.

  Examples of the polyester resin constituting the base sheet 11A 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 11A 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 11A is usually 20 to 200 μm, preferably 40 to 150 μm, and more preferably 60 to 100 μm, from the viewpoint of realizing desired spectral reflectance and spectral transmittance in the base sheet 11A.

  The base sheet 11A is preferably a colored resin sheet composed of a colored resin. By using a colored resin sheet as the base sheet 11A, the surface hue of the adherend can be well concealed even when the surface hue of the adherend to which the decorative sheet 10A is attached varies. Excellent design properties can be obtained. Moreover, stability of the color tone of the printing layer 12 provided on the base sheet 11A can be ensured. From the viewpoint of realizing the excellent heat shielding performance of the decorative sheet 10A, 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 11A 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 Pigments or dyes; metallic pigments composed of scaly foils such as aluminum and brass; pearlescent pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate, etc. The selected 1 type can be used individually or in combination of 2 or more types. However, the type and content of the colorant are selected so that the base sheet 11A satisfies the spectral characteristics in the visible light region and the near infrared region as described above. Conceptually speaking, the type and content of the colorant are selected so that characteristics as close as possible to the spectral characteristics shown in the idealized conceptual diagram of FIG.

  In the case where the base sheet 11A contains carbon black (black) as a colorant, from the viewpoint of realizing the excellent heat shielding performance of the decorative sheet 10A, the content of the carbon black is 100 mass of the resin forming the base sheet 11A. 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 of easily absorbing heat, and therefore, when the carbon black is used for the decorative sheet 10A, the decorative sheet 10A easily absorbs heat and the heat shielding performance is lowered.

  When the base sheet 11A contains titanium oxide as a white pigment, the crystal form of the 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 11A is usually based on 100 parts by mass of the resin constituting the base sheet 11A from the viewpoint of realizing the desired spectral reflectance and spectral transmittance in the base sheet 11A. 1 to 70 parts by mass, preferably 1 to 50 parts by mass.

  The spectral transmittance and spectral reflectance of the base sheet 11B affect the spectral transmittance and spectral reflectance of the decorative sheet 10B, respectively, and consequently affect the spectral absorption rate of the decorative sheet 10B. Therefore, by adjusting the spectral transmittance and the spectral reflectance of the base sheet 11B, the average spectral absorptivity in the wavelength region 360 to 2500 nm, the average spectral transmittance in the wavelength region 360 to 2500 nm, and the wavelength region 360 to 360 in the decorative sheet 10B. The average spectral transmittance at 600 nm, the spectral transmittance at a wavelength of 750 nm, the spectral transmittance at a wavelength of 800 nm, and the average spectral transmittance at a wavelength of 831 to 2500 nm can be adjusted.

  The average spectral transmittance in the wavelength region 360 to 2500 nm in the base material sheet 11B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit value of the average spectral transmittance in the wavelength region 360 to 2500 nm in the base sheet 11B is not particularly limited, but is preferably 95%, more preferably 93%, and still more preferably 90%.

  The average spectral transmittance in the wavelength region 360 to 600 nm in the base sheet 11B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit value of the average spectral transmittance in the wavelength region 360 to 600 nm in the base sheet 11B is not particularly limited, but is preferably 97.5%, more preferably 95%, and still more preferably 92.5%.

  The spectral transmittance at a wavelength of 750 nm in the base sheet 11B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit value of the spectral transmittance at a wavelength of 750 nm in the substrate sheet 11B is not particularly limited, but is preferably 97.5%, more preferably 95%.

  The spectral reflectance at a wavelength of 800 nm in the base sheet 11B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit of the spectral reflectance at a wavelength of 800 nm in the base sheet 11B is not particularly limited, but is preferably 97.5%, and more preferably 95%.

  The average spectral transmittance in the wavelength region 831 to 2500 nm in the substrate sheet 11B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit value of the average spectral transmittance in the wavelength region 831 to 2500 nm in the base sheet 11B is not particularly limited, but is preferably 95%, more preferably 93%, and still more preferably 90%.

  The average spectral reflectance in the wavelength region 360 to 2500 nm in the substrate sheet 11B is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. The lower limit value of the average spectral reflectance in the wavelength region 360 to 2500 nm in the base material sheet 11B is not particularly limited, but is preferably 3%, more preferably 5%, and still more preferably 10%.

  The average spectral reflectance in the wavelength region 360 to 600 nm in the substrate sheet 11B is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. In addition, the lower limit value of the average spectral reflectance in the wavelength region 360 to 600 nm in the base sheet 11B is not particularly limited, but is preferably 3%, more preferably 5%, and still more preferably 10%.

  The spectral reflectance at a wavelength of 750 nm in the base sheet 11B is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The lower limit value of the spectral reflectance at a wavelength of 750 nm in the base sheet 11A is not particularly limited, but is preferably 3%, more preferably 5%.

  The spectral reflectance at a wavelength of 800 nm in the base sheet 11B is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. In addition, the lower limit value of the spectral reflectance at a wavelength of 800 nm in the base sheet 11B is not particularly limited, but is preferably 3%, more preferably 5%.

  The average spectral reflectance at a wavelength of 831 to 2500 nm in the base sheet 11B is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. The lower limit value of the average spectral reflectance at a wavelength of 831 to 2500 nm (near infrared region) in the base sheet 11B is not particularly limited, but is preferably 3%, more preferably 5%, and still more preferably 10%.

  The spectral transmittance and spectral reflectance of the base sheet 11B can be adjusted by appropriately selecting the type of resin constituting the base sheet 11B, the thickness of the base sheet 11B, the transparency of the base sheet 11B, and the like. .

  As resin which comprises the base material sheet 11B, a polyester resin, polyolefin resin, etc. are mentioned, for example. 1 type of resin which comprises the base material sheet 11B may be single, and 2 or more types of combinations may be sufficient as it.

  Examples of the polyester resin constituting the base sheet 11B 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 11B 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 11B is usually 20 to 200 μm, preferably 40 to 150 μm, and more preferably 60 to 100 μm from the viewpoint of realizing desired spectral reflectance and spectral transmittance in the base sheet 11B.

  The base sheet 11B is preferably a transparent resin sheet made of a resin that is not colored.

  The base sheet 11A or 11B has an oxidation method or uneven surface on one or both sides in order to enhance interlayer adhesion between the base sheet 11A or 11B and other layers, adhesion to various adherends, or the like. A physical or chemical surface treatment such as law 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 11A or 11B, and each layer.

  The base sheet 11A or 11B 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 base sheet 11A or 11B is usually 1 to 50 parts by mass with respect to 100 parts by mass of the resin forming the base sheet 11A or 11B. The base sheet 11A or 11B 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 azomethine azo black pigment. The printed layer 12 has the effect of concealing the base sheet 11A or 11B in addition to the effect of imparting a dark color to the decorative sheet 10A or 10B and improving the design properties of the decorative sheet 10A or 10B. The printed layer 12 may be partially formed on one surface of the base sheet 11A or 11B so as to be recognized as a pattern, but the entire surface of the decorative sheet 10A or 10B on the surface protective layer side is dark. It is preferable that it is formed in the whole of one surface which the base material sheet 11A or 11B has so that it may be recognized. Of the area of one surface of the base sheet 11A or 11B, the ratio of the area of the region where the printing layer 12 is formed is preferably 50% or more, more preferably 80% or more, and most preferably 100%. is there. Examples of the printing method for forming the printing layer 12 include gravure printing, flexographic printing, silk screen printing, and the like.

  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.

  The printing layer 12 may be composed of only an azomethine azo black pigment or may contain components other than the azomethine azo black pigment. Examples of components other than the azomethine azo-based 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 other than azomethine azo-based black pigments, stabilizers, plasticizers, catalysts, and curing agents. Specific examples of the colorant are the same as the specific examples described above with respect to the colorant contained in the base sheet 11A. The printing layer 12 preferably does not contain carbon black (black). Since carbon black has the property of easily absorbing heat, the use of carbon black in the decorative sheet 10A or 10B makes the decorative sheet 10A or 10B easy to absorb heat, resulting in a decrease in heat shielding performance. It is.

  As printing ink used in order to form printing layer 12, what mixed azomethine azo system black pigment in a binder is mentioned, for example. The printing ink may contain a colorant other than the azomethine azo-based black pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like.

When the printing layer 12 is formed, the amount of printing ink applied per unit area (solid basis) of the surface to which the printing ink is applied (for example, one surface of the base sheet 11A or 11B) From the viewpoint of realizing a desired L ^* value, a ^* value and b ^* value in the sheet 10A or 10B and an average spectral absorptance in a desired wavelength range of 360 to 2500 nm, usually 0.5 to 15 g / m ² , preferably 1 10 to 10 g / m ² , more preferably 3 to 7 g / m ² .

The amount of azomethine azo-based black pigment contained in the printing layer 12, the thickness of the printing layer 12, and the like are the L ^* value, a ^* value and b ^* value of the L ^* a ^* b ^* color system in the decorative sheet 10A or 10B To affect. Therefore, by adjusting the amount of the azomethine azo black pigment contained in the printing layer 12, the thickness of the printing layer 12, and the like, the L ^* value of the L ^* a ^* b ^* color system in the decorative sheet 10A or 10B, a ^* Value and b ^* value can be adjusted.

The amount of the azomethine azo black pigment contained in the printing layer 12 realizes a desired L ^* value, a ^* value and b ^* value in the decorative sheet 10A or 10B, and an average spectral absorptance in a desired wavelength range of 360 to 2500 nm. From a viewpoint, it is 1-100 mass% normally with respect to the solid content total amount contained in the printing layer 12, Preferably it is 10-50 mass%, More preferably, it is 20-40 mass%. The ratio of the azomethine azo black pigment amount to the total solid content contained in the printing ink corresponds to the ratio of the azomethine azo black pigment amount to the total solid content contained in the printing layer 12.

The thickness of the printing layer 12 is usually 0.5 from the viewpoint of realizing a desired L ^* value, a ^* value and b ^* value in the decorative sheet 10A or 10B and an average spectral absorption rate in a desired wavelength range of 360 to 2500 nm. It is -15 micrometers, Preferably it is 1-10 micrometers, More preferably, it is 3-7 micrometers.

(Transparent resin layer)
The transparent resin layer 13 is provided between the printing layer 12 and the surface protective layer 14. 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 13 and / or between the transparent resin layer 13 and the surface protective layer 14, Other layers may be provided.

^L * ^a * ^{b *} color system of ^{L *} value in the transparent resin layer 13, ^{a *} and ^{b *} values are decorative ^L in the sheet 10A or 10B * ^a * ^{b *} color system of ^{L *} value, ^{a *} Affects the value and b ^* value. Accordingly, by adjusting the L ^* value, a ^* value, and b ^* value of the L ^* a ^* b ^* color system in the transparent resin layer 13, the color that corrects the color of the decorative sheet 10A or 10B in the transparent resin layer 13 It can function as a correction layer, and thereby the L ^* value, a ^* value, and b ^* value of the L ^* a ^* b ^* color system in the decorative sheet 10A or 10B can be adjusted. The transparent resin layer 13 also has an effect of protecting the printed layer 12 and improving scratch resistance.

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.

Examples of the resin constituting the transparent resin layer 13 include acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, and vinyl chloride in addition to the specific examples (polyester resin and polyolefin resin) described above with respect to the resin constituting the base sheet 11A or 11B. Examples thereof include resins and vinyl acetate resins. From the viewpoints of achieving desired L ^* values, a ^* values and b ^* values in the transparent resin layer 13, improving molding processability, improving scratch resistance, and the like, 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 11A or 11B and the resin constituting the transparent resin layer 13 are polyolefin resins.

  The transparent resin layer 13 is preferably transparent from the viewpoint of making the printed layer 12 visible more clearly. Here, the transparent includes colorless and transparent as well as colored and translucent. When the transparent resin layer 13 is colored, specific examples of the colorant contained in the transparent resin layer 13 are the same as the specific examples described above with respect to the colorant contained in the base sheet 11A. It is preferable that the transparent resin layer 13 does not contain carbon black (black). Since carbon black has the property of easily absorbing heat, the use of carbon black in the decorative sheet 10A or 10B makes the decorative sheet 10A or 10B easy to absorb heat, resulting in a decrease in heat shielding performance. It is.

The thickness of the transparent resin layer 13 is usually 20 to 130 μm from the viewpoint of realizing a desired L ^* value, a ^* value and b ^* value in the transparent resin layer 13 and an average spectral absorptance in a desired wavelength range of 360 to 2500 nm. The thickness is preferably 30 to 100 μm, more preferably 40 to 90 μm. 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 11A or 11B. 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 10A or 10B, and is a layer that imparts surface characteristics such as scratch resistance, abrasion resistance, and chemical resistance to the decorative sheet 10A or 10B. 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 10A or 10B can be improved. The surface protective layer 14 is preferably transparent from the viewpoint of making the printed layer 12 visible more clearly. Here, the transparent includes colorless and transparent as well as colored and translucent. When the surface protective layer 14 is colored, specific examples of the colorant contained in the surface protective layer 14 are the same as the specific examples described above with respect to the colorant contained in the base sheet 11A. The surface protective layer 14 preferably does not contain carbon black (black). Since carbon black has the property of easily absorbing heat, the use of carbon black in the decorative sheet 10A or 10B makes the decorative sheet 10A or 10B easy to absorb heat, resulting in a decrease in heat shielding performance. It is.

  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 10A or 10B 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 </ b> A or 10 </ b> B can have a primer layer and a back primer layer in any one of the respective layers as necessary in order to improve the adhesion between the respective layers. For example, a decorative member excellent in interlayer adhesion can be obtained by providing a primer layer as a back primer layer on the substrate sheet 11A or 11B side between the adherend and the substrate sheet 11A or 11B. 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 10A or 10B preferably has a concave shape in at least the surface protective layer 14. Since the decorative sheet 10A or 10B has a concave shape, the texture (tactile feeling) is particularly excellent. The concave shape only needs to be present at least in the surface protective layer 14, and there may be a shape reaching the base sheet 11 </ b> A or 11 </ b> B. 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 11A or 11B 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 10A or 10B, 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 10A or 10B is not broken during the concave processing, for example, embossing, and the concave shape is not finished. Excellent texture (tactile sensation) can be obtained, and as a result, excellent design can be 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 10A or 10B as an example. The decorative sheet 10A or 10B includes, for example, (a) a step of providing the printing layer 12 on the base sheet 11A or 11B, (b) a step of providing the transparent resin layer 13 on the printing layer 12, and (c) the transparent resin layer 13 It can be manufactured by applying the curable resin composition on the top and curing to form the surface protective layer 14 and sequentially producing the decorative sheet 10A or 10B.

  Step (a) is a step of providing the printing layer 12 on the base sheet 11A or 11B. The printing layer 12 is formed by applying and drying printing ink used for forming the printing layer 12 on the base sheet 11A or 11B. 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.

  Moreover, what is necessary is just to surface-treat before apply | coating the printing ink used for formation of the printing layer 12, when surface-treating to the base material sheet 11A or 11B. Even when a primer layer is provided between the base material sheet 11A or 11B and the printing layer 12, it may be provided before applying the printing ink used for forming the printing layer 12, and the base material sheet 11A or 11B. When the back primer layer is provided on the surface (back surface) opposite to the surface on which the print layer 12 is provided, it may be provided when the printing ink used for forming the print 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 a dark color and can exhibit heat shielding performance, for example, in a form laminated with an adherend, a wall, a ceiling, a floor, a balcony, a veranda Surface decorative boards for interior or exterior members of buildings such as window frames, doors, handrails, skirting boards, edges, moldings, etc .; kitchen, furniture, light electrical appliances, OA equipment, etc. Surface decorative panel for cabinets; surface decorative sheet for interior or exterior of vehicles; surface decorative sheet for communication equipment such as mobile phones; surface decorative sheet for paved roads such as roadways and sidewalks (stacked on the paved surface of paved roads) It can be suitably used as a decorative member for various uses such as a surface decorative plate for imparting colors, patterns, and the like.

[Decorative material]
Hereinafter, the decorative member according to the first embodiment and the second embodiment of the present invention will be described with reference to FIGS. 8 and 9. FIG. 8 is a side view schematically showing the configuration of the decorative member 20A according to the first embodiment of the present invention, and FIG. 9 schematically shows the configuration of the decorative member 20B according to the second embodiment of the present invention. FIG.

  As shown in FIG. 8, the decorative member 20A according to the first embodiment of the present invention is such that the adherend 21A and the decorative sheet 10A are opposed to the adherent 21A and the base sheet 11A of the decorative sheet 10A. Prepare for.

  As shown in FIG. 9, in the decorative member 20B according to the second embodiment of the present invention, the adherend 21B and the decorative sheet 10B are opposed to the adherent 21B and the base sheet 11B of the decorative sheet 10B. Prepare for.

  The average spectral reflectance at a wavelength of 360 to 2500 nm measured by irradiating the surface of the decorative member 20A or 20B with light having a wavelength of 360 to 2500 nm is preferably 40% or more, more preferably 45% or more, More preferably, it is 50% or more. Thereby, decorative member 20A or 20B can exhibit the thermal insulation performance based on near-infrared reflective performance more effectively. The upper limit of the average spectral reflectance at a wavelength of 360 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative member 20A or 20B with light of a wavelength of 360 to 2500 nm is not particularly limited, but preferably 90%, More preferably, it is 85%, and still more preferably 80%.

  The average spectral reflectance at a wavelength of 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative member 20A or 20B with light of a wavelength of 831 to 2500 nm is preferably 50% or more, more preferably 55% or more, and further More preferably, it is 60% or more. Thereby, decorative member 20A or 20B can exhibit the thermal insulation performance based on near-infrared reflective performance more effectively. The upper limit value of the average spectral reflectance of the wavelength 831 to 2500 nm measured by irradiating the surface protective layer side surface of the decorative member 20A or 20B with light of the wavelength 831 to 2500 nm is not particularly limited, but preferably 90%, More preferably, it is 85%, and still more preferably 80%.

  The spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative member 20A or 20B with light having a wavelength of 750 nm is 55% or more, and the surface protective layer side surface of the decorative member 20A or 20B has a wavelength of 800 nm. The spectral reflectance at a wavelength of 800 nm measured by irradiating the light is preferably 70% or more. Thereby, decorative member 20A or 20B can exhibit the thermal insulation performance based on near-infrared reflective performance more effectively. The spectral reflectance at a wavelength of 750 nm in the decorative member 20A or 20B is preferably 55% or more, more preferably 60% or more, still more preferably 65% or more, and still more preferably 70% or more. The upper limit of the spectral reflectance at a wavelength of 750 nm in the decorative member 20A or 20B is not particularly limited, but is preferably 95%, more preferably 90%. The spectral reflectance at a wavelength of 800 nm in the decorative member 20A or 20B is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more. The upper limit of the spectral reflectance at a wavelength of 800 nm in the decorative member 20A or 20B is not particularly limited, but is preferably 98%, more preferably 95%, and still more preferably 90%.

  It is preferable that the average spectral reflectance in the wavelength range 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative member 20A or 20B with light in the wavelength range 360 to 600 nm is 10% or less. Thereby, the decorative member 20A or 20B can exhibit a dark color more effectively. The average spectral reflectance in the wavelength region 360 to 600 nm in the decorative member 20A or 20B is preferably 8% or less, more preferably 6% or less, and still more preferably 4% or less. The lower limit value of the average spectral reflectance in the wavelength region 360 to 600 nm in the decorative sheet 10A is not particularly limited.

(Substrate)
Examples of the adherend 21A include plate materials such as flat plates and curved plates of various materials, 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 21A may be appropriately selected from the above according to the intended use, such as walls, ceilings, floors and other building interior and exterior members, window frames, doors, handrails, skirting boards, surrounding edges, malls, etc. When using a joinery, a wood member, a metal member, a resin member, or a combination of these is preferable.

  As the adherend 21B, it is preferable to use an adherend having a high average spectral reflectance in the near infrared region (wavelength range of more than 830 to 2500 nm). Since the spectral transmittance in the near-infrared region of the base material sheet 11B is high, if the average spectral reflectance in the near-infrared region (wavelength range of 830 to 2500 nm) of the adherend 21B is low, the heat shielding performance of the decorative member 20B is poor. On the other hand, if the average spectral reflectance of the near-infrared region (wavelength range 830 to 2500 nm) of the adherend 21B is high, the decorative member 20B exhibits a heat shielding performance based on the near-infrared reflection performance. be able to. The average spectral reflectance in the wavelength region 831 to 2500 nm in the adherend 21B is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more. The upper limit value of the average spectral reflectance in the wavelength region 831 to 2500 nm in the adherend 21B is not particularly limited, but is preferably 100%, more preferably 95%, and still more preferably 90%. The average spectral reflectance in the wavelength range 831 to 2500 nm in the adherend is measured in the same manner as the average spectral reflectance in the wavelength range 831 to 2500 nm in the base material sheet.

  The spectral reflectance of the adherend 21B can be adjusted, for example, by coating the surface of the member exemplified by the adherend 21A with a colorant. Further, when the adherend B is made of resin, it is adjusted by appropriately selecting the type of resin, the thickness of the adherend 21B, the type and amount of the colorant contained in the adherend 21B, and the like. be able to.

  The colorant may be appropriately selected depending on the application. For example, the adherend 21B can be colored colored or colored and opaque. In general, from the viewpoint of concealing the surface of the adherend 21B, it is preferably colored and opaque. Specific examples of the colorant used for the adherend 21B are the same as the specific examples described above with respect to the colorant contained in the base sheet 11A. From the viewpoint of realizing the excellent heat shielding performance of the decorative member 20B, the adherend 21B is preferably colored white (that is, contains a white pigment or is coated with a white pigment).

  What is necessary is just to select the thickness of the to-be-adhered material 21A or 21B 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 20A or 20B has an adhesive layer 22 between the adherend 21A and the decorative sheet 10A or between the adherend 21B and the decorative sheet 10B. Although the adhesive layer 22 can be omitted, in order to obtain excellent adhesion, the adherend 21A and the decorative sheet 10A or the adherend 21B and the decorative sheet 10B are bonded together via the adhesive layer 22. Is preferred.

  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 this invention, the manufacturing method is demonstrated taking the decorative member 20A or 20B as an example. The decorative member 20A or 20B includes the decorative sheet 10A and the adherend 21A or the decorative sheet 10B and the adherend 21B. (D) The base sheet 11A and the adherend 21A of the decorative sheet 10A or the decorative sheet It can be manufactured through a process of laminating the 10B base sheet 11B and the adherend 21B facing each other.

  As a method of laminating the adherend 21A and the decorative sheet 10A, or the adherend 21B and the decorative sheet 10B, for example, the decorative sheet 10A or 10B is a plate-shaped adherend with an adhesive interposed therebetween. A laminating method of laminating by pressing with a pressure roller, a plurality of side surfaces constituting the adherend 21A or 21B by a plurality of different rollers while supplying the decorative sheet 10A or 10B with an adhesive interposed therebetween Next, the decorative sheet 10A or 10B is sequentially laminated with pressure bonding, and heated with a heater through a silicone rubber sheet until the decorative sheet 10A or 10B fixed to the fixed frame softens to a predetermined temperature. Then, press the vacuum molding die against the heated and softened decorative sheet 10A or 10B, and at the same time suck the air from the vacuum molding die with a vacuum pump etc. Vacuum molding or the like bets 10A or 10B to firmly close contact with the vacuum molding die are preferably exemplified.

  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 further arbitrarily cut and subjected to optional decoration such as grooving or chamfering on the surface or 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 parts for exterior frames; window frames, doors, door frames and other fittings, handrails, skirting boards, around Surface decorative plates such as rims, malls, etc., cabinets, fences, etc .; surface decorative plates for cabinets such as kitchen equipment, furniture, light electrical appliances, OA equipment; surface decorative plates for interior or exterior of vehicles; mobile phones, etc. It can be used for a surface decorative board of a communication device; a surface decorative board for a paved road such as a roadway and a sidewalk (a surface decorative board for providing a color, a pattern, etc. 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]
1. Preparation of Base Material Sheet A polypropylene (PP) resin sheet having both surfaces subjected to corona discharge treatment was prepared as the base material sheet S1. This PP resin sheet is a colored resin sheet (thickness: 60 μm) colored white containing only 10 parts by mass of titanium oxide as a pigment with respect to 100 parts by mass of PP resin.

  In a state where the base sheet S1 exists alone (that is, a state where no layers are laminated on both surfaces of the base sheet S1), an average spectral reflectance (%) in the wavelength region 360 to 2500 nm in the base sheet S1. Was measured. The average spectral reflectance (%) in the wavelength range of 360 to 2500 nm is obtained by changing the wavelength by 1 nm from the wavelength of 360 nm to the wavelength of 2500 nm while changing each wavelength (that is, wavelengths of 360 nm, 361 nm, 362 nm,..., 2498 nm, 2499 nm, 2500 nm). ) Was measured, and the sum of the measured 2141 spectral reflectances (%) was divided by 2141. Spectral reflectivity (%) of each wavelength is measured by using a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, and the light of each wavelength is incident on the surface of the base sheet S1. Irradiation was performed at 5 degrees (the normal direction of the surface of the base sheet was set to 0 degree), and the ratio was measured as a ratio of the total reflected light flux to the parallel incident light flux (that is, the total light reflectance). The method for measuring the total light reflectance was based on JIS K 7375: 2008.

  In a state where the base sheet S1 exists alone (that is, a state where no layers are laminated on both surfaces of the base sheet S1), an average spectral transmittance (%) in the wavelength region 360 to 2500 nm in the base sheet S1. Was measured. The average spectral transmittance (%) in the wavelength range 360 to 2500 nm is obtained by changing the wavelength by 1 nm from the wavelength 360 nm to the wavelength 2500 nm, while changing the wavelength (that is, wavelengths 360 nm, 361 nm, 362 nm,..., 2498 nm, 2499 nm, 2500 nm). ) Was measured and the sum of the measured 2141 spectral transmittances was divided by 2141. Spectral transmittance (%) of each wavelength uses a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, and the light of each wavelength is incident on the surface of the base sheet S1. Irradiation was performed at 0 degree (the normal direction of the surface of the substrate sheet was 0 degree), and the ratio was measured as the ratio of the total transmitted light beam to the parallel incident light beam (that is, the total light transmittance). The measuring method of the total light transmittance was based on JIS K 7375: 2008.

FIG. 10 shows a spectral reflectance curve and a spectral transmittance curve in the wavelength region 360 to 2500 nm in the base sheet S1.
In the base sheet S1, the average spectral reflectance in the wavelength region 360 to 2500 nm is 69.3%, the average spectral reflectance in the wavelength region 360 to 600 nm is 91.7%, the spectral reflectance in the wavelength 750 nm is 93.8%, and the wavelength The spectral reflectance at 800 nm was 93.6%, and the average spectral reflectance in the near infrared region (wavelength region 831 to 2500 nm) was 66.8%.
In the base sheet S1, the average spectral transmittance in the wavelength region 360 to 2500 nm is 32.0%, the average spectral transmittance in the wavelength region 360 to 600 nm is 7.6%, the spectral transmittance in the wavelength 750 nm is 16.6%, and the wavelength The spectral transmittance at 800 nm was 18.17%, and the average spectral transmittance in the near infrared region (wavelength region 831 to 2500 nm) was 39.0%.

2. Manufacture and evaluation of decorative sheet (1) Formation of printing layer As printing ink, azomethine azo black pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) having a two-component curable acrylic-urethane resin as a binder and an average particle size of 0.2 μm A printing ink containing 40% by mass of “Chromofine Black A-1103”) based on solid content was prepared.
Printing ink is applied to the entire surface of one side of the substrate sheet S1 by a gravure printing method (application amount: 5 g / m ² on a solid basis) and cured to form a printed layer (thickness after curing: 4 μm). did. The formed printing layer is a printing layer having a full picture pattern in which the area occupied by the area of the printing layer formed on the one surface of the base sheet S1 is 100%. is there.

(2) 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). .

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

(4) 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).

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. For the L ^* a ^* b ^* color system, the L ^* value, a ^* value, and b ^* value are measured using a spectrocolorimeter (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the incident angle is 10 on the surface of the transparent resin layer. Light (D65 light source) was irradiated at a degree (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.

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

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

(7) 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 the decorative sheet of Example 1 was obtained.

(8) Evaluation and measurement concerning decorative sheet The following evaluation and measurement were performed on the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. In addition, FIG. 12 shows spectral reflectance and spectral transmittance in the wavelength range of 360 to 2500 nm in the decorative sheet of Example 1.

[Evaluation of dark color of decorative sheet]
The decorative sheet was visually observed from the surface protective layer side, and the dark color exhibited by the decorative sheet was evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: The dark color exhibited by the decorative sheet is not reddish.
B: The dark color exhibited by the decorative sheet is reddish.

[Measurement of L ^* a ^* b ^* color system L ^* value, a ^* value and b ^* value in decorative sheet]
The L ^* a ^* b ^* color system L ^* value, a ^* value, and b ^* value in the decorative sheet are measured using a spectrocolorimeter (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.). The side surface was irradiated with light (D65 light source) at an incident angle of 10 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). .

[Measurement of average spectral absorptance in wavelength range 360 to 2500 nm of decorative sheet]
The average spectral absorptance (%) in the wavelength region 360 to 2500 nm in the decorative sheet is expressed by the formula: average spectral absorptance (%) in the wavelength region 360 to 2500 nm = 100 (%) − average spectral reflectance in the wavelength region 360 to 2500 nm ( %) -Calculated based on the average spectral transmittance (%) in the wavelength range of 360 to 2500 nm.

  The average spectral reflectance (%) in the wavelength range of 360 to 2500 nm in the decorative sheet is obtained by changing the wavelength by 1 nm from the wavelength of 360 nm to the wavelength of 2500 nm while changing each wavelength (that is, wavelengths of 360 nm, 361 nm, 362 nm,..., 2498 nm, The spectral reflectance (%) of 2499 nm and 2500 nm) was measured, and the sum of the measured 2141 spectral reflectances was divided by 2141. 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.

  The average spectral transmittance (%) in the wavelength region 360 to 2500 nm in the decorative sheet is obtained by changing each wavelength by 1 nm from a wavelength of 360 nm to a wavelength of 2500 nm (that is, wavelengths 360 nm, 361 nm, 362 nm, ... 2498 nm, (2499 nm, 2500 nm) was measured, and the sum of the measured 2141 spectral transmittances was divided by 2141. Spectral transmittance (%) of each wavelength is measured using a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004, and the incident angle is 0 degree on the surface protective layer side surface of the decorative sheet ( Light of each wavelength was irradiated at a normal direction of the surface of the decorative sheet of 0 degree), and the ratio was measured as the ratio of the total transmitted light beam to the parallel incident light beam (that is, the total light transmittance). The measuring method of the total light transmittance was based on JIS K 7375: 2008. In addition, the spectral transmittance (%) of each wavelength was measured in a state where no layers were laminated on both sides of the decorative sheet.

[Measurement of average spectral absorptance of wavelength range 360 to 830 nm in decorative sheet]
The average spectral absorptance (%) in the wavelength region 360 to 830 nm in the decorative sheet is expressed by the formula: average spectral absorptance (%) in the wavelength region 360 to 830 nm = 100 (%) − average spectral reflectance in the wavelength region 360 to 830 nm ( %)-Calculated based on the average spectral transmittance (%) in the wavelength range of 360-830 nm.

  The average spectral reflectance (%) in the wavelength range of 360 to 830 nm in the decorative sheet is obtained by changing each wavelength by 1 nm from a wavelength of 360 nm to a wavelength of 830 nm, that is, each wavelength (that is, wavelengths of 360 nm, 361 nm, 362 nm,... 828 nm, The spectral absorptance (%) of 829 nm and 830 nm) was measured, and the sum of the measured 471 spectral absorptances was divided by 471. The method for measuring the spectral reflectance (%) at each wavelength is as described above.

  The average spectral transmittance (%) in the wavelength range of 360 to 830 nm in the decorative sheet is obtained by changing the wavelength by 1 nm from the wavelength of 360 nm to the wavelength of 830 nm while changing each wavelength (that is, wavelengths of 360 nm, 361 nm, 362 nm,... 828 nm, 829 nm, 830 nm) was measured, and the sum of the measured 471 spectral transmittances was divided by 471. The method for measuring the spectral transmittance (%) at each wavelength is as described above.

[Measurement of average spectral absorptance in wavelength range 831 to 2500 nm in decorative sheet]
The average spectral absorptance (%) in the wavelength range 831 to 2500 nm in the decorative sheet is expressed by the formula: average spectral absorptance (%) in the wavelength range 831 to 2500 nm = 100 (%) − average spectral reflectance in the wavelength range 831 to 2500 nm ( %) — Calculated based on the average spectral transmittance (%) in the wavelength range 831 to 2500 nm.

  The average spectral reflectance (%) in the wavelength region 831 to 2500 nm in the decorative sheet is changed from 183 nm to 8500 nm while the wavelength is changed by 1 nm from each wavelength (ie, 831 nm, 832 nm, 833 nm,..., 2498 nm, The spectral absorptance (%) of 2499 nm and 2500 nm) was measured, and the sum of the measured 1670 spectral absorptances was divided by 1670. The method for measuring the spectral reflectance (%) at each wavelength is as described above.

  The average spectral transmittance (%) in the wavelength region 831 to 2500 nm in the decorative sheet is changed from 1 to 360 nm each wavelength from 360 nm to 830 nm, while each wavelength (i.e., 831 nm, 832 nm, 833 nm, ... 2498 nm, The spectral transmittance (%) of 2499 nm and 2500 nm) was measured, and the sum of the measured 1670 spectral transmittances was divided by 1670. The method for measuring the spectral transmittance (%) at each wavelength is as described above.

[Measurement of Average Spectral Reflectance of Wavelength Range of 360 to 600 nm in Cosmetic Sheet]
The average spectral reflectance (%) in the wavelength range of 360 to 600 nm in the decorative sheet is obtained by changing the wavelength by 1 nm from the wavelength of 360 nm to the wavelength of 600 nm while changing each wavelength (that is, wavelengths of 360 nm, 361 nm, 362 nm,... 598 nm, 599 nm, 600 nm) was measured, and the sum of the measured 241 spectral reflectances was divided by 241. The method for measuring the spectral reflectance of each wavelength is as described above.

[Measurement of spectral reflectance of decorative sheet at wavelength of 750 nm or wavelength of 800 nm]
The spectral reflectance (%) at a wavelength of 750 nm or 800 nm in the decorative sheet is a spectrophotometer (V-670 manufactured by JASCO Corporation) in accordance with JIS K 0115: 2004. Is irradiated with light having a wavelength of 750 nm or 800 nm at an incident angle of 5 degrees (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 reflectance). did. 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.

[Measurement of average spectral reflectance in wavelength range 831 to 2500 nm of decorative sheet]
The average spectral reflectance (%) in the wavelength region 831 to 2500 nm in the decorative sheet is changed from 183 nm to 8500 nm while the wavelength is changed by 1 nm from each wavelength (ie, 831 nm, 832 nm, 833 nm,..., 2498 nm, The spectral reflectance (%) of 2499 nm and 2500 nm) was measured, and the sum of the measured 1670 spectral reflectances was divided by 1670. The method for measuring the spectral reflectance (%) at each wavelength is as described above.

[Measurement of average spectral transmittance in wavelength range 360 to 600 nm of decorative sheet]
The average spectral transmittance (%) in the wavelength range of 360 to 600 nm in the decorative sheet is obtained by changing each wavelength by 1 nm from a wavelength of 360 nm to a wavelength of 600 nm (that is, wavelengths of 360 nm, 361 nm, 362 nm,... 598 nm, 599 nm, 600 nm) is measured, and the sum of the measured 241 spectral transmittances is divided by 241. The method for measuring the spectral transmittance (%) at each wavelength is as described above.

[Measurement of spectral transmittance at wavelength of 750 nm or wavelength of 800 nm in decorative sheet]
The spectral transmittance (%) at a wavelength of 750 nm or 800 nm in the decorative sheet is a spectrophotometer (V-670 manufactured by JASCO Corporation) conforming to JIS K 0115: 2004. Is irradiated with light having a wavelength of 750 nm or a wavelength of 800 nm at an incident angle of 0 degree (the normal direction of the surface of the decorative sheet is 0 degree), and measured as a ratio of a total transmitted light beam to a parallel incident light beam (that is, a total light transmittance). did. The measuring method of the total light transmittance was based on JIS K 7375: 2008. In addition, the spectral transmittance (%) of each wavelength was measured in a state where no layers were laminated on both sides of the decorative sheet.

[Measurement of average spectral transmittance in wavelength range 831 to 2500 nm of decorative sheet]
The average spectral transmittance (%) in the wavelength range 831 to 2500 nm in the decorative sheet is 1 nm by changing the wavelength from 831 nm to 2500 nm while changing each wavelength (ie, wavelengths 831 nm, 832 nm, 833 nm,..., 2498 nm, The spectral transmittance (%) of 2499 nm and 2500 nm) was measured, and the sum of the measured 1670 spectral transmittances was divided by 1670. The method for measuring the spectral transmittance (%) at each wavelength is as described above.

[Example 2]
1. Preparation of Base Material Sheet A polypropylene (PP) resin sheet having both surfaces subjected to corona discharge treatment was prepared as the base material sheet S2. This PP resin sheet is a colored resin sheet (thickness: 60 μm) colored white, containing 7 parts by mass of titanium oxide as a pigment with respect to 100 parts by mass of PP resin.

  In the state where the base sheet S2 exists alone (that is, in a state where no layers are laminated on both surfaces of the base sheet S2), the average spectral reflectance (%) in the wavelength region 360 to 2500 nm in the base sheet S2. In addition, an average spectral transmittance (%) in a wavelength range of 360 to 2500 nm was measured. The measuring method is the same as that of the base sheet S1.

A spectral reflectance curve and a spectral transmittance curve in the wavelength region 360 to 2500 nm in the base material sheet S2 are shown in FIG.
In the base sheet S2, the average spectral reflectance in the wavelength region 360 to 2500 nm is 63.3%, the average spectral reflectance in the wavelength region 360 to 600 nm is 71.9%, the spectral reflectance in the wavelength 750 nm is 88.60%, and the wavelength The spectral reflectance at 800 nm was 88.58%, and the average spectral reflectance in the near infrared region (wavelength region 831 to 2500 nm) was 60.8%.
In the base sheet S2, the average spectral transmittance in the wavelength region 360 to 2500 nm is 46.4%, the average spectral transmittance in the wavelength region 360 to 600 nm is 13.1%, the spectral transmittance in the wavelength 750 nm is 28.98%, the wavelength The spectral transmittance at 800 nm was 31.11%, and the average spectral transmittance in the near infrared region (wavelength range 831 to 2500 nm) was 55.5%.

2. Manufacture of decorative sheet and evaluation and measurement on decorative sheet A decorative sheet of Example 2 was obtained by performing the same operation as in Example 1 except that the base sheet S2 was used instead of the base sheet S1. The decorative sheet of Example 2 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. FIG. 13 shows the spectral reflectance and spectral transmittance of the decorative sheet of Example 2 in the wavelength range of 360 to 2500 nm.

Example 3
A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the amount of the azomethine azo black pigment contained in the printing ink was changed to 11% by mass based on the solid content. The decorative sheet of Example 3 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. FIG. 14 shows the spectral reflectance and spectral transmittance in the wavelength range 360 to 2500 nm of the decorative sheet of Example 3.

Example 4
A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that the amount of the azomethine azo black pigment contained in the printing ink was changed to 26% by mass based on the solid content. The decorative sheet of Example 4 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. FIG. 15 shows the spectral reflectance and spectral transmittance in the wavelength range of 360 to 2500 nm in the decorative sheet of Example 4.

Example 5
A decorative sheet of Example 5 was obtained in the same manner as in Example 1 except that the amount of the azomethine azo black pigment contained in the printing ink was changed to 53% by mass based on the solid content. The decorative sheet of Example 5 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. FIG. 16 shows the spectral reflectance and spectral transmittance of the decorative sheet of Example 5 in the wavelength range of 360 to 2500 nm.

Example 6
1. Preparation of Base Sheet A polyethylene terephthalate (PET) resin sheet having both surfaces subjected to corona discharge treatment was prepared as the base sheet S3. This PET resin sheet is a colorless and transparent resin sheet (thickness: 60 μm).

  In the state where the base sheet S3 exists alone (that is, in a state where no layers are laminated on both sides of the base sheet S3), the average spectral transmittance (%) in the wavelength region 360 to 2500 nm in the base sheet S3. Was measured. The measuring method is the same as that of the base sheet S1.

  In the base sheet S3, the average spectral transmittance in the wavelength region 360 to 2500 nm is 88.1%, the average spectral transmittance in the wavelength region 360 to 600 nm is 87.0%, and the average spectrum in the near infrared region (wavelength region 831 to 2500 nm). The transmittance was 88.2%.

2. Manufacture of decorative sheet and evaluation and measurement on decorative sheet The point that the base sheet S3 was used instead of the base sheet S1 and the amount of azomethine azo black pigment contained in the printing ink was 53% by mass based on the solid content Except for the changed points, the same operation as in Example 1 was performed to obtain a decorative sheet of Example 6. The decorative sheet of Example 6 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 2. FIG. 17 shows the spectral reflectance and spectral transmittance in the wavelength range 360 to 2500 nm of the decorative sheet of Example 6.

[Comparative Example 1]
Except that the amount of the azomethine azo black pigment contained in the printing ink was changed to 20% by mass based on the solid content and the thickness after curing of the printing layer was changed to 2 μm, the same as in Example 1. The operation was performed to obtain a decorative sheet of Comparative Example 1. The decorative sheet of Comparative Example 1 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 3. FIG. 18 shows the spectral reflectance and spectral transmittance of the decorative sheet of Comparative Example 1 in the wavelength range of 360 to 2500 nm.

[Comparative Example 2]
Except that the amount of the azomethine azo black pigment contained in the printing ink was changed to 55% by mass based on the solid content, and the thickness after curing of the printing layer was changed to 2 μm, the same as in Example 1. Operation was performed to obtain a decorative sheet of Comparative Example 2. The decorative sheet of Comparative Example 2 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 3. FIG. 19 shows the spectral reflectance and spectral transmittance of the decorative sheet of Comparative Example 2 in the wavelength range of 360 to 2500 nm.

[Comparative Example 3]
Carbon black was used in place of the azomethine azo black pigment contained in the printing ink, the amount of carbon black contained in the printing ink was changed to 33% by mass based on the solid content, and after the printing layer was cured The decorative sheet of Comparative Example 3 was obtained by performing the same operation as in Example 1 except that the thickness was changed to 2 μm. The decorative sheet of Comparative Example 3 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 3. FIG. 20 shows the spectral reflectance and spectral transmittance of the decorative sheet of Comparative Example 3 in the wavelength range of 360 to 2500 nm.

[Comparative Example 4]
In place of the azomethine azo black pigment contained in the printing ink, Arctic Black411A (Fe-Cr, manufactured by Shepherd Color Japan) was used, and the amount of Fe-Cr contained in the printing ink was changed to 65% by mass based on the solid content. The decorative sheet of Comparative Example 4 was obtained by performing the same operation as in Example 1 except that the thickness of the printed layer was changed to 5 μm. The decorative sheet of Comparative Example 4 was evaluated and measured in the same manner as the decorative sheet of Example 1. The results of evaluation and measurement are shown in Table 3. FIG. 21 shows the spectral reflectance and spectral transmittance of the decorative sheet of Comparative Example 4 in the wavelength range of 360 to 2500 nm.

As shown in Table 2, the decorative sheets of Examples 1 to 6 using an azomethine azo pigment as a black pigment in the printed layer have an average spectral absorption of 33% or less in a wavelength range of 360 to 2500 nm. The average spectral absorptance in the visible light region (wavelength region 360 to 830 nm) is higher than 33%, and the average spectral absorptance in the near infrared region (wavelength region 831 to 2500 nm) is lower than 33%. . The decorative sheets of Examples 1 to 6 can exhibit a dark color when the average spectral absorptance in the visible light region is higher than 33%, and the average spectral absorptance in the near infrared region is lower than 33%. Heat shielding performance can be demonstrated. Further, as shown in Table 2, the decorative sheets of Examples 1 to 6 have L ^* values, a ^* values and b ^* values of L ^* a ^* b ^* color system of L ^* values: 30 or less, a ^* Value: 0 or more and 2.5 or less, and b ^* Value: -3 or more and 0.5 or less. As a result, the dark color visually evaluated is A (the dark color exhibited by the decorative sheet is not reddish) ).

  As shown in Table 2, in the decorative sheets of Examples 1 to 5, when the average spectral reflectance in the wavelength range 360 to 2500 nm is 25% or more, the average spectral absorptance in the wavelength range 360 to 2500 nm of 33% or less is obtained. Is realized.

  As shown in Table 2, the decorative sheets of Examples 1 to 5 have an average spectral reflectance of 10% or less in the wavelength range of 360 to 600 nm, a spectral reflectance of 750 nm of 50% or more, and a spectral reflectance of 800 nm. The average spectral reflectance in the wavelength region of 831 to 2500 nm is 30% or more. Therefore, the spectral reflectances of the decorative sheets of Examples 1 to 5 have a steep rise in the wavelength range of 600 to 800 nm, and the decorative sheets of Examples 1 to 5 are dark colors based on low spectral reflectances in the visible light range. And the display of the heat shielding performance based on the high spectral reflectance in the near-infrared region (wavelength range of 830 to 2500 nm) can be more effectively achieved.

  As shown in Table 2, in the decorative sheet of Example 6, when the average spectral transmittance in the wavelength range 360 to 2500 nm is 60% or more, the average spectral absorption rate in the wavelength range 360 to 2500 nm of 33% or less is realized. Has been.

  As shown in Table 2, the decorative sheet of Example 6 has an average spectral transmittance of 8% or less in a wavelength range of 360 to 600 nm, a spectral transmittance of a wavelength of 750 nm of 60% or more, and a spectral transmittance of a wavelength of 800 nm of 70%. In addition, the average spectral transmittance at a wavelength of 831 to 2500 nm is 75% or more. Thereby, the decorative sheet of Example 6 effectively balances the dark coloration based on the low spectral transmittance in the visible light region and the heat shielding performance based on the high spectral transmittance in the near infrared region. Can do.

As shown in Table 3, the decorative sheets of Comparative Examples 1 and 2 using an azomethine azo pigment as a black pigment in the printed layer have an average spectral absorption of 33% or less in a wavelength range of 360 to 2500 nm. The average spectral absorptance in the visible light region (wavelength region 360 to 830 nm) is higher than 33%, and the average spectral absorptance in the near infrared region (wavelength region 831 to 2500 nm) is lower than 33%. . However, the decorative sheets of Comparative Examples 1 and 2 have L ^* value: 30 or less, a ^* value: 0 or more and 2.5 or less, and b ^* value: -3 or more and 0.5 or less. Thus, the evaluation of the dark color visually is B (the dark color exhibited by the decorative sheet is reddish).

  As shown in Table 3, the decorative sheet of Comparative Example 3 using carbon black as the black pigment in the printed layer has an average spectral absorptance far exceeding 33% in the wavelength range of 360 to 2500 nm. The average spectral absorptance in the near infrared region (wavelength region 831 to 2500 nm) far exceeds 33%. Therefore, the decorative sheet of Comparative Example 3 does not have sufficient heat shielding performance.

  As shown in Table 3, the decorative sheet of Comparative Example 4 using Fe—Cr as the black pigment in the printed layer has a visible light range although the average spectral absorptance in the wavelength range of 360 to 2500 nm exceeds 33%. The average spectral absorptance in the wavelength range 360 to 830 nm is higher than 33%, and the average spectral absorptance in the near-infrared range (wavelength range 831 to 2500 nm) is lower than 33%. However, as shown in Table 3, the decorative sheet of Comparative Example 4 has a spectral reflectance at a wavelength of 750 nm far below 50% and a spectral reflectance at a wavelength of 800 nm far below 60%. Therefore, the spectral reflectance of the decorative sheet of Comparative Example 4 does not have a sharp rise in the wavelength range of 600 to 800 nm, and the decorative sheet of Comparative Example 4 has a dark coloration based on a low spectral reflectance in the visible light range. In addition, it is difficult to more effectively achieve both thermal insulation performance based on a high spectral reflectance in the near-infrared region (wavelength range from 830 to 2500 nm).

10A, 10B ... decorative sheet 11A, 11B ... base sheet 12 ... printed layer 13 ... resin layer 14 ... surface protective layer 20A, 20B ... decorative member 21A, 21B ... Substrate 22 ... Adhesive layer

Claims (22)

A decorative sheet having a base sheet, a printing layer containing an azomethine azo-based 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: -3 or more and 0.5 or less,
The decorative sheet, wherein an average spectral absorptivity in a wavelength range of 360 to 2500 nm measured by irradiating light in a wavelength range of 360 to 2500 nm on the surface of the decorative sheet on the surface protective layer side is 33% or less.   The decorative sheet according to claim 1, wherein an average spectral reflectance in a wavelength range of 360 to 2500 nm measured by irradiating light in a wavelength range of 360 to 2500 nm on the surface of the decorative sheet is 25% or more.   The decorative sheet according to claim 2, wherein an average spectral reflectance in the wavelength range 831 to 2500 nm measured by irradiating light in the wavelength range 831 to 2500 nm on the surface of the decorative sheet on the surface protective layer side is 30% or more.   Spectral reflectance at a wavelength of 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet with a wavelength of 750 nm is more than 50%, and the surface of the decorative sheet is irradiated with light having a wavelength of 800 nm The decorative sheet according to claim 2 or 3, wherein the spectral reflectance measured at a wavelength of 800 nm is 60% or more.   5. The average spectral reflectance in the wavelength region 360 to 600 nm measured by irradiating the surface protective layer side surface of the decorative sheet with light in the wavelength region 360 to 600 nm is 10% or less. The decorative sheet according to item.   In the state where the base sheet is present alone, the average spectral reflectance of the wavelength range 360 to 2500 nm measured by irradiating the surface of the base sheet with light in the wavelength range 360 to 2500 nm is 55% or more. The decorative sheet according to any one of claims 2 to 5.   The decorative sheet according to claim 1, wherein an average spectral transmittance in a wavelength range of 360 to 2500 nm measured by irradiating light in a wavelength range of 360 to 2500 nm on the surface of the decorative sheet is 60% or more.   The decorative sheet according to claim 7, wherein an average spectral transmittance in the wavelength range 831 to 2500 nm measured by irradiating light in the wavelength range 831 to 2500 nm on the surface of the decorative sheet on the surface protective layer side is 75% or more.   Spectral transmittance of wavelength 750 nm measured by irradiating the surface protective layer side surface of the decorative sheet is 60% or more, and irradiating the surface protective layer side surface of the decorative sheet with light of wavelength 800 nm The decorative sheet according to claim 7 or 8, wherein the spectral transmittance measured at a wavelength of 800 nm is 70% or more.   10. The average spectral transmittance in a wavelength range of 360 to 600 nm measured by irradiating light in a wavelength range of 360 to 600 nm on the surface of the decorative sheet on the surface protective layer side is 8% or less. The decorative sheet according to item.   In the state where the base sheet is present alone, the average spectral transmittance of the wavelength range 360 to 2500 nm measured by irradiating the surface of the base sheet with light in the wavelength range 360 to 2500 nm is 70% or more. The decorative sheet according to any one of claims 7 to 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 light are a ^* values: The decorative sheet according to any one of claims 1 to 11, which is -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 claims 1 to 12, 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 13, wherein the base sheet is a colored resin sheet.   The decorative sheet according to any one of claims 1 to 14, wherein the decorative sheet does not contain carbon black.   The decorative sheet according to any one of claims 1 to 15, wherein a ratio of the area of the region where the printed layer is formed to 50% or more of the area of one surface of the base sheet is 50% or more.   A decorative member comprising an adherend and the decorative sheet according to any one of claims 1 to 16 so that the adherend and the base sheet of the decorative sheet face each other.   The decorative member according to claim 17, wherein the adherend is at least one member selected from a wooden member, a metal member, and a resin member.   The makeup | decoration of Claim 17 or 18 whose average spectral reflectance of the wavelength range 360-2500 nm measured by irradiating the surface protective layer side surface of the said decorative member with the light of the wavelength range 360-2500 nm is 40% or more. Element.   The decorative member according to claim 19, wherein an average spectral reflectance in a wavelength region 831 to 2500 nm measured by irradiating light in a wavelength region 831 to 2500 nm on the surface of the decorative member on the surface protective layer side is 50% or more.   Spectral reflectance at a wavelength of 750 nm measured by irradiating light on the surface protective layer side of the decorative member with a wavelength of 750 nm is more than 55%, and light on the surface protective layer side of the decorative member is irradiated with light at a wavelength of 800 nm The decorative member according to claim 19 or 20, wherein the spectral reflectance measured at a wavelength of 800 nm is 70% or more.   The average spectral reflectance in a wavelength range of 360 to 600 nm measured by irradiating light in a wavelength range of 360 to 600 nm on the surface of the decorative member on the surface protective layer side is 10% or less. The decorative member according to Item.

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