JP2016165870A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which has heat shielding properties and can prevent warpage due to infrared light.SOLUTION: A decorative sheet 3 is produced by forming a printing layer 13 on which a pattern is printed, a transparent glossiness adjustment layer 15 for adjusting glossiness on the surface of the printing layer 13, and a projection 17 which is formed of an ionizing radiation-curable resin and has a shape synchronized with the pattern, on a thermoplastic resin base material layer 11 in this order. The projections 17 have a height of 30 μm or more and 100 μm or less, intervals between the projections 17 are 1 μm or more and 2 μm or less, and 20 pts.mass or more and 30 pts.mass or less of granular particles having a particle size of 3 μm or more and 10 μm or less are contained with respect to 100 pts.mass of the ionizing radiation-curable resin. The printing layer 13 contains a black pigment. The black pigment shall be a perylene-based black pigment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet used as a building material and a decorative material using the decorative sheet.

A decorative sheet is used for various uses such as indoor and outdoor buildings and furniture and furniture as a building material that is inexpensive and excellent in processability.
As decorative sheets having high weather resistance, decorative sheets using olefin-based materials are currently in practical use. The weather resistance is evaluated by actual outdoor exposure and accelerated weather resistance test. The weather resistance of a decorative sheet using an olefin-based material satisfies a practical condition. Such a decorative sheet is described in Patent Document 1, for example.

JP 2012-131112 A

  However, the existing decorative sheet is evaluated for weather resistance against ultraviolet light of sunlight, and although the prescription is applied, the weather resistance against infrared light has not been considered. In the decorative sheet, heat is stored by absorbing infrared light, and expansion is generated when the stored heat is transmitted to the base material of the decorative sheet. When the base material of the decorative sheet expands, the decorative material to which the decorative sheet is bonded is warped, and the beauty of the building material and the function of protecting the building are deteriorated.

  This invention is made | formed in view of such a point, and it aims at providing the decorative sheet and cosmetics which have heat insulation and can prevent the curvature by infrared light.

  In order to solve the above problems, a decorative sheet according to one embodiment of the present invention includes a thermoplastic resin base layer, a printed layer in which a pattern is printed on the thermoplastic resin base layer, and a surface of the printed layer. A transparent gloss adjusting layer for adjusting the gloss and a convex portion made of an ionizing radiation curable resin and having a shape synchronized with the pattern are formed in this order, and the convex portion has a height of 30 μm or more and 100 μm or less. And the interval between the convex portions is 1 μm or more and 2 mm or less, and 20 to 30 parts by mass of granular particles having a particle size of 3 μm to 10 μm with respect to 100 parts by mass of the ionizing radiation curable resin. The printing layer includes a black pigment, and the black pigment is a perylene black pigment.

  According to the present invention, it is possible to provide a decorative sheet and a decorative material that have heat shielding properties and can prevent warping due to infrared light.

It is sectional drawing of the decorative material using the decorative sheet of one Embodiment of this invention, and a decorative sheet.

Hereinafter, a decorative sheet and a decorative material according to an embodiment of the present invention will be described.
(Cosmetic materials)
FIG. 1 is a cross-sectional view for explaining a decorative material 1 of the present embodiment. The decorative material 1 of the present embodiment includes a decorative sheet 3, a base material 20, and an adhesive layer 21 that bonds the decorative sheet 3 and the base material 20.
The decorative material 1 of the present embodiment increases the transmittance of the printing layer 13 with respect to infrared light having a wavelength of 0.7 μm to 1000 μm, and reflects the transmitted infrared light by the thermoplastic resin substrate layer 11. 20 heat storage is prevented.

(Decorative sheet)
The decorative sheet 3 includes a thermoplastic resin base layer 11, a printed layer 13 in which a pattern is printed on the thermoplastic resin base layer 11, and a transparent gloss adjusting layer 15 that adjusts the gloss of the surface of the printed layer 13. And a convex portion 17 made of an ionizing radiation curable resin and having a shape synchronized with the pattern, is formed in this order. That is, the decorative sheet 3 has, from the thermoplastic resin base material layer 11 side, the thermoplastic resin base material layer 11, the printing layer 13, the transparent glossy layer 15, the convex portion 17, and the stain resistant thin film 19. .
Hereinafter, each layer of the decorative sheet 3 will be described.

<Thermoplastic resin base material layer>
As the thermoplastic resin base material layer 11 in the present invention, a printing layer 13 to be described later can be provided by printing or the like, and any known material can be used as long as it has processing suitability as the decorative sheet 3. . However, in the present embodiment, a polyester resin sheet, a polyolefin resin sheet, or the like is preferable as one that does not use vinyl chloride. Various additives such as conventionally known fillers, foaming agents, flame retardants, lubricants, antioxidants, ultraviolet absorbers, light stabilizers and the like are added to the thermoplastic resin base layer 11 in accordance with conventional methods as necessary. can do. Although the thickness of the thermoplastic resin base material layer 11 is based on the use of the decorative sheet 3, etc., about 50 micrometers-100 micrometers are preferable.

Moreover, in this embodiment, in order to improve the reflectance of the infrared light in the thermoplastic resin base material layer 11, you may add a titanium oxide to the said material and make it contain in a thermoplastic resin base material layer. At this time, in this embodiment, when the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide, the heat shielding property is improved.
Moreover, when using a titanium oxide as a hiding layer for the thermoplastic resin base material layer 11, the total of the content of titanium oxide as a hiding layer and the added titanium oxide should just be 23 mass parts or more. Moreover, when the thermoplastic resin base material layer 11 contains 23 mass parts or more of titanium oxide as a concealing layer, it is not necessary to add titanium oxide any more.

However, when the amount of titanium oxide added to the thermoplastic resin substrate layer 11 increases, the titanium oxide affects the film quality of the thermoplastic resin substrate layer 11. For this reason, suitable content of the titanium oxide of the thermoplastic resin base material layer 11 is 23 mass parts or more and 40 mass parts or less.
In the present embodiment, as shown in FIG. 1, a titanium oxide layer 111 may be provided by applying titanium oxide to the surface of the thermoplastic resin base material layer 11 on the printed layer 13 side. Even when the titanium oxide layer 111 is provided, if the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide by the titanium oxide layer 111, the thermoplastic resin base material layer 11 can be applied to the base material 20. Thermal insulation is improved. Under such conditions, the thickness of the titanium oxide layer 111 is preferably 5 μm to 10 μm.

<Print layer>
The printed layer 13 is provided for the purpose of imparting a desired pattern design to the target decorative sheet. In the present invention, a printing layer 13 having an appropriate pattern is provided on the surface of the thermoplastic resin substrate layer 11 by means such as a printing method.
The printing layer 13 is provided using an ink suitable for the thermoplastic resin base material layer 11. Specifically, if the thermoplastic resin base material layer 11 is a polypropylene resin, a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin is preferably used.

  As the colorant, a perylene-based black pigment is particularly used as a black pigment. A typical perylene black pigment is perylene black. Due to this point, in the present embodiment, the existing decorative sheet often uses carbon black as a black pigment, and the reflectance in the near infrared light region (0.781 μm to 2.5 μm) is low. Absorption of heat caused by heat can improve the problem of heat storage.

As the pigment other than the black pigment, at least one of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide is used for the printing layer 13.
The inventors of the present invention printed a wood grain pattern using the above colorants, and measured the total infrared light transmittance of the printed layer 13. According to this measurement, the transmittance of light having a wavelength of 0.781 μm to 2.5 μm was 40% or more. More detailed data of the transmittance of each pigment will be shown later.

In addition, for the printing layer 13, for example, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, drying agents, heat stabilizers, weathering stabilizers, curing agents, curing accelerators. Various additives such as an agent or a curing retarder can be appropriately added.
The method for forming the printing layer 13 is not particularly limited, and various conventional printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an ink jet printing method are used. can do. In addition, for example, in the case of a solid surface, in addition to the above-described various printing methods, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method Various coating methods such as a dip coating method can also be used. In addition, for example, the hand-drawn method, the ink sink method, the photographic method, the laser beam or electron beam drawing method, the partial vapor deposition method of metal or the like, the etching method, etc., or a combination of these methods can of course be performed.

Further, prior to the formation of the printing layer 13, if necessary, the surface of the thermoplastic resin substrate layer 11 is subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment. By performing the surface treatment, the adhesion between the thermoplastic resin base material layer 11 and the printing layer 13 can be improved.
There are no particular restrictions on the type of pattern that the printed layer 13 constitutes, and a wood grain pattern, stone pattern, cloth pattern, abstract pattern, geometric pattern, etc. that have been widely used in the field of decorative sheets, or simple coloring. In the case of aiming at color adjustment, it may be a solid monochrome color. In short, any desired picture can be adopted depending on the intended use of the decorative sheet.

<Transparent glossy layer>
The transparent glossy layer 15 of the present embodiment is a layer for adjusting the gloss of the surface of the decorative sheet 3. As the resin component (binder) of the transparent glossy layer 15, the versatility of adhesion to various transparent thermoplastic resin layers, the deformation followability when the decorative sheet 3 is bent into the conduit groove, and the scratch resistance From the point of view, a two-component curable urethane resin is selected. The transparent glossy layer 15 is obtained by applying a composition to which a gloss adjusting agent (also called a matting agent or a matting agent) is added or not added depending on the desired gloss. The gloss adjusting agent is not added when the surface has a high gloss, but is added when the surface has a low gloss. As the gloss adjusting agent, fine particles of silica, alumina (α-alumina, etc.), calcium carbonate, barium sulfate, kaolinite, aluminosilicate, etc., or organic matter (resin) such as polycarbonate, nylon, urethane resin, etc. are used. . The average particle diameter of the gloss adjusting agent is preferably about 1 μm to 10 μm, and the addition amount is appropriately selected according to the desired gloss, but is usually about 30 parts by mass at the maximum.

  The two-component curable urethane resin is a urethane resin mainly composed of polyol and having isocyanate as a crosslinking agent (curing agent). As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used.

  As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. Examples of the polyvalent isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate. Aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate are used. In addition, adducts or multimers of such various isocyanates can be used. Examples of the adduct or multimer include an adduct of tolylene diisocyanate and a tolylene diisocyanate trimer.

Of the isocyanates, aliphatic (or alicyclic) isocyanates are preferred in that they can also be weather-resistant and heat-resistant yellowing good, and specifically, for example, 1,6-hexamethylene diisocyanate can be used.
The glossiness of the transparent glossiness layer 15 is preferably designed by adding each glossiness adjusting agent and setting the mat portion to a reflection gloss coefficient value of about 3 to 5.

<Convex>
The convex portion 17 of the present embodiment is made of an ionizing radiation curable resin, has a height of 30 μm or more and 100 μm or less, and an interval between the convex portions 17 is 1 mm or more and 2 mm or less. In addition, as the ionizing radiation curable resin of the convex portion 17, a resin containing 20 to 30 parts by mass of granular particles having a particle size of 3 to 10 μm with respect to 100 parts by mass of the ionizing radiation curable resin is used. .

  An ionizing radiation curable resin is one having an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, a resin composition that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, a member appropriately selected from known polymerizable monomers, polymerizable oligomers and prepolymers commonly used as ionizing radiation or ultraviolet curable resin compositions is used.

  Specifically, as the polymerizable monomer, a (meth) acrylate monomer having a radically 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. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. There is. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  In the present embodiment, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the purpose of the present embodiment is not impaired for the purpose of reducing the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  In addition, 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 Etc. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . In addition, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can be used.

  The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Polyester (meth) acrylate oligomers include, for example, esterifying hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  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.

  In the present embodiment, organic particles such as resin and inorganic particles such as glass and silica are used as the granular particles contained in 100 parts by mass of the ionizing radiation curable resin. The particles are not particularly limited, but true spherical acrylic beads are particularly preferable from the viewpoints of touch and stain resistance. In the particle-containing process of the ionizing radiation curable resin, when the content of the particles is less than 20 parts by mass, the feeling of touch is hardly felt, and when the content is more than 30 parts by mass, the stain resistance tends to be deteriorated. When the particle size is smaller than 3 μm, the feeling of touch is not felt so much, and when it is larger than 10 μm, the stain resistance tends to be deteriorated.

Moreover, this embodiment can mix | blend various additives with the convex part 17 according to a desired physical property. Examples of additives include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, Plasticizers, antifoaming agents, fillers, solvents, colorants and the like are used.
Further, the shape of the projection 17 of the present embodiment in a top view is not particularly limited, and may be a regular shape such as a regular arrangement of circles, squares, hexagons, or an irregular pattern, An irregular pattern is preferable because it is excellent in touch, matte, gloss and design. Further, by synchronizing the convex portion 17 with the pattern pattern of the printing layer 17, a realistic feeling of the pattern can be obtained.

In this invention, it is preferable that the convex part 17 contains 10 mass parts or more and 50 mass parts or less of reactive silicone resin. Examples of the reactive silicone resin include materials having a silicon skeleton in the main chain, silicone oil used for a release agent, and the like, and in particular, the side chain has a silicon skeleton from the viewpoint of stain resistance. UV effect acrylate resins are preferred. Under such conditions, if the content of the reactive silicone resin is less than 10 parts by mass, the stain resistance tends to deteriorate, and if it exceeds 50 parts by mass, defects such as poor adhesion to the substrate due to silicon bleed out. Is defined by the possibility of occurrence.
Moreover, if the reactive silicone resin is the same as the resin used for the stain-resistant thin film coating resin layer 19 described later, the entire surface of the decorative sheet 3 is made of the same resin, which is preferable.

<Contamination resistant thin film>
The contamination-resistant thin film 19 of this embodiment is a thin film having a thickness of 0.5 μm or more and 1.5 μm or less using a coating resin as a material. The coating resin is not particularly limited, but a blocked isocyanate curable urethane resin is preferably used. Further, regarding the thickness, if it is thinner than 0.5 μm, a sufficient anti-staining effect cannot be obtained, and if it is thicker than 1.5 μm, the three-dimensional effect and the design are impaired.

(Base material)
The base material 20 is used by attaching (laminating) the decorative sheet 3 to the surface. The base material 20 includes various materials such as a metal base material and a wood base material. An example of the metal base material is an Alpolic material. The Alpolic material is an aluminum resin composite plate in which a resin material is sandwiched between metal plates that have been subjected to surface processing such as painting or mirror finishing. As the metal plate, aluminum, galvalume steel plate, stainless steel, titanium or the like is used. As the resin material, polyethylene alone or a material obtained by adding an inorganic material to polyethylene is used.
Moreover, as a wood-type base material, MDF (medium density fiberboard), a plywood, a particle board etc. are used, for example.
For attaching the sheet 3 to the base material 20, for example, an appropriate adhesive such as urethane or vinyl acetate is used.

(Adhesive layer)
Any adhesive layer 21 may be used as long as it is a known adhesive used for bonding a decorative sheet for floor and a base material. In the present embodiment, for example, the adhesive layer 21 can be formed using a reactive hot-melt adhesive. In particular, the adhesive layer 21 may be formed using a two-component polyurethane adhesive among reactive hot-melt adhesives. Among such adhesive layers 21, in this embodiment, it is particularly preferable to use a member that has been certified non-combustible according to the regulations of the Japan Wallcovering Association.

The adhesive layer 21 may contain an ultraviolet absorber or a light stabilizer. The thickness of the adhesive layer 21 is preferably about 5 μm to 50 μm.
According to the present embodiment described above, since the perylene-based black pigment is used as the black pigment, the light transmittance in the printing layer 13 is higher than that of the existing decorative sheet. Since the infrared light transmitted through the printing layer 13 is reflected by the thermoplastic resin base material layer 11, heat is not transmitted to the base material 20, and heat storage of the base material 20 can be prevented. And by preventing the heat storage of the base material 20, it is possible to obtain the cosmetic material 1 that is unlikely to warp even when used in an environment such as being exposed to sunlight.

In addition, this embodiment has a three-dimensional effect and a touch feeling excellent in visual and tactile sensation by containing granular particles with a limited particle size and ratio in the convex portion 17 made of an ionizing radiation curable resin. In addition, the decorative sheet 3 having excellent surface contamination resistance and the like can be provided.
The embodiment described above exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is based on the material, shape, structure, arrangement, etc. of the component parts. It is not specific to the above. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

  In addition, it should be noted that the drawings in the embodiments are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the above description.

Next, examples of the present invention will be described.
[Example 1]
In Example 1, 100 parts by mass of a polybutylene terephthalate resin, 3 parts by mass of a hindered phenol antioxidant, 1 part by mass of an ultraviolet absorber, 1 part by mass of a hindered amine light stabilizer, and 23 parts by mass of titanium oxide A thermoplastic resin base material layer having a thickness of 75 μm was prepared.

  Next, in Example 1, a printing layer was formed on the surface of the thermoplastic resin base material layer. The printed layer was produced by printing a wood grain pattern by gravure printing. For printing ink, a curing agent in which hexamethylene diisocyanate and isophorone diisocyanate are mixed in a ratio of 2: 8 to 100 parts by mass of urethane resin and vinyl chloride = vinyl acetate copolymer resin mixed in a ratio of 7: 3. 3 parts by mass were added, and 3 parts by mass of a pigment composed of isoindolinone, polyazo, phthalocyanine and perylene black was used.

After drying the printed layer, a transparent gloss adjusting layer was formed on the surface of the printed layer. The transparent gloss adjusting layer is adjusted to have a low gloss by adding silica powder, and the coating amount after drying an ultraviolet curable resin containing 20 parts by mass of a reactive silicone resin and an appropriate amount of an ultraviolet initiator is 10 g / was made by coating such that m ^2. The reflection gloss coefficient of the transparent gloss adjusting layer produced in Example 1 was 4.

In Example 1, after the transparent gloss adjusting layer was crosslinked and cured, a contamination-resistant thin film coating resin layer was produced. The antifouling thin film coating resin layer was produced by coating a blocked isocyanate curable urethane resin so that the coating amount after drying was 1 g / m ² . After drying the contamination-resistant thin film coating resin layer, convex portions made of ionizing radiation curable resin were prepared. The convex portion was a printing plate having a pattern that synchronizes with the pattern of the printing layer, and was produced by enlarging printing so that the height of the convex portion was 30 μm and the interval between the convex portions was 1 mm.
The ink used for the build-up printing was prepared by adding 30 parts by mass of urethane beads having a particle size of 5 μm and 20 parts by mass of a reactive silicone additive to 100 parts by mass of the ultraviolet curable resin. The decorative sheet of Example 1 was produced through the above steps.

[Example 2]
The decorative sheet of Example 2 was manufactured under the same conditions as the decorative sheet of Example 1 except for the conditions relating to the content of the urethane beads of the ionizing radiation curable resin serving as the convex portions. The convex part of the decorative sheet of Example 2 contains 20 parts by mass of urethane beads having a particle diameter of 5 μm.
[Comparative Example 1]
The decorative sheet of Comparative Example 1 was produced under the same conditions as the decorative sheet of Example 1 except for the conditions relating to the black pigment of the printed layer. The decorative sheet of Comparative Example 1 uses carbon black as the black pigment of the ink layer.

[Comparative Example 2]
The decorative sheet of Comparative Example 2 was produced under the same conditions as those of the decorative sheet of Example 1 except for the conditions relating to the content of the urethane beads of the ionizing radiation curable resin serving as the convex portions. The convex part of the decorative sheet of Comparative Example 2 contains 5 parts by mass of urethane beads having a particle diameter of 5 μm.
[Comparative Example 3]
The decorative sheet of Comparative Example 3 was manufactured under the same conditions as the decorative sheet of Example 1 except for the conditions relating to the content of the urethane beads of the ionizing radiation curable resin serving as the convex portions. The convex part of the decorative sheet of Comparative Example 3 contains 40 parts by mass of urethane beads having a particle diameter of 5 μm.

[Evaluation]
The inventors of the present invention evaluated the feel, contamination resistance, heat insulation performance, and heat storage performance of Example 1, Example 2, and Comparative Examples 1 to 3, respectively.
<Feel>
The inventors of the present invention performed a touch (feel) by blind evaluation. The blind evaluation was performed in a state where the evaluator cannot see the decorative sheet. Then, the evaluator touches the surface of the decorative sheet 3 of Example 1, Example 2 and Comparative Examples 1 to 3 and the surface of the decorative sheet for evaluation prepared for the touch evaluation, and feels to the touch. When a difference was felt, it was evaluated as “◯”, and when a difference in touch was not felt, it was evaluated as “x”. The decorative sheet for evaluation was produced under the same conditions as the decorative sheet of Example 1 except for the conditions relating to urethane beads. In the decorative sheet for evaluation, the ionizing radiation curable resin of the convex portion does not contain urethane beads.

<Contamination resistance>
The evaluation of the stain resistance was performed by applying a part of the surface of the decorative sheet with an oily black marker and wiping the part on which the black marker was applied with tissue paper. And the case where a black marker was easily wiped off was evaluated as "(circle)", and the case where the wiping residue generate | occur | produced was evaluated as "x".

<Heat insulation performance>
The inventors of the present invention measured the heat shielding performance using a method for measuring the solar reflectance of a coating film defined in JIS standard, K5602. The measurement was performed with a spectrophotometer UV3600 (product name) manufactured by Shimadzu Corporation. And according to the regulation of JIS standard K5602, if the solar reflectance of the coating film was 40% or more, it was evaluated as “◯”, and if it was 40% or less, it was evaluated as “x”.

<Heat storage performance>
In the evaluation of the heat storage performance, the inventors of the present invention bonded a decorative sheet to the surface of one side of an uncoated steel sheet having a length of 21 cm, a width of 29.7 cm, and a thickness of 0.5 mm using an adhesive. Produced. Then, a halogen sphere is installed at a position 15 cm away from the surface directly above the surface of the test piece, and the temperature of the front and back surfaces of the test piece is measured every minute while irradiating with halogen light for 120 minutes. The maximum temperature was recorded.

  Table 1 summarizes the evaluation of the heat shielding performance, the heat storage performance, and the weather resistance. According to Table 1, the decorative sheets of Example 1, Example 2, Comparative Example 2 and Comparative Example 3 using perylene black as a black pigment were changed from 60 ° C. to 62 ° C., whereas those of Comparative Example 1 The temperature of the test piece rose to 71 ° C. The difference is that Example 1, Example 2, Comparative Example 2 and Comparative Example 3 use a perylene-based black pigment, whereas Comparative Example 1 uses carbon black as a black pigment. It is thought that this occurred.

Further, Example 1 in which the convex portion includes 30 parts by mass of urethane beads in 100 parts by mass of the ultraviolet curable resin was evaluated as “◯” in both the touch and the stain resistance. Moreover, Example 2 which a convex part contains 20 mass parts of urethane beads in 100 mass parts of ultraviolet curable resin was evaluated as "(circle)" in both a touch and stain resistance. On the other hand, Comparative Example 2 in which the convex part includes 5 parts by mass of urethane beads in 100 parts by mass of the ultraviolet curable resin is evaluated as “x” in terms of feel. Such an evaluation is considered to have occurred because the urethane beads contained in the convex portions of Comparative Example 2 were less than the appropriate amount.
Further, Comparative Example 3 in which the convex portion includes 40 parts by mass of urethane beads in 100 parts by mass of the ultraviolet curable resin is evaluated as “x” in terms of contamination resistance. Such an evaluation is considered to have occurred because the amount of urethane beads contained in the convex portion of Comparative Example 3 is larger than an appropriate amount.

  The decorative base and decorative sheet of the present invention described above are suitable for use in an environment where they are exposed to sunlight because they do not easily warp even when irradiated with infrared light.

DESCRIPTION OF SYMBOLS 1 Cosmetic material 3 Cosmetic sheet 11 Thermoplastic resin base material layer 13 Print layer 15 Transparent gloss adjustment layer 17 Convex part 19 Antifouling thin film 20 Base material 21 Adhesive layer 111 Titanium oxide layer

Claims (6)

It consists of a thermoplastic resin base layer, a printed layer in which a pattern is printed on the thermoplastic resin base layer, a transparent gloss adjusting layer for adjusting the gloss of the surface of the printed layer, and an ionizing radiation curable resin. , And convex portions having a shape synchronized with the design pattern are formed in this order,
The convex portion has a height of 30 μm or more and 100 μm or less, and an interval between the convex portions of 1 μm or more and 2 mm or less, and a particle size of 3 μm or more and 10 μm or less with respect to 100 parts by mass of the ionizing radiation curable resin. Containing 20 to 30 parts by mass of particulate particles,
The decorative layer, wherein the printing layer contains a black pigment, and the black pigment is a perylene black pigment.   2. The print layer according to claim 1, wherein, in addition to the black pigment, the print layer includes at least one pigment of isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide. Makeup sheet.   The thermoplastic resin base material layer has a film made of a paint containing titanium oxide as a pigment on the surface on the side of the printing layer, or contains titanium oxide as a pigment. Makeup sheet.   The makeup according to any one of claims 1 to 3, wherein the convex portion contains 10 to 50 parts by mass of a reactive silicone resin with respect to 100 parts by mass of the ionizing radiation curable resin. Sheet.   5. The transparent contamination-resistant resin layer having a thickness of 0.5 μm or more and 1.5 μm or less is provided on a portion of the surface of the transparent gloss adjustment layer where the convex portions are not provided. The decorative sheet according to item.   A decorative material comprising the decorative sheet according to any one of claims 1 to 5 bonded to a base material.

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