Decorative sheet

Abstract

To provide a decorative sheet which has high texture with a three-dimensional effect even when viewed from various directions.SOLUTION: A decorative sheet 10 includes a colored resin layer 11, a pattern layer 12 provided on the surface side of the colored resin layer 11, a transparent resin layer 13 provided on the surface side of the pattern layer 12, and a surface protective layer 14 provided on the surface side of the transparent resin layer 13. The surface protective layer 14 has a first surface protective layer 14a provided on the transparent resin layer 13 side and a second surface protective layer 14b provided on a part of the surface side of the first surface protective layer 14a. The difference in 85-degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is within the range of 1 to 50, inclusive. The difference between the 60-degree specular gloss and the 85-degree specular gloss of the second surface protective layer 14b is within the range of 2 to 10, inclusive.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet used for the exterior of furniture, housing equipment, home appliances, and the like. [Background technology]

[0002] In decorative sheets used for the exterior of furniture, housing equipment, home appliances, etc., natural patterns such as wood grain and stone grain patterns are used to create a subdued design. In such decorative sheets, the surface is embossed or a matte or glossy layer is provided on the surface to create a sense of luxury. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-101663 A Summary of the Invention [Problem to be solved by the invention]

[0004] In the decorative sheets as described above, there is a demand for textures that are closer to the real thing, and for example, there is a strong demand for sheets that have a high level of texture that has a three-dimensional feel not only when viewed from the front, but also when viewed from various angles.

[0005] In view of the above, an object of the present invention is to provide a decorative sheet that has a three-dimensional, high-quality texture when viewed from various directions. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, the decorative sheet of the present invention is a decorative sheet comprising an opaque layer, a pattern layer provided on the surface side of the opaque layer, a transparent resin layer provided on the surface side of the pattern layer, and a surface protective layer provided on the surface side of the transparent resin layer, wherein the surface protective layer has a first surface protective layer provided on the transparent resin layer side and a second surface protective layer provided on a portion of the surface side of the first surface protective layer, and the difference in 85 degree specular gloss between the first surface protective layer and the second surface protective layer is in the range of 1 or more and 50 or less, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the other layer of the first surface protective layer and the second surface protective layer, which has a lower 85 degree specular gloss than one of the layers, is in the range of 2 or more and 10 or less.

[0007] Furthermore, in the decorative sheet according to the present invention, it is preferable that the other layer in the above-mentioned decorative sheet contains a gloss adjusting agent in particulate form, and that the gloss adjusting agent has a plurality of peaks in the particle size distribution.

[0008] In addition, the decorative sheet according to the present invention is preferably such that, in the decorative sheet described above, the other layer contains the gloss adjusting agent in an amount of 1% by mass or more and 30% by mass or less.

[0009] In addition, in the decorative sheet according to the present invention, in the decorative sheet described above, it is preferable that the gloss adjusting agent has a peak in the particle size distribution within the range of 1 μm or more and 10 μm or less.

[0010] In addition, the decorative sheet according to the present invention is preferably the decorative sheet described above, wherein the gloss adjusting agent has peaks in the particle size distribution in the range of 2 μm or more and 4 μm or less and in the range of 7 μm or more and 9 μm or less.

[0011] In addition, the decorative sheet of the present invention is preferably such that, in the decorative sheet described above, the second surface protective layer is provided on the surface side of the first surface protective layer so as to harmonize with the pattern of the pattern layer.

[0012] The decorative sheet according to the present invention is preferably the above-mentioned decorative sheet, further comprising embossments formed in the transparent resin layer and the surface protective layer and having at least one of a concave shape and a convex shape.

[0013] In the decorative sheet according to the present invention, it is preferable that the embossments are formed in the transparent resin layer and the surface protective layer so as to be in harmony with the pattern of the pattern layer. Effect of the Invention

[0014] According to the decorative sheet of the present invention, the difference in 85 degree specular gloss between the first surface protective layer and the second surface protective layer is within the range of 1 or more and 50 or less, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of one of the first surface protective layer and the second surface protective layer, which has a lower 85 degree specular gloss than the other layer, is within the range of 2 or more and 10 or less, so that the decorative sheet can have a high three-dimensional texture when viewed from various directions. [Brief description of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view showing a schematic structure of a first embodiment of a decorative sheet according to the present invention. [Diagram 2] FIG. 2 is a cross-sectional view showing a schematic structure of a second embodiment of a decorative sheet according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The embodiments of the decorative sheet according to the present invention will be described with reference to the drawings. Note that the present invention is not limited to the following embodiments described with reference to the drawings, and various technical matters described in each embodiment can be appropriately combined or replaced as necessary.

[0017] [First embodiment] A first embodiment of a decorative sheet according to the present invention will be described with reference to FIG.

[0018] <Overall structure of decorative sheet> As shown in Fig. 1, a pattern layer 12 having a pattern 12a is provided on the surface side (upper surface side in Fig. 1) of a colored resin layer 11, which is an opaque layer made of a colored resin. A transparent resin layer 13 made of a transparent resin is provided on the surface side (upper surface side in Fig. 1) of the pattern layer 12. A surface protection layer 14 that protects the surface side is provided on the surface side (upper surface side in Fig. 1) of the transparent resin layer 13.

[0019] The surface protective layer 14 has a first surface protective layer 14a made of a transparent resin provided on the transparent resin layer 13 side (lower side in FIG. 1), and a second surface protective layer 14b provided on a part of the surface side (upper side in FIG. 1) of the first surface protective layer 14a so as to match the pattern 12a of the pattern layer 12. A plurality of concave embossments 10a are formed on the transparent resin layer 13 and the surface protective layer 14 so as to match the pattern 12a of the pattern layer 12.

[0020] The decorative sheet 10 according to this embodiment preferably has a thickness of 100 μm or more and 300 μm or less, and more preferably 120 μm or more and 200 μm or less. In addition, the decorative sheet 10 preferably has a yield strength of 8 MPa or more and 70 MPa or less (preferably 10 MPa or more and 60 MPa or less), because it is easy to handle during processing and is less likely to crack or whiten. Here, the above layers 11 to 14 will be further described.

[0021] <Colored resin layer 11> The opaque colored resin layer 11 is made of a chlorine-based thermoplastic resin such as polyvinyl chloride resin or polyvinylidene chloride resin, and is colored opaquely by containing a colorant such as an organic pigment or an inorganic pigment, so that it can exhibit hiding power. As the colorant, an inorganic pigment is preferable, and examples of the colorant include calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and various other oxides.

[0022] The colored resin layer 11 may contain various additives as necessary, such as fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters.

[0023] The colored resin layer 11 preferably has a thickness in the range of 50 μm to 100 μm. If the thickness is 50 μm or more, the stability during production can be improved. If the thickness is 100 μm or less, the cost can be reduced.

[0024] <Pattern layer 12> The design layer 12 is formed by printing ink, paint, etc. Such printing ink, paint, etc. can be obtained, for example, by dissolving or dispersing a colorant such as a pigment or dye together with a binder resin in an appropriate dilution solvent.

[0025] Examples of the pigment include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. Examples of the binder resin include urethane resin, acrylic resin, vinyl chloride acetate resin, polyimide resin, nitrocellulose, and mixtures thereof. In particular, it is highly preferable for the binder resin to be a vinyl chloride-vinyl acetate copolymer, acrylic resin, or mixtures thereof, since they have high thermal fusion with chlorine-based thermoplastic resins such as polyvinyl chloride resin.

[0026] The pattern layer 12 can exhibit various functions by containing functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive assistants, drying agents, hardeners, hardening accelerators, hardening retarders, etc. Any pattern can be applied as the pattern 12a of the pattern layer 12, and examples of the pattern that can be applied include wood grain patterns, stone grain patterns, fabric patterns, abstract patterns, geometric patterns, letters, symbols, solid colors, combinations of these, and the like.

[0027] The pattern layer 12 preferably has a thickness in the range of 1 μm to 10 μm. When the thickness is 1 μm or more, the printing can be made clear. When the thickness is 10 μm or less, the printing workability during production can be improved and the production cost can be reduced. Such a printed layer 12 can be formed by applying printing ink, paint, etc., using various printing methods such as gravure printing and offset printing, or various coating methods such as gravure coating and roll coating.

[0028] <Transparent resin layer 13> The transparent resin layer 13 is made of a chlorine-based thermoplastic resin such as polyvinyl chloride resin or polyvinylidene chloride, and has transparency such as colorless transparency, colored transparency, or translucency, allowing the pattern layer 12 to be visually recognized. The transparent resin layer 13 preferably contains an ultraviolet absorbing agent such as a benzotriazole-based or triazine-based agent.

[0029] Examples of benzotriazoles include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and mixtures, modified products, polymers, and derivatives thereof.

[0030] Examples of triazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

[0031] It is preferable that the transparent resin layer 13 contains 0.5 parts by mass or more of an ultraviolet absorbing agent per 100 parts by mass of the chlorine-based thermoplastic resin constituting the layer, since this can reliably improve weather resistance.

[0032] The transparent resin layer 13 preferably has a thickness in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. If the thickness is 50 μm or more, weather resistance can be reliably improved. In addition, when attached to a wooden substrate or the like, the unevenness of the substrate surface can be absorbed to improve the application finish. On the other hand, if the thickness is 150 μm or less, a necessary and sufficient thickness can be achieved, and processing suitability (e.g. bending processability) can be improved, while manufacturing costs can be reduced.

[0033] <First surface protective layer 14a> The first surface protective layer 14a is made of a resin material such as an acrylic, urethane, acrylic silicone, fluorine, or epoxy resin, and has transparency such as colorless transparency, colored transparency, or translucency, so that the pattern layer 12 can be visually recognized through the transparent resin layer 13. The first surface protective layer 14a can also contain various additives such as ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, light scattering agents, and gloss adjusters, as necessary. These various additives are used in appropriate combinations as necessary.

[0034] Examples of the ultraviolet absorbing agent include the above-mentioned triazine-based agents, etc. Examples of the heat stabilizer include phenol-based agents, sulfur-based agents, phosphorus-based agents, hydrazine-based agents, etc. Examples of the light stabilizer include hindered amine-based agents, etc.

[0035] Examples of the hindered amines include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidylstearate, 1,2,2,6,6-pentamethyl-4-piperidylstearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2, 2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl) -2-Butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4 -Bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl)-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,Examples of the reaction product include 11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, a reaction product of cyclohexane with N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide, and a reaction product of 2-aminoethanol.

[0036] It is preferable that the first surface protective layer 14a contains an ultraviolet absorber in an amount of 0.5 parts by mass to 30 parts by mass and a light stabilizer in an amount of 0.5 parts by mass to 30 parts by mass, both per 100 parts by mass of the transparent resin constituting the first surface protective layer 14a, since this can reliably improve weather resistance without causing bleed-out.

[0037] The first surface protection layer 14a preferably has a thickness in the range of 3 μm to 100 μm. If the thickness is 3 μm or more, the strength required for protecting the surface can be obtained. On the other hand, if the thickness is 100 μm or less, the necessary and sufficient thickness can be obtained, and the processability (e.g., bending processability) can be improved and the manufacturing cost can be reduced.

[0038] <Second surface protective layer 14b> The second surface protective layer 14b is made of a resin material such as a two-component curing urethane resin and contains additives such as a gloss adjusting agent. An example of the two-component curing urethane resin is a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent). Examples of the gloss adjusting agent include particulate materials such as inorganic substances such as silica, alumina (α-alumina, etc.), calcium carbonate, barium sulfate, kaolinite, and aluminosilicate, or organic substances (resins) such as polycarbonate, nylon, and urethane resin.

[0039] The gloss adjuster (matting agent) preferably has a particle size distribution peak in the range of 1 μm to 10 μm. If the particle size is 1 μm or more, clogging of the plate is unlikely to occur during printing coating. If the particle size is 10 μm or less, the particle size is unlikely to chip even when impacted, and the deterioration of scratch resistance and gloss can be suppressed. In addition, the gloss adjuster (matting agent) preferably has multiple particle size distribution peaks. Specifically, it is preferable that the particle size distribution peaks are in the range of 2 μm to 4 μm and in the range of 7 μm to 9 μm.

[0040] The content of the gloss adjusting agent is preferably 1% by mass or more and 30% by mass or less. When the content is 1% by mass or more, gloss adjustment (matt) can be sufficiently performed. On the other hand, when the content is 30% by mass or less, sufficient transparency can be ensured.

[0041] The second surface protective layer 14b preferably has a thickness in the range of 1 μm to 10 μm. If the thickness is 1 μm or more, sufficient gloss adjustment can be performed. On the other hand, if the thickness is 10 μm or less, even if the layer is chipped due to an impact, the chipped portion can be made less noticeable.

[0042] <Surface protective layer 14> The surface protective layer 14 has a matte second surface protective layer 14b containing the above-mentioned gloss adjusting agent provided on a part of the surface of the above-mentioned glossy first surface protective layer 14a. As a result, in the surface protective layer 14, the difference in 85-degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is 1 to 50, and the difference between the 60-degree specular gloss and 85-degree specular gloss of the matte second surface protective layer 14b is 2 to 10.

[0043] Therefore, in the surface protective layer 14, the difference in 85-degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is from 1 to 50, and thus the gloss difference (contrast) expresses a visual three-dimensional effect and texture, thereby realizing a high level of design. Also, in the surface protective layer 14, the difference between the 60-degree specular gloss and the 85-degree specular gloss of the second surface protective layer 14b is from 2 to 10, and thus the surface protective layer 14 expresses a three-dimensional effect and texture closer to the real thing even when viewed from various directions, thereby realizing a high level of design.

[0044] <Method of manufacturing the decorative sheet 10> A method for manufacturing the decorative sheet 10 according to this embodiment will be described below. First, a transparent chlorine-based thermoplastic resin is mixed with additives such as an ultraviolet absorber, and the mixture is molded into a film shape while forming embossments 10a using an embossing plate or the like, to obtain a transparent resin layer 13. Next, a printing ink in which a binder resin and a colorant are mixed in a solvent is printed on the back side of the transparent resin layer 13, and the printing ink is cured and dried to form a design layer 12.

[0045] Next, a liquid obtained by mixing a transparent resin material such as an acrylic resin, additives such as an ultraviolet absorber and a light stabilizer, and a curing agent in a solvent is applied to the surface side of the transparent resin layer 13, and then cured and dried to provide a first surface protective layer 14a. Then, a gloss adjusting agent having a particle shape with multiple peaks in the particle size distribution is mixed into a transparent resin such as a two-component curing urethane resin, and printed on the surface side of the first surface protective layer 14a so as to match the pattern 12a of the pattern layer 12, and cured to provide a second surface protective layer 14b. In this way, the surface protective layer 14 is formed.

[0046] Finally, an opaque film-shaped colored resin layer 11 made of a chlorine-based thermoplastic resin containing a colorant is thermally laminated onto the design layer 12 and thermocompressed to obtain the decorative sheet 10.

[0047] <10 benefits of decorative sheets> In the decorative sheet 10 according to the present embodiment thus manufactured, as described above, the difference in 85 degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is within the range of 1 to 50, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the second surface protective layer 14b is within the range of 2 to 10. Therefore, the surface protective layer 14 can express a visual three-dimensional effect and texture due to its gloss difference (contrast), and can also express a three-dimensional effect and texture closer to the real thing when viewed from various directions, thereby achieving high designability.

[0048] Therefore, the decorative sheet 10 according to this embodiment can provide a high quality texture with a realistic three-dimensional feel when viewed from various directions.

[0049] In addition, since the peak of the particle size distribution of the gloss adjuster is in the range of 1 μm or more and 10 μm or less, clogging of the plate during printing coating is less likely to occur, and the plate is less likely to chip even when subjected to impact, thereby preventing a decrease in scratch resistance and gloss.

[0050] [Second embodiment] A second embodiment of the decorative sheet according to the present invention will be described with reference to Fig. 2. However, for parts similar to those in the above-mentioned embodiment, the same reference numerals as those used in the description of the above-mentioned embodiment will be used, and descriptions that overlap with those in the above-mentioned embodiment will be omitted.

[0051] <Overall structure of decorative sheet> As shown in Fig. 2, a pattern layer 22 having a pattern 12a is provided on the surface side (upper surface side in Fig. 2) of a colored resin layer 21, which is an opaque layer made of a colored resin. An anchor layer 25 made of a transparent resin is provided on the surface side (upper surface side in Fig. 2) of the pattern layer 22. A transparent adhesive layer 26 made of a transparent resin having adhesive properties is provided on the surface side (upper surface side in Fig. 2) of the anchor layer 25. A transparent resin layer 23 made of a transparent resin is provided on the surface side (upper surface side in Fig. 2) of the transparent adhesive layer 26.

[0052] A surface protective layer 14 is provided on the surface side (upper surface side in FIG. 2) of the transparent resin layer 23. A plurality of concave embossments 10a are formed on the transparent resin layer 23 and the surface protective layer 14 so as to match the pattern of the pattern layer 22.

[0053] The decorative sheet 20 according to this embodiment preferably has a thickness of 100 μm or more and 300 μm or less, and more preferably 120 μm or more and 200 μm or less. In addition, the decorative sheet 20 preferably has a yield strength of 5 MPa or more and 50 MPa or less, because it is easy to handle during processing and is less likely to crack or whiten. Here, the layers 21 to 23, 25, 26, etc. will be further described.

[0054] <Colored resin layer 21> The colored resin layer 21, which is an opaque layer, is made of a polyolefin-based thermoplastic resin such as a polyethylene resin or a polypropylene resin, and is colored opaquely by containing a coloring agent such as an organic pigment or an inorganic pigment, as in the case of the above-mentioned embodiment, so that it can exhibit hiding properties. As in the case of the above-mentioned embodiment, the colored resin layer 21 can also contain various additives as necessary. As in the case of the above-mentioned embodiment, the colored resin layer 21 preferably has a thickness in the range of 50 μm to 100 μm.

[0055] <Pattern layer 22> The pattern layer 22 is formed by printing ink, paint, etc., as in the case of the above-mentioned embodiment. The binder resin may be the same as the resin in the above-mentioned embodiment, but in particular, urethane resin is very preferable because it can enhance adhesion with polyolefin-based thermoplastic resins such as polyethylene resin and polypropylene resin. The pattern layer 22 may contain various functional additives as in the case of the above-mentioned embodiment. The pattern layer 22 preferably has a thickness in the range of 1 μm or more and 10 μm or less as in the case of the above-mentioned embodiment. Such a printing layer 22 can be formed in the same manner as in the case of the above-mentioned embodiment.

[0056] <Anchor layer 25> The anchor layer 25 is provided to improve adhesion to the colored resin layer 21 via the pattern layer 22, and has transparency such as colorless transparent, colored transparent, or semi-transparent, allowing the pattern layer 22 to be visually recognized. The anchor layer 25 can be made of, for example, urethane resin. The anchor layer 25 preferably has a thickness in the range of 1 μm to 10 μm.

[0057] <Transparent adhesive layer 26> The transparent adhesive layer 26 is provided to bond the transparent resin layer 23 and the anchor layer 25, and has transparency such as colorless transparency, colored transparency, or translucency, so that the pattern layer 22 can be seen through the anchor layer 25. The transparent adhesive layer 26 can be made of, for example, a polyolefin-based thermoplastic resin. The transparent adhesive layer 26 preferably has a thickness in the range of 1 μm or more and 20 μm or less.

[0058] <Transparent resin layer 23> The transparent resin layer 23 is made of a polyolefin thermoplastic resin such as a polyethylene resin or a polypropylene resin, and has transparency such as colorless transparency, colored transparency, or translucency, so that the pattern layer 22 can be seen through the transparent adhesive layer 26 and the anchor layer 25. As in the above-mentioned embodiment, the transparent resin layer 23 preferably contains an ultraviolet absorbing agent such as a benzotriazole-based or triazine-based agent. The transparent resin layer 23 preferably has a thickness similar to that in the above-mentioned embodiment.

[0059] That is, the decorative sheet 10 according to the above-mentioned embodiment is a case where a colored resin layer 11 and a transparent resin layer 13 made of a chlorine-based thermoplastic resin are applied. In contrast, the decorative sheet 20 according to the present embodiment is a case where a colored resin layer 21 and a transparent resin layer 23 made of a polyolefin-based thermoplastic resin are applied.

[0060] <Method of manufacturing the decorative sheet 20> A method for manufacturing the decorative sheet 20 according to this embodiment will be described below. First, a printing ink in which a binder resin and a colorant are mixed in a solvent is printed on the surface side of an opaque film-shaped colored resin layer 21 made of a polyolefin-based thermoplastic resin containing a colorant, and the printing ink is then cured and dried to form a pattern layer 22. Next, a urethane resin or the like is applied to the surface side of the pattern layer 22, and the coating is cured and dried to provide an anchor layer 25. Next, a transparent adhesive layer 26 and a transparent resin layer 23 are laminated by co-extruding a polyolefin-based thermoplastic resin onto the surface side of the anchor layer 25 while forming an embossment 10a with an embossing plate or the like by heating and melting the resin to form a film shape.

[0061] Then, a liquid obtained by mixing a transparent resin material such as an acrylic resin, additives such as an ultraviolet absorber and a light stabilizer, and a curing agent in a solvent is applied to the surface side of the transparent resin layer 23, and the liquid is cured and dried to provide the first surface protective layer 14a. Finally, a gloss adjusting agent having a particle shape with multiple peaks in the particle size distribution is mixed into a transparent resin such as a two-component curing urethane resin, and printed on the surface side of the first surface protective layer 14a so as to match the pattern 12a of the pattern layer 22, and cured to provide the second surface protective layer 14b. In this way, the surface protective layer 14 is formed, and the decorative sheet 20 can be obtained.

[0062] <20 Effects of Decorative Sheets> In the decorative sheet 20 according to this embodiment manufactured in this manner, similarly to the above-described embodiment, the difference in 85 degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is within a range of 1 to 50, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the second surface protective layer 14b is within a range of 2 to 10. Therefore, the surface protective layer 14 can express a visual three-dimensional effect and texture from its gloss difference (contrast), and can also express a three-dimensional effect and texture closer to the real thing when viewed from various directions, thereby achieving high designability.

[0063] Therefore, the decorative sheet 20 according to this embodiment can provide a high quality texture with a realistic three-dimensional feel when viewed from various directions, similar to the previously described embodiment.

[0064] Furthermore, as in the case of the above-described embodiment, the peak of the particle size distribution of the gloss adjusting agent is in the range of 1 μm or more and 10 μm or less, so that clogging and the like is less likely to occur on the plate during printing coating, and the plate is less likely to chip even when subjected to impact, thereby preventing a decrease in scratch resistance and gloss.

[0065] [Other embodiments] In the second embodiment described above, when the decorative sheet 20 is used by being attached to a wooden substrate or the like, it is preferable to provide a base layer made of urethane resin or the like on the back side of the colored resin layer 21. In this case, in addition to forming the pattern layer 22 by printing ink on the front side of the colored resin layer 21, it is possible to provide a base layer by printing urethane resin or the like on the back side of the colored resin layer 21.

[0066] In the above-mentioned embodiment, the decorative sheets 10, 20 are described in which the colored resin layer 11, 21 made of a colored resin is applied as the opaque layer, but the present invention is not limited thereto. As another embodiment, for example, a concealing layer (thickness: 1 μm to 10 μm) using an opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide can be used as the opaque layer in place of the colored resin layer 11, 21. Furthermore, a concealing layer can be provided between the colored resin layer 11, 21 and the pattern layer 12, 22 to form a decorative sheet in which the opaque layer is composed of the colored resin layer 11, 21 and the concealing layer.

[0067] In the above-mentioned embodiment, the decorative sheets 10, 20 having the transparent resin layer 13, 23 on which the concave embossment 10a is formed are described, but the present invention is not limited thereto. As other embodiments, for example, it is possible to use a decorative sheet having a transparent resin layer on which a convex embossment is formed, a decorative sheet having a transparent resin layer on which both concave and convex embossments are formed, or a decorative sheet having a transparent resin layer without embossing.

[0068] In the above-described embodiment, a matte second surface protective layer 14b containing a gloss adjusting agent is provided on a portion of the surface of a glossy first surface protective layer 14a not containing a gloss adjusting agent, thereby providing a surface protective layer 14 in which the difference in 85 degree specular gloss between the first surface protective layer 14a and the second surface protective layer 14b is 1 to 50, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the matte second surface protective layer 14b is 2 to 10. However, the present invention is not limited to this.

[0069] In another embodiment, for example, by providing a glossy second surface protective layer that does not contain a gloss adjusting agent on a portion of the surface of a matte first surface protective layer that contains a gloss adjusting agent, it is possible to obtain a surface protective layer in which the difference in 85 degree specular gloss between the first surface protective layer and the second surface protective layer is 1 or more and 50 or less, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the matte first surface protective layer is 2 or more and 10 or less.

[0070] Furthermore, as another embodiment, for example, by providing a matte second surface protective layer containing a gloss adjusting agent on a portion of the surface of a first surface protective layer which contains a gloss adjusting agent but is glossier than the second surface protective layer, it is possible to obtain a surface protective layer in which the difference in 85 degree specular gloss between the first surface protective layer and the second surface protective layer is 1 or more and 50 or less, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the matte second surface protective layer is 2 or more and 10 or less.

[0071] Furthermore, as another embodiment, for example, by providing a second surface protective layer that contains a gloss adjusting agent but is glossier than the first surface protective layer on a portion of the surface of a matte first surface protective layer containing a gloss adjusting agent, it is possible to obtain a surface protective layer in which the difference in 85 degree specular gloss between the first surface protective layer and the second surface protective layer is 1 or more and 50 or less, and the difference between the 60 degree specular gloss and the 85 degree specular gloss of the matte second surface protective layer is 2 or more and 10 or less.

[0072] In other words, of the first surface protective layer and the second surface protective layer, the one having a lower 85 degree specular gloss than the other layer has a difference between its 60 degree specular gloss and 85 degree specular gloss of 2 or more and 10 or less.

[0073] In addition, in the above-mentioned embodiment, the gloss regulator having two peaks in particle size distribution is described, but the present invention is not limited thereto. As another embodiment, for example, a gloss regulator having three or more peaks in particle size distribution can be applied. However, as in the above-mentioned embodiment, a gloss regulator having two peaks in particle size distribution is most preferable because it requires less effort for particle size adjustment. EXAMPLES

[0074] Examples of the decorative sheet according to the present invention will be specifically described below, but the present invention is not limited to only the following examples that are specifically described.

[0075] [Preparation of test specimens and comparison specimens] Test specimen 1 First, 100 parts by mass of transparent polyvinyl chloride (PVC) resin is mixed with 0.5 parts by mass of a triazine-based ultraviolet absorber, and the mixture is molded into a film shape to obtain a transparent resin layer (thickness: 80 μm).

[0076] Next, 10 parts by mass of colorant is added to 100 parts by mass of binder resin, which is a mixture of acrylic resin and vinyl chloride resin-vinyl acetate resin copolymer resin, and the printing ink mixed in a solvent is printed on the back side of the transparent resin layer and cured and dried to form a picture layer (thickness 2 μm).

[0077] Next, 90 parts by mass of an acrylic transparent resin material obtained by copolymerizing methyl methacrylate and 2-hydroxyethyl methacrylate in a mass ratio of 95:5 was mixed with 9 parts by mass of an ultraviolet absorber "Tinuvin (registered trademark) 479 (product number)" manufactured by BASF Japan Ltd., 1 part by mass of a light stabilizer "Tinuvin (registered trademark) 123 (product number)" manufactured by BASF Japan Ltd., and 10 parts by mass of a hardener "Takenate (registered trademark) D170 (product number)" manufactured by Mitsui Chemicals, Inc. in a solvent (240 parts by mass of ethyl acetate), and the resulting liquid was applied to the surface side of the transparent resin layer so that the mass after drying was 3 g / m 2 The resulting mixture is then cured and dried to provide a first surface protective layer (thickness: 4 μm).

[0078] Then, 20 parts by mass of a gloss adjuster made of silica having particle shapes with particle size distribution peaks at approximately 3 μm and 8 μm is mixed with 100 parts by mass of a transparent binder resin made of urethane resin, and printed and cured on the surface side of the first surface protection layer in harmony with the pattern of the pattern layer, thereby providing a second surface protection layer (thickness 2 μm).

[0079] Finally, a decorative sheet specimen 1 was prepared by thermally laminating (150°C) an opaque film-shaped colored resin layer (thickness 80 μm) containing 10 parts by mass of colorant per 100 parts by mass of polyvinyl chloride resin onto the pattern layer 12 side.

[0080] Test specimen 2 Decorative sheet specimen 2 was produced in the same manner as specimen 1, except that a gloss control agent made of silica having particle shapes with particle size distribution peaks at approximately 2 μm and 7 μm was used.

[0081] Test specimen 3 Decorative sheet specimen 3 was produced in the same manner as specimen 1, except that a gloss control agent made of silica having particle shapes with particle size distribution peaks at approximately 4 μm and 9 μm was used.

[0082] Test specimen 4 Decorative sheet specimen 4 was produced in the same manner as specimen 1, except that a gloss control agent made of silica having particle shapes with particle size distribution peaks at approximately 6 μm and 12 μm was used.

[0083] Test specimen 5 Decorative sheet specimen 5 was produced in the same manner as specimen 1, except that 1% by mass of a gloss adjusting agent was mixed with 100 parts by mass of the binder resin.

[0084] Test specimen 6 A decorative sheet specimen 6 was produced in the same manner as specimen 1, except that 30% by mass of a gloss adjusting agent was mixed with 100 parts by mass of the binder resin.

[0085] Test specimen 7 First, a printing ink made by adding 10 parts by mass of colorant to 100 parts by mass of binder resin made of urethane resin and mixing it in a solvent is printed on the surface side of an opaque film-shaped colored resin layer (70 μm thick) made of polypropylene (PP) resin containing a colorant, and then cured and dried to form a pattern layer (2 μm thick).

[0086] Next, an anchor layer (2 μm thick) is provided by applying urethane resin to the surface side of the design layer and curing and drying it. Next, a transparent adhesive layer (10 μm thick) and a transparent resin layer (70 μm thick) are laminated by co-extruding PP resin onto the surface side of the anchor layer while heating and melting it to form a film shape.

[0087] Then, a first surface protective layer and a second surface protective layer were provided to form a surface protective layer in the same manner as in specimen 1. In this way, specimen 7 of the decorative sheet was produced.

[0088] Comparison body 1 A comparative decorative sheet specimen 1 was prepared in the same manner as test specimen 1, except that a gloss control agent made of silica particles having a particle size distribution peak only at 3 μm was used.

[0089] Comparison body 2 Comparative decorative sheet specimen 2 was prepared in the same manner as specimen 1, except that a gloss control agent made of silica particles having a particle size distribution peak only at 8 μm was used.

[0090] Comparison 3 Comparative decorative sheet specimen 3 was prepared in the same manner as specimen 7, except that a gloss control agent made of silica particles having a particle size distribution peak only at 3 μm was used.

[0091] [Evaluation test method] <Specular gloss> The specular gloss was determined in accordance with the Japanese Industrial Standards (JIS) "Z8741". In Table 1, "G1(85)" is the 85-degree specular gloss of the first surface protective layer, "G2(85)" is the 85-degree specular gloss of the second surface protective layer, "G2(60)" is the 60-degree specular gloss of the second surface protective layer, "G(85-85)" is the difference in 85-degree specular gloss between the first surface protective layer and the second surface protective layer, and "G(85-60)" is the difference between the 60-degree specular gloss and the 85-degree specular gloss of the second surface protective layer. In addition, the gloss meter used was "Microgloss (registered trademark) 4561 (product number)" manufactured by BYK Corporation.

[0092] Visual Evaluation The appearance of the test specimens 1 to 7 and the comparative specimens 1 to 3 was visually inspected to evaluate their three-dimensional effect and texture. The results are shown in Table 1. In Table 1, the case where the three-dimensional effect and texture were sufficient is indicated by "○", and the case where the three-dimensional effect and texture were insufficient is indicated by "×".

[0093] Scratch Resistance Evaluation Steel wool rubbing tests were performed on test specimens 1 to 7 and comparative specimens 1 to 3 under the conditions shown below, and the damage state was visually confirmed to evaluate scratch resistance. The results are shown in Table 1. In Table 1, cases where there was almost no change in gloss are indicated with "○", cases where there was a slight change in gloss are indicated with "△", and cases where there was a clear change in gloss are indicated with "×".

[0094] Test conditions Steel wool: Bonstar (registered trademark) #1 (product number) manufactured by Bonstar Sales Co., Ltd. Load capacity: 200g ·Distance: 5cm ·Number of rubbing: 10 times back and forth rubbing

[0095] [Evaluation test results] The evaluation test results for test specimens 1 to 7 and comparative specimens 1 to 3 are shown in Table 1 below.

[0096] [Table 1]

[0097] As can be seen from Table 1, comparative gloss regulator 3, which has a transparent resin layer made of PP and a single-peak particle size distribution, had a "G(85-85)" of over 50 and a "G(85-60)" of over 10, failing to achieve a sufficient three-dimensional effect and texture. Comparative gloss regulators 1 and 2, which have a transparent resin layer made of PVC and a single-peak particle size distribution, had a "G(85-85)" of 50 or less, but also had a "G(85-60)" of over 10, failing to achieve a sufficient three-dimensional effect and texture.

[0098] In contrast, in specimens 1 to 7, which were gloss adjusters with a twin-peak particle size distribution, not only was "G(85-85)" 50 or less, but also "G(85-60)" was 10 or less, and sufficient three-dimensional effect and texture were obtained. Here, in specimen 7, in which the transparent resin layer is PP, "G(85-85)" was 50 or less, and "G(85-60)" was 10 or less, and sufficient three-dimensional effect and texture were obtained. In addition, in specimens 1 to 3 and 5 to 7, which were gloss adjusters with a particle size distribution peak of 10 μm or less, loss of the gloss adjuster from the second surface protective layer was suppressed, and good scratch resistance was also obtained.

[0099] Therefore, the effectiveness of the decorative sheet according to the present invention was confirmed. [Industrial Applicability]

[0100] The decorative sheet of the present invention has a high quality, three-dimensional texture when viewed from various directions, and can therefore be used extremely beneficially in a variety of industries, including as the exterior of furniture, housing equipment, and home appliances. [Explanation of symbols]

[0101] 10 Decorative Sheet 10a Emboss 11 Colored resin layer 12 Picture layer 12a Picture 13 Transparent resin layer 14 Surface protective layer 14a First surface protective layer 14b Second surface protective layer 20 Decorative Sheet 21 Colored resin layer 22 Picture layer 23 Transparent resin layer 25 Anchor Layer 26 Transparent adhesive layer

Claims

1. An opaque layer; A pattern layer provided on the surface side of the opaque layer; A transparent resin layer provided on the surface side of the design layer; a surface protective layer provided on the surface side of the transparent resin layer; A decorative sheet comprising: The surface protective layer is a first surface protective layer provided on the transparent resin layer side; a second surface protective layer provided on a portion of the surface side of the first surface protective layer; having The first surface protective layer and the second surface protective layer have a difference in 85-degree specular gloss within a range of 1 or more and 50 or less, Of the first surface protective layer and the second surface protective layer, the other layer having a lower 85 degree specular gloss than the other layer has a difference between its 60 degree specular gloss and its 85 degree specular gloss in the range of 2 to 10. A decorative sheet characterized by:

2. The other layer contains a gloss control agent in particle form, The gloss adjusting agent has a particle size distribution with multiple peaks.

2. The decorative sheet according to claim 1.

3. The other layer contains the gloss adjusting agent in an amount of 1% by mass or more and 30% by mass or less.

3. The decorative sheet according to claim 2.

4. The gloss adjusting agent has a peak in the particle size distribution in the range of 1 μm or more and 10 μm or less.

3. The decorative sheet according to claim 2.

5. The gloss adjusting agent has a particle size distribution peak in the range of 2 μm to 4 μm and in the range of 7 μm to 9 μm, respectively.

5. The decorative sheet according to claim 4.

6. The second surface protective layer is provided on the surface side of the first surface protective layer so as to match the pattern of the pattern layer.

2. The decorative sheet according to claim 1.

7. The transparent resin layer and the surface protective layer have embossments formed in at least one of a concave shape and a convex shape.

2. The decorative sheet according to claim 1.

8. The embossing is formed on the transparent resin layer and the surface protective layer so as to be in harmony with the pattern of the pattern layer.

8. The decorative sheet according to claim 7.

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