Laminate and decorative sheet

Abstract

To provide a laminate and a decorative sheet, capable of reducing the formation of cracks in a colored resin layer, even when the colored resin layer is provided following a pattern layer.SOLUTION: A decorative sheet 10 comprises a transparent base layer 11, a pattern layer 12 provided on the back side of the transparent base layer 11, and a colored resin layer 13 containing a pigment and provided on the back side of the pattern layer 12, wherein the colored resin layer 13 comprises a two-part curable resin, with a curing agent mixed in an amount of 6 pts.mass or more and 10 pts.mass or less per 100 pts.mass of a mixture of the resin and the pigment.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a laminate and a decorative sheet. [Background technology]

[0002] For example, decorative sheets used for building materials are required to have a concealing property so that they can be used regardless of the color tone of the building material they are covering. In addition, in order to reduce the amount of material used and to reduce costs when the sheets are no longer in use, they are required to be as thin as possible. Some decorative sheets have a colored resin layer in which a pigment is contained in the resin at a high concentration.

[0003] However, a colored resin layer containing a high concentration of pigment in the resin is prone to cracking, which not only impairs the appearance but also reduces physical properties and adhesion. Therefore, for example, Patent Document 1 below proposes that the pigment content and thickness of the layer be adjusted to suppress the occurrence of cracks. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-224062 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, even if a colored resin layer does not cause cracks when provided next to a base layer, cracks may occur when provided next to a design layer.

[0006] This problem is not limited to the decorative sheets described above, but can occur in any laminate that includes a base layer made of resin, a pattern layer provided on the back surface of the base layer, and a pigment-containing colored resin layer provided on the back surface of the pattern layer, such as a packaging material that requires light-blocking properties.

[0007] In view of the above, an object of the present invention is to provide a laminate and a decorative sheet which are capable of suppressing the occurrence of cracks in a colored resin layer even when a colored resin layer is provided next to a design layer. [Means for solving the problem]

[0008] In order to solve the above-mentioned problems, the laminate of the present invention is a laminate comprising a transparent substrate layer, a pattern layer provided on the back surface of the transparent substrate layer, and a colored resin layer containing a pigment provided on the back surface of the pattern layer, wherein the colored resin layer contains a two-component curing resin and is mixed with 6 parts by mass or more and 10 parts by mass or less of a curing agent per 100 parts by mass of a mixture of the resin and the pigment.

[0009] In the laminate according to the present invention, it is preferable that the colored resin layer is a mixture of 300 parts by mass or more and 1000 parts by mass or less of the pigment with respect to 100 parts by mass of the resin.

[0010] In the laminate according to the present invention, it is preferable that the two-component curing resin in the above-mentioned laminate is a mixture of a polyurethane resin and an isocyanate curing agent.

[0011] In the laminate according to the present invention, it is preferable that the design layer in the above-mentioned laminate contains a polyurethane resin.

[0012] The laminate according to the present invention is preferably the above-mentioned laminate, further comprising a barrier layer provided on the back surface of the colored resin layer.

[0013] The laminate according to the present invention is preferably the laminate described above, further comprising an underlayer provided on the rear surface of the barrier layer.

[0014] The laminate according to the present invention is preferably the laminate described above, further comprising a surface protective layer provided on the surface of the transparent substrate layer.

[0015] On the other hand, in order to solve the above-mentioned problems, the decorative sheet according to the present invention is characterized by comprising the above-mentioned laminate. Effect of the Invention

[0016] According to the laminate and decorative sheet of the present invention, the colored resin layer has sufficient strength and toughness, so that even if the colored resin layer is provided on a pattern layer, it can withstand stress associated with the difference in volume change rate between the colored resin layer and the pattern layer when drying, thereby suppressing the occurrence of cracks. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic configuration of a main embodiment of a decorative sheet using a laminate according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The laminate and 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.

[0019] [Main embodiment] A main embodiment of a decorative sheet utilizing a laminate according to the present invention will be described with reference to FIG.

[0020] <Overall structure of decorative sheet> As shown in Fig. 1, a design layer 12 having a design printed thereon is provided on the back surface (the bottom surface in Fig. 1) of a transparent substrate layer 11 containing a transparent resin as a support. A colored resin layer 13 containing a pigment to provide hiding properties is provided on the back surface (the bottom surface in Fig. 1) of the design layer 12.

[0021] A barrier layer 14 that suppresses gas permeation is provided on the back surface (lower surface in FIG. 1) of the colored resin layer 13. A base layer 15 that improves adhesion to an attachment surface such as a flooring material or a wall surface is provided on the back surface (lower surface in FIG. 1) of the barrier layer 14. A surface protection layer 16 that contains a transparent resin that protects the outermost surface and adjusts the gloss is provided on the front surface (upper surface in FIG. 1) of the transparent substrate layer 11. The above-mentioned layers 11 to 16 of the decorative sheet 10 according to this embodiment will be described in more detail below.

[0022] <Transparent base material layer 11> A film in which a weathering agent or the like is added to a transparent thermoplastic resin is applied as the transparent substrate layer 11. The thermoplastic resin constituting the transparent substrate layer 11 is not particularly limited, and the same material as the thermoplastic resin used as a substrate or the like in conventional decorative sheets can be used.

[0023] Specific examples of thermoplastic resins include polyolefin-based resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate, polyarylate, and polycarbonate; and olefin-based resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, and ethylene-unsaturated carboxylic acid copolymer metal neutralized product (ionomer). Examples of the resin include polyolefin-based resins such as poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polyacrylamide, and other acrylic resins, polyamide-based resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, styrene-based resins such as polystyrene, AS resin, and ABS resin, vinyl-based resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, and polyvinyl butyral, fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer, and mixtures, copolymers, composites, and laminates of two or more of these resins.

[0024] In particular, in view of the recent increase in social interest in environmental issues, it is not preferable to use a thermoplastic resin containing chlorine (halogen), such as polyvinyl chloride resin, as the thermoplastic resin, and it is preferable to use a non-halogen thermoplastic resin. In particular, from the viewpoints of various physical properties, processability, versatility, economic efficiency, etc., it is preferable to use a polyester resin (amorphous or biaxially stretched) or a polyolefin resin as the non-halogen thermoplastic resin, and more preferably, a polyolefin resin. For example, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more as the polyolefin resin.

[0025] The transparent substrate layer 11 preferably contains, as necessary, one or more additives selected from various additives 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.

[0026] The transparent substrate layer 11 preferably has a thickness of 50 μm or more and 150 μm or less, and more preferably 70 μm or more and 120 μm or less. When the transparent substrate layer 11 has a thickness of 50 μm or more, the decorative sheet 10 can be given a suitable strength when used as a flooring material, and scratch resistance can be improved. In particular, when the transparent substrate layer 11 has a thickness of 70 μm or more, the strength can be further increased, and scratch resistance can be more reliably improved.

[0027] On the other hand, when the thickness of the transparent substrate layer 11 is 150 μm or less, the decorative sheet 10 can be made both thin and strong while suppressing defects such as whitening and cracking during processing, i.e., improving processability, and maintaining sufficient transparency to allow the pattern of the pattern layer 12 to be seen from the front side (the side of the base layer 15). In particular, when the thickness of the transparent substrate layer 11 is 120 μm or less, the decorative sheet 10 can be made both thin and strong while more reliably improving processability.

[0028] <Pattern layer 12> The design layer 12 is formed by printing a design with ink such as polyurethane resin by a printing method or the like, and is provided mainly for the purpose of imparting design. As the printing method, various printing methods such as gravure printing, offset printing, letterpress printing, flexographic printing, screen printing, inkjet printing, and electrostatic printing can be applied.

[0029] Examples of inks that can be used include polyurethane-based resins, vinyl chloride-vinyl acetate-based inks (cyan, magenta, yellow), and colorants such as organic or inorganic dyes or pigments. It is also possible to use inks in which various additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, defoamers, leveling agents, surfactants, and drying agents are dispersed in a binder made of a synthetic resin or the like together with a solvent or diluent.

[0030] The type of pattern of the picture layer 12 may be any type depending on the purpose of use, the preferences of the user, etc., and common examples include wood grain patterns, stone patterns, abstract patterns, etc. The types of patterns are not limited to the types exemplified above, and may be, for example, a full-surface solid print.

[0031] <Colored resin layer 13> The colored resin layer 13 is, for example, printed by a two-component curing resin containing a pigment by gravure printing or the like, and is provided mainly for the purpose of imparting hiding power. Examples of pigments include titanium oxide. The pigment content is preferably 300 parts by mass or more and 1000 parts by mass or less (particularly 825 parts by mass or less) per 100 parts by mass of resin. If the content is less than 300 parts by mass, it becomes difficult to sufficiently conceal, which is undesirable, and if the content exceeds 1000 parts by mass, the amount of resin connecting the pigments together becomes insufficient, making it difficult to form a layer, which is undesirable.

[0032] An example of a two-component curing resin is a mixture of a polyurethane resin and an isocyanate curing agent. The curing agent must be mixed in an amount of 6 to 10 parts by mass per 100 parts by mass of the mixture of the resin and the pigment. If the amount is less than 6 parts by mass, when the resin is applied on the pattern layer 12, it cannot withstand the stress caused by the difference in the volume change rate from the pattern layer 12 when it dries, and cracks are likely to occur, and if the amount exceeds 10 parts by mass, insufficient hiding is likely to occur.

[0033] The colored resin layer 13 preferably has a thickness of 3 μm to 15 μm, more preferably 5 μm to 9 μm. If the thickness is less than 3 μm, it is difficult to sufficiently conceal the colored resin layer 13, which is undesirable, and if the thickness exceeds 15 μm, it is too thick and prone to cracking and insufficient drying, which is undesirable.

[0034] <Barrier layer 14> The barrier layer 14 is formed by coating or printing, for example, a two-component curing acrylic resin using a bar coater or gravure printing method, and is provided mainly for the purpose of suppressing gas permeation.

[0035] The barrier layer 14 is 1 g / m 2 It is preferable that the content is 3 g / m or more. 2 It is more preferable that the barrier layer 14 has a thickness of 6 g / m or more. 2 In other words, the barrier layer 14 has a solid content of 1 g / m or less. 2 More than 6g / m 2 It is preferable to apply or print a two-component curing acrylic resin so that the solid content is 3 g / m or less. 2 It is more preferable to apply or print a two-component curing acrylic resin so that the thickness is 1 g / m or more. 2 If it is less than 6 g / m, it may be difficult to sufficiently suppress the permeation of gases and liquids. 2 If the amount exceeds this range, the liquid will become excessive and take a long time to evaporate, which may result in insufficient drying, which may cause adverse effects.

[0036] <Base layer 15> The undercoat layer 15 is formed, for example, by printing a polyurethane resin using a gravure printing method or the like, and is provided primarily for the purpose of improving adhesion. It also has functions such as surface stabilization after surface treatment, imparting tackiness, and preventing deterioration of the adhesive.

[0037] The undercoat layer 15 is 1 g / m 2 More than 5g / m 2 In other words, the solid content of the undercoat layer 15 is preferably 1 g / m or less. 2 More than 5g / m 2 It is preferable to print the polyurethane resin so that the thickness is 1 g / m 2 If it is less than 5 g / m, it may be difficult to fully exert the function as a base. 2 If the amount exceeds this range, the liquid will become excessive and take a long time to evaporate, which may result in insufficient drying, which may cause adverse effects.

[0038] <Surface protective layer 16> The surface protective layer 16 is printed by various printing methods and is provided for the purpose of imparting functions (surface properties) such as abrasion resistance, water resistance, weather resistance, scratch resistance, stain resistance, design, etc. The surface protective layer 16 has a degree of transparency (for example, colorless transparent, colored transparent, translucent, etc.) that allows various layers located on the back surface side to be seen through.

[0039] The thickness of the surface protection layer 16 is not particularly limited, but if it is too thick or too thin, it will be ineffective, and if it is too thick, it will have reduced flexibility and be prone to cracking, so the thickness is preferably 2 μm or more and 20 μm or less, and more preferably 4 μm or more and 10 μm or less.

[0040] In order to provide weather resistance, the surface protective layer 16 preferably contains an ultraviolet absorbing agent such as a benzotriazole, benzoate, benzophenone, triazine, cyanoacrylate, etc. In addition, the surface protective layer 16 preferably contains a hindered amine-based light radical scavenger (hindered amine-based light stabilizer) in order to capture harmful radicals and prevent deterioration of the resin itself due to light, heat, water, etc.

[0041] Moreover, it is preferable that the surface protective layer 16 is subjected to an antiviral treatment. Examples of the antiviral treatment include adding an antiviral agent to the surface of the surface protective layer 16, and applying an antiviral agent to the surface of the surface protective layer 16. As the antiviral agent, for example, a silver-based inorganic additive carrying silver ions (for example, "Bioside (registered trademark) TB-B100 (product number)" manufactured by Taisho Technos Co., Ltd.) is preferably used. Furthermore, it is preferable that the surface protective layer 16 contains various functional additives such as an antibacterial agent and an antifungal agent.

[0042] The surface protective layer 16 has a high gloss undercoat layer 16A provided on the entire surface of the transparent substrate layer 11, and a low gloss matte topcoat layer 16B provided on a portion of the surface of the undercoat layer 16A so as to match the pattern of the pattern layer 12. Since the surface protective layer 16 has the undercoat layer 16A and the topcoat layer 16B, the various functional agents described above can be added to both the undercoat layer 16A and the topcoat layer 16B, or only to the topcoat layer 16B located on the surface side of the surface protective layer 16.

[0043] 《Undercoat layer 16A》 The material of the undercoat layer 16A may be, for example, a thermosetting resin, an ionizing radiation curing resin, etc. The thermosetting resin may be, for example, a reaction product such as an acrylic urethane resin that uses an acrylic polyol compound as a base compound and an isocyanate compound as a curing agent.

[0044] Examples of the acrylic polyol compound include acrylic polymer compounds having hydroxyl groups in the side chains, which are obtained by blending and copolymerizing ordinary acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate with monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate, and, if necessary, copolymerizable polymerizable monomers such as styrene, α-methylstyrene, vinyl toluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl versatate, ethyl vinyl ether, acrylonitrile, and methacrylonitrile.

[0045] Examples of isocyanate compounds that can be used include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), etc. When weather resistance is taken into consideration, non-yellowing isocyanate compounds that do not have an aromatic ring, that is, aliphatic or alicyclic isocyanate compounds, are preferred.

[0046] The ionizing radiation curable resin may be, for example, a composition mainly composed of at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group, which has the property of undergoing a crosslinking reaction when irradiated with ionizing radiation. Additives such as a polymerization initiator and a sensitizer may be added to the ionizing radiation curable resin as necessary.

[0047] Examples of the prepolymer or oligomer having a polymerizable unsaturated bond that can be used include melamine (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polyol (meth)acrylate. As the monomer, for example, monofunctional monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; bifunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, and hexanediol diacrylate; and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate can be used.

[0048] The ionizing radiation for curing the ionizing radiation curable resin is electromagnetic waves or charged particles having energy capable of causing a curing reaction of the molecules in the ionizing radiation curable resin (composition). Generally, ultraviolet rays or electron beams are used, but visible light, X-rays, ion beams, etc. can also be used.

[0049] Examples of the ultraviolet light source that can be used include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. The wavelength of the ultraviolet light is usually preferably in the range of 190 nm to 380 nm.

[0050] As the electron beam source, various electron beam accelerators can be used, such as Cockcroft-Walton type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Among them, those capable of irradiating electrons having an energy in the range of 100 keV to 1000 keV are particularly preferred, and those capable of irradiating electrons having an energy in the range of 100 keV to 300 keV are more preferred.

[0051] The undercoat layer 16A contains a filler. For example, inorganic filler, organic filler, etc. can be applied as the filler. For example, spherical, irregular, plate-like, needle-like, fibrous, etc. can be applied as the particle shape of the filler. By containing the filler, the undercoat layer 16A forms unevenness on the surface, and these unevenness forms unevenness on the surface of the topcoat layer 16B, that is, the surface of the surface protection layer 16. Note that the topcoat layer 16B does not contain such a filler.

[0052] The undercoat layer 16A preferably has a filler content of 5% by mass to 35% by mass based on the total solid content, and the undercoat layer 16A preferably has a thickness of 1 μm to 15 μm, more preferably 2.5 μm to 6.5 μm.

[0053] 《Top coat layer 16B》 The material of the topcoat layer 16B is a silicone-modified acrylic urethane resin. The silicone-modified acrylic urethane resin is a resin obtained by adding an isocyanate compound to an acrylic polyol compound and a reactive silicone oil and then curing the mixture. By using the silicone-modified acrylic urethane resin, it is possible to improve the stain resistance and to create a matte design.

[0054] The reactive silicone oil may be, for example, one obtained by introducing a primary hydroxyl group into the terminal alkyl group of a polysiloxane resin. The thickness of the topcoat layer 16B is preferably 1 μm or more and 5 μm or less, and more preferably 1.5 μm or more and 3.5 μm or less.

[0055] Embossed section In order to impart a three-dimensional design to the surface of the surface protection layer 16, an embossed portion 16a is formed on the outermost surface side in harmony with the pattern (e.g., a wood grain vessel pattern) of the pattern layer 12. The embossed portion 16a can have any concave-convex shape, such as a wood grain vessel shape, a stone grain shape, a cloth grain shape, an abstract pattern shape, a Japanese paper shape, a suede shape, a leather shape, a matte texture shape, a sand grain shape, a hairline shape, a group of parallel straight lines, or a combination of these.

[0056] <Method of manufacturing decorative sheet 10> A method for manufacturing the decorative sheet 10 according to the present embodiment as described above will now be described. First, a film made of a thermoplastic resin is prepared as the transparent substrate layer 11, and a pattern is printed on the back surface of the film, which is one side of the film, using an ink such as a polyurethane resin by a printing method or the like to provide a pattern layer 12. Next, a two-component curing resin containing a pigment is printed on the pattern layer 12 by a gravure printing method or the like to provide a colored resin layer 13. At this time, the curing agent is mixed in an amount of 6 parts by mass to 10 parts by mass with respect to 100 parts by mass of the mixture of the resin and the pigment.

[0057] Next, a two-component curing acrylic resin is applied or printed on the colored resin layer 13 by a bar coater, gravure printing, or the like to provide a barrier layer 14. Then, a polyurethane resin is printed on the barrier layer 14 by gravure printing, or the like to provide an undercoat layer 15. Then, a thermosetting resin or an ionizing radiation curing resin is applied to the surface that will become the other side of the transparent substrate layer 11 and cured to provide an undercoat layer 16A.

[0058] Furthermore, an isocyanate compound is added to the acrylic polyol compound and reactive silicone oil, and the mixture is applied onto the undercoat layer 16A in a manner corresponding to the pattern of the pattern layer 12, and then cured to provide the topcoat layer 16B. By providing the surface protective layer 16 having the embossed portions 16a in this manner, the decorative sheet 10 can be obtained.

[0059] <Action and effect of decorative sheet 10> In the decorative sheet 10 according to the present embodiment thus manufactured, the colored resin layer 13 made of a two-component curing resin is mixed with 6 to 10 parts by mass of a curing agent per 100 parts by mass of the mixture of resin and pigment. Therefore, since the colored resin layer 13 has sufficient strength and toughness, even if the colored resin layer 13 is provided on the design layer 12, it can withstand the stress caused by the difference in the volume change rate between the colored resin layer 13 and the design layer 12 when drying, and therefore no cracks will occur.

[0060] Therefore, according to the decorative sheet 10 of this embodiment, even if the colored resin layer 13 is provided next to the design layer 12, the occurrence of cracks in the colored resin layer 13 can be suppressed.

[0061] In addition, since the colored resin layer 13 and the picture layer 12 are bridged together to increase their strength, the adhesive strength of the decorative sheet 10 can be increased.

[0062] [Other embodiments] In the above embodiment, the decorative sheet 10 is provided with the barrier layer 14, the base layer 15, and the surface protective layer 16, but the present invention is not limited to this. In other embodiments, the barrier layer 14, the base layer 15, and the surface protective layer 16 can be omitted as appropriate depending on the purpose, etc.

[0063] In the above embodiment, the case of the decorative sheet 10 has been described, but the present invention is not limited thereto. For example, any laminate including a transparent substrate layer, a pattern layer provided on the back surface of the transparent substrate layer, and a pigment-containing colored resin layer provided on the back surface of the pattern layer, such as a packaging material that requires light blocking properties, can be applied in the same manner as the decorative sheet 10 of the above embodiment. EXAMPLES

[0064] Examples of the laminate and decorative sheet according to the present invention will be specifically described below, but the present invention is not limited to only the specific examples described below.

[0065] [Production of test specimens and comparison specimens] Test specimen 1 A wood grain pattern was printed with polyurethane resin ink by gravure printing on the back side of a transparent base layer (70 μm thick) made of a polypropylene resin film to form a pattern layer. Next, an isocyanate curing agent (6 parts by mass) was mixed with the base agent (100 parts by mass) of a mixture of a polyurethane two-component curing resin and titanium oxide (825 parts by mass per 100 parts by mass of resin), and printed on the pattern layer by gravure printing to form a colored resin layer (7 μm thick).

[0066] Then, on the other surface of the transparent substrate layer, a highly glossy undercoat layer (4.5 μm thick) was formed by coating and curing an acrylic urethane-based two-component curing resin containing an acrylic polyol compound as a base material and an isocyanate compound as a curing agent, which contained an inorganic filler (35 mass%). Furthermore, a topcoat layer (2.5 μm thick) was formed by adding an isocyanate compound curing agent to an acrylic polyol compound and reactive silicone oil as a base material, coating the undercoat layer in a manner corresponding to the pattern of the pattern layer, and curing the mixture. By forming a surface protective layer in this way, a decorative sheet specimen 1 was produced.

[0067] Test specimen 2 A barrier layer (5 g / m2) was created by printing a two-component curing acrylic resin on the colored resin layer using the gravure printing method. 2 A decorative sheet specimen 2 was prepared in the same manner as specimen 1, except for providing the following:

[0068] Test specimen 3 Decorative sheet specimen 3 was produced in the same manner as specimen 2, except that the amount of hardener mixed in the colored resin layer was 8 parts by mass.

[0069] Test specimen 4 Decorative sheet specimen 4 was produced in the same manner as specimen 2, except that the amount of hardener mixed in the colored resin layer was 10 parts by mass.

[0070] Comparison body 1 A comparative decorative sheet sample 1 was produced in the same manner as test sample 1, except that the design layer was omitted and the amount of hardener mixed in the colored resin layer was 4 parts by mass.

[0071] Comparison body 2 A comparative decorative sheet sample 2 was produced in the same manner as test sample 1, except that the amount of hardener mixed into the colored resin layer was 4 parts by mass.

[0072] Comparison 3 A comparative decorative sheet sample 3 was produced in the same manner as test sample 2, except that the amount of hardener mixed into the colored resin layer was 12 parts by mass.

[0073] [Test Contents] <Crack check> The appearance of test specimens 1 to 4 and comparative specimens 1 to 3 was visually inspected to check for the presence or absence of cracks. The results are shown in the following Table 1. In Table 1, "◯" indicates a case where there was no crack, and "×" indicates a case where there was a crack.

[0074] Concealment The color difference ΔE was obtained when the test specimens 1 to 4 and the comparative specimens 1 to 3 were placed on a medium density fiberboard made of softwood (light-colored MDF) and on a medium density fiberboard made of hardwood (dark-colored MFD). At this time, the CIE standard illuminant D65 was used and measurements were taken with a color difference meter "CR-400" manufactured by Konica Minolta, Inc. The results are shown in Table 1. In Table 1, "○" indicates that the color difference ΔE was 2.0 or less and thus the hiding power was high, and "×" indicates that the color difference ΔE was more than 2.0 and thus the hiding power was low.

[0075] <Adhesion strength> First, a water-based urethane adhesive was applied to create an adhesive layer (80 g / m 2 A 3 mm thick medium density fiberboard (MDF) with a tensile strength of 111 kg / m was attached to the back of each of the test specimens 1 to 4 and the comparative specimens 1 to 3, and compressed and fixed (111 kg / m 2 × 72 hours) to prepare decorative boards of test specimens 1 to 4 and comparative specimens 1 to 3.

[0076] Then, two cuts (1 inch wide) were made with a cutter for test specimens 1-4 and comparative specimens 1-3, and the adhesion strength required to peel the cut portion of the decorative sheet from the MDF was measured. The results are shown in Table 1 below. In Table 1, "◯" indicates that the adhesion strength is the same as or greater than that of comparative specimen 1, indicating sufficient adhesion strength, and "×" indicates that the adhesion strength is less than that of comparative specimen 1, indicating insufficient adhesion strength.

[0077] [Test Results] The test results are shown in Table 1.

[0078] [Table 1]

[0079] As can be seen from Table 1, in comparative sample 1 without a design layer, even though the hardener in the colored resin layer was 4 parts by mass, no cracks were generated and the sample had high concealing properties. However, in comparative sample 2 with a design layer, cracks were generated and the adhesive strength was reduced. In comparative sample 3 with 12 parts by mass of hardener in the colored resin layer, there was no crack generation or reduction in adhesive strength, but there was insufficient concealment.

[0080] In contrast, specimens 1 to 4, in which the curing agent in the colored resin layer was 6 to 10 parts by mass, not only had sufficient hiding power but also did not develop cracks, but also demonstrated sufficient adhesive strength.

[0081] From the above, it is recognized that the laminate and decorative sheet of the present invention can suppress the occurrence of cracks in the colored resin layer and increase the adhesive strength to the substrate, even when a colored resin layer is provided next to a design layer. [Industrial Applicability]

[0082] The laminate and decorative sheet of the present invention can suppress the occurrence of cracks in the colored resin layer even when a colored resin layer is provided next to a design layer, and can therefore be used with great advantage in various industries including the construction industry. [Explanation of symbols]

[0083] 10 Decorative Sheet 11 Transparent base layer 12 Picture layer 13 Colored resin layer 14 Barrier Layer 15 Base layer 16 Surface protective layer 16A Undercoat layer 16B Top coat layer 16a Embossed section

Claims

1. A transparent substrate layer; A pattern layer provided on the back surface of the transparent substrate layer; a colored resin layer containing a pigment provided on the back surface of the picture layer; A laminate comprising: The colored resin layer contains a two-component curing resin, and is obtained by mixing 6 parts by mass or more and 10 parts by mass or less of a curing agent with respect to 100 parts by mass of a mixture of the resin and the pigment. A laminate comprising:

2. The colored resin layer is a mixture of 300 parts by mass or more and 1000 parts by mass or less of the pigment with respect to 100 parts by mass of the resin. The laminate according to claim 1 .

3. The two-component curing resin is a mixture of a polyurethane resin and an isocyanate curing agent. The laminate according to claim 1 .

4. The design layer contains a polyurethane resin. The laminate according to claim 1 .

5. A barrier layer is provided on the back surface of the colored resin layer. The laminate according to claim 1 .

6. A base layer is provided on the back surface of the barrier layer. The laminate according to claim 5 .

7. A surface protective layer is provided on the surface of the transparent substrate layer. The laminate according to claim 1 .

8. The laminate according to any one of claims 1 to 7 is used. A decorative sheet characterized by:

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