Decorative sheet and decorative material

Abstract

To provide a decorative sheet that maintains scratch and abrasion resistance, ensuring that impact marks or cracks from dropped items remain inconspicuous.SOLUTION: A decorative sheet 1 includes sequentially laminated layers as follows: a colored thermoplastic resin layer 2, a pattern layer 3, a transparent thermoplastic resin layer 5, and a surface protective layer 6 containing an ionizing radiation-curable resin. The transparent thermoplastic resin layer 5, structured as a multilayer having three or more layers, is a single layer formed through extrusion molding using a resin composition containing a transparent polypropylene-based thermoplastic resin. A nanosized additive is applied solely to a specific layer of the multilayer in the transparent thermoplastic resin layer 5. Specifically, the nanosized additive is applied solely to one of the two layers on the surface protective layer 6 side.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Conventionally, many decorative sheets using olefin resins have been proposed. In addition, decorative sheets in which nano-sized additives are added to the resin layer that constitutes the decorative sheet for the purpose of improving scratch resistance have also been proposed (for example, see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-168830 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, flooring in which a decorative sheet or decorative paper with a printed wood grain pattern is bonded to a substrate has come into widespread use. When an end user drops something on a flooring with this decorative sheet bonded to it, the decorative sheet may tear or crack, or the substrate may become exposed, resulting in poor appearance. For this reason, there has been a demand for a decorative sheet that is less likely to cause poor appearance, such as scratches on the floor, even when an object is dropped on it.

[0005] Therefore, this invention has been made with attention to the above-mentioned unresolved problems in the conventional art, and aims to provide a decorative sheet that is less susceptible to impact scratches and cracks caused by falling objects while maintaining scratch resistance and abrasion resistance. [Means for solving the problem]

[0006] According to one embodiment of the present invention, a decorative sheet is provided in which a colored thermoplastic resin layer, a design layer, a transparent thermoplastic resin layer, and a surface protective layer containing an ionizing radiation curable resin are laminated in this order, the transparent thermoplastic resin layer is a single layer formed by extrusion molding using a resin composition containing a transparent polypropylene-based thermoplastic resin so as to form a multi-layer structure of three or more layers, and nano-sized additives are added to only a specific layer of the multiple transparent thermoplastic resin layers, the specific layer being one of the two layers on the surface protective layer side.

[0007] According to another aspect of the present invention, there is provided a decorative material comprising the decorative sheet of the above aspect and a substrate provided on the side of the colored thermoplastic resin layer opposite the pattern layer via an adhesive layer. Effect of the Invention

[0008] According to one aspect of the present invention, it is possible to realize a decorative sheet that is resistant to impact scratches and cracks caused by falling objects while maintaining scratch resistance and abrasion resistance. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic example of the configuration of a decorative sheet according to the present invention. [Diagram 2] FIG. 1 is a cross-sectional view showing a schematic example of a configuration of a decorative material according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] An embodiment of the present invention will now be described with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. differ from the actual ones. Furthermore, the embodiments shown below are examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, structures, etc. of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims.

[0011] [Configuration of decorative sheet] FIG. 1 is a cross-sectional view showing a schematic example of the configuration of a decorative sheet 1. As shown in FIG. The decorative sheet 1 is a polypropylene-based decorative sheet to be attached to substrates such as wood-based substrates, inorganic substrates, synthetic resin substrates, and metal substrates, and is a decorative sheet particularly for areas where scratch resistance, impact resistance, and caster resistance are required, such as floors. The decorative sheet 1 comprises a colored thermoplastic resin layer 2 as a base sheet, a picture pattern layer 3, an adhesive layer 4, a transparent thermoplastic resin layer 5, and a surface protection layer 6 laminated in this order.

[0012] The colored thermoplastic resin layer 2 functions as a buffer layer and is a layer for improving abrasion resistance. The picture pattern layer 3 is a layer for imparting design to the decorative sheet 1 with a desired design. The adhesive layer 4 is a layer for adhering the picture pattern layer 3 to the transparent thermoplastic resin layer 5. The transparent thermoplastic resin layer 5 is a layer for preventing scratches from occurring to the decorative sheet 1. The surface protection layer 6 is provided on the outermost layer of the decorative sheet 1, and is a layer provided for imparting functions such as weather resistance, scratch resistance, stain resistance, and design to the decorative sheet 1.

[0013] Next, each layer will be described in detail. [Colored thermoplastic resin layer] The colored thermoplastic resin layer 2 is a sheet-shaped thermoplastic resin composition obtained by adding a pigment, an inorganic filler, a stabilizer, etc. to a thermoplastic resin. For example, a polyethylene resin can be used as the thermoplastic resin. The thermoplastic resin is not limited to a polyethylene resin, and other resins such as a polypropylene resin can also be used.

[0014] The thickness of the colored thermoplastic resin layer 2 is not particularly limited and can be set according to the product characteristics, but is usually preferably in the range of 50 μm to 200 μm. If the thickness of the colored thermoplastic resin layer 2 is within the above numerical range, it can fully exhibit the hiding power required as a decorative sheet, and also has sufficient strength as a substrate and can suppress deterioration of scratch resistance. If necessary, additives may be blended into the colored thermoplastic resin layer 2. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, and colorants described below. The blending amount of additives can be appropriately set depending on the product characteristics.

[0015] The colorant is not particularly limited, and known colorants such as pigments and dyes can be used. For example, inorganic pigments such as titanium white, zinc oxide, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black; organic pigments (including dyes) such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and aniline black; metal pigments such as aluminum and brass; and pearlescent (pearl) pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (concealing coloring), which can be selected arbitrarily. For example, when the background color of the adherend (the base material to which the decorative sheet is adhered) is to be colored and concealed, opaque coloring may be selected. On the other hand, when the background pattern of the adherend can be visually observed, transparent coloring may be selected.

[0016] One or both sides of the colored thermoplastic resin layer 2 may be subjected to a surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, etc., as necessary. For example, when corona discharge treatment is performed, the surface tension of the surface of the colored thermoplastic resin layer 2 may be set to 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

[0017] A primer layer (e.g., a back primer layer for facilitating adhesion of an adherend, or a front primer layer for facilitating formation of a picture pattern layer) may be provided on one or both sides of the colored thermoplastic resin layer 2 as necessary. By providing a primer layer, it is possible to increase interlayer adhesion with an adjacent layer (e.g., an adherend). Details of the back primer layer (primer layer 7) will be described later.

[0018] [Pattern layer] The picture pattern layer 3 imparts design to the decorative sheet 1 with a desired pattern, and the type of pattern is not particularly limited. Examples include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-stained patterns, geometric figures, letters, symbols, and abstract patterns. The method for forming the picture pattern layer 3 is not particularly limited, and for example, it may be formed by a printing method using a colored ink, coating agent, etc. obtained by dissolving (or dispersing) a known colorant (dye or pigment) together with a binder resin in a solvent (or dispersion medium).

[0019] Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, Prussian blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; and luminous pigments. These colorants can be used alone or in combination of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizers, surfactants, and the like.

[0020] Examples of binder resins include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, etc. These resins can be used alone or in combination of two or more.

[0021] Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion mediums) can be used alone or in combination of two or more.

[0022] Examples of printing methods used to form the picture pattern layer 3 include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. When forming a solid picture pattern layer over the entire surface, examples of coating methods include roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating. In addition, hand-drawing, ink-flowing, photography, transfer printing, laser beam drawing, electron beam drawing, partial deposition of metals, etching, and the like may be used, or may be used in combination with other forming methods.

[0023] The thickness of the picture pattern layer 3 is not particularly limited and can be appropriately set depending on the product characteristics, but the layer thickness at the time of coating is preferably 1 μm to 15 μm, and the layer thickness after drying is preferably 0.1 μm to 10 μm. Various additives such as an ultraviolet absorbing agent, a radical scavenger, a dispersing agent, etc. may be added to the picture pattern layer 3 as necessary.

[0024] [Adhesive layer] The adhesive layer 4 is not particularly limited as long as it is transparent, and does not include colorless transparent, colored transparent, translucent, etc. For example, as the adhesive layer 4, an adhesive known in the field of decorative sheets can be used. Examples of adhesives known in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins, and vinyl acetate resins, and curable resins such as thermosetting urethane resins. Two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent may also be used.

[0025] The adhesive layer 4 can be formed, for example, by applying an adhesive onto the picture pattern layer 3, applying a transparent polypropylene-based resin that constitutes the transparent thermoplastic resin layer 5, and then drying and curing the applied adhesive. The conditions such as the drying temperature and drying time are not particularly limited, and may be set appropriately depending on the type of adhesive. The method of applying the adhesive is not particularly limited, and may be, for example, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, or the like.

[0026] The thickness of the adhesive layer 4 is not particularly limited, but the thickness after drying is preferably 0.1 μm or more and 30 μm or less, and more preferably 1 μm or more and 20 μm or less. If the picture pattern layer 3 and the transparent thermoplastic resin layer 5 can be bonded together without providing the adhesive layer 4, the adhesive layer 4 does not necessarily have to be provided.

[0027] [Transparent thermoplastic resin layer] The transparent thermoplastic resin layer 5 is a support for the decorative sheet 1 and is made of a polypropylene-based thermoplastic resin. The thickness of the transparent thermoplastic resin layer 5 is preferably 70 μm or more and 150 μm or less. If the thickness of the transparent thermoplastic resin layer 5 is within the range of 70 μm or more and 150 μm or less, sufficient effects can be obtained in terms of impact resistance and caster resistance. In terms of design, the presence of the transparent thermoplastic resin layer 5, in combination with the picture pattern layer 3, has the effect of stabilizing depth and dimension.

[0028] 1, the transparent thermoplastic resin layer 5 is formed by laminating, in this order from the picture pattern layer 3 side, an adhesive resin layer 51, an intermediate layer 52, and an upper layer 53. The adhesive resin layer 51, the intermediate layer 52, and the upper layer 53 are each made of a resin composition containing a transparent polypropylene resin, and these three layers are formed by extrusion molding. In addition, in the drawing of Figure 1, the transparent thermoplastic resin layer 5 is depicted as if the adhesive resin layer 51, the intermediate layer 52, and the upper layer 53 form separate layers, but in reality, the adhesive resin layer 51, the intermediate layer 52, and the upper layer 53 are continuous and form a single-layer sheet with no interface.

[0029] In the transparent thermoplastic resin layer 5, a nano-sized additive is added to either the intermediate layer 52 or the upper layer 53, and no nano-sized additive is added to the other layer or the adhesive resin layer 51. That is, in the transparent thermoplastic resin layer 5, a nano-sized additive is added only to the upper layer 53 or only to the intermediate layer 52, and no nano-sized additive is added to the other two layers. In this way, by adding a nano-sized additive only to the upper layer 53 or only to the intermediate layer 52 in the transparent thermoplastic resin layer 5 and not to the other two layers, the hardness of only a part of the transparent thermoplastic resin layer 5 is increased, and the hardness can be reduced compared to the case where a nano-sized additive is added to the entire transparent thermoplastic resin layer 5. Therefore, by providing a soft region in a part of the transparent thermoplastic resin layer 5, the impact when an object is dropped on the decorative sheet 1 is absorbed, thereby suppressing the occurrence of poor appearance such as tearing or cracking of the decorative sheet. Furthermore, of the three layers constituting the transparent thermoplastic resin layer 5, nano-sized additives are added to only one of the two layers located closer to the surface protection layer 6. This makes it possible to efficiently adjust the hardness by adjusting the hardness closer to the surface, where poor appearance is more likely to occur.

[0030] In addition, when the transparent thermoplastic resin layer 5 includes four or more layers, it is preferable to add the nano-sized additive to only one specific layer of the four or more layers, and it is preferable that one of the two layers located on the surface protective layer 6 side is designated as the specific layer, and the nano-sized additive is added only to this specific layer, and not to the other layers except for the specific layer. An antiviral agent may be added to the transparent thermoplastic resin layer 5. For example, a silver-based inorganic additive (Biocide TB-B100) carrying silver ions manufactured by Taisho Technos Co., Ltd. may be used as the antiviral agent. The antiviral agent is not limited to being added to the transparent thermoplastic resin layer 5, and the antiviral agent may be applied only to the surface of the transparent thermoplastic resin layer 5 facing the surface protective layer 6. In addition, various additives such as an ultraviolet absorber, a radical scavenger, an antioxidant, and a processing stabilizer may be added to the transparent thermoplastic resin layer 5 as necessary.

[0031] [Upper layer] The upper layer 53 is composed of a transparent thermoplastic resin made of transparent polypropylene resin, and when a nano-sized additive is added, it is composed of a transparent polypropylene resin and a transparent thermoplastic resin formed by adding a nucleating agent vesicle having a single-layer outer membrane and encapsulating a nucleating agent as a nano-sized additive. The transparent polypropylene resin contained in the upper layer 53 does not have to be the same as the transparent polypropylene resin in the intermediate layer 52, and can be selected arbitrarily.

[0032] [Polypropylene resin] The polypropylene resin used in the transparent thermoplastic resin layer 5 may be a highly flexible random polypropylene resin having an ethylene content, or a mixture of a known amorphous polypropylene resin with a random polypropylene resin or a homopolypropylene resin having high crystallinity. In applications where processability such as bending is more important, for example, a random polypropylene resin having an ethylene content within a predetermined range or a known amorphous polypropylene resin may be mixed with a highly crystalline homopolypropylene resin.

[0033] In this embodiment, the polypropylene resin used in the transparent thermoplastic resin layer 5 may contain 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin, which is a propylene homopolymer having an isotactic pentad fraction (mmmm fraction) of 95% or more, relative to the mass of the total polypropylene resin. If the highly crystalline homopolypropylene resin is less than 30% by mass, the crystallinity is insufficient and sufficient strength may not be obtained.

[0034] Here, the isotactic pentad fraction (mmmm fraction) is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating a resin material at a predetermined resonance frequency by 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclear species) with a mass of 13, and specifies the atomic arrangement, electronic structure, and molecular microstructure in the resin material. The pentad fraction of a crystalline polypropylene resin is the ratio of five propylene units lined up as determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. The pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface, and basically, the higher the pentad fraction, the higher the crystallinity.

[0035] The polypropylene resin of this embodiment may be, for example, a mixture of polypropylene resin (a) with free-end long-chain branching and polypropylene resin (b) without free-end long-chain branching, in which the molecular weight distribution Mw / Mn, defined as the mass average molecular weight / number average molecular weight of the mixture, is in the range of 1 to 5, and the isotactic index, defined as the boiling heptane soluble residue fraction, of the mixed resin of polypropylene resin (a) and polypropylene resin (b) is in the range of 1 to 90%. This makes it possible to suppress whitening and cracking during folding processing after the decorative sheet 1 is bonded to, for example, a floor base material layer 21 described below.

[0036] Here, the molecular weight distribution is defined as the ratio Mw / Mn, where Mn=Σ(Mi×Ni) / ΣNi and Mw=Σ(Ni×Mi2) / Σ(Ni×Mi), where Mw / Mn is the number average molecular weight when there are Ni molecules with molecular weight Mi. The closer to 1, the narrower the molecular weight distribution and the higher the uniformity. If this molecular weight distribution is kept below 5, the molecular weight can be made to a necessary and sufficient size, which helps to suppress whitening and cracking. Generally, the molecular weight distribution can be measured by gel permeation chromatography (GPC).

[0037] In addition, the isotactic index, which is defined as the boiling heptane soluble residue fraction, is useful as an index for investigating the degree of crystallinity in polypropylene resin. Specifically, a sample is extracted with boiling n-heptane for a certain period of time, and the mass (%) of the unextracted portion is calculated to calculate the isotactic index. In detail, the cylindrical filter paper is dried at 110±5°C for 2 hours, left in a constant temperature and humidity room for more than 2 hours, and then 8g to 10g of the sample (powder or flake form) is placed in the cylindrical filter paper and precisely weighed using a weighing cup and tweezers. This is set on top of an extractor containing about 80cc of heptane, and the extractor and cooler are assembled. This is heated in an oil bath or electric heater, and extraction is performed for 12 hours. The heating is adjusted so that the number of drops from the cooler is 130 or more per minute. Next, the cylindrical filter paper containing the extraction residue is taken out and placed in a vacuum dryer to dry for 5 hours at 80°C and a vacuum of 100mmHg or less. After drying, leave it in a constant temperature and humidity room for 2 hours, then weigh it accurately and calculate the isotactic index by (P / Po) x 100, where Po is the sample mass (g) before extraction and P is the sample mass (g) after extraction.

[0038] By setting the isotactic index at 90% or less, the sheet stiffness caused by polypropylene crystals can be suppressed. Methods for lowering the isotactic index include, for example, using an amorphous polypropylene component (syndiotactic polypropylene, adactic polypropylene, etc.) in part, randomly copolymerizing one or more olefin monomers such as ethylene or α-olefin, and adding various rubber components (such as ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), isoprene rubber (IR), etc.).

[0039] In addition, the melt tension of the mixed resin of polypropylene resin (a) and polypropylene resin (b) (tension when extruding at 60 mm / min at 230°C and taking up at 2 mm / min using a 2.0 mm diameter nozzle capillary rheometer) is preferably in the range of 100 mN to 500 mN, more preferably in the range of 300 mN to 400 mN. If it exceeds 500 mN, the melt viscosity becomes too high and stable film formation becomes impossible. If it is 100 mN or less, the long chain branching components become insufficient, making it difficult to obtain the desired performance.

[0040] In addition, by setting the melt flow rate at 230°C of the mixture of polypropylene resin (a) and polypropylene resin (b) in the range of 5g / 10min to 50g / 10min as specified by JIS-K6760, the molecular weight can be maintained at a certain value or more and a stable film formation state can be maintained. A more suitable range of the melt flow rate is in the range of 10g / 10min to 30g / 10min, and more preferably in the range of 10g / 10min to 25g / 10min. If the melt flow rate exceeds 50g / 10min, the effect (neck-in) of the resin melt-extruded from the T-die during melt extrusion through the T-die to gather in the center increases, and the end thickness of the resin melt-extruded from the T-die increases. The increase in the thickness of the end affects the decrease in cooling efficiency and the thickness stability in the width direction, making it difficult to form a stable film. Furthermore, if the rate is lower than 5 g / 10 min, the draw resonance of the molten resin will deteriorate, and the molten resin will not be able to keep up with the gap between the speed of the molten resin immediately after it leaves the T-die (initial speed) and the speed of the resin immediately after it touches the cooling roll, making it difficult to produce a stable film.

[0041] [Nucleating Agent Vesicle] The nano-sized additive contained in the upper layer 53 is used by being added to the polypropylene resin in the form of nucleating agent vesicles encapsulated in vesicles having a single-layer outer membrane. The upper layer 53 contains a nucleating agent, which can improve the crystallinity and can improve the scratch resistance, impact resistance, caster resistance, etc. of the decorative sheet 1. Note that in this embodiment, the nucleating agent in the resin constituting the upper layer 53 may be encapsulated in vesicles with a portion of the nucleating agent exposed.

[0042] It is preferable that the average particle size of the nano-sized nucleating agent is less than half the wavelength range of visible light. Specifically, since the wavelength range of visible light is within the range of 400 nm or more and 750 nm or less, it is preferable that the average particle size is less than 375 nm.

[0043] Nano-sized nucleating agents have extremely small particle diameters, so the number of nucleating agents present per unit volume and the surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes close, so that when crystal growth occurs from the surface of one nucleating agent particle added to the polypropylene resin, the end from which the crystal is growing immediately comes into contact with the end of the crystal growing from the surface of another nucleating agent particle adjacent to the one nucleating agent particle, and the ends of the crystals inhibit each other's growth, stopping the growth of each crystal. For this reason, the average particle size of the spherulites in the crystalline part of the crystalline polypropylene resin can be reduced, for example, the spherulite size can be reduced to 1 μm or less. As a result, a colored polypropylene film with high crystallinity and high hardness can be obtained, and the stress concentration between the spherulites that occurs during bending processing can be efficiently dispersed, so that a colored polypropylene film that suppresses cracking and whitening during bending processing can be realized.

[0044] Here, when the nucleating agent is simply added, the particle size of the nucleating agent in the polypropylene resin increases due to secondary aggregation, and the number of crystal nuclei relative to the amount of nucleating agent added may be significantly smaller than when the nucleating agent is added as a vesicle. As a result, the average particle size of the spherulites in the crystalline portion of the polypropylene resin becomes large, and cracking and whitening during bending may not be suppressed. Therefore, it may not be possible to improve the elastic modulus and processability by increasing the crystallinity at the same time.

[0045] In addition, as a method for nano-sizing the nucleating agent, for example, a solid-phase method in which the nucleating agent is mainly mechanically pulverized to obtain nano-sized particles, a liquid-phase method in which nano-sized particles are synthesized or crystallized in a solution in which the nucleating agent or the nucleating agent is dissolved, and a gas-phase method in which nano-sized particles are synthesized or crystallized from a gas or vapor containing the nucleating agent can be appropriately used. Examples of the solid-phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, and a jet mill. Examples of the liquid-phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid-phase reduction method, and a hydrothermal synthesis method. Examples of the gas-phase method include an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

[0046] The method of nano-sizing the nucleating agent is preferably the supercritical reverse phase evaporation method. The supercritical reverse phase evaporation method is a method of producing a capsule (nano-sized vesicle) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030MPa), and carbon dioxide under temperature or pressure conditions above the critical point means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical condition.

[0047] In addition, a specific nano-processing method using the supercritical reverse phase evaporation method involves first injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance, and stirring the mixture to generate an emulsion of supercritical carbon dioxide and aqueous phase. Next, the pressure is reduced, causing the carbon dioxide to expand and evaporate, resulting in phase inversion, and generating nanocapsules (nanovesicles) in which the phospholipids cover the surface of the nucleating agent particles with a single layer membrane. Unlike conventional encapsulation methods in which the outer membrane on the surface of the nucleating agent particles becomes multiple membranes, this supercritical reverse phase evaporation method makes it easy to generate capsules with a single layer membrane, making it possible to prepare capsules with smaller diameters.

[0048] The nucleating agent vesicle can be prepared by, for example, the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method, etc. Among these, the supercritical reverse phase evaporation method is particularly preferred. The outer membrane constituting the nucleating agent vesicle is, for example, composed of a monolayer membrane, and the outer membrane is composed of a substance containing a biological lipid such as a phospholipid.

[0049] In this embodiment, a nucleating vesicle whose outer membrane is composed of a material containing a biological lipid such as a phospholipid is referred to as a nucleating liposome. Examples of phospholipids constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin; and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0050] Other substances that become the outer membrane of the vesicle include dispersants such as nonionic surfactants and mixtures of these with cholesterols or triacylglycerol. Among these, the nonionic surfactants may be one or more of polyglycerol ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly 2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The cholesterols may be, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, cholecalciferol, etc.

[0051] The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet 1 of this embodiment, it is preferable that the nucleating agent vesicle is a radical scavenger liposome having an outer membrane containing a phospholipid, and by forming the outer membrane from a phospholipid, it is possible to improve the compatibility between the resin material, which is the main component of the upper layer 53, and the vesicle.

[0052] The nucleating agent is not particularly limited as long as it is a substance that is the starting point of crystallization when the resin crystallizes. Examples of the nucleating agent include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts that are non-melting and can be expected to have good transparency, but if the material itself can be made transparent by the nano-processing, colored quinacridone, cyanine blue, talc, and the like can also be used. In addition, a non-melting nucleating agent may be appropriately mixed with melting benzylidene sorbitol.

[0053] As described above, adding the nucleating agent encapsulated in vesicles to the resin composition has the effect of dramatically improving the dispersibility of the nucleating agent in the resin material, i.e., in the transparent thermoplastic resin layer 5. On the other hand, it is expected that there may be cases where it is difficult to directly identify the nucleating agent encapsulated in the vesicles based on the structure and properties of the finished decorative sheet 1, depending on the circumstances, and this may be considered impractical. The reasons for this are as follows.

[0054] The nucleating agent added in the form of a vesicle is in a dispersed state with high dispersibility, and even in the state of the produced decorative sheet 1, the nucleating agent is highly dispersed in the transparent thermoplastic resin layer 5. However, in the production process of the decorative sheet 1, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and these treatments may cause the outer membrane of the vesicle containing the nucleating agent to be crushed or a chemical reaction to occur. For this reason, the treatment process of the decorative sheet 1 may cause the outer membrane of the nucleating agent in the completed decorative sheet 1 to be crushed or the state of the chemical reaction to vary, so that the nucleating agent is likely not to be enclosed (enveloped) by the outer membrane. If the nucleating agent is not enclosed by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself in a numerical range, and it is also expected that it may be difficult to determine whether the constituent material of the crushed outer membrane is the outer membrane of the vesicle or a material added separately from the nucleating agent. Thus, although this embodiment differs from the prior art in that the nucleating agent is highly dispersed in the decorative sheet 1, it is conceivable that there may be cases in which it is impractical to determine within a numerical range the structure and characteristics of the decorative sheet 1 that are analyzed based on measurements, whether this is because the nucleating agent is added in the form of vesicles encapsulating the nucleating agent.

[0055] [Middle class] The intermediate layer 52 is composed of a thermoplastic resin made of transparent polypropylene resin, and when a nano-sized additive is added, it is composed of a transparent thermoplastic resin formed by adding a nucleating agent vesicle having a single-layer outer membrane and a nucleating agent encapsulated therein as a nano-sized additive.

[0056] The transparent polypropylene resin and nano-sized additives used in the intermediate layer 52 are the same as those used in the upper layer 53, and therefore a detailed description thereof will be omitted.

[0057] [Adhesive resin layer] The adhesive resin layer 51 is formed, for example, from a transparent polypropylene resin that has been acid-modified, that is, from an acid-modified resin.

[0058] [Surface protective layer] An ionizing radiation curable resin, for example an acrylic resin composition, can be used for the surface protective layer 6. By forming the surface protective layer 6 made of an ionizing radiation curable resin, it is possible to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet 1.

[0059] The ionizing radiation curable resin is not particularly limited, and a transparent resin mainly composed of a prepolymer (including oligomer) and / or a monomer containing a radical polymerizable double bond in the molecule that can undergo a polymerization / crosslinking reaction when irradiated with ionizing radiation such as ultraviolet light or an electron beam can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a crosslinking curing reaction.

[0060] Specifically, the prepolymer or monomer has a (meth)acryloyl group in the molecule. Examples of the compound include a compound having a radical polymerizable unsaturated group such as a (meth)acryloyloxy group, a cationic polymerizable functional group such as an epoxy group, etc. Also preferred is a polyene / thiol-based prepolymer obtained by combining a polyene with a polythiol. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0061] Examples of prepolymers having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, etc. The molecular weight of these is usually preferably 250 or more and about 100,000.

[0062] Examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0063] Examples of prepolymers having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of polyenes include those obtained by adding allyl alcohol to both ends of polyurethanes made of diols and diisocyanates.

[0064] The ionizing radiation used to cure 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). Usually, ultraviolet rays or electron beams are used, but visible light, X-rays, ion beams, etc. may also be used. Examples of sources of ultraviolet light 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 ultraviolet light is usually preferably 190 nm or more and 380 nm or less.

[0065] 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 of 100 keV to 1000 keV, preferably 100 keV to 300 keV, are particularly preferred.

[0066] The surface protective layer 6 can be formed, for example, by applying an ionizing radiation curable resin onto the transparent thermoplastic resin layer 5 by a known coating method such as gravure coating or roll coating, and then curing the ionizing radiation curable resin by irradiating it with ionizing radiation. The thickness of the surface protective layer 6 is not particularly limited and can be appropriately set depending on the characteristics of the final product, but is usually from 0.1 μm to 50 μm, and preferably from 1 μm to 20 μm.

[0067] The surface protective layer 6 may contain various additives, such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, light scattering agents, and gloss adjusters, as required. The surface protective layer 6 may also contain functional additives, such as antibacterial agents, antifungal agents, and antiviral agents, as required.

[0068] [Primer layer] A primer layer 7 is formed on the surface of the colored thermoplastic resin layer 2 opposite to the picture pattern layer 3. The primer layer 7 is not necessarily required, and may be provided as necessary.

[0069] For example, polyester resin, polyurethane resin, or a mixture thereof can be used as the primer layer 7. Furthermore, by using a two-liquid type of polyol and isocyanate, the adhesion between the colored thermoplastic resin layer 2 and the primer layer 7 and the cohesive strength of the primer layer 7 itself are improved. Examples of polyols include acrylic polyols and polyester polyols. Examples of isocyanates include aromatic polyols such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic polyols such as hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. Aromatic polyols are preferred in terms of rapid reactivity and heat resistance.

[0070] The thickness of the primer layer 7 is preferably 1 μm or more and 10 μm or less. If the thickness of the primer layer 7 is less than 1 μm, it may be dissolved depending on the type of solvent of the adhesive, and the primer layer 7 may disappear, so that the adhesion may not be improved.

[0071] [Composition of decorative material] FIG. 2 is a cross-sectional view that illustrates an example of the configuration of the decorative material 20. As shown in FIG. The decorative material 20 is formed by bonding the colored thermoplastic resin layer 2 constituting the decorative sheet 1 and the floor base material layer 21 via a back surface adhesive layer 22. When a primer layer 7 of the colored thermoplastic resin layer 2 is provided, the primer layer 7 and the floor base material layer 21 are bonded together via the back surface adhesive layer 22.

[0072] [Back adhesive layer 22] A back adhesive layer 22 is formed between the colored thermoplastic resin layer 2 and the flooring base layer 21. The back adhesive layer 22 may be formed by applying a composition for forming the back adhesive layer 22 onto the flooring base layer 21, or may be formed by applying a composition for forming the back adhesive layer 22 onto the colored thermoplastic resin layer 2. The adhesive contained in the back adhesive layer 22 can be arbitrarily selected from, for example, urethane-based, acrylic-based, polyester-based, etc., depending on the combination with the thermoplastic resin contained in the colored thermoplastic resin layer 2.

[0073] The coating amount of the composition for forming the back adhesive layer 22 is 3 g / m 2 More than 20g / m 2 It is preferable that the coating amount of the composition for forming the back adhesive layer 22 is within the following range: 2 If the coating amount of the composition for forming the back surface adhesive layer 22 is less than 20 g / m, the adhesion between the colored thermoplastic resin layer 2 and the flooring base material layer 21 may be insufficient overall. 2 If this exceeds the limit, the application of the composition for forming the back adhesive layer 22 may become uneven, which may result in uneven adhesion between the colored thermoplastic resin layer 2 and the flooring base material layer 21.

[0074] [Base material layer for floor] As the material for the floor base material layer 21, any material similar to the base material (layer) in known floor materials, such as wood-based, metal-based, or synthetic resin-based materials, can be used.

[0075] [Method for manufacturing decorative sheet 1] A brief description will now be given of a method for producing the decorative sheet 1. Here, a case in which a nano-sized additive is added to the upper layer 53 will be described.

[0076] First, the picture pattern layer 3 is formed on the colored thermoplastic resin layer 2 by, for example, printing. Next, a resin composition containing molten transparent polypropylene resin and nano-sized additives to form upper layer 53, a resin composition containing molten transparent polypropylene resin but not containing nano-sized additives to form intermediate layer 52, and a resin composition containing molten transparent polypropylene resin to form adhesive resin layer 51 are extruded from a multi-layer extruder to form multiple layers, which are laminated on top of the picture pattern layer 3 to form a transparent thermoplastic resin layer 5 consisting of a laminated structure of the adhesive resin layer 51, intermediate layer 52 and upper layer 53 on top of the picture pattern layer 3.

[0077] Finally, a resin composition, for example, a urethane-based resin to which a curing agent, an ultraviolet absorber, and a light stabilizer have been added, is applied onto the transparent thermoplastic resin layer 5, and then the resin composition is dried to form the surface protective layer 6. In this manner, the decorative sheet 1 according to this embodiment is produced. When forming a decorative sheet 1 including an adhesive layer 4, a step of forming the adhesive layer 4 between the picture design layer 3 and the transparent thermoplastic resin layer 5 may be provided.

[0078] [Method of manufacturing decorative material 20] A method for producing the decorative material 20 will now be briefly described.

[0079] First, an adhesive that will become the back adhesive layer 8 is applied to the surface of the above-mentioned decorative sheet 1 on the side of the colored thermoplastic resin layer 2. Next, the decorative sheet 1 and the floor base material layer 21 are bonded together using a laminator to produce the decorative material 20. When the decorative sheet 1 is provided with a primer layer 7, the back surface adhesive layer 8 may be formed on the primer layer 7. [Effects of this embodiment] The decorative sheet 1 according to this embodiment is formed by laminating in this order a colored thermoplastic resin layer 2, a picture pattern layer 3, a transparent thermoplastic resin layer 5, and a surface protective layer 6. Furthermore, the transparent thermoplastic resin layer 5 is a single layer formed by extrusion molding using a resin composition containing a transparent polypropylene-based thermoplastic resin so as to have three or more layers, and among the multiple layers of the transparent thermoplastic resin layer 5, a nano-sized additive is added to only one specific layer, specifically, to only one of the two layers on the surface protective layer side.

[0080] With this configuration, the region of the transparent thermoplastic resin layer 5 closer to the surface protective layer 6 becomes a soft resin compared to when nano-sized additives are added to the entire transparent thermoplastic resin layer 5. Therefore, the surface hardness is ensured by the surface protective layer 6, and the impact of a dropped object can be absorbed by providing a relatively soft region in a part of the transparent thermoplastic resin layer 5, so that when an end user drops an object, the decorative sheet can be prevented from tearing, cracking, or causing defects in appearance such as the underlying substrate being visible. In this way, the occurrence of defects in appearance such as cracks can be prevented, and commercial rights can be maintained, and end users can be more satisfied, leading to an expansion of market share.

[0081] Furthermore, for example, in the case of a transparent thermoplastic resin layer 5 consisting of three layers, namely, an adhesive resin layer 51, an intermediate layer 52, and an upper layer 53, by adding a nano-sized additive to only one of the intermediate layer 52 and the upper layer 53, which are the layers closer to the surface protective layer 6, the hardness near the surface, where poor appearance is likely to occur, can be efficiently adjusted. EXAMPLES

[0082] Examples and comparative examples of the decorative sheet 1 according to the present invention will be described below. Note that the present invention is not limited to the following examples.

[0083] Example 1 A colored sheet made of polyethylene resin having a thickness of 55 μm (manufactured by RIKEN TECHNOS CORPORATION) was prepared as the colored thermoplastic resin layer 2 . A wood grain pattern was printed on one surface of this colored sheet by gravure printing using urethane ink to form a picture pattern layer 3. As the urethane ink, gravure ink ("Lamistar" manufactured by Toyo Ink Co., Ltd.) was used. Next, a multi-layer extruder was used to extrude the heated and melted polypropylene resin into a sheet having a thickness of 90 μm onto the other surface of the colored sheet, and a transparent thermoplastic resin layer 5 serving as a scratch-resistant clear layer was formed by extrusion lamination. As the polypropylene resin, a resin composition containing polypropylene resin without nano-sized additives for the upper layer 53, a resin composition containing polypropylene resin with nano-sized additives for the intermediate layer 52, and a resin composition containing polypropylene resin without nano-sized additives for the adhesive resin layer 51 were used.

[0084] Next, an ultraviolet-curable resin ("acrylic urethane resin" manufactured by DIC Graphics) was coated on the surface of the transparent thermoplastic resin layer 5 serving as a highly scratch-resistant layer to form a surface protective layer 6. In this way, the colored thermoplastic resin layer 2, the picture pattern layer 3, the transparent thermoplastic resin layer 5, and the surface protective layer 6 were laminated together, forming a decorative sheet 1 in which the nano-sized additives were added only to the middle layer 52 of the transparent thermoplastic resin layer 5, and no additives were added to the upper layer 53 and the adhesive resin layer 51.

[0085] Example 2 The decorative sheet 1 was formed in the same manner as in Example 1 above, except that the polypropylene resins used were a resin composition containing polypropylene resin with added nano-sized additives for the upper layer 53, a resin composition containing polypropylene resin with no added nano-sized additives for the middle layer 52, and a resin composition containing polypropylene resin with no added nano-sized additives for the adhesive resin layer 51.

[0086] Comparative Example 1 A decorative sheet was formed in the same manner as in Example 1 above, except that the polypropylene resins used were a resin composition containing polypropylene resin with added nano-sized additives for the upper layer, a resin composition containing polypropylene resin with added nano-sized additives for the middle layer, and a resin composition containing polypropylene resin without added nano-sized additives for the adhesive resin layer. (Evaluation method and criteria) The decorative sheets of the Examples and Comparative Examples prepared as described above were subjected to performance evaluation. The evaluation method and evaluation criteria were as follows.

[0087] (Scratch resistance) For each decorative sheet, a scratch test using a sapphire needle was carried out in accordance with JIS K5600-5-5 to measure the load at which the sheet started to be scratched. The load was varied in increments of 10 g. The load at which damage began to occur was rated as "◯" when it was 40 g or more, and "×" when it was 30 g or less. (Scratch test) A coin scratch test was conducted on each decorative sheet, and the load at which no continuous scratches were produced on the surface of the decorative sheet was measured. In the coin scratch test, a 10 yen coin was placed on the surface of the decorative sheet, and the test was started with a load of 1 kg, and the load was gradually increased by 1 kg at a time.

[0088] When no continuous scars were produced, the load was 2 kg or more and was marked as "◯", and when it was 1 kg or less, it was marked as "X". (Evaluation of dent resistance) To evaluate the dents made to flooring materials when a falling object was dropped, a DuPont impact test was conducted in accordance with JIS K-5400. The dents made to the flooring materials were visually confirmed under conditions of a hitting radius of 6.35 mm, a weight of 500 g, and a height of 500 mm.

[0089] The case where the cracks were not noticeable was marked with "O", and the case where the cracks were noticeable was marked with "X". (Evaluation Results) The evaluation results for each decorative sheet are as shown in Table 1 below.

[0090] [Table 1]

[0091] As shown in Table 1, in both cases where nano-sized additives were added only to the middle layer 52 (Example 1) and where nano-sized additives were added only to the upper layer 53 (Example 2), all evaluation items were favorable, and it was confirmed that scratch resistance and abrasion resistance were maintained and the occurrence of cracks due to falling objects could be suppressed. On the other hand, when nano-sized additives were added to both the upper layer 53 and the intermediate layer 52, the sapphire scratch test was favorable, but cracks were noticeable in the DuPont impact test.

[0092] The present invention can have the following configurations, for example. (1) A colored thermoplastic resin layer; A pattern layer and A transparent thermoplastic resin layer; a surface protection layer containing an ionizing radiation curable resin; and The decorative sheet is characterized in that the transparent thermoplastic resin layer is a single layer formed by extrusion molding using a resin composition containing a transparent polypropylene-based thermoplastic resin so as to have three or more layers, and a nano-sized additive is added to only a specific layer of the multiple layers of the transparent thermoplastic resin layer, and the specific layer is one of the two layers on the surface protective layer side.

[0093] (2) the transparent thermoplastic resin layer is a single layer having three layers including an adhesive resin layer provided on the side of the picture pattern layer, The decorative sheet according to (1) above, characterized in that the nano-sized additive is added to only one of the other two layers, excluding the adhesive resin layer, out of the three layers.

[0094] (3) The decorative sheet according to (1) or (2) above, A decorative material comprising: a substrate provided on the surface of the colored thermoplastic resin layer opposite the picture pattern layer via an adhesive layer. [Explanation of symbols]

[0095] 1 Decorative sheet 2 Colored thermoplastic resin layer 3. Pattern layer 4 Adhesive layer 5 Transparent thermoplastic resin layer 6 Surface protective layer 20 Cosmetic materials 21 Floor base material layer 22 Back adhesive layer 51 Adhesive resin layer 52 Middle Class 53 Upper layer

Claims

1. A colored thermoplastic resin layer; A pattern layer and A transparent thermoplastic resin layer; a surface protection layer containing an ionizing radiation curable resin; and The decorative sheet is characterized in that the transparent thermoplastic resin layer is a single layer formed by extrusion molding using a resin composition containing a transparent polypropylene-based thermoplastic resin so as to have three or more layers, and a nano-sized additive is added to only a specific layer of the multiple layers of the transparent thermoplastic resin layer, and the specific layer is one of the two layers on the surface protective layer side.

2. the transparent thermoplastic resin layer is a single layer having three layers including an adhesive resin layer provided on the side of the picture pattern layer, 2. The decorative sheet according to claim 1, wherein the nano-sized additive is added to only one of the other two layers other than the adhesive resin layer among the three layers.

3. The decorative sheet according to claim 1 or 2, A decorative material comprising: a substrate provided on the surface of the colored thermoplastic resin layer opposite the picture pattern layer via an adhesive layer.

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