Decorative sheet and method for manufacturing decorative sheet

Abstract

To provide a decorative sheet having a transparent resin layer which has high transparency from the viewpoint of designability, and excellent scratch resistance on the surface.SOLUTION: A decorative sheet includes at least a concealing layer 2, a pattern printing layer 3, a transparent resin layer 4 and a top coat layer 5 in this order, or a decorative sheet includes at least a concealing layer 2, a transparent resin layer 4 and a top coat layer 5 in this order, and has an embossed pattern 4a on the side of the top coat layer 5 of the transparent resin layer 4, wherein a value of a peak intensity ratio x calculated using the following expression from an absorption spectrum obtained in Fourier type infrared spectroscopy of the transparent resin sheet as the transparent resin layer 4 satisfies 0.65≤x≤0.85, and the transparent resin sheet is formed by adding a nano-sized nucleating agent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet used as a building material for the exterior and interior of buildings, the surface of fittings, the surface material of home appliances, etc., and relates to a decorative sheet having a transparent resin layer made of a transparent resin sheet in which a peak intensity ratio x calculated from an absorption spectrum obtained by Fourier infrared spectroscopy is specified to be within a predetermined range, and a method for manufacturing the decorative sheet. [Background technology]

[0002] In recent years, as shown in Patent Documents 1 to 5, many decorative sheets using olefin resins have been proposed as alternatives to decorative sheets made of polyvinyl chloride.

[0003] However, although these decorative sheets do not use polyvinyl chloride resin and thus suppress the generation of toxic gases and the like during incineration, they use ordinary polypropylene sheets or soft polypropylene sheets, which give them poor surface scratch resistance that is far inferior to the scratch resistance of conventional polyvinyl chloride decorative sheets.

[0004] Therefore, in order to eliminate these drawbacks, the present inventors proposed a decorative sheet having excellent surface scratch resistance and post-processability, as described in Patent Document 6. However, as the applications of decorative boards using such decorative sheets continue to expand and consumers' awareness of quality continues to increase, there is a demand for improvements in surface scratch resistance and post-processability for V-groove bending and the like.

[0005] In general, the mechanical properties of crystalline resins such as polypropylene can be changed by controlling the crystallinity, which is the ratio of crystalline to amorphous components in the resin, and factors for controlling this crystallinity include material factors such as the molecular structure of the resin itself and the addition of a nucleating agent, and process factors such as the molding conditions when processing the crystalline resin. In the present invention, the inventors have conducted extensive research, particularly focusing on process factors, and have completed a decorative sheet equipped with a resin sheet in which the range of crystallinity that provides excellent scratch resistance is specified by controlling the process factors. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-128843 [Patent Document 2] Japanese Patent Application Publication No. 4-083664 [Patent Document 3] Japanese Patent Application Publication No. 6-001881 [Patent Document 4] Japanese Patent Application Publication No. 6-198831 [Patent Document 5] Japanese Patent Application Publication No. 9-328562 [Patent Document 6] Patent No. 3772634 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a decorative sheet having a transparent resin layer that is highly transparent from the standpoint of design and has excellent surface scratch resistance, and a method for producing the decorative sheet. [Means for solving the problem]

[0008] In order to achieve the above object, the decorative sheet of the first aspect of the present invention is a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a top coat layer, in this order; or A decorative sheet comprising at least a transparent resin layer mainly composed of 90-100% by weight of polypropylene resin, in this order, and a topcoat layer, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, characterized in that the value of the peak intensity ratio x calculated from the absorption spectrum obtained in Fourier infrared spectroscopy measurement of the transparent resin sheet as the transparent resin layer using the following formula 1 is 0.65≦x≦0.85, and the transparent resin sheet is formed by adding a nano-sized nucleating agent. Here, in formula 1, I997 is the wave number of 997 cm -1 The peak intensity value of I938 is the wave number 938cm -1 The peak intensity value of I973 is the wave number 973 cm -1 The peak intensity values ​​are shown.

[0009]

number

[0010] By providing the decorative sheet according to the first aspect of the present invention, it is possible to provide a decorative sheet having a transparent resin layer with high transparency and excellent scratch resistance. Also, by providing the decorative sheet according to the first aspect of the present invention, it is possible to provide a decorative sheet which can reliably maintain the concealing property of the back side of the transparent layer by the concealing layer, and which has high design freedom due to the transparent layer.

[0011] A decorative sheet according to a second aspect of the present invention is a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer, in this order; or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer, in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, characterized in that the value of the peak intensity ratio x calculated using the above formula 1 from the absorption spectrum obtained in Fourier infrared spectroscopy measurement of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, and the transparent resin sheet is formed by adding a nucleating agent, and the nucleating agent is a metal salt of benzoic acid, a metal salt of pimelic acid, a metal salt of rosin, chitocridone, cyanine blue, or talc.

[0012] The decorative sheet of the third aspect of the present invention is a decorative sheet comprising at least a concealing layer, a picture-printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer, in this order; or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer, in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, characterized in that the value of the peak intensity ratio x calculated using the above formula 1 from the absorption spectrum obtained in Fourier infrared spectroscopy measurement of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, and the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles in which a nucleating agent is encapsulated in a vesicle having a single-layer outer membrane.

[0013] The decorative sheet of the fourth aspect of the present invention is characterized in that the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles in which the nucleating agent is encapsulated in a vesicle having a single-layer outer membrane.

[0014] The method for producing a decorative sheet of the present invention includes producing a decorative sheet having at least a concealing layer, a picture-printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a top coat layer in this order, or % as a main component and a topcoat layer, in that order, and the transparent resin layer has an embossed pattern on the surface of the topcoat layer side, characterized in that nano-sized nucleating agent vesicles having a vesicle with a single-layer outer membrane and encapsulating a nucleating agent are added to the crystalline polypropylene resin by supercritical reverse phase evaporation, and a transparent resin sheet is formed as the transparent resin layer so that the value of the peak intensity ratio x calculated using the above formula 1 from the absorption spectrum obtained in Fourier infrared spectroscopy measurement is 0.65≦x≦0.85. The method for producing a decorative sheet of the present invention is a method for producing a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, wherein the crystalline polypropylene resin The present invention is characterized in that a nucleating agent vesicle having a monolayer outer membrane and encapsulating a nucleating agent is added to a polypropylene resin by supercritical reverse phase evaporation, and a transparent resin sheet is formed as the transparent resin layer so that the value of the peak intensity ratio x calculated using the above formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy measurement is 0.65≦x≦0.85, and the nucleating agent is a metal salt of benzoic acid, a metal salt of pimelic acid, a metal salt of rosin, chitocridone, cyanine blue, or talc. Effect of the Invention

[0015] According to the present invention, it is possible to provide a decorative sheet having a transparent resin layer that has high transparency from the standpoint of design and excellent surface scratch resistance.

[0016] Furthermore, by adding a nano-sized nucleating agent to a transparent resin sheet, more specifically, a nucleating agent vesicle in which a nucleating agent is encapsulated in a vesicle having a single-layer outer membrane, a decorative sheet with extremely high transparency can be provided. [Brief description of the drawings]

[0017] [Figure 1] 1 is a cross-sectional view showing a first embodiment of a decorative sheet of the present invention. [Diagram 2] FIG. 3 is a cross-sectional view showing a second embodiment of the decorative sheet of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The decorative sheet of the present invention is a decorative sheet comprising at least a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and it is important that the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier infrared spectroscopy measurement of the transparent resin sheet as the transparent resin layer using the following formula 1 is x≧0.65. Here, in formula 1, I997 is the wave number of 997 cm -1 The peak intensity value of I938 is the wave number 938cm -1 The peak intensity value of I973 is the wave number 973 cm -1 The peak intensity values ​​are shown.

[0019]

number

[0020] In particular, the peak intensity ratio x of the transparent resin sheet is preferably 0.65≦x≦0.85. By setting the peak intensity ratio x within the above range, it is possible to provide a decorative sheet having a transparent resin layer with extremely excellent scratch resistance.

[0021] In the decorative sheet of the present invention, the peak intensity value x of the transparent resin sheet is set within the above range by controlling the film-forming conditions as process factors. At this time, it is important that the transparent resin sheet is formed to a thickness of 20 to 200 μm. If the thickness is thinner than the above range, scratch resistance cannot be ensured, and if the thickness is thicker than the above range, the resin sheet is not cooled uniformly in the thickness direction, and as a result, the resin cannot be cured uniformly. The transparent resin layer is preferably formed to a thickness of 30 to 150 μm.

[0022] The film-forming conditions for setting the peak intensity ratio x within the above range may be any conditions capable of adjusting the crystallinity of the polypropylene resin, and in the present invention, the crystallinity is adjusted by adjusting the resin temperature, cooling temperature, cooling time, etc. By controlling one or more of these conditions, the peak intensity ratio x can be set within the above range.

[0023] More specifically, the resin temperature is the temperature at which the molten resin is extruded during film formation, and the higher the resin temperature (the higher the temperature), the higher the peak intensity ratio x. The cooling temperature is the temperature at which the extruded resin is cooled, and the higher the cooling temperature (the higher the temperature), the higher the peak intensity ratio x. As for the cooling time, the peak intensity ratio x increases by lengthening the time it takes to pass through the vicinity of the crystallization temperature of the polypropylene resin (100 to 130°C). By combining the above conditions, the crystallization and crystal size in the resin can be controlled, and the peak intensity ratio x can be appropriately adjusted.

[0024] Here, Fourier infrared spectrometry will be described. First, infrared spectrometry is a measurement method that obtains information about the chemical structure and state of a substance by measuring infrared light absorbed by the substance, utilizing the principle that the amount of infrared light, which is light with a wavelength of 2.5 to 25 μm, absorbed by the substance changes based on the vibration and rotational motion of the molecules of the substance. A specific measurement method is to irradiate the substance with infrared light from a light source, generate an interference wave by synthesizing the divided transmitted light and reflected light, and calculate the light intensity of each wave number component from the signal intensity of the interference wave to measure the infrared spectrum. Particularly, in the present invention, the calculation of the interference wave is performed using the Fourier transform method, and the measurement is performed by Fourier infrared spectrometry, which is a method for measuring infrared spectra. A graph in which the wave number obtained by the above method is plotted on the horizontal axis and the measured absorbance (or transmittance) on the vertical axis is called an infrared absorption spectrum (or infrared transmission spectrum), and a unique pattern is recognized for each substance. In this case, the absorbance on the vertical axis changes as the peak intensity value at a given wavenumber in proportion to the concentration or thickness of the substance, or, in the case of a crystalline resin, the amount of crystalline or amorphous parts, making it possible to perform quantitative analysis from the height or area of ​​the peak.

[0025] In the present invention, the above-mentioned characteristics of the infrared absorption spectrum are utilized to obtain the absorbance at the wave number 997 cm corresponding to the absorbance of the crystalline part of the polypropylene transparent resin sheet in the absorption spectrum obtained by the above-mentioned measurement. -1 and the wavenumber 973 cm corresponding to the absorbance of the amorphous part of the transparent resin sheet. -1 The ratio of the peak intensity of the transparent resin sheet to the peak intensity of the 997 cm wavenumber, i.e., the peak intensity ratio x which represents the crystallinity of the polypropylene, is calculated using the above formula 1, the relationship between the peak intensity ratio x and the scratch resistance of the transparent resin sheet is clarified, and a decorative sheet having excellent scratch resistance is provided in which a transparent resin sheet having a peak intensity ratio x within a predetermined range is used for the transparent resin layer. -1 Peak intensity and wave number 973cm -1 The peak intensities are at wavenumber 938 cm -1 Background correction was performed using the peak intensity of

[0026] In addition, in the decorative sheet of the present invention, it is important to form the transparent resin sheet as the transparent resin layer by adding a nano-sized nucleating agent, and in particular, it is preferable to form the transparent resin sheet by adding a nucleating agent vesicle encapsulated in a vesicle having a single-layer outer membrane. By adding the nucleating agent vesicle to the polypropylene resin, the crystallinity of the polypropylene resin can be increased. By improving the transparency, a transparent resin sheet having extremely high transparency can be obtained.

[0027] The nucleating agent vesicle can be prepared by supercritical reverse phase evaporation. Supercritical reverse phase evaporation is a method for preparing nano-sized vesicles (capsules) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature conditions above the critical point 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 conditions above the critical point or pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition.

[0028] Specifically, an emulsion of supercritical carbon dioxide and aqueous phase is generated by injecting an aqueous phase into a mixture of supercritical carbon dioxide, phospholipids, and a nucleating agent as an encapsulating substance, and stirring the mixture. After that, when the pressure is reduced, the carbon dioxide expands and evaporates, causing a phase inversion, and nanovesicles are generated in which the phospholipids cover the surface of the nucleating agent nanoparticles with a monolayer membrane. This supercritical reverse phase evaporation method can generate vesicles with a monolayer membrane, making it possible to obtain vesicles of extremely small sizes.

[0029] The average particle size of the nucleating agent vesicle is preferably 1 / 2 or less of the visible light wavelength (400 to 750 nm), more specifically 200 nm to 375 nm or less. The nucleating agent vesicle is present in the resin composition in a state where the outer membrane of the vesicle is broken and the nano-sized nucleating agent is exposed. By making the particle size of the nucleating agent extremely small within the above range, it is possible to realize a transparent resin sheet with low light scattering and high transparency.

[0030] The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes, and examples thereof include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, chitocridone, cyanine blue, talc, etc. In particular, in the present invention, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts, which are expected to have transparency.

[0031] Examples of phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidiethanolamine, 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 phosphoryethanolamine, and ceramide phosphorylglycerol.

[0032] The crystalline polypropylene resin is not particularly limited, but it is preferable to use a highly crystalline homopolypropylene resin which is a propylene homopolymer, i.e., a homopolymer, having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more.

[0033] The pentad fraction (mmmm fraction) is calculated from a numerical value (electromagnetic wave absorptivity) obtained by resonating the resin composition constituting the transparent resin layer 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 composition. The pentad fraction of a 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. Such a 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 of the sheet, and therefore the better the scratch resistance.

[0034] The configuration of the decorative sheet of the present invention and a specific example of a method for producing this decorative sheet will be described below with reference to Figs.

[0035] 1 shows a first embodiment of the decorative sheet 1 of the present invention, and the decorative sheet 1 is formed by laminating a primer layer 6, a concealing layer 2, a picture print layer 3, a transparent resin layer 4, and a top coat layer 5 in this order from the side of the substrate B to which the decorative sheet 1 is attached. Examples of the substrate B include wood boards, inorganic boards, and metal plates.

[0036] For the primer layer 6, a binder such as nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc., can be used alone or modified from each of them. These can be in any form, such as water-based, solvent-based, or emulsion type. In addition, the curing method can be selected from a one-liquid type that cures alone, a two-liquid type that uses a curing agent in combination with a base agent, and a type that cures by irradiation with ultraviolet rays or electron beams. A common curing method is a two-liquid type that cures by combining an isocyanate-based curing agent with a urethane-based base agent, which is suitable from the viewpoints of workability, cost, and cohesive strength of the resin itself. In addition to the above binders, colorants such as pigments and dyes, extender pigments, solvents, and various additives are added. In particular, since the primer layer 6 is located on the rearmost surface of the decorative sheet 1, taking into consideration that the decorative sheet 1 will be wound up as a continuous plastic film (web-like), inorganic fillers such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added to prevent blocking, such as films adhering to each other and becoming difficult to slide or peeling off, and to improve adhesion to the adhesive. The layer thickness is preferably within the range of 0.1 to 3 μm, as the purpose is to ensure adhesion to the substrate B.

[0037] Basically, the material used for the primer layer 6 can be used for the concealing layer 2, but if the concealing property is important, it is preferable to use opaque pigments such as titanium oxide and iron oxide as the pigment. In order to further improve the concealing property, it is also preferable to add metals such as gold, silver, copper, and aluminum. In general, flaky aluminum is often added. The concealing layer 2 can be formed using the above materials by a comma coater, knife coater, lip coater, metal vapor deposition, sputtering, or the like. If the layer thickness is less than 2 μm, the concealing property is insufficient, and if it exceeds 10 μm, the cohesive force of the resin material as the main component becomes weak, so it is appropriate to make the thickness about 2 to 10 μm.

[0038] The pattern-printed layer 3 may be made of the same material as the primer layer 6. Examples of versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. The pattern-printed layer 3 may be formed by applying gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like to the transparent resin layer 4 using the above-mentioned materials. In addition to the method of forming the pattern-printed layer 3 by applying an ink made of a mixture of the binder and pigment, it is also possible to apply a pattern by vapor deposition or sputtering of various metals.

[0039] The transparent resin layer 4 may be a transparent resin sheet 4 formed by molding a resin composition containing 90-100% by weight of crystalline polypropylene resin as the main component, and optionally adding various additives such as existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, catalyst scatterers, colorants, light scattering agents, and gloss adjusters. In particular, for the decorative sheet 1 of the present invention, it is important to control the molding conditions and use a transparent resin sheet 4 having a peak intensity ratio x calculated from the infrared absorption spectrum measured by Fourier infrared spectroscopy using the above formula 1 such that x≧0.65. At this time, the transparent resin sheet The thickness of the sheet 4 is set to 20 to 200 μm. Specific examples of the molding conditions include the melting temperature of the resin composition, temperature conditions such as the extrusion temperature and roll temperature in film formation, and transport conditions such as the sheet winding speed. By controlling these temperature conditions and transport conditions, the crystallinity of the transparent resin sheet 4 obtained by adjusting the cooling rate during film formation is adjusted, and the peak intensity ratio x is set to x≧0.65, preferably 0.65≦x≦0.85.

[0040] Furthermore, a nucleating agent vesicle is added to the resin composition constituting the transparent resin layer 4. This makes it possible to easily improve the crystallinity of the resin composition, and to obtain a transparent resin sheet 4 with extremely excellent transparency.

[0041] As the heat stabilizer, a phenol-based, sulfur-based, phosphorus-based, hydrazine-based, etc. can be used. As the flame retardant, aluminum hydroxide, magnesium hydroxide, etc. can be used. As the ultraviolet absorbing agent, a benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, etc. can be used. As the light stabilizer, a hindered amine-based, etc. can be used.

[0042] The topcoat layer 5 can be appropriately selected from polyurethane, acrylic, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, etc. The form of the material is not particularly limited, and may be water-based, emulsion, solvent-based, etc. The curing method can be appropriately selected from one-liquid type that cures alone, two-liquid type that uses a curing agent together with a base agent, and type that cures by irradiation with ultraviolet rays or electron beams. In particular, a urethane-based base agent mixed with an isocyanate-based curing agent for curing is suitable from the viewpoints of workability, cost, cohesive strength of the resin itself, etc.

[0043] Here, a detailed film-forming flow of the transparent resin sheet 4 will be described. First, pellets of a resin composition to which various existing additives have been added as described above are put into a melt extruder, and the pellets are melted into a liquid form by heating and kneading, and the liquid resin composition is extruded from a T-die provided at the extrusion port toward a cooling roll provided downstream in a predetermined width. At this time, the liquid resin composition extruded from the T-die proceeds to crystallize until it reaches the cooling roll, and is completed by contacting the cooling roll. The cooling roll rotates around the central axis of the roll at a predetermined rotation speed, and the resin composition in contact with the cooling roll becomes a sheet-like transparent resin sheet 4, is transported downstream at a predetermined transport speed, and is finally wound up on a winding roll. In the present invention, in order to set the peak intensity ratio x of the obtained transparent resin sheet 4 within a predetermined range, the temperature of the resin composition extruded from the melt extruder, the temperature of the cooling roll, and the transport speed of the sheet as film-forming conditions are adjusted.

[0044] The decorative sheet 1 of this embodiment is formed by laminating the above-mentioned materials by the above-mentioned method on one side of the transparent resin sheet 4 formed by the above-mentioned film production flow, in the order of the picture printed layer 3, the concealing layer 2, and the primer layer 6. When an embossed pattern 4a is to be provided on the transparent resin layer 4, the transparent resin sheet 4 is pressed using an embossing mold roll to provide the embossed pattern 4a on the other side of the transparent resin sheet 4. Furthermore, a top coat layer 5 is formed on the side of the embossed pattern 4a to obtain the decorative sheet 1.

[0045] In the decorative sheet 1 of the first embodiment, it is preferable that the primer layer 6 is 0.1 to 3.0 μm, the concealing layer 2 is 2 to 10 μm, the picture printed layer 3 is 20 to 200 μm, the transparent resin sheet 4 as the transparent resin layer 4 is 20 to 100 μm, and the top coat layer 5 is 3 to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 130 to 500 μm.

[0046] 2 shows a second embodiment of the decorative sheet 1 of the present invention, and the decorative sheet 1 is formed by laminating a primer layer 6, a base fabric layer 7, a pattern printed layer 3, an adhesive layer 8, a transparent resin layer 4, and a top coat layer 5 in this order from the side of the substrate B to which the decorative sheet 1 is attached. Examples of the substrate B include wood boards, inorganic boards, and metal plates.

[0047] The primer layer 6, the picture print layer 3, the transparent resin layer 4 and the top coat layer 5 may have the same configuration as in the first embodiment.

[0048] The raw cloth layer 7 may be any of the following: paper such as tissue paper, titanium paper, and resin-impregnated paper; synthetic resins such as polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate polymer, polyvinyl alcohol, and acrylic; or foams of these synthetic resins; rubbers such as ethylene-propylene polymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, and polyurethane; organic or inorganic nonwoven fabrics; synthetic paper; and metal foils such as aluminum, iron, gold, and silver. When a raw cloth resin sheet 7 containing a polyolefin resin as the main component is used as the raw cloth layer 7, the surface is inactive, so it is preferable to subject both sides of the raw cloth resin sheet 7 to a surface activation treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, and dichromate treatment. Furthermore, a primer layer 6 may be provided between the raw cloth resin sheet 7 and the picture print layer 3 to ensure sufficient adhesion. Furthermore, when it is desired to impart concealment properties to the decorative sheet 1, a concealment layer 2 may be provided, or opaque pigments or the like may be added to the raw resin sheet 7 itself to impart concealment properties.

[0049] The adhesive layer 8 can be made of an acrylic, polyester, polyurethane, etc. In general, a two-liquid type material with a urethane polyol as the base agent and an isocyanate as the hardener is used because of its workability, cost, and high cohesive strength.

[0050] In the decorative sheet 1 of this embodiment, first, both sides of the original resin sheet 7 as the original layer 7 are subjected to corona treatment, and the pattern printed layer 3 and the primer layer 6 are laminated on one side of the original resin sheet 7 in this order. Then, the transparent resin sheet 4 as the transparent resin layer 4 formed by the above-mentioned film formation flow and the original resin sheet 7 on which the pattern printed layer 3 and the primer layer 6 are laminated are bonded and laminated by a method such as a method using heat and pressure, an extrusion lamination method, or a dry lamination method, via an adhesive layer 8, to form a laminated film. At this time, when an embossed pattern 4a is provided on the surface of the transparent resin layer 4, the embossed pattern 4a is formed on the laminated film by a method using heat and pressure, or a method using a cooling roll on which unevenness is formed. Finally, a topcoat layer 5 is laminated on the surface of the transparent resin layer 4 of the laminated film to obtain the decorative sheet 1.

[0051] In the decorative sheet 1 of the second embodiment, taking into consideration printing workability, cost, etc., it is desirable that the base layer 7 be 100 μm to 250 μm, the adhesive layer 8 be 1 μm to 20 μm, the transparent resin layer 4 be 20 μm to 200 μm, and the top coat layer 5 be 3 μm to 20 μm, and it is preferable that the total thickness of the decorative sheet 1 be in the range of 130 μm to 500 μm.

[0052] In the decorative sheet 1 of the present invention, as in the above embodiment, for the transparent resin sheet 4 as the transparent resin layer 4, the value of the peak intensity ratio x calculated using Formula 1 from the absorption spectrum obtained in Fourier infrared spectroscopy is within the range of x≧0.65, more preferably 0.65≦x≦0.85, thereby making it possible to provide a decorative sheet 1 having superior scratch resistance compared to conventional decorative sheets.

[0053] Furthermore, in the decorative sheet 1 of the present invention, a nano-sized nucleating agent, more specifically, a nucleating agent vesicle in which a nucleating agent is encapsulated in a vesicle having a single-layer outer membrane, is added to the resin composition that constitutes the transparent resin sheet 4, thereby achieving high dispersibility of the nucleating agent in the resin composition and improving the crystallinity of the resin composition by the nucleating agent, thereby providing a decorative sheet 1 having a transparent resin sheet 4 with high transparency.

[0054] Specific examples of the decorative sheet 1 and the method for producing the decorative sheet 1 of the present invention will be described below.

[0055] <Examples 1 to 6, Comparative Examples 1 and 2> In Examples 1 to 6 of the present invention and Comparative Examples 1 and 2, a resin composition obtained by adding 500 PPM of a hindered phenol-based antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals), 2000 PPM of a benzotriazole-based ultraviolet absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals), 2000 PPM of a hindered amine-based light stabilizer (Chimasorb 944, manufactured by Ciba Specialty Chemicals), and 1000 PPM of a phosphate metal salt-based nucleating agent (Adeka STAB NA-21, manufactured by ADEKA) to a highly crystalline homopolypropylene resin is subjected to the above-mentioned film formation flow using a melt extruder to form a transparent resin sheet 4 having a thickness of 100 μm to be used as the transparent resin layer 4. The peak intensity ratio x of each of the obtained transparent resin sheets 4 is shown in Table 1.

[0056] <Examples 7 to 10> In Examples 7 to 10 of the present invention, a resin containing 500 PPM of a hindered phenol-based antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals), 2000 PPM of a benzotriazole-based ultraviolet absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals), 2000 PPM of a hindered amine-based light stabilizer (Chimasorb 944, manufactured by Ciba Specialty Chemicals), and 1000 PPM of a nucleating agent vesicle was added to a highly crystalline homopolypropylene resin, and the resin was subjected to the above-mentioned film formation flow using a melt extruder to form a transparent resin sheet 4 having a thickness of 100 μm to be used as the transparent resin layer 4. The peak intensity ratio x of each of the obtained transparent resin sheets 4 is shown in Table 1.

[0057] The nucleating agent vesicle is prepared by sealing 100 parts by weight of methanol, 82 parts by weight of a phosphate metal salt nucleating agent (Adeka STAB NA-21, manufactured by ADEKA Corporation), and 5 parts by weight of phosphatidylcholine in a high-pressure stainless steel container maintained at 60°C, injecting carbon dioxide so that the pressure is 20 MPa to create a supercritical state, and then injecting 100 parts by weight of ion-exchanged water while vigorously stirring and mixing. After stirring for 15 minutes while maintaining the temperature and pressure in the container, carbon dioxide is discharged and the pressure is returned to atmospheric pressure to obtain a nucleating agent vesicle having a single-layer outer membrane and containing the phosphate metal salt nucleating agent. The particle size of the obtained nucleating agent vesicle was 0.05 to 0.8 μm.

[0058] Next, both sides of each of the transparent resin sheets 4 of Examples 1 to 10 and Comparative Examples 1 and 2 obtained by the above method were subjected to a corona treatment to make the surface wettability 40 dyn / cm or more, and one surface of the transparent resin sheet 4 was subjected to pattern printing with a two-component curing urethane ink (V180, manufactured by Toyo Ink Mfg. Co., Ltd.) to form a pattern-printed layer 3. In addition, a two-component curing urethane ink (V180, manufactured by Toyo Ink Mfg. Co., Ltd.) having hiding properties was applied on top of the pattern-printed layer 3 in an amount of 6 g / m. 2 A two-component curing urethane ink (PET-E, Regiuser, manufactured by Dainichi Seika Chemicals Co., Ltd.) was applied on the concealing layer 2 at a coating amount of 1 g / m 2The primer layer 6 was formed by applying a coating amount of 3 g / m2 of a two-component curing urethane top coat (W184, manufactured by Dainippon Ink Co., Ltd.) to the other surface of the transparent resin sheet 4. Then, an embossed pattern 4a was formed by pressing the other surface of the transparent resin sheet 4 using an embossing die roll. 2 A decorative sheet 1 having a layer thickness of 110 μm was obtained as shown in FIG.

[0059] For the decorative sheets 1 of Examples 1 to 10 and Comparative Examples 1 and 2 obtained by the above method, a coin scratch evaluation test for evaluating scratch resistance and a haze value measurement test for evaluating transparency were carried out.

[0060] The coin scratch evaluation test and the haze value measurement test will be described in detail below.

[0061] <Coin scratch evaluation test> First, in the coin scratch evaluation test, a coin is placed in contact with the surface of each decorative sheet 1 obtained by the above method and fixed using a jig, and the coin is slid across the jig at a constant speed while a load of 1, 2, 3, or 4 kg is applied to evaluate scratch resistance by examining whether or not the surface of the decorative sheet 1 is scratched. Note that in this evaluation test, because it may be used in places where a significant load is applied, such as floors, decorative sheets 1 that are not scratched under a load of 2 kg or more were judged to pass.

[0062] <Haze value measurement test> Here, the haze value is a percentage value obtained by subtracting the integral value (linear transmittance) of only the linear components of the light beams emitted from the other surface from the integral value (total light transmittance) of all the light beams emitted from the other surface when the light incident from one surface of the object is emitted to the other surface, and the smaller the value, the higher the transparency. This haze value is determined by the internal haze, which is determined by the internal state of the object, such as the degree of crystallinity and spherulite size in the crystal part, and the external haze, which is determined by the surface state of the object, such as the presence or absence of unevenness on the entrance surface and exit surface. In the present invention, when simply referring to the haze value, it means a value determined by the internal haze and the external haze. In this embodiment, the haze value measurement test was performed on each transparent resin sheet using a haze value measurement tester (manufactured by Nippon Denshoku Industries Co., Ltd.; NDH2000). A blank measurement was performed in advance with nothing attached to the sample holder. In the measurement of each transparent resin sheet, a sample was attached to a sample holder and the sample transmission measurement was performed under the same conditions as the blank measurement, and the ratio of the sample transmission measurement to the blank measurement, expressed as a percentage, was calculated as the haze value. In the present invention, a haze value of less than 15% was judged to be acceptable.

[0063] The results of the coin scratch evaluation test and the haze value measurement test are shown in Table 1.

[0064] [Table 1]

[0065] As shown in Table 1, the evaluation test results of each decorative sheet 1 show that each decorative sheet 1 of Examples 1 to 10, in which the peak intensity ratio x of the transparent resin sheet 4 is x≧0.65, was not scratched even in a coin scratch test with a load of 2 kg or more, and had a haze value of 14% or less, which revealed that it had very excellent scratch resistance and transparency. Note that it was not possible to form a film from a transparent resin sheet 4 with x>0.85. Furthermore, each decorative sheet 1 of Comparative Examples 1 and 2, in which the peak intensity ratio x of the transparent resin sheet 4 is x<0.65, was found to have significant scratches in a coin scratch test with a load of 1 kg or less, and had a haze value of 15.1 or more, which showed poor scratch resistance and transparency.

[0066] Moreover, in Examples 7 to 10 in which nucleating agent vesicles were added, the haze values ​​were extremely low at 8.4%, 8.1%, 7.2% and 6.8%, and it is clear that the films had excellent transparency.

[0067] From the above results, it became clear that a decorative sheet 1 having excellent scratch resistance and transparency can be obtained by setting the peak intensity ratio x of the transparent resin sheet 4 as the transparent resin layer 4 to x≧0.65, preferably 0.65≦x≦0.85.

[0068] It has also been revealed that by adding nucleating agent vesicles to the transparent resin sheet 4, the dispersibility of the nucleating agent in the transparent resin sheet 4 can be improved, thereby obtaining a decorative sheet 1 that is extremely transparent and has excellent design properties.

[0069] The decorative sheet 1 and the method for producing the decorative sheet 1 of the present invention are not limited to the above-mentioned embodiments and examples, and various modifications are possible within the scope that does not impair the characteristics of the invention. [Explanation of symbols]

[0070] 1 Decorative sheet 2. Hidden Layer 3. Pattern printing layer 4 Transparent resin layer, transparent resin sheet 4a Embossed pattern 5 Topcoat layer 6 Primer layer 7 Original fabric layer, original fabric resin sheet 8 Adhesive layer

Claims

1. A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and further comprising an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, a value of a peak intensity ratio x calculated by using the following formula 1 from an absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, The transparent resin sheet is formed by adding a nano-sized nucleating agent. A decorative sheet characterized by: In Formula 1, I997 is the wave number 997 cm －１ The peak intensity value of I938 is the wave number 938 cm －１ The peak intensity value of I973 is the wave number 973 cm －１ The peak intensity values ​​are shown. [0010]

2. A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and further comprising an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, a value of a peak intensity ratio x calculated by using the following formula 1 from an absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, The transparent resin sheet is formed by adding a nucleating agent, The nucleating agent is a metal salt of benzoic acid, a metal salt of pimelic acid, a metal salt of rosin, chitocridone, cyanine blue, or talc. A decorative sheet characterized by: In Formula 1, I997 is the wave number 997 cm －１ The peak intensity value of I938 is the wave number 938 cm －１ The peak intensity value of I973 is the wave number 973 cm －１ The peak intensity values ​​are shown. [0010]

3. A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and further comprising an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, a value of a peak intensity ratio x calculated by using the following formula 1 from an absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, The transparent resin sheet is formed by adding nano-sized nucleating agent vesicles in which a nucleating agent is encapsulated in a vesicle having a single-layer outer membrane. A decorative sheet characterized by: In Formula 1, I997 is the wave number 997 cm －１ The peak intensity value of I938 is the wave number 938 cm －１ The peak intensity value of I973 is the wave number 973 cm －１ The peak intensity values ​​are shown. [0010]

4. 3. The decorative sheet according to claim 1, wherein the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles having a single-layer outer membrane and encapsulating the nucleating agent therein.

5. A method for producing a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and having an embossed pattern on a surface of the transparent resin layer facing the topcoat layer, comprising: A method for producing a decorative sheet, comprising the steps of: adding nano-sized nucleating agent vesicles, in which a nucleating agent is encapsulated in a vesicle having a single-layer outer membrane by supercritical reverse phase evaporation, to the crystalline polypropylene resin; and forming a transparent resin sheet as the transparent resin layer so that the peak intensity ratio x value calculated from the absorption spectrum obtained by Fourier infrared spectroscopy using the following formula 1 is 0.65≦x≦0.

85. [0010]

6. A method for producing a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer mainly composed of 90 to 100% by weight of crystalline polypropylene resin, and a topcoat layer in this order, and having an embossed pattern on a surface of the transparent resin layer facing the topcoat layer, comprising: A nucleating agent vesicle having a single-layer outer membrane and encapsulating a nucleating agent is added to the crystalline polypropylene resin by a supercritical reverse phase evaporation method, and a transparent resin sheet is formed as the transparent resin layer so that the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier infrared spectroscopy using the following formula 1 is 0.65≦x≦0.85; 10. A method for producing a decorative sheet, wherein the nucleating agent is a metal salt of benzoic acid, a metal salt of pimelic acid, a metal salt of rosin, chitocridone, cyanine blue, or talc. [0010]

Images