Cosmetic sheet and method for producing the same

Abstract

To provide a decorative sheet excellent in scratch resistance while capable of preventing an elongation at print processing and of reducing occurrence of flexural whitening or a crack, and a manufacturing method of the decorative sheet.SOLUTION: A decorative sheet 1 includes a substrate layer 2 composed of a pigmented polypropylene film formed by mixing an inorganic pigment in a polypropylene resin. Furthermore, the substrate layer 2 contains a nano-sized nucleating agent. Furthermore, the substrate layer 2 has a value 0.7-0.9 of peak intensity ratio x calculated from an absorption spectrum obtained at Fourier-type infrared spectroscopy. Furthermore, the substrate layer 2 is 50-150 μm thick.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a decorative sheet used for the exterior and interior finishing materials of buildings, the surfaces of furniture, the surface materials of home appliances, etc., and a method for manufacturing the same.

Background Art

[0002] In recent years, as shown in Patent Document 1, many decorative sheets using olefin resins (for example, polypropylene sheets) have been proposed as decorative sheets that replace polyvinyl chloride decorative sheets for which environmental protection problems are a concern. These decorative sheets do not use vinyl chloride resin, so the generation of toxic gases and the like during incineration is suppressed. However, generally, polypropylene sheets have problems such as inferior scratch resistance due to their low elastic modulus, and being easily stretched when tension is applied to the sheet during sheet production such as printing.

[0003] By the way, a decorative sheet is attached to the surface of a substrate such as a wooden substrate, a metal substrate, or a non-combustible substrate to form a decorative board, and the decorative sheet imparts design properties according to the purpose to the decorative board. Therefore, the decorative sheet needs to cover the surface of the substrate so that it cannot be seen completely as necessary. In this case, it is necessary to use a decorative sheet that is colored at least by a pigment and has concealability. And, as the simplest configuration of a decorative sheet, it can be said that it is a configuration consisting only of a colored single-layer (single layer) substrate layer. In the case of a decorative sheet consisting only of such a substrate layer, usually, the design that can be imparted is limited to a solid color without a pattern. However, for example, a glittering feeling can be imparted by adding a glitter material such as aluminum flakes or pearl pigments as a pigment, so sufficient design expression is possible. Also, when it is desired to impart a higher design, it is also effective to apply a decoration such as printing to the surface of the substrate layer.

[0004] On the one hand, as described above, since the colored polypropylene film has a low elastic modulus, when it is used as a single-layer decorative sheet, it is necessary to improve scratch resistance and prevent elongation even when tension is applied during processing such as printing. Regarding the elongation during tension application, in the case of conventional colored polypropylene films, improvement can be achieved by increasing the layer thickness to about 50 μm or more. Also, regarding scratch resistance, in the case of conventional colored polypropylene films, as in Patent Document 2 and Patent Document 3, improvement can be achieved by providing a transparent resin layer made of polypropylene resin or a top coat layer using a urethane-based thermosetting resin composed of polyol and isocyanate.

[0005] In addition, as in Patent Document 2 and Patent Document 3, by optimally selecting the polypropylene resin used for the colored polypropylene film, it is possible to improve scratch resistance and elongation during printing processing. However, while increasing crystallinity improves the elastic modulus, the breaking stress does not increase proportionally to the elastic modulus, so the film itself becomes more likely to break, and problems such as breakage are likely to occur during printing processing. Furthermore, during post-processing as a decorative sheet, especially during bending processing such as V-cutting, problems such as cracking and whitening at the bending points are likely to occur.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] Conventionally, for a decorative sheet using a colored polypropylene film alone or a decorative sheet having a colored polypropylene film as a base material layer, compatibility with printing (difficulty in stretching, etc.), scratch resistance, and bendability are required to coexist. The present invention has been made paying attention to the above points, and it is possible to improve scratch resistance, suppress elongation during printing, and reduce the occurrence of bend whitening and cracking. An object of the present invention is to provide a decorative sheet using a colored polypropylene film alone, a decorative sheet having a colored polypropylene film as a base material layer, or a method for manufacturing these decorative sheets.

Means for Solving the Problems

[0008] The inventors of the present invention encapsulated a nucleating agent for improving the crystallinity of polypropylene, for example, in vesicles having an outer membrane of a single-layer film and vesiculated it to add it as a nucleating agent vesicle. Furthermore, by repeatedly examining and experimenting with various manufacturing processes and setting the crystallinity within an optimal range, it has been found that a decorative sheet and a method for manufacturing the same that improve the above problems can be provided. To achieve the object, a decorative sheet according to one aspect of the present invention has a base material layer made of a colored polypropylene film obtained by mixing an inorganic pigment with a polypropylene resin. The base material layer contains a nucleating agent of nanosize, the thickness of the base material layer is 50 μm or more and 150 μm or less, and the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy measurement is 0.7 or more and 0.9 or less. In the decorative sheet according to one aspect of the present invention, the nucleating agent may be contained in the state of a nucleating agent vesicle encapsulated by an outer membrane and vesiculated. Here, the nucleating agent vesicle has a structure in which a nucleating agent is encapsulated in a capsule-shaped vesicle having an outer membrane of a single-layer film, and can be prepared, for example, by a supercritical reverse evaporation method. The nucleating agent is a substance that serves as a starting point for crystallization in a crystalline polypropylene resin.

Effects of the Invention

[0009] According to one aspect of the present invention, a nucleating agent for improving the crystallinity of polypropylene is, for example, vesicularized and added as a nucleating agent vesicle, and by optimizing the value of the peak intensity ratio and the film thickness obtained in Fourier transform infrared spectroscopy, it is possible to provide a decorative sheet having printability (such as difficulty in stretching), scratch resistance, and bendability.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thicknesses of the respective layers, etc. are different from the actual ones. Further, 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 does not specify the materials, shapes, structures, etc. of the constituent parts as the following. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

[0012] 「Configuration」 The decorative sheet 1 according to the embodiment shown in FIG. 1 is an example in the case of a single-layer structure of only the base material layer 2 (raw fabric layer). The base material layer 2 of the present embodiment is composed of a colored polypropylene film. The base material layer 2 made of a colored polypropylene film has an inorganic pigment mixed in the polypropylene resin for coloring and contains a nano-sized nucleating agent. In the present embodiment, the nucleating agent may be contained, for example, in a state of a nucleating agent vesicle encapsulated by an outer film and vesicularized.

[0013] The thickness of the base material layer 2 is 50 μm or more and 150 μm or less, and the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy is 0.7 or more and 0.9 or less. The polypropylene resin constituting the base material layer 2 preferably has 50% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

[0014] The addition amount of the nano-sized nucleating agent is preferably 0.01 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the polypropylene resin. When using a nucleating agent vesicle, the addition amount of the nucleating agent vesicle is preferably 0.01 part by mass or more and 0.5 part by mass or less in terms of the nucleating agent in the nucleating agent vesicle with respect to 100 parts by mass of the polypropylene resin. The nucleating agent vesicle is preferably a nucleating agent liposome having an outer membrane made of phospholipid.

[0015] If necessary, a pattern layer 3 may be formed (laminated) on one surface of the base material layer 2 to improve the design property. Also, in the decorative sheet 1, at least one of the transparent resin layer 4 and the top coat layer 5 may be laminated on one surface side of the base material layer 2. The decorative sheet 1 illustrated in FIG. 2 is an example in which the pattern layer 3, the transparent resin layer 4, and the top coat layer 5 are laminated in this order on one surface of the decorative sheet 1. One of the transparent resin layer 4 or the top coat layer 5 may be omitted. Also, the pattern layer 3 may be omitted.

[0016] Here, at least one of the transparent resin layer 4 and the top coat layer 5 may be provided with an embossed uneven pattern (embossed pattern 4a) depending on the design requirements. Ink can be embedded in the embossed pattern 4a to further improve the design. Also, if there is a problem with the adhesion between the pattern layer 3 and the transparent resin layer 4, an adhesive resin layer 4b may be appropriately provided. When providing the adhesive resin layer 4b, it is formed by a coextrusion method of the transparent resin layer 4 and the adhesive resin layer 4b. The adhesive resin layer 4b is, for example, a resin such as polypropylene, polyethylene, or acrylic that has been acid-modified. The thickness of the adhesive resin layer 4b is desirably 2 μm or more for the purpose of improving the adhesive strength. Further, depending on requirements such as scratch resistance, it is also possible to laminate a plurality of layers of at least one of the transparent resin layer 4 and the top coat layer 5, and other known layers may be arranged as well.

[0017] In FIGS. 1 and 2, reference numeral B represents a substrate. The substrate B is a substrate to which the decorative sheet 1 is bonded. The substrate B is not particularly limited, and examples include wood boards, inorganic boards, metal plates, composite boards made of a plurality of materials, and the like. An appropriate primer layer 6, a concealment layer (not shown), or the like may be provided between the decorative sheet 1 and the substrate B. The tensile elastic modulus of the decorative sheet 1 of the present embodiment, particularly the range of the tensile elastic modulus of the base material layer 2 alone, is preferably 850 MPa or more and 1600 MPa or less. If the tensile elastic modulus is less than 850 MPa, there is a risk that defects during printing cannot be suppressed. If the tensile elastic modulus exceeds 1600 MPa, since the crystallinity is too high, even when a nucleating agent (for example, a nucleating agent vesicle) is used, there is a risk that defects such as whitening and cracking may occur during bending.

[0018] Next, each layer constituting the decorative sheet 1 will be described. <Base material layer 2> The base material layer 2 is made of a colored polypropylene film. The colored polypropylene film uses polypropylene resin as the main raw material, and an inorganic pigment is mixed into the polypropylene resin for coloring. Further, a nano-sized nucleating agent is added to the base material layer 2 to increase crystallinity. In this embodiment, the nano-sized nucleating agent may be added in the state of a nucleating agent vesicle.

[0019] (Polypropylene resin) It is preferable to use high-crystalline homopolypropylene, which will be described later, for the polypropylene resin, but it is not limited to high-crystalline homopolypropylene. In applications that place more importance on processability such as bending processing, for high-crystalline homopolypropylene, for example, a random polypropylene resin having an ethylene content within a predetermined range or a known amorphous polypropylene resin can be mixed.

[0020] The value of the peak intensity ratio x calculated from the absorption spectrum obtained in the Fourier transform infrared spectroscopy of the base material layer 2 made of the colored polypropylene film is adjusted to be 0.7 or more and 0.9 or less. When the peak intensity ratio x is less than 0.7, it is impossible to suppress problems during printing, and it is highly likely that it will be difficult to ensure the necessary scratch resistance in practical use. On the other hand, when the peak intensity ratio x exceeds 0.9, since the crystallinity is too high, even when a nucleating agent vesicle is used, there is a possibility that problems such as whitening and cracking will occur during bending processing.

[0021] Here, Fourier-transform infrared spectroscopy will be described. First, infrared spectroscopy is a measurement method that utilizes the principle that when infrared light, which is light with a wavelength of 2.5 μm to 25 μm, is absorbed by a substance, the amount absorbed changes based on the vibration and rotational motion of the molecules of the substance. By measuring the infrared light absorbed by the substance, information regarding the chemical structure and state of the substance can be obtained. The specific measurement method involves irradiating the substance with infrared light from a light source, generating an interference wave by combining the transmitted light and the reflected light that have been split, and measuring the infrared spectrum by calculating the intensity of light at each frequency component from the signal intensity of the interference wave. In particular, in this embodiment, the calculation of the interference wave is performed using the Fourier transform method, and the measurement is carried out by Fourier-transform infrared spectroscopy, which is a method of measuring the infrared spectrum. A graph with the wavenumber obtained by the above method plotted on the horizontal axis and the measured absorbance (or transmittance) plotted on the vertical axis is called an infrared absorption spectrum (or infrared transmission spectrum), and a unique pattern can be observed for each substance. At this time, the absorbance on the vertical axis changes the value of the peak intensity at a predetermined wavenumber in proportion to the concentration, thickness of the substance, or in the case of a crystalline substance, the amount of the crystalline part or the amorphous part. Therefore, quantitative analysis can also be performed from the height or area of the peak.

[0022] In this embodiment, by utilizing the above-described characteristics of the infrared absorption spectrum, the wavenumber 997 cm corresponding to the absorbance of the crystalline part of the colored polypropylene film in the absorption spectrum obtained by the aforementioned measurement -1 of the peak intensity, and the wavenumber 973 cm corresponding to the absorbance of the amorphous part of the film -1 of the peak intensity ratio, that is, the peak intensity ratio x representing the crystallinity of polypropylene, is calculated using the following formula, and the relationship between the peak intensity ratio x and the rigidity of the colored polypropylene film is clarified, and a decorative sheet excellent in rigidity is provided by adopting a colored polypropylene film with a peak intensity ratio x within a predetermined range as the base material layer. Note that the peak intensity at a wavenumber of 997 cm -1 and the peak intensity at a wavenumber of 973 cm -1 are each corrected for background using the peak intensity at a wavenumber of 938 cm -1 of the peak intensity.

[0023]

Number

[0024] Also, it is important that the thickness of the base material layer 2 made of the colored polypropylene film is 50 μm or more and 150 μm or less. When the thickness of the base material layer 2 is less than 50 μm, even if the peak intensity ratio x is within the optimal range, the film strength will be insufficient, making it difficult to suppress problems during printing or deterioration of scratch resistance. On the other hand, when the thickness of the base material layer 2 exceeds 150 μm, there is a risk of problems such as whitening and cracking during bending. In this embodiment, it is preferable to use a highly crystalline polypropylene resin as the polypropylene resin. In particular, it is preferable to use a highly crystalline homopolypropylene resin, which is a propylene homopolymer with an isotactic pentad fraction (mmmm fraction) of 95% or more, in the range of 50% by mass or more and 100% by mass or less based on the mass of the total polypropylene resin.

[0025] The crystallization temperature of the polypropylene resin is generally in the range of 100 to 130°C, and when a nucleating agent is added, it is in the range of 110 to 140°C. In the colored polypropylene film of the decorative sheet 1 of this embodiment, by controlling the cooling time from the crystallization temperature within this range to the curing completion temperature by a known cooling process, the value of the peak intensity ratio x is adjusted to 0.7 or more and 0.9 or less. Also, when a polypropylene resin with an isotactic pentad fraction (mmmm fraction) of less than 95% is used, due to insufficient crystallinity, the peak intensity ratio x may be lower than the preferred range even when the cooling process is controlled. Similarly, when the highly crystalline homopolypropylene resin is less than 50% by mass, due to insufficient crystallinity, the peak intensity ratio x may be lower than the preferred range even when the cooling process is controlled.

[0026] Here, the isotactic pentad fraction (mmmm fraction) is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating a resin material at a predetermined resonance frequency by means of 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclide) with a mass of 13, and defines the atomic arrangement, electronic structure, and fine structure of the molecule in the resin material. And the pentad fraction of the crystalline polypropylene resin refers to the ratio of five consecutive propylene units 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.

[0027] (Inorganic pigment) As the inorganic pigment, known inorganic pigments typified by titanium oxide for imparting hiding power can be used. Examples of inorganic pigments for coloring include composite oxides such as iron-zinc, chromium-antimony, and iron-aluminum, and iron oxide, etc., and their blending can be freely adjusted according to the desired color. Further, as the inorganic pigment, a brightening material such as an aluminum flake or a pearl pigment can also be added. Also, for example, an organic pigment such as carbon black may be used in combination. Furthermore, additives such as fatty acid metal salts may be added to improve dispersibility and extrusion suitability.

[0028] (Nucleating agent vesicle) Moreover, the base material layer 2 contains a nano-sized nucleating agent. The nano-sized nucleating agent may be added to and used in the polypropylene resin in the form of a nucleating agent vesicle, for example, encapsulated in a vesicle having an outer membrane of a single-layer film. Since the base material layer 2 contains a nucleating agent, the crystallinity can be improved, and the scratch resistance (scratch resistance) of the base material layer 2 can be improved. In this embodiment, the nucleating agent in the resin constituting the base material layer 2 may be encapsulated in a vesicle with a part of the nucleating agent exposed. It is preferable that the average particle size of the nano-sized nucleating agent is 1 / 2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is 400 nm or more and 750 nm or less, it is preferable that the average particle size is 375 nm or less.

[0029] Nano-sized nucleating agents have extremely small particle sizes, so the amount of nucleating agent present per unit volume is The number and surface area of ​​the nucleating agent particles increase inversely proportional to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes closer, 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 hinder each other's growth, stopping the growth of each crystal, so that 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 generated during bending can be efficiently dispersed, so that a colored polypropylene film that suppresses cracking and whitening during bending can be realized.

[0030] 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 less than when added as a nucleating agent vesicle. As a result, the average particle size of the spherulites in the crystalline part of the polypropylene resin increases, and compared to when added as a nucleating agent vesicle, it tends to be more difficult to suppress cracking and whitening during bending. Therefore, when the nucleating agent is simply added, it tends to be more difficult to achieve both improved elastic modulus and processability by increasing the crystallinity, compared to when added as a nucleating agent vesicle.

[0031] The base material layer 2 made of a colored polypropylene film that constitutes the cosmetic sheet 1 of the present embodiment preferably contains 0.01 to 0.5 parts by mass, preferably 0.05 to 0.3 parts by mass, of a nucleating agent (nucleating agent vesicle) in terms of the addition amount of the nucleating agent with respect to 100 parts by mass of the polypropylene resin as the main component. When the addition amount of the nucleating agent (nucleating agent vesicle) is less than 0.01 part by mass, the crystallinity may not be sufficiently improved and the required elastic modulus (hardness) may not be achieved. Also, when the addition amount exceeds 0.5 part by mass, the spherulite growth may be inhibited due to an excessive number of crystal nuclei, and as a result, the crystallinity may not be sufficiently improved and the required elastic modulus (hardness) may not be achieved.

[0032] In addition, as a method for nanosizing the nucleating agent, for example, a solid-phase method in which the nucleating agent is mainly mechanically pulverized to obtain nanoparticles, a liquid-phase method in which nanoparticles are synthesized or crystallized in a solution in which the nucleating agent or the nucleating agent is dissolved, a gas-phase method in which nanoparticles are synthesized or crystallized from a gas or vapor composed of the nucleating agent or the nucleating agent, etc. 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, a jet mill, etc. Examples of the liquid-phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid-phase reduction method, a hydrothermal synthesis method, etc. Further, examples of the gas-phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, etc.

[0033] As a method for nanosizing the nucleating agent, the supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method of producing capsules (nanosized vesicles) encapsulating a target substance using carbon dioxide under supercritical conditions or under temperature or pressure conditions above the critical point. Supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 °C) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, 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 conditions.

[0034] Also, as a specific nano - processing method by the supercritical reverse phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, a phospholipid as an outer - membrane - forming substance, and a nucleating agent as an encapsulated substance, and stirred to generate an emulsion of supercritical carbon dioxide and the aqueous phase. Next, by reducing the pressure, carbon dioxide expands and evaporates, causing a phase inversion, and generating nanocapsules (nanovesicles) in which the phospholipid covers the surface of the nucleating agent particles with a monolayer membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer membrane becomes a multi - layer membrane on the surface of the nucleating agent particles, capsules with a monolayer membrane can be easily generated, so that smaller - diameter capsules can be prepared. Note that the nucleating agent vesicles can be prepared, for example, by 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 them, the supercritical reverse phase evaporation method is particularly preferred. The outer membrane constituting the nucleating agent vesicles is composed of, for example, a monolayer membrane. Also, the outer membrane is composed of a substance containing a biological lipid such as a phospholipid.

[0035] In this specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome. Examples of the phospholipid constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0036] Examples of other substances that form the outer membrane of the vehicle include nonionic surfactants and dispersants such as mixtures of these with cholesterol or triacylglycerol. Among these, examples of nonionic surfactants include one or more of polyglycerol ethers, dialkyl glycerols, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene polyoxypropylene copolymers, polybutadiene-polyoxyethylene copolymers, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymers, polyethylene oxide-polyethyl ethylene copolymers, polyoxyethylene-polycaprolactam copolymers, etc. Examples of cholesterol include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or colecalciferol, etc.

[0037] Also, the outer membrane of the liposome may be formed from a mixture of phospholipid and a dispersant. In the cosmetic sheet 1 of the present embodiment, it is preferable that the nucleating agent vehicle is a radical scavenging liposome having an outer membrane made of phospholipid. By configuring the outer membrane from phospholipid, the compatibility between the resin material, which is the main component of the base material layer 2, and the vehicle can be made good.

[0038] The nucleating agent is not particularly limited as long as it is a substance that serves as a crystallization starting point when the resin crystallizes. Examples of the nucleating agent include metal phosphate esters, metal benzoates, metal pimelates, metal rosins, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nanosizing treatment, it is preferable to use metal phosphate esters, metal benzoates, metal pimelates, and metal rosins, which are non-melting types and can be expected to have good transparency. However, when the material itself can be made transparent by the nanosizing treatment, colored quinacridone, cyanine blue, talc, etc. can also be used. Further, a melting type of benzylidene sorbitol may be appropriately mixed and used with the non-melting type of nucleating agent.

[0039] As described above, one of the features (matters specifying the invention) of the cosmetic sheet 1 of the present embodiment is that "the base material layer 2 contains a nucleating agent encapsulated in vesicles". By adding the nucleating agent to the resin composition in a state where it is encapsulated in vesicles, the dispersibility of the nucleating agent in the resin material, that is, in the base material layer 2, is dramatically improved. However, this feature is applied to the completed cosmetic It can be considered difficult and unrealistic to directly specify the structure and properties of an object in the state of Sheet 1 depending on the situation. The reasons are as follows. The nucleating agent added in the state of the vehicle has high dispersibility and is in a dispersed state. Even in the state of the produced decorative sheet 1, the nucleating agent is highly dispersed in the base material layer 2. However, in the production process of the decorative sheet 1 after producing the base material layer 2 by adding the nucleating agent to the resin composition constituting the base material layer 2 in the state of the vehicle, various treatments such as compression treatment and curing treatment are usually applied to the laminate. Due to such treatments, the outer membrane of the vehicle containing the nucleating agent may be crushed or chemically reacted, and there is a high possibility that the nucleating agent is not encapsulated (covered) by the outer membrane. This is because the state in which the outer membrane is crushed or chemically reacted varies depending on the treatment process of the decorative sheet 1. And in situations such as the nucleating agent not being encapsulated by the outer membrane, it is difficult to specify the physical properties themselves within a numerical range. It is also assumed that it may be difficult to determine whether the constituent material of the crushed outer membrane is the outer membrane of the vehicle or a material added separately from the nucleating agent. Thus, although the invention of the present application differs from the prior art in that the nucleating agent is highly dispersed in the base material layer 2, it is assumed that it may be unrealistic to specify within a numerical range obtained by analyzing the structure and properties based on measurement in the state of the decorative sheet 1 as to whether it is because the nucleating agent was added in the state of the vehicle encapsulating it. Here, the nucleating agent vehicle having the above configuration may also be contained in the transparent resin layer 4 or the top coat layer 5.

[0040] (Pattern layer 3) On the surface of the colored polypropylene film (base material layer 2), a pattern layer 3 for adding a pattern to the decorative sheet 1 can be provided. As the pattern, for example, a wood grain pattern, a stone grain pattern, a sand grain pattern, a tile sticker pattern, a brick stack pattern, a cloth pattern, a leather grain pattern, geometric figures, etc. can be used. Furthermore, an undercoat solid ink layer (not shown) may be provided between the base material layer 2 and the pattern layer 3 according to the degree of the desired design. The undercoat solid ink layer is provided so as to cover the entire surface of the base material layer 2. Further, the undercoat solid ink layer may be a multi-layer of two or more layers as necessary, such as concealability. Furthermore, the pattern layer 3 may be formed by laminating the number of color separation plates necessary to express the required design. Thus, the pattern layer 3 and the undercoat solid ink layer form various combinations according to the required design, that is, the design to be expressed, but are not particularly limited.

[0041] The constituent materials of the undercoat solid ink layer and the pattern layer 3 are not particularly limited. For example, printing inks or coating agents formed by dissolving and dispersing a matrix and a coloring agent such as a dye or a pigment in a solvent can be used. As the matrix, for example, various synthetic resins such as oily nitrocellulose resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, fluorine resin, silicone resin, rubber resin, etc., or mixtures or copolymers thereof can be used. Further, as the coloring agent, for example, inorganic pigments such as carbon black, titanium white, zinc white, valve pattern, lead yellow, ultramarine blue, cadmium red, etc., organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments, etc., or mixtures thereof can be used. Further, as the solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, etc., or mixtures thereof can be used.

[0042] Further, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retardants may be added to the undercoat solid ink layer and the pattern layer 3 in order to impart various functions. Here, the undercoat solid ink layer and the pattern layer 3 are, for example, gravure printing method, offset printing It can be formed by various printing methods such as the gravure printing method, the screen printing method, the electrostatic printing method, and the inkjet printing method. Also, since the base solid ink layer covers the entire surface of the base material layer 2, it can also be formed by various coating methods such as the roll coating method, the knife coating method, the microgravure coating method, and the die coating method. These printing methods and coating methods may be selected separately according to the layer to be formed, but it is efficient to select the same method for batch processing.

[0043] (Transparent resin layer 4) The resin material used as the main component of the transparent resin layer 4 is preferably composed of an olefin resin. In addition to polypropylene, polyethylene, polybutene, etc., α-olefins (for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) homopolymerized or copolymerized of two or more kinds, and those copolymerized of ethylene or α-olefin and other monomers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer. Also, when improving the surface strength of the decorative sheet 1, it is preferable to use a highly crystalline polypropylene resin as in the case of the base material layer 2. Here, in this specification, the main component refers to 90% by mass or more of the target material unless otherwise specified.

[0044] When providing the transparent resin layer 4, the layer thickness of the transparent resin layer 4 is preferably 50 μm or more and 100 μm or less. When it is less than 50 μm, the effect of improving the scratch resistance of the surface of the transparent resin layer 4 is low, and the significance of providing the transparent resin layer 4 may be reduced. When it exceeds 100 μm, the rigidity of the decorative sheet 1 is too high, and there is a risk of problems such as whitening and cracking in bending processing. However, when providing the top coat layer 5 on the transparent resin layer 4, the layer thickness of the transparent resin layer 4 may be less than 50 μm. In addition, the resin composition constituting the transparent resin layer 4 may contain various functional additives such as a heat stabilizer, a light stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss modifier as necessary. These various functional additives can be appropriately selected and used from well-known ones.

[0045] (Top coat layer 5) When further improvement in scratch resistance and adjustment of gloss are required, the top coat layer 5 can be provided on the surface of the transparent resin layer 4. As the resin material of the main component of the top coat layer 5, for example, it can be appropriately selected and used from resin materials such as polyurethane-based, acrylic-silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, amino alkyd-based, and urea-based. The form of the resin material is not particularly limited, such as aqueous, emulsion, solvent-based, etc. The curing method can also be appropriately selected and carried out, such as one-component type, two-component type, ultraviolet curing method, etc.

[0046] As the resin material used as the main component of the top coat layer 5, u using isocyanate Retane-based materials are suitable from the viewpoints of workability, price, cohesive force of the resin itself, etc. For isocyanates, for example, adducts, burettes, isocyanurate derivatives such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc. can be appropriately selected and used as curing agents. However, considering weather resistance, a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a linear molecular structure is preferred. In addition, when improving surface hardness, it is preferable to use a resin cured by active energy rays such as ultraviolet rays or electron beams. These resins can be used in combination with each other. For example, by making a hybrid type of a thermosetting type and a photocuring type, improvement of surface hardness, suppression of curing shrinkage, and improvement of adhesion can be achieved.

[0047] A matting agent can be added to the top coat layer 5 for matting adjustment. A commercially available known matting agent may be used. For example, fine particles made of inorganic materials such as silica, glass, alumina, calcium carbonate, barium sulfate, etc. may be used. Or, fine particles made of organic materials such as acrylic can also be used. However, when high transparency is required, it is desirable to use fine particles of silica, glass, acrylic, etc. with high transparency. In particular, among fine particles such as silica and glass, a matting agent with a low bulk density formed by secondary aggregation of fine primary particles rather than solid spherical particles has a high matting effect with respect to the added amount. Therefore, by using such a matting agent, the added amount of the matting agent can be reduced.

[0048] In addition, in order to impart various functions to the top coat layer 5, functional additives such as antibacterial agents and antifungal agents may be added. Further, an ultraviolet absorber and a light stabilizer may be added as necessary. As the ultraviolet absorber, for example, benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and cyanoacrylate-based ones can be used. As the light stabilizer, hindered amine-based ones can be used. The layer thickness of the top coat layer 5 is preferably 3 μm or more and 15 μm or less. When it is less than 3 μm, the effect of improving scratch resistance is low, and the significance of providing the top coat layer 5 may be reduced. When it exceeds 15 μm, cracks and fractures may occur during bending processing, and there may be problems such as design problems and deterioration of weather resistance.

[0049] <Manufacturing method> A manufacturing example of the decorative sheet 1 will be described. A nucleating agent vesicle is prepared by encapsulating a nucleating agent in a vesicle and vesiculating the nucleating agent, and the prepared nucleating agent vesicle is added to a polypropylene resin together with an inorganic pigment to prepare a resin material for the base material layer. The nucleating agent vesicle is prepared, for example, by encapsulating the nucleating agent in a vesicle having a single-layer film by the supercritical reverse phase evaporation method and vesiculating it. As the polypropylene resin to be used, it is preferable to use a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more in 50% by mass or more and 100% by mass or less thereof.

[0050] The above resin material for the base material layer is heated and melted, and formed into a sheet shape having a thickness of 50 μm or more and 150 μm or less by extrusion molding or the like to obtain the base material layer 2. At this time, by adjusting the cooling time from the crystallization temperature to the completion temperature of curing by a known adjustment method, the value of the peak intensity ratio x calculated from the absorption spectrum obtained in the Fourier transform infrared spectroscopy of the base material layer 2 is controlled to be 0.7 or more and 0.9 or less. Furthermore, if necessary, a pattern layer 3 is formed on the upper surface of the base material layer 2 by printing, and a transparent At least one of the resin layer 4 and the top coat layer 5 is formed by printing. In addition, in the above manufacturing method, the case of manufacturing the base material layer 2 using the nucleating agent vesicle has been described, but the present invention is not limited thereto. For example, the base material layer 2 may be manufactured by replacing the nucleating agent vesicle with a nano-sized nucleating agent not encapsulated in a vesicle.

[0051] <Function and others> (1) The decorative sheet 1 of the present embodiment has a base material layer 2 made of a colored polypropylene film obtained by mixing an inorganic pigment with a polypropylene resin. The base material layer 2 contains a nano-sized nucleating agent. The thickness of the base material layer 2 is 50 μm or more and 150 μm or less, and the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy is 0.7 or more and 0.9 or less. Also, the tensile elastic modulus of the base material layer 2 is 850 MPa or more and 1600 MPa or less. According to this configuration, by adding a nucleating agent that improves the crystallinity of polypropylene and further optimizing the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy and the film thickness, it is possible to provide the decorative sheet 1 capable of achieving both printability (difficulty in stretching, etc.) and scratch resistance and bendability.

[0052] (2) In the decorative sheet 1 of the present embodiment, it is preferable that 50% by mass or more and 100% by mass or less of the polypropylene resin constituting the base material layer 2 is a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more. According to this configuration, it becomes possible to more reliably adjust the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy to 0.7 or more and 0.9 or less.

[0053] (3) In the decorative sheet 1 of the present embodiment, it is preferable that the addition amount of the nucleating agent to the base material layer 2 is 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the polypropylene resin. According to this configuration, the crystallinity of the colored polypropylene constituting the base material layer 2 is sufficiently improved, and it becomes possible to surely secure a tensile elastic modulus of 850 MPa or more and 1600 MPa or less, which is necessary.

[0054] (4) It is preferable that the nucleating agent of the decorative sheet 1 of the present embodiment is a nucleating agent vesicle in which the nucleating agent is encapsulated in a vesicle having an outer film of a single-layer film. According to this configuration, the nucleating agent for improving the crystallinity of polypropylene is vesiculated and added as a nucleating agent vesicle, and further, by optimizing the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy and the film thickness, it is possible to provide the decorative sheet 1 capable of achieving both printability (such as difficulty in stretching) and scratch resistance and bendability.

[0055] (5) It is preferable that the decorative sheet 1 of the present embodiment is formed by adding the nucleating agent vesicle so as to be in the range of 0.05 parts by mass or more and 0.5 parts by mass or less in terms of the nucleating agent in the nucleating agent vesicle with respect to 100 parts by mass of the polypropylene resin. According to this configuration, the nucleating agent for improving the crystallinity of polypropylene is vesiculated and added as a nucleating agent vesicle, and further, by optimizing the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy and the film thickness, it is possible to provide the decorative sheet 1 capable of achieving both printability (such as difficulty in stretching) and scratch resistance and bendability.

[0056] (6) It is preferable that the addition amount of the nucleating agent vesicle to the base material layer 2 of the decorative sheet 1 of the present embodiment is 0.05 parts by mass or more and 0.5 parts by mass or less in terms of the nucleating agent in the nucleating agent vesicle with respect to 100 parts by mass of the polypropylene resin. According to this configuration, the crystallinity of the colored polypropylene constituting the base material layer 2 is sufficiently improved , and it becomes possible to surely secure a tensile elastic modulus of 850 MPa or more and 1600 MPa or less, which is necessary.

[0057] (7) The cosmetic sheet 1 of the present embodiment preferably has a nucleating agent vesicle which is a nucleating agent liposome having an outer membrane made of phospholipid. According to this configuration, the compatibility between the resin material which is the main component of the base material layer 2 and the vesicle can be made good. (8) The cosmetic sheet 1 of the present embodiment preferably has a pattern layer 3 laminated on one surface of the base material layer 2. According to this configuration, the design property of the cosmetic sheet 1 can be improved. (9) The cosmetic sheet 1 of the present embodiment preferably has at least one of a transparent resin layer 4 and a top coat layer 5 laminated on one surface side of the base material layer 2.

[0058] [Examples] Hereinafter, specific examples of the cosmetic sheet 1 of the present embodiment will be described. (Method for producing nucleating agent vesicle) First, the method for producing the nucleating agent liposome used in this example will be described. The nucleating agent liposome is prepared by using the above-described supercritical reverse evaporation method. 100 parts by mass of methanol, 70 parts by mass of a phosphoric acid ester metal salt-based nucleating agent (Adekastab NA-21; manufactured by ADEKA) as a nucleating agent, and 5 parts by mass of phosphatidylcholine as a phospholipid constituting the outer membrane of the vesicle are placed in a high-pressure stainless steel container maintained at 60 ° C and sealed. Carbon dioxide is injected into the container so that the pressure becomes 20 MPa to bring it into a supercritical state. Then, while vigorously stirring the inside of the container, 100 parts by mass of ion-exchanged water is injected. After further stirring and mixing for 15 minutes while maintaining the temperature and pressure in the supercritical state, carbon dioxide is discharged from the container and returned to atmospheric pressure to obtain a nucleating agent vesicle in which the nucleating agent is encapsulated in a vesicle having an outer membrane of a single-layer film made of phospholipid.

[0059] (Example 1) As a raw material for the colored polypropylene film, 78 parts by mass of a highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 °C), and a molecular weight distribution MWD (Mw / Mn) of 2.3 was used. 6 parts by mass of titanium oxide pigment as an inorganic pigment, 16 parts by mass of chromium-antimony composite oxide pigment, and 0.01 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent were added, and extrusion molding was carried out using a melt extruder to form a base material layer 2 made of a colored polypropylene film with a thickness of 55 μm. (Example 2) Except that 0.5 part by mass of the above-mentioned nucleating agent vesicle was added as a nucleating agent, the same as in Example 1, extrusion molding was carried out using a melt extruder to form a base material layer 2 with a thickness of 55 μm.

[0060] (Example 3) As a raw material for the colored polypropylene film, 39 parts by mass of a highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 °C), and a molecular weight distribution MWD (Mw / Mn) of 2.3 was used. 39 parts of a random polypropylene resin with a melt flow rate (MFR) of 12 g / 10 min (230 °C) containing 4% ethylene component, 6 parts by mass of titanium oxide pigment as an inorganic pigment, 16 parts by mass of chromium-antimony composite oxide pigment, and 0.01 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent were added, and extrusion molding was carried out using a melt extruder to form a base material layer 2 made of a colored polypropylene film with a thickness of 55 μm.

[0061] (Example 4) Except that 0.5 part by mass of the above-mentioned nucleating agent vesicle was added as a nucleating agent, the same as in Example 3, extrusion molding was carried out using a melt extruder to form a base material layer 2 with a thickness of 55 μm. (Example 5) The same as in Example 1, extrusion molding was carried out using a melt extruder to form a base material layer 2 with a thickness of 145 μm. (Example 6) The same as in Example 2, extrusion molding was carried out using a melt extruder to form a base material layer 2 with a thickness of 145 μm. (Example 7) In the same manner as in Example 3, an extruder was used for extrusion molding to form a base material layer 2 with a thickness of 145 μm. (Example 8) In the same manner as in Example 4, an extruder was used for extrusion molding to form a base material layer 2 with a thickness of 145 μm.

[0062] (Example 9) Pattern printing was performed on the surface of the base material layer 2 with a thickness of 55 μm prepared in the same manner as in Example 1 to form a pattern layer 3. The pattern layer 3 was formed using an ink obtained by adding 0.5 part by mass of a hindered amine-based light stabilizer (Chimasorb 944; manufactured by BASF) to a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) based on the binder resin content of the ink. Also, a primer layer 6 was formed on the back surface of the base material layer 2. The primer layer 6 was formed by printing the same two-component urethane ink as the pattern layer 3. Subsequently, 0.5 part by mass of a hindered amine-based light stabilizer (Chimasorb 944 manufactured by BASF) and 0.5 part by mass of a benzotriazole-based ultraviolet absorber (Tinuvin 328 manufactured by BASF) were mixed with 100 parts by mass of a crystalline polypropylene resin (pentaad fraction 97.8%, molecular weight distribution 2.3, MFR 18 g / 10 min), and the mixture was co-extruded with a polyethylene-based easy-adhesion resin using an extruder to form a transparent resin layer 4 with a thickness of 60 μm and an adhesive resin layer 4b with a thickness of 10 μm. Next, a dry lamination adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.; coating amount 2 g / m 2 ) was applied to the surface of the base material on which the pattern layer 3 was formed. Subsequently, through the formed adhesive resin layer 4b, the pattern layer 3 side of the base material to which the adhesive was applied and the transparent resin layer 4 were laminated by an extrusion lamination method. Further, after pressing was performed on the transparent resin layer 4 side surface of the sheet formed by lamination using an embossing die roll to apply an embossed pattern 4a, a two-component curable urethane top coat (W184 manufactured by DIC Graphics Co., Ltd.) was applied at a coating amount of 3 g / m 2 to form a top coat layer 5. Thus, the decorative sheet 1 shown in FIG. 2 was obtained.

[0063] (Example 10) For the substrate layer 2 with a thickness of 55 μm prepared in the same manner as in Example 2, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1. (Example 11) For the substrate layer 2 with a thickness of 55 μm prepared in the same manner as in Example 3, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1. (Example 12) For the substrate layer 2 with a thickness of 55 μm prepared in the same manner as in Example 4, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1.

[0064] (Example 13) For the substrate layer 2 with a thickness of 145 μm prepared in the same manner as in Example 5, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1. (Example 14) For the substrate layer 2 with a thickness of 145 μm prepared in the same manner as in Example 6, a transparent resin layer 4 and a top coat layer 5 were formed to obtain a decorative sheet 1. (Example 15) For the substrate layer 2 with a thickness of 145 μm prepared in the same manner as in Example 7, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1. (Example 16) For the substrate layer 2 with a thickness of 145 μm prepared in the same manner as in Example 8, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1.

[0065] (Example 17) Except for using a nucleating agent without an outer membrane instead of the above-mentioned nucleating agent vesicles, an extruded substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using an extrusion machine in the same manner as in Example 7. (Example 18) Except for using a nucleating agent without an outer membrane instead of the above-mentioned nucleating agent vesicles, an extruded substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using an extrusion machine in the same manner as in Example 8. (Example 19) Except for using a nucleating agent without an outer membrane instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 5. (Example 20) Except for using a nucleating agent without an outer membrane instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 6.

[0066] (Comparative Example 1) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 55 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 1. (Comparative Example 2) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 55 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 2. (Comparative Example 3) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 55 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 3. (Comparative Example 4) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 55 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 4.

[0067] (Comparative Example 5) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 5. (Comparative Example 6) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 6. (Comparative Example 7) Except for using an untreated nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 7. (Comparative Example 8) Except for using the unprocessed nucleating agent instead of the above-mentioned nucleating agent vesicles, a substrate layer 2 with a thickness of 145 μm was formed by extrusion molding using a melt extruder in the same manner as in Example 8.

[0068] (Comparative Example 9) Similar to Comparative Example 2, a substrate layer 2 with a thickness of 155 μm was formed by extrusion molding using a melt extruder. Then, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet T1. (Comparative Example 10) Similar to Example 2, a substrate layer 2 with a thickness of 155 μm was formed by extrusion molding using a melt extruder. Then, a transparent resin layer 4 and a top coat layer 5 were formed in the same manner as in Example 9 to obtain a decorative sheet 1. (Comparative Example 11) Similar to Example 2, a substrate layer 2 with a thickness of 45 μm was formed by extrusion molding using a melt extruder.

[0069] (Comparative Example 12) As raw materials for the colored polypropylene film, to 31.2 parts by mass of a highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 °C), and a molecular weight distribution MWD (Mw / Mn) of 2.3, 46.8 parts of a random polypropylene resin with a melt flow rate (MFR) of 12 g / 10 min (230 °C) containing 4% ethylene component, 6 parts by mass of titanium oxide pigment as an inorganic pigment, 16 parts by mass of a chromium-antimony composite oxide pigment, and 0.5 part by mass of the above-mentioned nucleating agent vesicles as a nucleating agent were added, and extrusion molding was performed using a melt extruder to form a substrate layer 2 made of a colored polypropylene film with a thickness of 55 μm.

[0070] (Comparative Example 13) As a raw material for the colored polypropylene film, 39 parts by mass of a highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a melt flow rate (MFR) of 15 g / 10 min (230 °C), and a molecular weight distribution MWD (Mw / Mn) of 2.3 was mixed with 39 parts of a random polypropylene resin with a melt flow rate (MFR) of 12 g / 10 min (230 °C) containing 4% ethylene component, 6 parts by mass of titanium oxide pigment as an inorganic pigment, 16 parts by mass of a chromium-antimony composite oxide pigment, and 1.0 part by mass of the above-mentioned nucleating agent vesicle as a nucleating agent, and then extrusion molding was carried out using a melt extruder to produce a base material layer 2 made of a colored polypropylene film with a thickness of 55 μm.

[0071] (Evaluation) For the above Examples 1 to 20 and Comparative Examples 1 to 13, Fourier transform infrared spectroscopy measurement, measurement of tensile modulus, defects during printing (printing processability), scratch resistance, bend processability, and wrapping process smoothness (surface uniformity during wrapping process) were evaluated. <Fourier transform infrared spectroscopy measurement> For Fourier transform infrared spectroscopy measurement, a Fourier transform infrared spectroscopy apparatus (Spectrum Spotlight 400) manufactured by PerkinElmer was used to obtain an absorption spectrum from 4000 cm -1 to 700 cm -1 From the obtained absorption spectrum, the peak intensity ratios at wave numbers 997 cm -1 , 973 cm -1 , and 938 cm -1 were extracted, and the peak intensity ratio x was calculated by the following formula.

[0072] [Equation]

[0073] <Tensile modulus> For the measurement of tensile modulus, an autograph (AGS-500NX) manufactured by Shimadzu Corporation was used to conduct a tensile test at a tensile speed of 50 mm / min, and the tensile modulus was calculated. <Defects during printing (printing processability)> The pattern layer 3 was formed by gravure printing using a gravure printing machine. At that time, the base material layer 2 was stretched by tension, and the problem of misalignment during lamination of each color was evaluated as a printing defect. When no alignment adjustment was required at all, it was rated as "◎"; when it could be easily adjusted by automatic alignment, it was rated as "○"; when attention was required for alignment adjustment, it was rated as "△"; when alignment adjustment was impossible and printing could not be continued, it was rated as "×". Also, when the film during printing was broken frequently and there was a problem with mass productivity, it was rated as "×". Note that if the evaluation is "△" or higher, there is no problem with the printing process.

[0074] <Scratch resistance> Regarding scratch resistance, it was evaluated by conducting a pencil hardness test. In the pencil hardness test, a 3B pencil was used, the angle of the pencil was fixed at 45 ± 1° with respect to the decorative sheet 10, and it was slid with a load of 750 kg applied to the pencil to observe the surface state of the decorative sheet 10 (in accordance with the old JIS standard JISK5400). The test was conducted 5 times, and the scratches and marks of the pencil were evaluated. When no scratches or marks were visible at all, it was rated as "◎"; when slight pencil marks were visible, it was rated as "○"; when pencil marks were visible, it was rated as "△"; when pencil scratches or breaks in the colored polypropylene film were visible, it was rated as "×". Note that if the evaluation is "○" or higher, there is no practical problem. Also, if the evaluation is "△" or higher, although it is limited to applications such as furniture or vertical surfaces at a high position where people do not touch, no problems will occur. It is preferable that the evaluation is "○" or higher.

[0075] <Bending process suitability> In the bending process suitability test, on one surface of medium density fiberboard (MDF) as the base material layer 2, each decorative sheet 1 of Examples 1 to 20 and Comparative Examples 1 to 13 obtained by the above method was pasted using a urethane-based adhesive. For the other surface of the base material layer 2, a V-shaped groove was made up to the boundary where the base material layer 2 and the decorative sheet 1 were bonded together so that the opposite decorative sheet 1 would not be scratched. Next, the base material layer 2 was bent along the V-shaped groove up to 90 degrees so that the surface of the decorative sheet 1 became a mountain fold, and it was observed using an optical microscope whether whitening, cracks, etc. occurred in the bent part of the surface of the decorative sheet 1, and the state of the bending processability was evaluated. The case where no whitening or cracks were seen at all was rated as "◎", the case where slight whitening was seen in part was rated as "○", the case where whitening was seen in part was rated as "△", and the case where whitening was seen on the entire surface or cracks were seen in part was rated as "×". Note that if the evaluation is "△" or higher, there is no practical problem.

[0076] <Surface uniformity during wrapping process> In the surface uniformity test during the wrapping process, a square timber obtained by laminating 3 to 5 sheets of lumber or particle board between two medium density fiberboards (MDFs) was used as the base material layer 2, and each decorative sheet 1 of Examples 1 to 20 and Comparative Examples 1 to 13 obtained by the above method was pasted by wrapping using a hot melt adhesive to obtain a decorative board. Subsequently, the surface where the decorative sheet 1 was bonded to the end of the lumber was observed visually to check for surface irregularities caused by the unevenness of the lumber, the step at the bonding part of the lumber, etc. Further, the obtained decorative board was left in an environment of 80°C and 85% humidity for 1000 hours, and the surface irregularities at the same location and the peeling of the decorative sheet 1 were confirmed. The case where no irregularities or steps were seen and it was smooth both initially and after 1000 hours was rated as "◎", the case where the surface appeared slightly rough was rated as "○", the case where irregularities or steps were seen in part was rated as "△", and the case where irregularities or steps were seen on the entire surface or the peeling of the decorative sheet 10 was seen after 1000 hours was rated as "×". Note that if the evaluation is "△" or higher, there is no practical problem, but it is preferably "○" or higher. These evaluation results are shown in Table 1.

[0077]

Table 1

[0078] As can be seen from Table 1, in the cosmetic sheets 1 of Examples 1 to 8 and 17 to 20, while ensuring a practical situation regarding defects and strength during printing, it can be seen that both bending process is achievable. Furthermore, for the cosmetic sheets 1 of Examples 9 to 16, by laminating the pattern layer 3, the transparent resin layer 4, and the top coat layer 5 on Examples 1 to 9, it can be seen that while achieving both high design and high scratch resistance, both bending process is achievable. On the other hand, in the cosmetic sheets 1 of Comparative Examples 1 to 9, since a micro-sized nucleating agent that is not vesiculated was used, the improvement in strength due to the improvement in crystallinity is not sufficient, and particularly when the film thickness is thin and when the blending ratio of the highly crystalline homopolypropylene resin is low, defects occur during printing. Also, even when there are no defects during printing, there are cases where the strength required for the cosmetic sheet 1 is insufficient or defects occur during bending. These are considered to be caused by the low ability to improve crystallinity compared to the vesiculated nucleating agent and the relatively large spherulite size.

[0079] Moreover, in the cosmetic sheets 1 of Comparative Examples 10 to 13, at least one of the film thickness of the base material layer 2 and the peak strength x exceeds the numerical range of the present application, and it can be seen that any of the evaluation results has a problem.

[0080] Here, in Comparative Example 11, although automatic alignment adjustment was possible, the film during printing broke frequently, and products could not be made. This is considered to be because although the peak strength x and the tensile elastic modulus were sufficient, the thickness was too thin, so the film could not withstand the tension fluctuations during printing, resulting in an increased frequency of breakage.

[0081] ​From the above, it became clear that the cosmetic sheets 1 of Examples 1 to 20 are cosmetic sheets 1 that achieved compatibility in all aspects of defects during printing (printing process suitability), scratch resistance, and bending process suitability. Furthermore, it became clear that the cosmetic sheets 1 of Examples 1 to 20 also have wrapping process smoothness. Note that the cosmetic sheet of the present invention is not limited to the above-described embodiments and examples, and various modifications are possible without impairing the features of the invention.

Explanation of Reference Numerals

[0082] 1... Cosmetic sheet, 2... Base material layer, 3... Pattern layer, 4... Transparent resin layer, 4a... Embossed pattern, 4b... Adhesive resin layer, 5... Top coat layer, 6... Primer layer, B... Substrate

Claims

1. A base material layer made of a colored polypropylene film obtained by mixing an inorganic pigment into a polypropylene resin, the base material layer containing a nano-sized nucleating agent, the thickness of the base material layer being 50 μm or more and 150 μm or less, and the value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier transform infrared spectroscopy being 0.7 or more and 0.9 or less. The base material layer further contains a fatty acid metal salt as an additive. The inorganic pigment contains titanium oxide and iron oxide, or contains only titanium oxide. The nucleating agent is a nucleating agent vesicle in which only the nucleating agent is encapsulated in a vesicle having an outer membrane of a single-layer film. The nucleating agent contains a non-melting type nucleating agent and a melting type nucleating agent. The non-melting type nucleating agent is a metal salt of phosphate ester, a metal salt of benzoic acid, a metal salt of pimelic acid, or a metal salt of rosin. The melting type nucleating agent is benzylidene sorbitol, and the cosmetic sheet is characterized by this. Here, in the following formula, I997 is the peak intensity value at a wave number of 997 cm －１ , I938 is the peak intensity value at a wave number of 938 cm －１ , and I973 is the peak intensity value at a wave number of 973 cm －１ . 【Number 1】

2. The cosmetic sheet according to Claim 1, wherein the tensile elastic modulus is 850 MPa or more and 1600 MPa or less.

3. The cosmetic sheet according to Claim 1 or Claim 2, wherein 50% by mass or more and 100% by mass or less of the polypropylene resin consists of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

4. The cosmetic sheet according to any one of Claims 1 to 3, wherein the addition amount of the nano-sized nucleating agent is 0.01 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the polypropylene resin.

5. The cosmetic sheet according to any one of Claims 1 to 4, wherein the nucleating agent vesicle is added in a range of 0.01 part by mass or more and 0.5 part by mass or less in terms of the nucleating agent in the nucleating agent vesicle with respect to 100 parts by mass of the polypropylene resin.

6. The cosmetic sheet according to any one of Claims 1 to 5, wherein the nucleating agent vesicle is a nucleating agent liposome having an outer membrane made of phospholipid.

7. The cosmetic sheet according to any one of Claims 1 to 6, wherein the addition amount of the nucleating agent vesicle is 0.01 part by mass or more and 0.5 part by mass or less in terms of the nucleating agent in the nucleating agent vesicle with respect to 100 parts by mass of the polypropylene resin.

8. The decorative sheet according to any one of claims 1 to 7, characterized in that a pattern layer is laminated on one surface of the base material layer.

9. The decorative sheet according to claim 2, characterized in that the tensile elastic modulus is that of the base material layer.

10. The decorative sheet according to any one of claims 1 to 9, characterized in that the nano-sized nucleating agent contains a metal benzoate, a metal pimelate, a metal rosinate, benzylidene sorbitol, quinacridone, cyanine blue, or talc.

11. The decorative sheet according to any one of claims 1 to 9, characterized in that the base material layer does not contain aluminosilicate, metal hydroxide, lithium silicate, silica gel, or alumina.

12. The decorative sheet according to any one of claims 1 to 11, characterized in that the base material layer does not contain a foaming agent and 1,2-polybutadiene, respectively.

13. A method for manufacturing the decorative sheet according to any one of claims 1 to 12, characterized in that a base material layer with a tensile elastic modulus of 850 MPa or more and 1600 MPa or less and a thickness of 50 μm or more and 150 μm or less is produced from a resin material obtained by adding a nano-sized nucleating agent to a polypropylene resin mixed with an inorganic pigment.

14. The method for manufacturing a decorative sheet according to claim 13, characterized in that the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier transform infrared spectroscopy is controlled to be 0.7 or more and 0.9 or less when manufacturing the base material layer.

15. The method for manufacturing a decorative sheet according to claim 13 or claim 14, characterized in that the tensile elastic modulus of the base material layer is controlled to be 850 MPa or more and 1600 MPa or less when manufacturing the base material layer.

16. The method for manufacturing a decorative sheet according to any one of claims 13 to 15, characterized in that the nucleating agent is encapsulated in vesicles by a supercritical reverse phase evaporation method.

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