Cosmetic sheet, cosmetic material, and method for manufacturing cosmetic sheet

Abstract

To provide a decorative sheet that has high scratch resistance and can improve designability when processed, a decorative material using the decorative sheet, and a manufacturing method for the decorative sheet.SOLUTION: A decorative sheet 1 comprises: a raw fabric layer 12 that has a substrate layer 12A containing a resin material and a skin layer 12B that is arranged on al least one surface of the substrate layer 12A and contains a resin material and a nucleating agent or inorganic particles; and a top coat layer 14 arranged on the skin layer 12B formed on one surface of the raw fabric layer 12. A rugged shape is disposed on the surface of the skin layer 12B arranged on the surface in the top coat layer side of the substrate layer 12A, and an arithmetic average roughness Ra of the surface of the skin layer 12B on which the rugged shape is disposed is within a range from 3 μm to 6 μm.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a cosmetic sheet, a cosmetic material, and a method for manufacturing a cosmetic sheet.

Background Art

[0002] A composite film including a base material layer containing a resin film and a colored layer is used as a cosmetic sheet. The cosmetic sheet used indoors is attached to the surfaces of fixtures such as interior doors and entrance storage, and trim materials such as moldings, baseboards, window frames, and door frames. Since such cosmetic sheets are used in various indoor environments such as high-temperature environments and environments exposed to light (sunlight, ultraviolet rays, etc.), cosmetic sheets having heat resistance, weather resistance, etc. have been proposed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, fixtures and trim materials are easily damaged as parts of furniture because people open and close them, objects are placed on them, or they are disposed near the floor. Therefore, cosmetic sheets used for fixtures and trim materials require higher scratch resistance than general cosmetic sheets. In addition, cosmetic sheets tend to be shaped by embossing with minute irregularities (e.g., satin embossing) on the surface in order to improve a flat design feeling and touch feeling (tactile sensation), and further enhance versatility. However, if the embossed portions on the surface are made too flat, it becomes easy to pick up surface irregularities (so-called substrate undulations) of the adherend (underlying substrate or building material) of the cosmetic sheet, and the irregularities of the underlying substrate may become prominent. In this case, the designability when attached to and processed on the underlying substrate or building material may be inferior to that of a conventional olefin sheet shaped with a wood grain emboss or the like. The present disclosure has been made in view of such problems, and an object thereof is to provide a decorative sheet having high scratch resistance and capable of improving the design property when processed, a decorative material using the decorative sheet, and a method for manufacturing the decorative sheet.

Means for Solving the Problems

[0005] In order to solve the above problems, a decorative sheet according to one aspect of the present disclosure includes a base material layer containing a resin material, and a skin layer provided on at least one surface of the base material layer and containing a resin material and a nucleating agent or inorganic particles, and a raw sheet layer having the same, and a top coat layer provided on the skin layer formed on one surface of the raw sheet layer. The skin layer containing the nucleating agent contains polypropylene resin as the resin material, and the thickness of the base material layer is 100 μm or more and 200 μm or less. The skin layer provided on the surface of the base material layer on the top coat layer side Table of is characterized in that the arithmetic mean roughness Ra of the surface is in the range of 3 μm or more and 6 μm or less.

[0006] Further, a decorative material according to another aspect of the present disclosure includes the above-described decorative sheet and a base material to which the decorative sheet is bonded to at least one surface thereof.

[0007] Further, a method for manufacturing a decorative sheet according to still another aspect of the present disclosure is the method for manufacturing the above-described decorative sheet, including a step of encapsulating a nucleating agent in a vesicle to generate a nucleating agent vesicle obtained by vesiculating the nucleating agent, and a step of applying and curing a second resin material containing the nucleating agent vesicle on at least one surface of a base material layer formed using a first resin material to form a raw sheet layer provided with a skin layer on at least one surface of the base material layer, and a step of applying and curing a third resin material on the skin layer formed on one surface of the raw sheet layer to form a top coat layer. As polypropylene resin In the step of forming the raw sheet layer, the arithmetic mean roughness Ra of the surface of the skin layer provided on the surface on the top coat layer side is in the range of 3 μm or more and 6 μm or less. The thickness of the base material layer is 100 μm or more and 200 μm or less. In the step of forming the raw sheet layer, the skin layer provided on the surface on the top coat layer side Table of is characterized in that the arithmetic mean roughness Ra of the surface is in the range of 3 μm or more and 6 μm or less.

Effects of the Invention

[0008] According to an aspect of the present disclosure, it is possible to provide a decorative sheet having high scratch resistance and capable of improving the design property when processed, a decorative material using the decorative sheet, and a method for manufacturing the decorative sheet.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0010] Hereinafter, the present disclosure will be described through embodiments. However, the following embodiments do not limit the invention according to the claims. Also, not all combinations of the features described in the embodiments are essential for the solution means of the invention. Further, the drawings schematically show the invention according to the claims, and dimensions such as the width and thickness of each part are different from the actual ones, and these ratios are also different from the actual ones.

[0011] The laminate according to the first embodiment of the present disclosure will be described. The decorative sheet according to the present disclosure is, for example, a decorative sheet to be applied to a wall surface, a fixture, a furniture, etc., and in particular, it is a decorative sheet preferably used for a molding material such as a door frame, a window frame, a lintel, a partition, and a baseboard that are pre-incorporated into a building. In the following description, the side in contact with the pasting surface of the decorative sheet may be referred to as "down", and the side opposite to the side in contact with the pasting surface (the surface) may be referred to as "up". Hereinafter, each aspect of each embodiment of the present disclosure will be described with reference to the drawings.

[0012] 1. First Embodiment (1.1) Basic Configuration of Decorative Sheet FIG. 1 is a cross-sectional view for explaining a configuration example of the cosmetic sheet 1 according to an embodiment of the present disclosure. As shown in FIG. 1, the cosmetic sheet 1 includes a primer layer 11, a base fabric layer 12, and a top coat layer 14. The cosmetic sheet 1 is configured by laminating the primer layer 11, the base fabric layer 12, a coloring layer 13, and the top coat layer 14 in this order.

[0013] The primer layer 11 is a layer provided to improve the adhesiveness between the cosmetic sheet 1 and the wall surface, building materials, base materials, etc. to which the cosmetic sheet 1 is attached. The base fabric layer 12 is a layer that serves as the base material of the cosmetic sheet 1, absorbs irregularities and steps on the attachment surface to improve the construction finish of the cosmetic sheet 1, and is a layer for concealing the color and pattern of the attachment surface. Further, the base fabric layer 12 is a layer for suppressing scratches generated on the cosmetic sheet 1 and giving the cosmetic sheet a design and a soft and comfortable touch. The coloring layer 13 is a layer for imparting a desired color to the cosmetic sheet 1. The top coat layer 14 is provided on the uppermost surface of the cosmetic sheet 1 and is a layer provided for protecting the cosmetic sheet 1 and adjusting the gloss of the surface of the cosmetic sheet 1. Hereinafter, each layer of the primer layer 11, the base fabric layer 12, the coloring layer 13, and the top coat layer 14 will be described in detail. In the cosmetic sheet 1, the primer layer 11 and the coloring layer 13 may be omitted. For example, if the base material side to which the cosmetic sheet 1 is attached has a function as a primer layer, the primer layer 11 can be omitted. Also, for example, when it is not necessary to impart a specific color to the cosmetic sheet 1, the coloring layer 13 can be omitted. That is, for the cosmetic sheet 1, it is sufficient that the top coat layer 14 is formed on at least one surface side of the base fabric layer 12.

[0014] <Base fabric layer> The original substrate layer 12 has a base material layer 12A and a skin layer 12B provided on at least one surface of the base material layer 12A. The original substrate layer 12 is configured such that the skin layer 12B is provided on the upper surface of the base material layer 12A (the surface on the side of the top coat layer 14 described later) or on both surfaces of the base material layer 12A. In the present embodiment, the original substrate layer 12 having a configuration in which the skin layer 12B is provided on both surfaces of the base material layer 12A will be described. The original substrate layer 12 may be formed, for example, by co-extrusion so that the thickness ratio of "skin layer 12B: base material layer 12A: skin layer 12B" is "0.5:9:0.5".

[0015] [Base material layer] The base material layer 12A is a layer formed by mixing an inorganic pigment for coloring into a resin material. The base material layer 12A is, for example, a white polypropylene film in which a white pigment is mixed into a polypropylene resin. The thickness of the base material layer 12A is preferably, for example, 40 μm or more and 200 μm or less, and more preferably 100 μm or more and 160 μm or less. When the thickness of the base material layer 12A is 40 μm or more, the concealment required for the decorative sheet can be sufficiently exhibited, and the strength as a base material can be sufficiently provided, suppressing the deterioration of scratch resistance. On the other hand, when the thickness of the base material layer 12A is 200 μm or less, it is possible to suppress the occurrence of problems such as whitening and cracking during bending.

[0016] (Resin material) Examples of the resin material constituting the base material layer 12A include thermoplastic resins. There are no particular restrictions on the thermoplastic resin, and the same materials as those of the thermoplastic resins conventionally used as the base material layer or the like in decorative sheets can be used. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate, polyarylate, and polycarbonate; olefin-based copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, and ethylene-unsaturated carboxylic acid copolymer metal neutralized product (ionomer); acrylic resins such as poly(meth)acrylonitrile, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polyacrylamide; polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon; styrene resins such as polystyrene, AS resin, and ABS resin; vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, and polyvinyl butyral; fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer; or mixtures, copolymers, composites, laminates, etc. of two or more of them can be used.

[0017] In particular, in view of the increasing social concern about environmental problems in recent years, it is not preferable to use a thermoplastic resin containing chlorine (halogen) such as polyvinyl chloride resin as the thermoplastic resin, and it is preferable to use a non-halogen-based thermoplastic resin. In particular, from the viewpoints of various physical properties, processability, versatility, economy, etc., it is most preferable to use a polyester-based resin (amorphous or biaxially stretched) or a polyolefin-based resin, particularly a polyolefin-based resin as the non-halogen-based thermoplastic resin. For example, as the polyolefin-based resin, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

[0018] In the base material layer 12A, if necessary, for example, one or more selected from various additives such as a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, a fungicide, a friction reducing agent, a light scattering agent, and a gloss adjusting agent may be added. Note that the base material layer 12A preferably has concealability for concealing the pasting surface of the decorative sheet 1 such as a wall surface from the surface (upper surface) of the decorative sheet 1. The base material layer 12A preferably contains a single-color colorant. As the colorant, it is preferable to use a known inorganic pigment typified by titanium oxide, which is a white pigment for imparting concealability. If the concealability is low, the pattern of the pasting surface of the decorative sheet 1 is transmitted, which is not preferable. By containing an inorganic pigment, a decorative sheet 1 having good concealability can be obtained.

[0019] [Skin layer] The skin layer 12B is a layer containing a resin material and a nucleating agent for improving the crystallinity of the resin material, and has an uneven shape on the surface. In the present embodiment, the nucleating agent is added to the resin material in a state of a nucleating agent vesicle encapsulated by an outer membrane and vesiculated. The thickness of the skin layer 12B is preferably, for example, 1 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less. When the thickness of the skin layer 12B is 1 μm or more, the scratch resistance of the cosmetic sheet 1 becomes sufficiently high. Further, when the thickness of the skin layer 12B is 50 μm or less, the flexibility of the cosmetic sheet 1 does not become too high, and even when the attachment surface to which the cosmetic sheet 1 is attached is not flat, the cosmetic sheet 1 can be applied in a state of being in close contact with the attachment surface.

[0020] (Resin material) Examples of the resin material constituting the skin layer 12B include thermoplastic resins. The thermoplastic resin is not particularly limited, and the same resin material as that of the base material layer 12A can be used.

[0021] (Nucleating agent) The skin layer 12B contains a nano-sized nucleating agent. The nano-sized nucleating agent is preferably added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having an outer membrane of a single-layer film. Further, in the present embodiment, the nucleating agent in the resin constituting the skin layer 12B may be encapsulated in the vesicle with a part of the nucleating agent exposed. Since the skin layer 12B contains a nucleating agent, the crystallinity can be improved, and the scratch resistance (scuff resistance) of the cosmetic sheet 1 can be improved. The nano-sized nucleating agent preferably has an average particle size of 1 / 2 or less of the wavelength region of visible light. Specifically, since the wavelength region of visible light is 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.

[0022] Since the nucleating agent with nano-size has an extremely small particle size, the number and surface area of the nucleating agent present per unit volume increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes closer. When crystal growth occurs from the surface of a single nucleating agent particle added to the resin, the end of the growing crystal immediately contacts the end of the crystal growing from the surface of another nucleating agent particle adjacent to the single nucleating agent particle, and the growth of each crystal stops because the growth of the ends of each other's crystals is inhibited. Therefore, in the crystalline part of the crystalline resin, the average particle diameter of the spherulites can be reduced, for example, the spherulite size can be reduced to 1 μm or less. As a result, a high-hardness resin film with a high degree of crystallinity can be obtained, and since the stress concentration between spherulites generated during bending processing is efficiently dispersed, a resin film that suppresses cracking and whitening during bending processing can be realized.

[0023] When the nucleating agent is simply added, the particle size becomes larger due to the secondary aggregation of the nucleating agent in the resin. On the other hand, when the nucleating agent vesicles are added, the dispersibility in the resin is improved, so the number of crystal nuclei with respect to the amount of the added nucleating agent increases significantly compared to the case where the nucleating agent is simply added. For this reason, the average particle diameter of the spherulites in the crystalline part of the resin becomes smaller, and the occurrence of cracking and whitening during bending processing can be suppressed. Therefore, by adding the nucleating agent vesicles, the degree of crystallinity can be further increased, and it becomes possible to better balance the improvement of the elastic modulus and the processability.

[0024] The skin layer 12B is formed of a resin material in which a nucleating agent is added, for example, in the range of preferably 0.05 parts by mass or more and 0.5 parts by mass or less, more preferably 0.1 parts by mass or more and 0.3 parts by mass or less, with respect to 100 parts by mass of a polypropylene resin as a main component. When using a nucleating agent vesicle, the addition amount of the nucleating agent to the resin material is the addition amount converted to the nucleating agent in the nucleating agent vesicle. When the addition amount of the nucleating agent is less than 0.05 parts by mass, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the skin layer 12B may not be sufficiently improved. Further, when the addition amount of the nucleating agent exceeds 0.5 parts by mass, the spherulite growth of the polypropylene is conversely inhibited due to an excessive number of crystal nuclei, and as a result, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the skin layer 12B may not be sufficiently improved. Here, the "main component" shall mean a resin material that occupies 50% by mass or more of the resin material constituting the skin layer 12B.

[0025] Further, as a method for nanosizing the nucleating agent, for example, a solid phase method of mainly mechanically pulverizing the nucleating agent to obtain nano-sized particles, a liquid phase method of synthesizing or crystallizing nano-sized particles in a solution in which the nucleating agent or the nucleating agent is dissolved, a gas phase method of synthesizing or crystallizing nano-sized particles 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.

[0026] As a method for nano-sizing a nucleating agent, the supercritical reverse phase evaporation method is preferred. The supercritical reverse phase evaporation method is a method for producing capsules (nano-sized 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.

[0027] Also, as a specific nano-sizing treatment 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 encapsulating 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 capsules with a smaller diameter can be prepared. The nucleating agent vesicles are 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, or the like. Among these, the nucleating agent vesicles are preferably adjusted using the supercritical reverse phase evaporation method in particular.

[0028] The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane. Further, the outer membrane is composed of a substance containing a biological lipid such as a phospholipid, for example. In the present embodiment, the nucleating agent vesicle contained in the skin layer 12B is preferably a nucleating agent liposome having the outer membrane containing a phospholipid. 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 phospholipids 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.

[0029] Examples of other substances that form the outer membrane of the vesicle 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 ether, dialkylglycerol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethyl ethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. Examples of cholesterol include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or colecalciferol, etc.

[0030] 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 vesicle 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 cosmetic sheet 1, and the vesicle can be made good. 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 benzylidene sorbitol may be appropriately mixed and used with the non-melting type nucleating agent.

[0031] As described above, the cosmetic sheet 1 of the present embodiment is characterized in that the skin layer 12B contains a resin material and a nucleating agent. Further, the cosmetic sheet 1 of the present embodiment is characterized in that when forming the skin layer 12B, a nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. By adding the nucleating agent encapsulated in vesicles to the resin composition, the dispersibility of the nucleating agent in the resin material, that is, in the skin layer 12B, is dramatically improved. On the other hand, it can be considered difficult and unrealistic to directly specify the nucleating agent encapsulated in vesicles based on the structure and properties of the object in the state of the completed cosmetic sheet 1 depending on the situation. The reason is as follows.

[0032] The nucleating agent added in the state of the vehicle has high dispersibility and is in a dispersed state, and is highly dispersed in the skin layer 12B even in the state of the laminate which is the precursor of the produced cosmetic sheet 1. However, in the manufacturing process of the cosmetic sheet 1, usually, various processes such as compression treatment and curing treatment are performed on the laminate, and in such processes, the outer membrane of the vesicle containing the nucleating agent may be crushed or a chemical reaction may occur. For this reason, due to the treatment process of the cosmetic sheet 1, the outer membrane of the nucleating agent in the completed cosmetic sheet 1 may be crushed or the state of the chemical reaction may vary, so there is a high possibility that the nucleating agent is not encapsulated (covered) by the outer membrane. And when the nucleating agent is not encapsulated by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself within a numerical range, and 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 vesicle or a material added separately from the nucleating agent. Thus, although the present disclosure is different from the prior art in that the nucleating agent is highly dispersed in the cosmetic sheet 1, it is also assumed that in the state of the cosmetic sheet 1, it is impractical to specify within a numerical range obtained by analyzing its structure and properties based on measurement whether it is because it was added in the state of a vesicle containing the nucleating agent.

[0033] At least one surface of the skin layer 12B has an uneven shape. Specifically, the uneven shape may be provided on the skin layer 12B on the surface side (top coat layer 14 side), or may be provided on both the skin layer 12B on the surface side and the back side (primer layer 11 side).

[0034] The arithmetic mean roughness Ra of the surface of the skin layer 12B having the uneven shape (for example, the surface of the skin layer 12B on the top coat layer 14 side) is preferably 3 μm or more and 6 μm or less. In addition, the ten-point mean roughness Rz (RzJIS) of the surface of the skin layer 12B having the concavo-convex shape is preferably 10 μm or more and 20 μm or less, and more preferably 15 μm or more and 20 μm or less. Further, the maximum height Ry of the local peaks of the concavo-convexities on the surface of the skin layer 12B having the concavo-convex shape is preferably 17 μm or more and 30 μm or less, and more preferably 20 μm or more and 30 μm or less. Furthermore, the average interval S between the local peaks of the concavo-convexities on the surface of the skin layer 12B having the concavo-convex shape is preferably 300 μm or more and 500 μm or less, and more preferably 400 μm or more and 500 μm or less. Here, the arithmetic mean roughness Ra, the maximum height Ry of the concavo-convexities, the ten-point mean roughness Rz, and the average interval S between the local peaks are values defined in JIS B0601:1994.

[0035] Since the surface of the skin layer 12B having the concavo-convex shape has the above-described arithmetic mean roughness Ra, ten-point mean roughness Rz, maximum height Ry, and average interval S between the local peaks, it is possible to obtain the decorative sheet 1 with high scratch resistance and a soft and pleasant touch. In addition, the decorative sheet 1 in which the surface of the skin layer 12B has the concavo-convex shape as described above has high scratch resistance and a soft and pleasant touch (tactile sensation), and can impart a fine satin-like design feeling (flat design feeling) to the outermost surface (the surface of the top coat layer 14) to such an extent that the feeling of the concavo-convexities is hardly distinguishable visually. That is, since the surface of the skin layer 12B on the top coat layer 14 side has the above-described concavo-convex shape, the surface of the top coat layer of the decorative sheet 1 has a satin-like concavo-convex shape (fine concavo-convexities). Here, if the unevenness appearing on the surface of the cosmetic sheet 1 (the surface of the top coat layer) is too fine, that is, if the surface of the top coat layer is too flat, it becomes easier to pick up the surface unevenness (substrate unevenness) of the base material or the trim material that becomes the adherend of the cosmetic sheet, and the design property when processed into a decorative material may be reduced. Therefore, in the cosmetic sheet 1 according to the present embodiment, as described above, an uneven shape is provided on at least the surface of the skin layer 12B on the top coat layer 14 side, and the uneven shape is formed so as to be the arithmetic mean roughness Ra, the ten-point mean roughness Rz, the maximum height Ry, and the average interval S of local peaks described above. Thereby, when the cosmetic sheet 1 is incorporated into a trim material or pasted on a base material and processed into a decorative material, the surface unevenness (substrate unevenness) of the trim material or the base material is made less conspicuous, and the design property during processing can be improved. Further, since the cosmetic sheet 1 has an uneven shape as described above on at least the surface of the skin layer 12B on the top coat layer 14 side, fine unevenness with a satin finish is formed on the outermost surface (the surface of the top coat layer 14). Therefore, it is possible to obtain a preferable and calm appearance as a cosmetic sheet used for a trim material incorporated into a fixture. In addition, the cosmetic sheet 1 having an uneven shape as described above on at least the surface of the skin layer 12B on the top coat layer 14 side can maintain stain resistance by forming fine unevenness on the outermost surface. More specifically, since the unevenness on the outermost surface of the cosmetic sheet 1 is fine, it becomes difficult for large particle stains to enter. Further, by coating the concave portions of the uneven shape of the skin layer 12B with the top coat layer 14, it is possible to suppress the adhesion of small particle stains. Thereby, good stain resistance can be imparted to the cosmetic sheet 1.

[0036] <Coloring layer> The coloring layer 13 is provided between the top coat layer 14 and the base fabric layer 12, and is a layer containing, for example, a matrix and a coloring agent such as a dye or a pigment. For the coloring layer 13, for example, a printing ink or a coating agent in which a matrix and a coloring agent such as a dye or a pigment are dissolved and dispersed in a solvent can be used. The thickness of the coloring layer 13 is preferably in the range of 3 μm or more and 20 μm or less. Coloring layer When the thickness of 13 is within this numerical range, printing can be made clear, the print workability in manufacturing the decorative sheet 1 can be improved, and the manufacturing cost can be suppressed.

[0037] (Matrix) As the matrix, for example, various synthetic resins such as oil-based nitrocellulose resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, fluororesin, silicone resin, rubber resin, etc., or mixtures, copolymers, etc. of these can be used.

[0038] (Colorant) The inorganic pigments as the colorants constituting the colored layer 13 are not particularly limited, and examples include natural inorganic pigments and synthetic inorganic pigments. Examples of natural inorganic pigments include earth pigments, calcined earth, and mineral pigments. Examples of synthetic inorganic pigments include oxide pigments, hydroxide pigments, sulfide pigments, silicate pigments, phosphate pigments, carbonate pigments, metal powder pigments, and carbon pigments. Also, a mixed pigment obtained by mixing one or more of natural inorganic pigments and synthetic inorganic pigments may be used. More specifically, as the inorganic pigment, for example, carbon black, titanium white, zinc white, red lead, yellow lead, ultramarine blue, cadmium red, etc. can be used. Also, an organic pigment may be used as the colorant constituting the colored layer 13. As the organic pigment, organic pigments such as carbon black, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments, or mixtures thereof can be used. Inorganic pigments and organic pigments may be used in combination. Furthermore, additives such as fatty acid metal salts may be added to improve dispersibility and extrusion suitability.

[0039] Also, in the colored layer 13, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retardants may be added to impart various functions. Here, the coloring layer 13 can be formed by various printing methods such as gravure printing method, offset printing method, screen printing method, electrostatic printing method, inkjet printing method, etc. These printing methods may be separately selected according to the layer to be formed, but it is efficient to select the same method for batch processing.

[0040] <Top coat layer> The top coat layer 14 is composed of a resin material. The material that is the main component of the resin material constituting the top coat layer 14 is 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, urea-based, etc. The form of the resin material is not particularly limited, such as aqueous, emulsion, solvent-based, etc. Regarding the curing method of the resin material, it can be appropriately selected and carried out, such as one-component type, two-component type, ionization radiation (for example, ultraviolet ray) curing method, heat curing method, photo-curing type, etc.

[0041] As the resin material used as the main component of the top coat layer 14, a urethane-based material using isocyanate is suitable from the viewpoints of workability, price, cohesive force of the resin itself, etc. As the isocyanate, for example, adducts, burettes, isocyanurates and other curing agents which are 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) can be appropriately selected and used. Among them, from the viewpoint of weather resistance, it is preferable to use hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a linear molecular structure. In addition, when improving the surface hardness, it is preferable to use a resin (ionizing radiation curable resin) that is cured by active energy rays such as ultraviolet rays and 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. Also, by making a hybrid type of a thermosetting type and an ionizing radiation curable type, it is possible to satisfy scratch resistance and at the same time make it difficult for whitening or cracking of the top coat layer 14 to occur in bending processing.

[0042] The top coat layer 14 may contain a matting agent for matting adjustment. As the matting agent, known commercially available materials may be used. For example, fine particles composed of inorganic materials such as silica, glass, alumina, calcium carbonate, and barium sulfate may be used. Also, fine particles composed of organic materials such as acrylic may be used as the matting agent. However, when high transparency is required, it is preferable to use fine particles such as silica, glass, and acrylic with high transparency as the matting agent. In particular, among fine particles such as silica and glass, a matting agent with a low bulk density in which fine primary particles are secondarily aggregated rather than solid spherical particles has a high matting effect with respect to the added amount. Therefore, by using a matting agent with a low bulk density, the added amount of the matting agent can be reduced.

[0043] Also, the matting agent contained in the top coat layer 14 is preferably adjusted so that the glossiness of the decorative sheet 1 is 10 or less. As described above, when the base material layer 12A contains a matting agent, it is necessary to adjust so that the glossiness of the entire decorative sheet 1 is 10 or less. When the glossiness of the decorative sheet 1 is 10 or less, a decorative sheet 1 having a calm appearance can be obtained. Here, the glossiness value indicates, for example, the value of 60-degree specular gloss conforming to JIS Z 8741. For this reason, the harmony with patterned furniture and fixtures is improved, and a more preferable appearance can be obtained as a decorative sheet used for moldings such as door frames, window frames, lintels, partitions, and moldings that are incorporated into a building in advance.

[0044] Also, in order to impart various functions to the top coat layer 14, the top coat layer 14 may contain functional additives such as antibacterial agents and antifungal agents. Further, the top coat layer 14 may contain an ultraviolet absorber and a light stabilizer as needed. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers. Also, examples of the light stabilizer include hindered amine-based light stabilizers.

[0045] The layer thickness of the top coat layer 14 is preferably in the range of 3 μm or more and 15 μm or less. When the layer thickness of the top coat layer 14 is 3 μm or more, the effect of improving scratch resistance is enhanced. Also, when the layer thickness of the top coat layer 14 is 15 μm or less, the occurrence of cracks and fractures during bending can be suppressed, and deterioration of the design and weather resistance of the decorative sheet 1 can be suppressed.

[0046] Note that the decorative sheet and the decorative material of the present disclosure are not limited to the above-described embodiments and examples, and various modifications are possible without impairing the features of the invention.

[0047] <Primer layer> The primer layer 11 is provided on the surface of the base fabric layer 12 opposite to the top coat layer 14. As the primer layer 11, for example, a polyester resin, a polyurethane resin, a mixture thereof, or the like can be used. Further, by using a two-component type of polyol and isocyanate, the adhesion between the colored layer 13 and the primer layer 11 and the cohesive force of the primer layer 11 itself are improved. Examples of the polyol include acrylic polyol and polyester polyol. Examples of the isocyanate include aromatic types such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic types such as hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. It is preferable to use an aromatic polyol for the primer layer 11 in terms of the speed of reaction and heat resistance.

[0048] The thickness of the primer layer 11 is preferably 1 μm or more. By setting the thickness of the primer layer 11 to 1 μm or more, it is possible to prevent the adhesive from being dissolved by the solvent and the primer layer 11 from disappearing, resulting in a decrease in adhesion. Note that when the unevenness of the surface on which the decorative sheet 1 is applied is large, it is advisable to perform caulking with putty or the like in advance and apply the primer as needed.

[0049] (1.2) Method for manufacturing a decorative sheet A manufacturing example of the cosmetic sheet 1 will be described. An inorganic pigment or the like is added to a resin material such as a polypropylene resin as needed and melt-kneaded to obtain a resin material for a base material layer containing an inorganic pigment or the like to be the base material layer 12A. Next, a nucleating agent vesicle is mixed with a resin material such as a polypropylene resin to obtain a resin material containing a nucleating agent vesicle for the skin layer 12B. Subsequently, the resin material for the base material layer 12A and the resin material containing the nucleating agent vesicle for the skin layer 12B that have been heated and melted are simultaneously extruded from an extruder so as to be laminated in the order of, for example, the resin material containing the nucleating agent vesicle / the resin material for the base material layer / the resin material containing the nucleating agent vesicle, and cooled by a plurality of cooling rolls to form a laminated film. Thereby, the raw material layer 12 in which the skin layer 12B / the base material layer 12A / the skin layer 12B are laminated is obtained.

[0050] Subsequently, in the raw material layer 12, an embossing plate is pressed onto the surface of the skin layer 12B on at least one surface side of the base material layer 12A to impart a predetermined uneven shape. When imparting the uneven shape, for example, the embossing plate may be pressed onto the surface of the skin layer 12B using an embossing machine. Thereby, a predetermined uneven shape is transferred to at least one surface of the skin layer 12B. Specifically, the embossing plate for imparting an uneven shape to the skin layer 12B may have an uneven shape that enables the arithmetic mean roughness Ra, the ten-point mean roughness Rz, the maximum height Ry of the local peaks of the unevenness, and the average interval S between the local peaks of the unevenness on the surface of the skin layer 12B that becomes the formation surface of the top coat layer 14 or the colored layer 13 in the completed cosmetic sheet to be within the above-mentioned ranges. Note that the method for forming the uneven shape on the surface of the skin layer 12B is not limited to this, and the uneven shape of the embossing plate may be transferred to the surface of the skin layer 12B by heat, or a method such as providing embossing simultaneously with cooling using a cooling roll having an uneven pattern on the surface when forming the raw material layer 12 using an extruder may be used.

[0051] Subsequently, a resin material such as a urethane-based resin is applied to the surface that becomes the back surface of the base fabric layer 12 to form the primer layer 11. Further, a resin material containing a coloring pigment is applied and cured on one surface of the base fabric layer 12 to form the coloring layer 13. Finally, a resin material (resin material for top coat) such as an acrylic urethane resin is applied and cured to form the top coat layer 14. The coloring layer 13 and the top coat layer 14 may be provided on the side of the skin layer 12B having the uneven shape. In addition, when forming each layer, a surface treatment such as corona treatment may be performed on the coating surface. As described above, the primer layer 11, the base fabric layer 12, the coloring layer 13, and the top coat layer 14 are laminated in this order, and the decorative sheet of the first embodiment in which the uneven shape is formed on the surface of the skin layer 12B provided on at least one of the base fabric layers 12 can be obtained.

[0052] Thus, the method for manufacturing the decorative sheet 1 includes a step of encapsulating a nucleating agent in a vesicle and generating a nucleating agent vesicle formed by vesiculating the nucleating agent, and at least one surface of the base material layer 12A formed using a resin material for the base material layer (an example of the first resin material). A step of forming the base fabric layer 12 provided with the skin layer 12B on at least one surface thereof by applying and curing a resin material (an example of the second resin material) containing the nucleating agent vesicle, and a resin material for top coat (an example of the third resin material) on the skin layer 12B formed on one surface of the base fabric layer 12. And a step of forming the top coat layer 14 by applying and curing. Further, in the step of forming the base fabric layer 12 of the method for manufacturing the decorative sheet 1, an uneven shape is provided on the surface of the skin layer 12B provided on the surface on the top coat layer 14 side, and the arithmetic mean roughness Ra of the surface is in the range of 3 μm or more and 6 μm or less. Thereby, it is possible to produce the decorative sheet 1 having high scratch resistance and capable of improving the design property when processed.

[0053] (1.3) Effects of the First Embodiment The decorative sheet 1 as described above has the following effects. (1) The decorative sheet 1 of this embodiment has a base material layer 12A containing a resin material, and a skin layer 12B provided on at least one surface of the base material layer 12A and containing a resin material and a nucleating agent, that is, a raw sheet layer 12, and a top coat layer 14 provided on the skin layer 12B formed on one surface of the raw sheet layer 12. An uneven shape is provided on the surface of the skin layer 12B provided on the surface of the base material layer 12A on the top coat layer side, and the arithmetic mean roughness Ra of the surface of the skin layer 12B provided with the uneven shape is in the range of 3 μm or more and 6 μm or less. According to this configuration, it is possible to obtain the decorative sheet 1 that imparts high scratch resistance to the decorative sheet 1 and improves the designability when processed by making the surface unevenness (substrate roughness) of the base substrate and building materials less noticeable. (2) Further, in the decorative sheet 1 of this embodiment, it is preferable that the maximum height Ry of the unevenness on the surface of the skin layer 12B provided with the uneven shape is in the range of 17 μm or more and 30 μm or less. According to this configuration, the substrate roughness of the base substrate and building materials can be made less noticeable, and the designability when processed can be further improved. (3) Further, in the decorative sheet 1 of this embodiment, it is preferable that the average interval S between local peaks on the surface of the skin layer 12B provided with the uneven shape is in the range of 300 μm or more and 500 μm or less. According to this configuration, the substrate roughness of the base substrate and building materials can be made less noticeable more reliably, and the designability when processed can be improved more reliably. (4) Further, in the decorative sheet 1 of this embodiment, it is preferable that the ten-point average roughness Rz of the surface of the skin layer 12B provided with the uneven shape is 10 μm or more and 20 μm or less. According to this configuration, the substrate roughness of the base substrate and building materials can be made even less noticeable, and the designability when processed can be further improved.

[0054] (5) Further, in the decorative sheet 1 of this embodiment, it is preferable that the glossiness is 10 or less. According to this configuration, it is possible to impart a calm appearance to the decorative sheet 1 and improve the designability. (6) Also, it is preferable that the surface of the top coat layer 14 of the cosmetic sheet 1 of the present embodiment has an uneven shape with a satin finish. According to this configuration, a flat design feeling can be imparted to improve the design property, and a soft and comfortable touch (tactile feeling) can be imparted.

[0055] (7) Also, in the cosmetic sheet 1 of the present embodiment, it is preferable that the base material layer 12A contains a single-color coloring agent. According to this configuration, a cosmetic sheet 1 with good concealability can be obtained. (8) Also, it is preferable that the cosmetic sheet 1 of the present embodiment includes a coloring layer 13 provided between the top coat layer 14 and the base fabric layer 12. According to this configuration, a desired color can be imparted to the cosmetic sheet 1, and the concealability and design property can be improved. (9) Also, it is preferable that the cosmetic sheet 1 of the present embodiment includes a primer layer 11 provided on the surface of the base fabric layer 12 opposite to the top coat layer 14. According to this configuration, the adhesiveness between the cosmetic sheet 1 and the wall surface, building materials, base materials, etc. to which the cosmetic sheet 1 is adhered can be improved.

[0056] (10) Also, in the cosmetic sheet 1 of the present embodiment, it is preferable that the skin layer includes a nucleating agent vesicle in which a nanosize nucleating agent is encapsulated in a vesicle having an outer membrane of a single-layer film. According to this configuration, the crystallinity of the resin material constituting the skin layer 12B can be sufficiently improved, and a cosmetic sheet 1 with higher scratch resistance can be obtained. (11) Also, in the cosmetic sheet 1 of the present embodiment, it is preferable that the nucleating agent vesicle is a nucleating agent liposome having the outer membrane containing phospholipid. According to this configuration, the compatibility between the resin material, which is the main component of the skin layer 12B, and the vesicle can be made good. (12) Also, in the cosmetic sheet 1 of the present embodiment, it is preferable that the skin layer 12B is formed of a resin material in which a nucleating agent is added in the range of 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the resin material. According to this configuration, the crystallinity of the resin material constituting the skin layer 12B can be sufficiently improved, and the decorative sheet 1 with sufficiently high scratch resistance can be obtained.

[0057] 2. Second Embodiment Hereinafter, the decorative sheet according to the second embodiment of the present disclosure will be described with reference to FIG. 2. FIG. 2 is a cross-sectional view for explaining a configuration example of the decorative sheet 2 according to the second embodiment of the present disclosure. The decorative sheet 2 according to the present embodiment is a decorative sheet applied to, for example, a wall surface, a fixture, a furniture, etc., similar to the decorative sheet 1. In particular, it is a decorative sheet preferably used for trim materials such as door frames, window frames, baseboards, partitions, and moldings that are pre-incorporated into a building.

[0058] The decorative sheet 2 includes a primer layer 11, a base fabric layer 22, a colored layer 13, and a top coat layer 14. That is, the decorative sheet 2 is different from the decorative sheet 1 according to the first embodiment in that it includes the base fabric layer 22 instead of the base fabric layer 12.

[0059] Hereinafter, the base fabric layer 12 will be described. Note that since the other layers (the primer layer 11, the colored layer 13, and the top coat layer 14) other than the base fabric layer 12 have the same configuration as the layers of the decorative sheet 1, the description thereof will be omitted.

[0060] (2.1) Basic Configuration of Decorative Sheet [Base Fabric Layer] The base fabric layer 22 has a base material layer 22A and a skin layer 22B provided on at least one surface of the base material layer 22A. The base fabric layer 22 has a configuration in which the skin layer 22B is provided on the upper surface of the base material layer 22A (the surface on the side of the top coat layer 14 to be described later) or on both surfaces of the base material layer 22A. In the present embodiment, the base fabric layer 22 having a configuration in which the skin layer 22B is provided on both surfaces of the base material layer 22A will be described.

[0061] [Base Material Layer] Since the base material layer 22A has the same configuration as the base material layer 12A according to the first embodiment, the description thereof will be omitted. Here.

[0062] [Skin layer] The skin layer 22B is a layer containing a resin material and an inorganic material. In the cosmetic sheet 1 according to the first embodiment, a highly damage-resistant resin sheet having high crystallinity is formed from a resin material containing a nucleating agent to form the skin layer 12B. On the other hand, in the cosmetic sheet 2 according to the second embodiment, instead of the nucleating agent, a resin material containing inorganic particles with high hardness is used to form the skin layer 22B having high hardness, thereby obtaining a cosmetic sheet 2 having high damage resistance.

[0063] Examples of the inorganic particles include fine particles made of inorganic materials such as nano-sized silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate. The skin layer 22B is formed of a resin material in which inorganic particles are added in the range of 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the resin material, for example.

[0064] Similar to the base sheet layer 12, at least the surface of the skin layer 22B on the top coat layer 14 side has an uneven shape. The arithmetic mean roughness Ra, the ten-point mean roughness Rz, the maximum height Ry of the unevenness, and the average interval S of the local peaks on the surface of the skin layer 22B are the same as those of the skin layer 12B. Even when inorganic particles are used instead of the nucleating agent, since the skin layer 22B has an uneven shape, a cosmetic sheet 2 having high damage resistance, a flat surface, and a soft and comfortable touch can be obtained.

[0065] The base sheet layer 22 is formed, for example, by heating and melting an inorganic particle-containing polypropylene resin containing nano-sized inorganic particles and co-extrusion molding it together with a nucleating agent vesicle-containing resin material, so that the skin layer 22B is provided on at least one surface of the base material layer 22A.

[0066] (2.2) Effects of the second embodiment The cosmetic sheet 2 as described above has the following effects in addition to the effects of the first embodiment. The cosmetic sheet 2 of this embodiment contains a resin material and inorganic particles, and has a raw sheet layer 22 with increased hardness. Further, an uneven shape is provided on the surface of the skin layer 12B provided on the surface of the base material layer 12A on the top coat layer side, and the arithmetic mean roughness Ra of the surface of the skin layer 12B provided with the uneven shape is in the range of 3 μm or more and 6 μm or less. According to this configuration, it is possible to obtain a cosmetic sheet 1 that imparts high scratch resistance to the cosmetic sheet 1 and improves the design property when processed by making the surface unevenness (substrate roughness) of the underlying substrate or building material less noticeable.

[0067] 3. Third Embodiment The decorative material according to the third embodiment of the present disclosure will be described with reference to FIG. 3. FIG. 3 is a cross-sectional view for explaining a configuration example of a decorative material 10 according to the third embodiment of the present disclosure. (Decorative Material) The decorative material 10 includes a cosmetic sheet 1 and a base material 15 to which the cosmetic sheet 1 is bonded to at least one surface. Specifically, in the decorative material 10, a coloring layer 13 and a top coat layer 14 are laminated in this order on one surface side of the raw sheet layer 12, and a primer layer 11 provided on the other surface side of the raw sheet layer 12 and the base material 9 are bonded together. That is, the decorative material 10 is different from the cosmetic sheet 1 according to the first embodiment in that it includes the base material 9.

[0068] Hereinafter, the base material 15 will be described. Since the cosmetic sheet 1 has the same configuration as that of the first embodiment described above, the description thereof will be omitted.

[0069] [Base Material] As the base material 15, for example, a base material for furniture and carpentry materials is assumed, and materials such as plywood made from Southeast Asian timber, particle board, medium density fiberboard (hereinafter referred to as MDF), ordinary plywood defined in Japanese Agricultural and Forestry Standards, etc. can be used. In addition, a base material made of an olefin resin added with wood powder can also be used. The thickness of the base material 15 is preferably about 3 mm or more and 25 mm or less. Note that the base material 15 may be a metal such as aluminum, a resin such as plastic, or a composite material thereof. By forming the base material 15, it is possible to provide a decorative material 10 that can suppress the occurrence of scratches caused by a person opening and closing furniture or the like, placing an object thereon, or being disposed near the floor. Further, in the decorative material 10, the primer layer 11 may be provided on one surface of the base material 15 instead of the decorative sheet 1, and the decorative sheet 1 and the base material 15 may be bonded together via the primer layer on the base material 15. In the present embodiment, the base material 15 is bonded to the decorative sheet 1, but the decorative material 10 may be formed using the decorative sheet 2 instead of the decorative sheet 1.

[0070] <Effect of the Third Embodiment> The decorative material 10 according to the present embodiment has the following effects in addition to the effects of the first and second embodiments. (15) The decorative material 10 of the present embodiment includes a decorative sheet (decorative sheets 1 and 2) and a base material 15 to which the decorative sheet is bonded to at least one surface. According to this configuration, the decorative material 10 has high scratch resistance and can suppress the occurrence of scratches on the decorative material 10 during the use of furniture and the like, and can improve the designability during processing.

Example

[0071] Hereinafter, the decorative sheet according to the present disclosure will be described with reference to examples. In the examples, decorative sheets having the configurations described in the following examples and comparative examples were produced and bonded onto a flooring material to evaluate the decorative sheets.

[0072] <Example 1> A single-color decorative sheet was produced by the following procedure. A white polypropylene resin containing 30% by mass of a white pigment and 1% by mass of a weathering agent was obtained by mixing the white pigment and the weathering agent with a polypropylene resin and melt-kneading them. Next, a nucleating agent vesicle was mixed with a transparent polypropylene resin to obtain a nucleating agent vesicle-containing polypropylene resin containing 0.1% by mass of the nucleating agent vesicle. Subsequently, the heated and melted white polypropylene resin and the nucleating agent vesicle-containing polypropylene resin were simultaneously extruded from an extruder so as to be laminated in the order of nucleating agent vesicle-containing polypropylene resin / white polypropylene resin / nucleating agent vesicle-containing polypropylene resin, and cooled with a cooling roll to form a laminated film. At this time, as the cooling roll on one side of the white polypropylene resin, a cooling roll having an uneven shape on the surface was used, and as the cooling roll on the other side, a cooling roll having a smooth surface was used. As a result, a colored original reaction layer having a layer thickness of 140 μm was obtained, which had a white base layer and transparent skin layers provided on both sides of the base layer, and an uneven shape was formed on the skin layer on one surface side of the base layer.

[0073] At this time, in the extruder, the extrusion amounts of the respective resins were adjusted so that the thickness ratios of the skin layer, the base layer, and the skin layer were 0.5:9:0.5. Next, an embossing plate was pressed on the skin layer on one surface side of the colored original reaction layer to form an uneven shape. The plate pressing was performed by pressing the embossing plate using an embossing machine. By pressing the embossing plate, unevenness with an arithmetic mean roughness Ra of 4.749 μm, a ten-point mean roughness Rz of 16.767 μm, a maximum uneven height Ry of 23.207 μm, and an average interval S of local peaks of the unevenness of 412.5 μm was transferred to the top coat layer forming surface of the completed decorative sheet, that is, the surface of the surface-side skin layer. As the shape of the embossing plate in Example 1, one having a width of 260 μm and a plate depth of 20 μm was used. Here, the width of the embossing plate indicates the width of the unevenness in the embossing plate, and the plate depth of the embossing plate indicates the depth of the concave portion of the embossing plate.

[0074] Subsequently, a two-component urethane resin was gravure-printed on the other surface (smooth surface) of the colored original reaction layer so that the solid content was 1 g / m 2It was applied so as to form a primer layer. Further, after corona treatment was performed on one surface (the surface having irregularities) of the colored original layer, an acrylic two-component curable resin (manufactured by DIC Graphic Co., Ltd., acrylic urethane resin) was applied and cured to a thickness of 6 μm to form a top coat layer. As described above, a primer layer, a colored original layer, and a top coat layer were laminated in this order, and the decorative sheet of Example 1 in which irregularities were formed on the surface of the colored original layer on the top coat layer side was obtained.

[0075] <Example 2> As an embossing plate used for transferring the uneven shape to the skin layer, one having a width of 300 μm and a plate depth of 20 μm was used. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the top coat layer forming surface of the completed decorative sheet, that is, the surface side of the skin layer on the top coat layer side, was 5.103 μm, the ten-point mean roughness Rz was 16.267 μm, the maximum height Ry of the unevenness was 25.654 μm, and the average interval S between the local peaks of the unevenness was 450.2 μm. Otherwise, in the same manner as in Example 1, the decorative sheet of Example 2 was obtained.

[0076] <Example 3> As an embossing plate used for transferring the uneven shape to the skin layer, one having a width of 200 μm and a plate depth of 20 μm was used. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the surface side of the completed decorative sheet was 5.75 μm, the ten-point mean roughness Rz was 19.398 μm, the maximum height Ry of the unevenness was 27.167 μm, and the average interval S between the local peaks of the unevenness was 379.2 μm. Otherwise, in the same manner as in Example 1, the decorative sheet of Example 3 was obtained.

[0077] <Comparative Example 1> As the shape of the embossing plate used for transferring the uneven shape to the skin layer, one having a width of 100 μm and a plate depth of 25 μm was used. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the surface side of the completed decorative sheet was 2.592 μm, the ten-point mean roughness Rz was 11.177 μm, the maximum height Ry of the unevenness was 13.897 μm, and the average interval S between the local peaks of the unevenness was 210.2 μm. Otherwise, in the same manner as in Example 1, the decorative sheet of Comparative Example 1 was obtained.

[0078] <Comparative Example 2> The shape of the embossing plate used for transferring the concavo-convex shape to the skin layer was the same as in Comparative Example 1, and the pressure when pressing the embossing plate was adjusted to a pressure stronger than that in Comparative Example 1. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the front side of the completed cosmetic sheet was 2.933 μm, the ten-point mean roughness Rz was 11.881 μm, the maximum height Ry of the unevenness was 16.967 μm, and the average interval S between the local peaks of the unevenness was 200.9 μm. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Comparative Example 2 was obtained.

[0079] <Comparative Example 3> As the shape of the embossing plate used for transferring the concavo-convex shape to the skin layer, one having a width of 160 μm and a plate depth of 25 μm was used. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the front side of the completed cosmetic sheet was 2.897 μm, the ten-point mean roughness Rz was 10.876 μm, the maximum height Ry of the unevenness was 14.581 μm, and the average interval S between the local peaks of the unevenness was 203.8 μm. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Comparative Example 3 was obtained.

[0080] <Comparative Example 4> As the shape of the embossing plate used for transferring the concavo-convex shape to the skin layer, one having a width of 200 μm and a plate depth of 25 μm was used. As a result, the arithmetic mean roughness Ra of the surface of the skin layer on the front side of the completed cosmetic sheet was 2.839 μm, the ten-point mean roughness Rz was 10.855 μm, the maximum height Ry of the unevenness was 16.043 μm, and the average interval S between the local peaks of the unevenness was 286.2 μm. Otherwise, in the same manner as in Example 1, a cosmetic sheet of Comparative Example 4 was obtained.

[0081] <Comparative Example 5> A conventional cosmetic sheet in which a coloring original layer was formed using a polypropylene resin not containing a nucleating agent vesicle as a material for forming the skin layer was used as Comparative Example 5. For the cosmetic sheet of Comparative Example 5, the arithmetic mean roughness Ra of the surface of the skin layer on the front side was 4.931 μm, the ten-point mean roughness Rz was 16.806 μm, the maximum height Ry of the unevenness was 24.216 μm, and the average interval S between the local peaks of the unevenness was 383.6 μm.

[0082] <Evaluation> (Scratch hardness test) For each of the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5, the hardness (pencil hardness) of the hardest pencil that did not cause scratches on the surface (the base fabric layer or the top coat layer) of the cosmetic sheet was measured by the scratch hardness (pencil method) test specified in JIS K5600-5-4:1999. The scratch hardness test was performed using the equipment described in JIS K5600-5-4:1999. In this evaluation, when the hardness of the hardest pencil that did not cause scratches on the surface of the cosmetic sheet was "2B" or higher, the scratch resistance was evaluated as good (〇), and when it was "3B" or lower, the scratch resistance was evaluated as insufficient (×).

[0083] (Evaluation of the design property of the cosmetic sheet alone) The examiners visually confirmed the design sense of the surfaces of each of the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5, and confirmed whether there was a flat design sense on the surface. The evaluation of the design sense was performed by 10 examiners, and the evaluation was based on the number of people who answered that there was a flat design sense on the surface. That is, in this evaluation, it was evaluated whether the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5 were cosmetic sheets with a design sense in which it was difficult to visually feel the uneven shape. In this evaluation, it was judged that the more people who answered that there was a flat design sense on the surface, the better.

[0084] (Evaluation of the design property when the cosmetic sheet is processed) Each of the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5 was attached to a substrate to produce a decorative material, and the examiners visually confirmed the surface of the cosmetic sheet attached to the substrate (the surface of the decorative material). That is, in this evaluation, it was evaluated whether the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5 were cosmetic sheets with a design sense in which the unevenness (substrate roughness) of the substrate surface was not noticeable during processing into a decorative material. This evaluation was performed by 10 examiners, and the evaluation was based on the number of people who answered that the surface of the decorative material had a flat design sense, that is, the substrate roughness was not noticeable. In this evaluation, it was judged that the more people who answered that the substrate gloss was not noticeable, the better. Specifically, among 10 testers, if 8 or more testers answered that the substrate gloss was not noticeable, it was evaluated as "〇"; if 5 or more testers answered that the substrate gloss was not noticeable, it was evaluated as "△"; if less than 5 testers answered that the substrate gloss was not noticeable, it was evaluated as "×".

[0085] (Evaluation of stain resistance) Using the method compliant with the JAS stain B test, for each of the cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 to 5, a 10-mm-wide line was drawn on each surface with black magic (for example, "Magic Ink" manufactured by Teranishi Chemical Industry Co., Ltd.) and red crayon, left for 4 hours, then wiped off with a solvent or detergent, and the surface state was observed. At that time, if there was no significant change, it was rated as "○"; if there was some remaining color, it was rated as "△"; if there was clear remaining color, it was rated as "×".

[0086] Table 1 below shows an excerpt of the configurations of each example and each comparative example, and the evaluation results.

[0087]

Table 1

[0088] As shown in Table 1, it was confirmed that the cosmetic sheets of Examples 1 to 3, which have high crystallinity by containing a nucleating agent and have a skin layer with an uneven shape on the surface, have improved scratch resistance compared to the cosmetic sheet of Comparative Example 5 that does not contain a nucleating agent. In particular, the cosmetic sheets of Examples 1 to 3 had a pencil hardness of HB (2B or more) in the scratch hardness test, and good results were obtained compared to Comparative Example 5. On the other hand, it was confirmed that the cosmetic sheet of Comparative Example 5 with a skin layer that does not contain a nucleating agent had a pencil hardness of 3B in the scratch hardness test and low scratch resistance in the scratch hardness test.

[0089] In addition, in the cosmetic sheets of Examples 1 to 3 where the arithmetic mean roughness Ra of the skin layer surface is 3 μm or more and 6 μm or less, the ten-point mean roughness Rz is 10 μm or more and 20 μm or less, the maximum height Ry of the unevenness is 17 μm or more and 30 μm or less, and the average interval S of the local peaks of the unevenness is 300 μm or more and 500 μm or less, the evaluation of the design property of the cosmetic sheet alone and the design property when the cosmetic sheet is processed (attached to the base material) are both "△" or higher, and it was confirmed that the design property is high. In particular, the cosmetic sheets of Examples 1 to 3 all have a design property of "〇" during processing. Compared with the cosmetic sheets of Comparative Examples 1 to 4, it was confirmed that the roughness of the base material is not prominent and the design feeling of the processed cosmetic sheet (the cosmetic sheet attached to the base material) is improved.

[0090] From the above evaluation results, it was confirmed that the cosmetic sheet provided with a skin layer having high crystallinity by containing a nucleating agent has higher scratch resistance than the cosmetic sheet not having such a skin layer. In addition, it was confirmed that the cosmetic sheet in which the surface of the skin layer has an uneven shape and has a predetermined arithmetic mean roughness Ra, ten-point mean roughness Rz, maximum height Ry of the unevenness, and average interval S of the local peaks can improve the design property when processed.

[0091] The scope of the present disclosure is not limited to the illustrated and described exemplary embodiments, but also includes all embodiments that bring about equivalent effects to those intended by the present disclosure. Furthermore, the scope of the present disclosure is not limited to the combination of the features of the invention defined by the claims, but may be defined by any desired combination of the specific features among all the disclosed features.

Explanation of Signs

[0092] 1, 2 Cosmetic sheet 10 Cosmetic material 11 Primer layer 12, 22 Base fabric layer 12A, 22A Base material layer 12B, 22B Skin layer 13 Coloring layer 14 Top coat layer

Claims

1. A base material layer containing a resin material, and a skin layer provided on at least one surface of the base material layer and containing a resin material and a nucleating agent or inorganic particles, and a base fabric layer having the same; A top coat layer provided on the skin layer formed on one surface of the base fabric layer; Comprising; The skin layer containing the nucleating agent contains a polypropylene resin as the resin material; The thickness of the base material layer is 100 μm or more and 200 μm or less; A decorative sheet in which the arithmetic mean roughness Ra of the surface of the skin layer provided on the surface of the base material layer on the top coat layer side is in the range of 3 μm or more and 6 μm or less.

2. The maximum height Ry of the unevenness on the surface of the skin layer is in the range of 17 μm or more and 30 μm or less The decorative sheet according to claim 1.

3. The maximum height Ry of the unevenness on the surface of the skin layer is in the range of 27 μm or more and 30 μm or less The decorative sheet according to claim 2.

4. The average interval S between the local peaks on the surface of the skin layer is in the range of 300 μm or more and 500 μm or less The decorative sheet according to any one of claims 1 to 3.

5. The ten-point average roughness Rz of the surface of the skin layer is 10 μm or more and 20 μm or less The decorative sheet according to any one of claims 1 to 4.

6. The top coat layer contains a gloss adjuster, and the glossiness value indicating the value of the 60-degree specular gloss conforming to JIS Z 8741 is 10 or less The decorative sheet according to any one of claims 1 to 5.

7. The surface of the top coat layer has an uneven shape with a satin finish The decorative sheet according to any one of claims 1 to 6.

8. The base material layer contains a single-color colorant The decorative sheet according to any one of claims 1 to 7.

9. Comprising a colored layer provided between the top coat layer and the base fabric layer The decorative sheet according to any one of claims 1 to 8.

10. The skin layer contains a nucleating agent vesicle in which a nano-sized nucleating agent is encapsulated in a vesicle having an outer membrane of a single-layer film The decorative sheet according to any one of claims 1 to 9.

11. The nucleating agent vesicle is a nucleating agent liposome having an outer membrane containing a phospholipid The decorative sheet according to claim 10.

12. The skin layer is formed of a resin material in which the nucleating agent is added in the range of 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the resin material The decorative sheet according to claim 10 or claim 11.

13. The skin layer contains, as the inorganic particles, at least one of nano-sized silica, glass, alumina, titanium nia, zirconia, calcium carbonate, and barium sulfate The cosmetic sheet according to any one of claims 1 to 9.

14. The skin layer is formed of a resin material in which the inorganic particles are added in a range of 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the resin material. The cosmetic sheet according to claim 13.

15. A cosmetic sheet according to any one of claims 1 to 14, and a base material to which the cosmetic sheet is adhered to at least one surface thereof, A cosmetic material comprising the same.

16. A step of encapsulating a nucleating agent in a vesicle to form a nucleating agent vesicle in which the nucleating agent is vesiculated, A step of forming a raw sheet layer provided with a skin layer on at least one surface of a base material layer formed of a first resin material by applying and curing a polypropylene resin as a second resin material containing the nucleating agent vesicle on at least one surface of the base material layer, A step of forming a top coat layer by applying and curing a third resin material on the skin layer formed on one surface of the raw sheet layer, Comprising, The thickness of the base material layer is 100 μm or more and 200 μm or less, In the step of forming the raw sheet layer, the arithmetic mean roughness Ra of the surface of the skin layer provided on the surface on the top coat layer side is in the range of 3 μm or more and 6 μm or less. A method for manufacturing a cosmetic sheet.

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