JP7439481B2 - Decorative sheet and method for manufacturing decorative sheet - Google Patents

Description

The present disclosure relates to a decorative sheet and a method for manufacturing a decorative sheet.

A composite film including a base layer containing a resin film and a colored layer is used as a decorative sheet. Decorative sheets used indoors are pasted on fittings such as interior doors and entrance storage, and on the surfaces of fixtures such as partitions, edges, baseboards, window frames, and door frames. Decorative sheets of this type are used in a variety of indoor environments, including high-temperature environments and environments exposed to light (sunlight, ultraviolet rays, etc.), so decorative sheets with heat resistance and weather resistance have been proposed. (For example, see Patent Document 1).

Japanese Patent Application Publication No. 2018-167504

However, fittings and fixtures are easily opened and closed by people, items are placed on them, and are placed close to the floor, making them susceptible to damage from parts of the furniture. For this reason, decorative sheets used for fittings and fixtures need to have higher scratch resistance than general decorative sheets.
The present disclosure has been made in view of such problems, and its purpose is to obtain a decorative sheet with high scratch resistance.

In order to solve the above problems, a decorative sheet according to one embodiment of the present disclosure includes a base layer containing a resin material, and a base layer that is provided on at least one surface of the base layer, and includes a resin material and nucleating agent or inorganic particles. and a top coat layer provided on the skin layer formed on one side of the raw fabric layer, the surface of the skin layer provided on the top coat layer side. It is characterized by having an uneven shape.

In addition, a method for manufacturing a decorative sheet according to another aspect of the present disclosure is the method for manufacturing a decorative sheet described above, in which a nucleating agent is formed by encapsulating a nucleating agent in vesicles and converting the nucleating agent into vesicles. The process of generating vesicles and applying a second resin material containing nucleating agent vesicles to at least one surface of the base layer formed using the first resin material and curing the base material layer. A top coat layer is formed by forming a raw fabric layer provided with a skin layer on at least one side, and applying and curing a third resin material on the skin layer formed on one side of the raw fabric layer. In the step of forming the original fabric layer, an uneven shape is provided on the surface of the skin layer provided on the surface facing the top coat layer.

According to the aspect of the present disclosure, a decorative sheet with high scratch resistance can be obtained.

FIG. 1 is a cross-sectional view illustrating a configuration example of a decorative sheet according to a first embodiment of the present disclosure. It is a sectional view showing one example of composition of a decorative sheet concerning a second embodiment of the present disclosure.

Hereinafter, the present disclosure will be explained through embodiments, but the following embodiments do not limit the claimed invention. Furthermore, not all combinations of features described in the embodiments are essential to the solution of the invention. Further, the drawings schematically show the claimed invention, and dimensions such as the width and thickness of each part are different from the actual ones, and the ratios thereof are also different from the actual ones.

A laminate according to a first embodiment of the present disclosure will be described. The decorative sheet according to the present disclosure is, for example, a decorative sheet applied to walls, fittings, furniture, etc., and is particularly used for door frames, window frames, baseboards, partitions, and surrounding edges that are pre-assembled into buildings. This is a preferable decorative sheet. In the following description, the side that contacts the adhesive surface of the decorative sheet may be referred to as "lower", and the side (front) opposite to the side that contacts the adhesive surface of the decorative sheet may be referred to as "upper".
Hereinafter, each aspect of each embodiment of the present disclosure will be described with reference to the drawings.

1. First Embodiment (1.1) Basic Configuration of Decorative Sheet FIG. 1 is a sectional view for explaining one configuration example of a decorative sheet 1 according to an embodiment of the present disclosure. As shown in FIG. 1, the decorative sheet 1 includes a primer layer 11, a raw fabric layer 12, and a top coat layer 14. The decorative sheet 1 is constructed by laminating a primer layer 11, a raw fabric layer 12, a colored layer 13, and a top coat layer 14 in this order.

The primer layer 11 is a layer provided to improve the adhesiveness between the decorative sheet 1 and a surface to which the decorative sheet 1 is attached, such as a wall surface. The original fabric layer 12 is a layer that serves as a base material for the decorative sheet 1, and it absorbs irregularities and steps on the surface to which it is applied, improving the finish of the decorative sheet 1, and also changing the color and pattern of the surface to which it is applied. This is a layer for concealment. Further, the raw fabric layer 12 is a layer for suppressing scratches occurring on the decorative sheet 1 and giving the decorative sheet a soft and comfortable touch. The colored layer 13 is a layer that imparts a desired color to the decorative sheet 1. The top coat layer 14 is a layer provided on the uppermost surface of the decorative sheet 1 to protect the decorative sheet 1 and adjust the gloss of the surface of the decorative sheet 1.
Hereinafter, each layer of the primer layer 11, the raw fabric layer 12, the colored layer 13, and the top coat layer 14 will be explained in detail.

<Original fabric layer>
The raw fabric layer 12 includes a base layer 12A and a skin layer 12B provided on at least one surface of the base layer 12A. The raw fabric layer 12 has a structure in which a skin layer 12B is provided on the upper surface of the base material layer 12A (the surface on the side of the colored layer 13 described later) or on both surfaces of the base material layer 12A. In this embodiment, a raw fabric layer 12 having a structure in which skin layers 12B are provided on both sides of a base layer 12A will be described.

[Base material layer]
The base material layer 12A is a layer formed by mixing a resin material with an inorganic pigment for coloring. The base layer 12A is, for example, a white polypropylene film in which a white pigment is mixed with a polypropylene resin.
The thickness of the base layer 12A is, for example, preferably 40 μm or more and 200 μm or less, more preferably 120 μm or more and 160 μm or less. When the thickness of the base layer 12A is 40 μm or more, it can sufficiently exhibit the hiding properties required for a decorative sheet, has sufficient strength as a base material, and suppresses deterioration of scratch resistance. be able to. On the other hand, when the thickness of the base layer 12A is 200 μm or less, problems such as whitening and cracking can be suppressed during bending.

(resin material)
Examples of the resin material constituting the base layer 12A include thermoplastic resin. The thermoplastic resin is not particularly limited, and materials similar to thermoplastic resins used as base layers and the like in conventional 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, propylene-α-olefin copolymer, polyethylene terephthalate, Polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerization Polyester resins such as polyethylene terephthalate, polyarylate, polycarbonate, ethylene-vinyl acetate copolymer olefin copolymer resins such as ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymers, metal neutralized products (ionomers), etc. Polyolefin resins, poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, acrylic resins such as polyacrylamide, 6-nylon, 6,6-nylon, 6,10- Polyamide resins such as nylon, styrene resins such as polystyrene, AS resins, ABS resins, vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene fluoride, Fluororesins such as polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer, etc., or mixtures, copolymers, composites, laminates, etc. of two or more thereof. Can be used.

In particular, in view of the growing social concern about environmental issues in recent years, it is not desirable to use thermoplastic resins that contain chlorine (halogen), such as polyvinyl chloride resin, and it is preferable to use non-halogen-based thermoplastic resins. Preference is given to using thermoplastic resins. In particular, polyester resins (amorphous or biaxially oriented) or polyolefin resins, especially polyolefin resins, are used as non-halogen thermoplastic resins from the viewpoint of various physical properties, processability, versatility, economic efficiency, etc. Most preferably. For example, as the polyolefin 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.

The base material layer 12A may contain, for example, 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, and an anti-mold agent, as necessary. One or more kinds of additives selected from various additives such as a lubricant, a lubricant, a light scattering agent, and a gloss modifier may be added. Note that the base layer 12A preferably has a concealing property that hides the surface to which the decorative sheet 1 is attached, such as the wall surface, from the surface (upper surface) of the decorative sheet 1.
It is preferable that the base layer 12A contains a colorant. As the colorant, it is preferable to use a known inorganic pigment represented by titanium oxide, which is a white pigment for imparting hiding properties. If the concealment property is low, the pattern on the surface to which the decorative sheet 1 is attached will be transparent, which is not preferable. By containing an inorganic pigment, a decorative sheet 1 with good hiding properties can be obtained.

[Skin layer]
The skin layer 12B is a layer containing a resin material and a nucleating agent that improves the crystallinity of the resin material, and has an uneven surface. In this embodiment, the nucleating agent is added to the resin material in the form of nucleating agent vesicles which are enclosed in an outer membrane and formed into vesicles.
The thickness of the skin layer 12B is, for example, preferably 1 μm or more and 50 μm or less, 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 decorative sheet 1 becomes sufficiently high. In addition, when the thickness of the skin layer 12B is 50 μm or less, the bendability of the decorative sheet 1 does not become too high than necessary, and the decorative sheet 1 can be applied even when the surface to which the decorative sheet 1 is applied is not flat. It can be installed in close contact with the surface.

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

(Nucleating agent)
The skin layer 12B contains a nano-sized nucleating agent. The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a monolayer outer membrane. Further, in this embodiment, the nucleating agent in the resin constituting the skin layer 12B may be encapsulated in a vesicle with a portion of the nucleating agent exposed. Since the skin layer 12B contains a nucleating agent, the degree of crystallinity can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 1 can be improved.
The average particle size of the nano-sized nucleating agent is preferably 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, the average particle size is preferably 375 nm or less.

Since nano-sized nucleating agents have extremely small particle sizes, the number of nucleating agents present per unit volume and the surface area increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes shorter, so that when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the end where the crystal is growing will immediately The nucleating agent particle contacts the end of a crystal growing from the surface of another nucleating agent particle adjacent to the nucleating agent particle, and the ends of each crystal inhibit the growth of each crystal, thereby stopping the growth of each crystal. Therefore, the average particle diameter of spherulites in the crystal part of the crystalline resin can be reduced, for example, the spherulite size can be reduced to 1 μm or less. As a result, it is possible to create a highly hard resin film with a high degree of crystallinity, and the stress concentration between the spherulites that occurs during bending is efficiently dispersed, resulting in a resin that suppresses cracking and whitening during bending. film can be realized.

When a nucleating agent is simply added, the particle size increases due to secondary aggregation of the nucleating agent in the resin. On the other hand, when adding nucleating agent vesicles, the dispersibility in the resin improves, so the number of crystal nuclei for the amount of nucleating agent added increases significantly compared to when the nucleating agent is simply added. do. Therefore, the average particle size of spherulites in the crystalline portion of the resin becomes small, and the occurrence of cracks and whitening during bending can be suppressed. Therefore, by adding nucleating agent vesicles, the degree of crystallinity can be further increased, and it becomes possible to achieve both improved elastic modulus and processability.

For example, the skin layer 12B preferably contains 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, based on 100 parts by mass of the polypropylene resin as the main component. It is formed from a resin material to which a nucleating agent is added within a certain range. When using a nucleating agent vesicle, the amount of the nucleating agent added to the resin material is the amount added in terms of the nucleating agent in the nucleating agent vesicle. If the amount of the nucleating agent added is less than 0.05 parts by mass, the degree of crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the skin layer 12B may not be sufficiently improved. Furthermore, when the amount of the nucleating agent added exceeds 0.5 parts by mass, the growth of polypropylene spherulites is inhibited due to excessive crystal nuclei, and as a result, the crystallinity of polypropylene is not sufficiently improved. There is a possibility that the scratch resistance of the skin layer 12B may not be sufficiently improved.
Here, the term "main component" refers to a resin material that accounts for 50% by mass or more of the resin material that constitutes the skin layer 12B.

In addition, methods for nano-forming nucleating agents include, for example, the solid phase method, which mainly involves mechanically crushing the nucleating agent to obtain nano-sized particles, and the solid phase method, which involves dissolving the nucleating agent or the nucleating agent. methods such as the liquid phase method, which synthesizes and crystallizes nano-sized particles in a nucleating solution, and the gas-phase method, which synthesizes and crystallizes nano-sized particles from a nucleating agent or gas/steam containing the nucleating agent. It can be used as appropriate. Examples of solid phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, jet mills, and the like. Further, examples of the liquid phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid phase reduction method, and a hydrothermal synthesis method. Furthermore, examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

As a method for nano-forming the nucleating agent, a supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method of producing capsules (nano-sized vesicles) containing a target substance using carbon dioxide under supercritical state, temperature conditions or pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ± 0.0030 MPa) or above, and under a temperature condition above the critical point or Carbon dioxide under pressure means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical condition.

In addition, as a specific nano-forming process using supercritical reversed-phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance. Then, by stirring, an emulsion of supercritical carbon dioxide and an aqueous phase is generated. Next, by reducing the pressure, the carbon dioxide expands and evaporates, causing phase inversion, and the phospholipid generates nanocapsules (nanovesicles) in which the surface of the nucleating agent particles is covered with a monolayer film. By using this supercritical reversed-phase evaporation method, unlike the conventional encapsulation method in which the outer film forms a multilayer film on the surface of the nucleating agent particles, it is possible to easily produce capsules with a single layer film. Small diameter capsules can be prepared.
The nucleating agent vesicles are prepared by, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, or the like. Nucleating agent vesicles are preferably prepared using supercritical reverse phase evaporation.

The outer membrane constituting the nucleating agent vesicle is composed of, for example, a single layer membrane. Further, the outer membrane is composed of a substance containing biological lipids such as phospholipids.
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 phospholipids constituting the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Examples include sphingophospholipids such as glycerophospholipids, sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

Other substances forming the outer membrane of the vesicle include, for example, nonionic surfactants and dispersants such as mixtures of these and cholesterols or triacylglycerols. Among these, examples of nonionic surfactants include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene copolymer. , polybutadiene-polyoxyethylene copolymer, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. One type or two or more types can be used. As the cholesterol, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or cholecalciferol can be used.

Furthermore, the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet 1 of the present embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having an outer membrane made of phospholipid. The compatibility between the main component resin material and vesicles can be improved.
The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Examples of the nucleating agent include phosphate metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano treatment, it is preferable to use phosphate ester metal salts, benzoate metal salts, pimelic acid metal salts, and rosin metal salts, which are non-melting and can be expected to have good transparency. If the material itself can be made transparent by nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. Furthermore, molten benzylidene sorbitol may be appropriately mixed with the non-melted nucleating agent.

As described above, the decorative sheet 1 of this embodiment is characterized in that the skin layer 12B contains a resin material and a nucleating agent. Furthermore, the decorative sheet 1 of this 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. There is. Adding the nucleating agent to the resin composition in a state in which it is encapsulated in vesicles has the effect of dramatically improving the dispersibility of the nucleating agent into the resin material, that is, into the skin layer 12B. On the other hand, it may be difficult to directly identify the nucleating agent encapsulated in the vesicles based on the structure and properties of the finished decorative sheet 1, and this may be impractical. . The reason is as follows.

The nucleating agent added in the form of vesicles has high dispersibility and is in a dispersed state, and even in the state of the laminate which is the precursor of the produced decorative sheet 1, it is highly concentrated in the skin layer 12B. Distributed. However, in the manufacturing process of the decorative sheet 1, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and these treatments may cause the outer membrane of the vesicles containing the nucleating agent to fracture or cause chemical reactions. There are cases where Therefore, depending on the processing process of the decorative sheet 1, the state in which the outer membrane of the nucleating agent in the finished decorative sheet 1 is crushed or chemically reacted varies, and the nucleating agent is not enclosed (enveloped) in the outer membrane. There is a high possibility that there will be no. If the nucleating agent is not included in the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself in a numerical range, and whether the constituent material of the fractured outer membrane is the outer membrane of the vesicle. It may be difficult to determine whether the material was added separately from the nucleating agent. As described above, although the present disclosure is different from the conventional decorative sheet 1 in that the nucleating agent is blended in a highly dispersed manner, the nucleating agent is added in the form of vesicles containing the nucleating agent. It is conceivable that it may be impractical to determine whether this is due to the structure or characteristics of the decorative sheet 1 based on a numerical range analyzed based on measurements.

At least one surface of the skin layer 12B has an uneven shape. The uneven shape is provided on one or both of the skin layer 12B on the front side (colored layer 13 side) and the skin layer 12B on the back side (primer layer 11 side). It is preferable that it is provided in 12B.

<Colored layer>
The colored layer 13 is a layer containing, for example, a matrix and a coloring agent such as a dye or a pigment. For the colored 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 colored layer 13 is preferably within the range of 3 μm or more and 20 μm or less. When the thickness of the colored layer 13 is within this numerical range, printing can be made clearer, printing workability when manufacturing the decorative sheet 1 can be improved, and manufacturing costs can be suppressed.

(matrix)
Examples of the matrix include oil-based nitrified cotton resin, two-component urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, and fluorine resin. Various synthetic resins such as resins, silicone resins, and rubber resins, or mixtures and copolymers thereof can be used.

(colorant)
The inorganic pigment as a coloring agent constituting the colored layer 13 is not particularly limited, and examples thereof include natural inorganic pigments and synthetic inorganic pigments. Examples of natural inorganic pigments include earth pigments, fired earth pigments, 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. Furthermore, one or a mixed pigment of two 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, Bengara, yellow lead, navy blue, cadmium red, etc. can be used.
Further, as the coloring agent constituting the colored layer 13, an organic pigment may be used. As the organic pigment, organic pigments such as carbon black, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and 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.

Furthermore, in order to impart various functions to the colored layer 13, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator, and a curing agent are added. Functional additives such as retarders may also be added.
Here, the colored layer 13 can be formed by various printing methods such as a gravure printing method, an offset printing method, a screen printing method, an electrostatic printing method, and an inkjet printing method. Although these printing methods may be selected separately depending on the layer to be formed, it is efficient to select the same method and perform batch processing.

<Top coat layer>
Top coat layer 14 is made of a resin material. The main component of the resin material constituting the top coat layer 14 is, for example, polyurethane-based, acrylic silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, or urea-based resin. Appropriate materials are selected and used. The form of the resin material is not particularly limited, and may be water-based, emulsion, solvent-based, or the like. The curing method for the resin material can be appropriately selected from one-liquid type, two-liquid type, ultraviolet curing method, thermosetting method, photocuring type, etc.

As the resin material used as the main component of the top coat layer 14, a urethane-based resin material using isocyanate is preferable from the viewpoints of workability, price, cohesive force of the resin itself, and the like. Isocyanates include, for example, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), and bis(methyl isocyanate). The curing agent can be appropriately selected from adducts, burettes, and isocyanurates of derivatives such as cyclohexane (HXDI) and trimethylhexamethylene diisocyanate (TMDI). Among these, from the viewpoint of weather resistance, it is preferable to use hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure. In addition, in order to improve the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays and electron beams. Note that these resins can be used in combination with each other. For example, by using a hybrid type of thermosetting type and photocuring type, it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. can be achieved.

The top coat layer 14 may contain a gloss adjuster for gloss adjustment. As the gloss modifier, any commercially known material may be used, and for example, fine particles made of inorganic materials such as silica, glass, alumina, calcium carbonate, barium sulfate, etc. may be used. Furthermore, fine particles made of an organic material such as acrylic can also be used as the gloss modifier. However, when high transparency is required, it is preferable to use fine particles of highly transparent silica, glass, acrylic, etc. as the gloss modifier. In particular, among fine particles such as silica and glass, a gloss modifier with a low bulk density, which is made up of secondary agglomerations of fine primary particles rather than solid spherical particles, has a high matting effect depending on the amount added. Therefore, by using a gloss modifier with a low bulk density, the amount of the gloss modifier added can be reduced.

Further, the gloss adjuster 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 layer 12A contains a gloss adjuster, it is necessary to adjust the gloss of the entire decorative sheet 1 to 10 or less. When the glossiness of the decorative sheet 1 is 10 or less, the decorative sheet 1 can have a calm appearance. This improves the harmony with patterned furniture and fittings, giving it a more desirable appearance as a decorative sheet used for door frames, window frames, baseboards, partitions, and surrounding edges that are pre-assembled into buildings. .

Further, 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. Moreover, the top coat layer 14 may contain an ultraviolet absorber and a light stabilizer as necessary. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers. Examples of the light stabilizer include hindered amine light stabilizers.

The 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 becomes high. Furthermore, when the top coat layer 14 has a thickness of 15 μm or less, it is possible to suppress the occurrence of cracks and cracks during bending, and to suppress deterioration of the design and weather resistance of the decorative sheet 1.

<Primer layer>
As the primer layer 11, for example, polyester resin, polyurethane resin, a mixture thereof, etc. can be used. Furthermore, 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 polyols include acrylic polyols and polyester polyols. Examples of isocyanates include aromatic ones such as tolylene diisocyanate and 4,4' diphenylmethane diisocyanate, and aliphatic ones such as hexamethylene diisocyanate, isophorone diisocyanate and xylene diisocyanate. For the primer layer 11, it is preferable to use an aromatic polyol in terms of quick reactivity and heat resistance.

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, thereby preventing the adhesion from decreasing.
In addition, if the surface on which the decorative sheet 1 is to be applied has large irregularities, it is preferable to seal the surface with putty or the like in advance, and apply a primer if necessary.

The arithmetic mean roughness Ra of the surface (on the top coat layer 14) of the decorative sheet 1 configured as above is preferably 2.0 μm or more and 4.5 μm or less, and preferably 2.5 μm or more and 3.0 μm or less. It is more preferable. Further, the ten-point average roughness Rz (Rz _JIS ) of the surface of the decorative sheet 1 is preferably 12 μm or more and 30 μm or less, more preferably 15 μm or more and 20 μm or less. Furthermore, the average distance S between the local peaks of the irregularities on the surface of the decorative sheet 1 is preferably 90 μm or more and 200 μm or less, and more preferably 90 μm or more and 130 μm or less. Here, the arithmetic mean roughness Ra and the ten-point mean roughness Rz are values defined in JIS B0601:2001, and the average spacing S of local peaks is a value defined in JIS B0601:1994.

By forming the uneven shape of the skin layer 12B so that the surface of the decorative sheet 1 has the above-described arithmetic mean roughness Ra, ten-point mean roughness Rz, and average interval S of local peaks, it has high scratch resistance and softness. A decorative sheet 1 with a pleasant touch can be obtained. In addition, the decorative sheet 1 having such an uneven shape has high scratch resistance, has a soft and comfortable touch, and can obtain a fine satin-like design that makes the unevenness difficult to see with the naked eye. Such a decorative sheet 1 can obtain a calm appearance that is suitable as a decorative sheet used for a fixture to be incorporated into fittings.

(1.2) Method for manufacturing decorative sheet An example of manufacturing the decorative sheet 1 will be described.
If necessary, an inorganic pigment or the like is added to a resin material such as a polypropylene resin, and the mixture is melt-kneaded to obtain a resin material for a base layer containing an inorganic pigment, etc., which will become the base layer 12A. Next, nucleating agent vesicles are mixed with a resin material such as polypropylene resin to obtain a nucleating agent vesicle-containing resin material for the skin layer 12B. Subsequently, the heated and melted resin material for the base layer 12A and the nucleating agent vesicle-containing resin material for the skin layer 12B are mixed into, for example, base layer resin material/nucleating agent vesicle containing resin material/base layer resin. The materials were simultaneously extruded from an extruder so as to be laminated in order, and cooled with a cooling roll to form a laminated film. At this time, a cooling roll having a predetermined uneven shape on its surface is used as at least one of the cooling rolls. As a result, the skin layer 12B/base material layer 12A/skin layer 12B are laminated to obtain an original fabric layer 12 in which a predetermined uneven shape is transferred to the surface of at least one skin layer 12B.

Subsequently, a resin material such as urethane resin is applied to the back surface of the original fabric layer 12 to form the primer layer 11 . Furthermore, a colored layer 13 is formed by coating and curing a resin material containing a colored pigment on the surface of the raw fabric layer 12 on the colored layer 13 side. Finally, a top coat layer 14 is formed by applying and curing a resin material such as acrylic urethane resin. In addition, when forming each layer, the coated surface may be subjected to surface treatment such as corona treatment.
As described above, the primer layer 11, the raw fabric layer 12, the colored layer 13, and the top coat layer 14 are laminated in this order, and an uneven shape is formed on the surface of the skin layer 12B provided on at least one of the raw fabric layers 12. A decorative sheet of one embodiment can be obtained.

(1.3) Effects of the first embodiment The decorative sheet 1 as described above has the following effects.
(1) In the decorative sheet 1 of this embodiment, the skin layer 12B of the raw fabric layer 12 contains a resin material and a nano-sized nucleating agent, and the average particle size of spherulites in the crystal part of the crystalline resin is small and high. It is crystallized, and the surface of the skin layer 12B has a predetermined uneven shape.
According to this configuration, scratches occurring on the decorative sheet 1 can be suppressed, and a decorative sheet 1 that is soft and comfortable to the touch can be obtained.

(2) The decorative sheet 1 of the present embodiment has a skin layer 12B that is highly crystallized by adding a nucleating agent 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. is preferred.
According to this configuration, the degree of crystallinity of the resin material constituting the skin layer 12B is sufficiently improved, and a decorative sheet 1 with sufficiently high scratch resistance can be obtained.

(3) In the decorative sheet 1 of the present embodiment, it is preferable that the skin layer 12B is formed of a resin material to which nucleating agent vesicles, which are enclosed in the outer membrane and formed into vesicles, are added.
According to this configuration, the degree of crystallinity of the resin material constituting the skin layer 12B is sufficiently improved, and a decorative sheet 1 with even higher scratch resistance can be obtained.
(4) In the decorative sheet 1 of the present embodiment, the nucleating agent vesicles are preferably nucleating agent liposomes having an outer membrane made of phospholipid.
According to this configuration, the compatibility between the resin material, which is the main component of the skin layer 12B, and the vesicles can be made good.

(5) In the decorative sheet 1 of the present embodiment, the arithmetic mean roughness Ra of the surface of the skin layer 12B having an uneven shape is 2.0 μm or more and 4.5 μm or less, and the ten-point average roughness Rz is 12 μm or more and 30 μm or less. It is preferable that the average interval S of the local peaks is 90 μm or more and 200 μm or less.
According to this configuration, the scratch resistance and feel of the decorative sheet 1 can be further improved.
(6) The decorative sheet 1 of this embodiment is preferably adjusted to have a gloss level of 10 or less.
According to this configuration, the design of the decorative sheet 1 can be improved.

2. Second Embodiment Hereinafter, a decorative sheet according to a second embodiment of the present disclosure will be described using FIG. 2.
FIG. 2 is a cross-sectional view for explaining one 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, like the decorative sheet 1, is a decorative sheet applied to, for example, walls, fittings, furniture, etc., and is particularly applied to door frames, window frames, baseboards, partings, and surrounding edges. It is a decorative sheet that is preferably used as a fixture to be incorporated into a building in advance.

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

The raw fabric layer 12 will be explained below. Note that each layer other than the raw fabric layer 12 (primer layer 11, colored layer 13, and top coat layer 14) has the same structure as each layer of the decorative sheet 1, so the explanation will be omitted.

(2.1) Basic composition of decorative sheet <raw fabric layer>
The raw 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 raw fabric layer 22 has a structure in which a skin layer 22B is provided on the upper surface of the base material layer 22A (the surface on the colored layer 13 side to be described later) or on both surfaces of the base material layer 22A. In this embodiment, a raw fabric layer 22 having a structure in which skin layers 22B are provided on both sides of a base layer 22A will be described.

[Base material layer]
The base material layer 22A has the same configuration as the base material layer 12A according to the first embodiment, so a description thereof will be omitted.

[Skin layer]
The skin layer 22B is a layer containing a resin material and an inorganic material. In the decorative sheet 1 according to the first embodiment, a highly scratch-resistant resin sheet having high crystallinity was formed using a resin material containing a nucleating agent to form the skin layer 12B. On the other hand, in the decorative sheet 2 according to the second embodiment, the skin layer 22B having high hardness is made of a resin material containing high hardness inorganic particles instead of the nucleating agent, so that the decorative sheet 2 has high scratch resistance. obtain.

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

Similar to the raw fabric layer 12, at least one surface of the skin layer 22B has an uneven shape. The arithmetic mean roughness Ra, ten-point average roughness Rz, and average spacing S of local peaks of 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 a nucleating agent, the skin layer 22B has an uneven shape, so that the surface of the decorative sheet 2 itself is flat but has high scratch resistance, and the decorative sheet 2 has a soft and comfortable feel. can be obtained.

The raw fabric layer 22 is formed on at least one surface of the base layer 22A by, for example, heating and melting an inorganic particle-containing polypropylene resin containing nano-sized inorganic particles and coextruding it together with a nucleating agent vesicle-containing resin material. A skin layer 22B is provided and formed.

(2.2) Effects of the second embodiment The decorative sheet 2 as described above has the following effects in addition to the effects (5) and (6) of the first embodiment.
(7) The decorative sheet 2 of this embodiment includes a resin material and inorganic particles, and has a highly hardened raw fabric layer 22.
According to this configuration, scratches occurring on the decorative sheet 1 can be suppressed, and a decorative sheet 1 that is soft and comfortable to the touch can be obtained.

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 are produced, and the decorative sheet is pasted onto flooring material. was evaluated.

<Example 1>
A single-color decorative sheet was created using the following procedure.
A white pigment and a weathering agent were mixed with a polypropylene resin and melt-kneaded to obtain a white polypropylene resin containing 30% by mass of the white pigment and 1% by mass of the weathering agent. Next, nucleating agent vesicles were mixed with the transparent polypropylene resin to obtain a nucleating agent vesicle-containing polypropylene resin containing 0.1% by mass of nucleating agent vesicles. Subsequently, the heated and melted white polypropylene resin and nucleating agent vesicle -containing polypropylene resin are simultaneously extruded from an extruder so that they are 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, a cooling roll having an uneven surface was used as the cooling roll on one side of the white polypropylene resin, and a cooling roll with a smooth surface was used as the cooling roll on the other side. As a result, a colored raw fabric layer with a layer thickness of 140 μm was obtained, which had a white base material layer and a transparent skin layer provided on both sides of the base material layer, and an uneven shape was formed on one surface of the skin layer. Ta.

At this time, in the extruder, the extrusion amount of each resin was adjusted so that the thickness ratio of the skin layer, base material layer, and skin layer was 0.5:9:0.5. In addition, the uneven shape on the surface of one cooling roll has an arithmetic mean roughness Ra of 2.589 μm, a ten-point average roughness Rz of 16.330 μm, and an average of the local peaks of the unevenness of the top coat layer forming surface of the finished decorative sheet. The shape was such that unevenness with a spacing S of 92.8 μm could be transferred.

Subsequently, a two-component urethane resin was applied to the other surface (smooth surface) of the colored original fabric layer by gravure printing so that the solid content was 1 g/m ² to form a primer layer. Furthermore, after corona treatment was applied to one surface (surface with irregularities) of the colored raw material layer, a 6 μm thick acrylic two-component curing resin (manufactured by DIC Graphics, acrylic urethane resin) was applied. This was applied and cured to form a top coat layer.
As described above, a decorative sheet of Example 1 was obtained in which the primer layer, the colored raw fabric layer, and the top coat layer were laminated in this order, and the unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side.

<Example 2>
A colored original fabric layer was produced by the same method as in Example 1. At this time, the uneven shape on the surface of one cooling roll has an arithmetic mean roughness Ra of 2.551 μm and a ten-point average roughness Rz of 17.147 μm of the top coat layer forming surface of the finished decorative sheet, and a local peak of the unevenness. The shape was such that unevenness with an average interval S of 117.1 μm could be transferred.

One surface (the surface with irregularities) of the colored original fabric layer was subjected to corona treatment, and a colored polypropylene resin was applied and cured by gravure printing to a solid content of 5 g/m ² to form a colored layer. A top coat layer was formed on the surface of the colored layer in the same manner as in Example 1.
As a result, a decorative sheet of Example 2 was obtained, in which the primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side.

<Example 3>
When forming the skin layer, a colored raw fabric layer was formed using a colored polypropylene resin to which a beige colored pigment was added by mixing titanium oxide and iron oxide in place of the white pigment. At this time, the uneven shape on the surface of one cooling roll has an arithmetic mean roughness Ra of 2.979 μm and a ten-point average roughness Rz of 19.519 μm on the surface on which the top coat layer is formed of the completed decorative sheet. The shape was such that unevenness with an average interval S of 128.2 μm could be transferred. Other than this, a colored original fabric layer, a colored layer, and a top coat layer were formed in the same manner as in Example 2.
As described above, a decorative sheet of Example 3 was obtained, in which the primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side.

<Example 4>
The uneven shape on the surface of one of the cooling rolls was determined based on the arithmetic mean roughness Ra of the top coat layer forming surface of the completed decorative sheet of 4.209 μm, the ten-point average roughness Rz of 22.605 μm, and the average spacing S of the local peaks of the unevenness. The shape was such that unevenness with a diameter of 199.4 μm could be transferred. Except for this, the primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order in the same manner as in Example 2, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side.Example 4 I got a cosmetic sheet.

<Example 5>
The uneven shape on the surface of one of the cooling rolls was determined based on the arithmetic mean roughness Ra of the top coat layer forming surface of the completed decorative sheet of 3.300 μm, the ten-point average roughness Rz of 24.674 μm, and the average spacing S of the local peaks of the unevenness. The shape was such that unevenness with a diameter of 149.0 μm could be transferred. Example 5 The primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order in the same manner as in Example 2 except for this, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side. I got a cosmetic sheet.

<Example 6>
The uneven shape on the surface of one of the cooling rolls was determined based on the arithmetic mean roughness Ra of the top coat layer forming surface of the completed decorative sheet of 2.586 μm, the ten-point average roughness Rz of 23.495 μm, and the average spacing S of the local peaks of the unevenness. The shape was such that unevenness with a diameter of 131.0 μm could be transferred. Example 6 except for this, a primer layer, a colored raw fabric layer, a colored layer, and a top coat layer were laminated in this order in the same manner as in Example 2, and irregularities were formed on the surface of the colored raw fabric layer on the top coat layer side. I got a cosmetic sheet.

<Example 7>
The uneven shape on the surface of one of the cooling rolls was determined based on the arithmetic mean roughness Ra of the top coat layer forming surface of the completed decorative sheet of 2.997 μm, the ten-point average roughness Rz of 25.461 μm, and the average spacing S of the local peaks of the unevenness. The shape was such that unevenness with a diameter of 141.7 μm could be transferred. Example 7 The primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order in the same manner as in Example 2 except for this, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side. I got a cosmetic sheet.

<Comparative example 1>
A colored original fabric layer was formed using a polypropylene resin containing no nucleating agent vesicles as a material for forming the base layer. At this time, the uneven shape on the surface of one cooling roll has an arithmetic mean roughness Ra of 5.569 μm, a ten-point average roughness Rz of 37.152 μm, and a roughness of the local peaks of the uneven surface of the top coat layer forming surface of the completed decorative sheet. The shape was such that unevenness with an average interval S of 233.9 μm could be transferred. Other than this, a colored original fabric layer, a colored layer, and a top coat layer were formed in the same manner as in Example 2.
As a result, a decorative sheet of Comparative Example 1 was obtained, in which the primer layer, the colored raw fabric layer, the colored layer, and the top coat layer were laminated in this order, and unevenness was formed on the surface of the colored raw fabric layer on the top coat layer side.

<Evaluation>
(Scratch test)
A coin scratch test was conducted on each of the decorative sheets of Examples 1 to 7 and Comparative Example 1, and when no continuous scratches were found on the surface of the decorative sheet (original fabric layer or top coat layer). The load was measured. In the scratch test, a 10 yen coin was applied to the surface of the decorative sheet, the test was started with a load of 1 kg, and the load was gradually increased in 1 kg increments until the test reached 4 kg.

(Scratch hardness test)
The surface of the decorative sheet (original fabric layer or The hardness of the hardest pencil that did not cause any scars on the top coat layer (pencil hardness) was measured. Note that the scratch hardness test was conducted using the equipment described in JIS K5600-5-4:1999.

(Tactile evaluation)
The texture of each surface of each of the decorative sheets of Examples 1 to 7 and Comparative Example 1 was checked by touching the surfaces of the decorative sheets with their hands, and it was confirmed whether a comfortable texture was obtained. The tester judged the tactile sensation based on the evaluation standard of "comfortable touch", when the surface of the decorative sheet was smooth and did not feel sticky or stuck when lightly touched.
The tactile sensation was evaluated by 10 examiners, and if 8 or more examiners answered that the touch was comfortable, it would be rated "A," and if 6 or more examiners answered that it was comfortable to the touch, it would be rated "A." If less than 5 examiners answered that the texture was pleasant to the touch, the evaluation was rated as "C".

(Evaluation of design sense)
A tester visually checked the design on the surface of each of the decorative sheets of Examples 1 to 7 and Comparative Example 1 to see if the surface had a flat design. The design impression was evaluated by 10 testers, and the evaluation was based on the number of people who answered that the surface had a flat design impression. That is, in this evaluation, it was evaluated whether the decorative sheets of Examples 1 to 7 and Comparative Example 1 were decorative sheets with a design that made it difficult to visually perceive uneven shapes. In evaluating the design feel, it was determined that the more people answered that the design had a flat surface, the better.

Table 1 below shows excerpts of the configurations of each Example and each Comparative Example. Furthermore, Table 2 below shows the evaluation results of each Example and each Comparative Example.

As shown in Table 1, the decorative sheets of Examples 1 to 7, which contain a nucleating agent and have a skin layer with high crystallinity and an uneven surface, were compared with the decorative sheet of Comparative Example 1. It was confirmed that scratch resistance was improved. In particular, the decorative sheets of Examples 1 to 7 had a load of 4.0 kg that caused continuous scars in the scratch test, and a pencil hardness of 3B or higher in the scratch hardness test, which is better than Comparative Example 1. The results were obtained. On the other hand, it was confirmed that the decorative sheet of Comparative Example 1, which includes a skin layer that does not contain a nucleating agent, had a low load capacity of 2.0 kg in the scratch test and low scratch resistance in the scratch hardness test.

Further, an embodiment in which the arithmetic mean roughness Ra of the skin layer surface is 2.5 μm or more and 3.0 μm or less, the ten-point average roughness Rz is 15 μm or more and 20 μm or less, and the average interval S of the local peaks of the unevenness is 90 μm or more and 130 μm or less. It was confirmed that in the decorative sheets of Examples 1 to 3, the pencil hardness was further improved as compared to the decorative sheets of Examples 4 to 7, and the feel of the decorative sheets to the touch was improved.

From the above evaluation results, a decorative sheet that contains a nucleating agent and has a skin layer with high crystallinity and an uneven surface has better scratch resistance than a decorative sheet that does not have such a skin layer. It was confirmed that it was high. In addition, a decorative 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, and average spacing of local peaks S has further improved scratch resistance and is soft. Provides a comfortable touch.

The scope of the present disclosure is not limited to the exemplary embodiments shown and described, but also includes all embodiments giving equivalent effect to the object of the present disclosure. Furthermore, the scope of the present disclosure is not limited to the combinations of inventive features delineated by the claims, but may be defined by any desired combinations of specific features of each and every disclosed feature.

1, 2 Decorative sheet 11 Primer layer 12, 22 Original fabric layer 12A, 22A Base layer 12B, 22B Skin layer 13 Colored layer 14 Top coat layer

Claims (13)

A raw fabric layer having 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 the resin material and a nucleating agent or inorganic particles;
a top coat layer provided on the skin layer formed on one side of the raw fabric layer;
Equipped with
The surface roughness of the surface of the skin layer provided between the base layer and the top coat layer on the top coat layer side is rougher than the surface roughness of the surface of the skin layer on the base layer side. A makeup sheet. The thickness of the base material layer is 60 μm or more and 200 μm or less.
The decorative sheet according to claim 1. The thickness of the skin layer is 1 μm or more and 50 μm or less.
The decorative sheet according to claim 1 or 2. 3. The skin layer is formed of a resin material to which the nucleating agent is added within a range of 0.05 parts by mass or more and 0.5 parts by mass or less based on 100 parts by mass of the resin material. The decorative sheet according to any one of the above. The decorative sheet according to claim 1, wherein the skin layer contains at least one of nano-sized silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate as the inorganic particles. The skin layer is formed of a resin material to 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, based on 100 parts by mass of the resin material. Cosmetic sheet. The decorative sheet according to at least one of claims 1 to 6 , wherein the arithmetic mean roughness Ra of the surface of the top coat layer is 2.0 μm or more and 4.5 μm or less. The decorative sheet according to at least one of claims 1 to 7 , wherein the surface of the decorative sheet has a ten-point average roughness Rz of 12 μm or more and 30 μm or less. The decorative sheet according to at least one of claims 1 to 8 , wherein an average interval S of local peaks on the surface of the decorative sheet is 90 μm or more and 200 μm or less. The decorative sheet according to at least one of claims 1 to 9 , having a glossiness of 10 or less. The decorative sheet according to at least one of claims 1 to 10 , wherein the load at which continuous scars occur in a scratch test is 4.0 kg or more. The decorative sheet according to at least one of claims 1 to 11 , which has a pencil hardness of 3B or more in a scratch hardness (pencil method) test specified in JIS K5600-5-4:1999. A method for manufacturing a decorative sheet according to any one of claims 1 to 12 , comprising:
A step of generating a nucleating agent vesicle by encapsulating a nucleating agent in a vesicle and turning the nucleating agent into a vesicle;
A second resin material containing the nucleating agent vesicles is applied to at least one surface of the base layer formed using the first resin material , and the surface roughness of the surface opposite to the base layer is such that forming a raw fabric layer with a skin layer provided on at least one surface of the base layer by curing the skin layer so that the surface roughness is rougher than that of the surface on the base layer side; ,
forming a top coat layer by applying and curing a third resin material on the skin layer formed on one side of the raw fabric layer;
Equipped with
A method for manufacturing a decorative sheet, wherein in the step of forming the original fabric layer, an uneven shape is provided on the surface of the skin layer provided on the surface facing the top coat layer.

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