Cosmetic sheet and cosmetic board

Abstract

To provide a decorative sheet and a decorative plate using the decorative which can reduce the number of manufacturing processes, and have high hardness and excellent scratch resistance while being thin.SOLUTION: There is provided a decorative sheet 10, where a printing pattern layer 50 on which a pattern is printed, and a coloring layer 40 are formed in this order on a back face side of a transparent raw fabric layer 20 that is a single-layer film, a surface protective layer 60 is formed on a surface side of the transparent raw fabric layer 20, and a laminate layer composed of other films is not provided on both the surface side and the back face side of the transparent raw fabric layer 20, wherein the transparent raw fabric layer 20 contains at least any one of a nucleating agent and an inorganic filler, and a transparent olefinic thermoplastic resin, and the surface protective layer 60 contains an ionizing radiation curable resin.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a decorative sheet and a decorative board used for surface decoration such as floor materials.

Background Art

[0002] Conventionally, in recent years, olefin-based materials have been mainly used for decorative sheets due to problems with gases during combustion (see Patent Documents 1 to 3).

[0003] In order to protect the pattern from surface wear, a multi-layered decorative sheet is widely used, in which a transparent olefin sheet is laminated on a printed colored olefin sheet (see paragraph

[0034] and FIG. 1 of Patent Document 2, and paragraph

[0059] and FIG. 1 of Patent Document 3).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the above-described conventional decorative sheet, a printing process and a lamination process are required during manufacturing. For this reason, there is a first problem that the number of manufacturing steps of the decorative sheet increases, and for example, inline processing in one step cannot be achieved.

[0006] In addition, since the conventional decorative sheet is multi-layered, it is not easy to make the sheet thinner, and there is a second problem that it is impossible to achieve both a thickness up to the limit of film formation and sufficient hardness of the sheet.

[0007] Furthermore, due to the limitations in film formation on the conventional cosmetic sheet, when the film is made thinner, the hardness of the sheet cannot be obtained, making it difficult to align the printing as the sheet stretches, resulting in a third problem of inferior surface physical properties when made into a decorative board.

[0008] In view of the above-mentioned first to third problems, an object of the present disclosure is to provide a cosmetic sheet that can reduce the number of manufacturing steps, has high hardness and excellent scratch resistance while being a thin film, and a decorative board using the cosmetic sheet.

Means for Solving the Problems

[0009] In order to solve the above problems, a cosmetic sheet according to an aspect of the present disclosure has a printed pattern layer with a pattern printed thereon and a coloring layer sequentially formed on the back side of a base web layer that is a single-layer film, and a surface protection layer is formed on the front side of the base web layer. The cosmetic sheet does not have a laminate layer formed of another film on either the front side or the back side of the base web layer. The base web layer is formed by including either a nucleating agent or an inorganic filler and a transparent olefin-based thermoplastic resin. It is composed of a core layer and two skin layers disposed with the core layer therebetween, and only the two skin layers are formed by including either one of the nucleating agent or the inorganic filler and the olefin-based thermoplastic resin. The surface protection layer is formed by including a radiation-curable resin.

[0010] Moreover, a decorative board according to another aspect of the present disclosure has the above-mentioned cosmetic sheet and a substrate to which the above-mentioned cosmetic sheet is bonded to at least one surface.

Effects of the Invention

[0011] According to the aspect of the present disclosure, it is possible to reduce the number of manufacturing steps, and it is possible to provide a cosmetic sheet that has high hardness and excellent scratch resistance while being a thin film, and a decorative board using the cosmetic sheet.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0013] 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 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.

[0014] The laminate according to the first embodiment of the present disclosure will be described. The cosmetic sheet according to the present disclosure is, for example, a cosmetic sheet applied to a wall surface, a floor material, etc., and in particular, a cosmetic sheet preferably used for a floor material. In the following description, the side in contact with the pasting surface of the cosmetic sheet may be referred to as "down", and the side opposite to the side in contact with the pasting surface (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.

[0015] 1. First Embodiment (1.1) Basic Configuration of Cosmetic Sheet FIG. 1 is a cross-sectional view for explaining a configuration example of a cosmetic sheet 10 according to the first embodiment of the present disclosure (hereinafter referred to as "the present embodiment"). In FIG. 1, 10 is a cosmetic sheet. Although not shown, for example, it is used indoors, pasted on the surface of a wall material, a floor material, etc., and used by matching the patterns of the wall material and the floor material for each house or room. The decorative sheet 10 includes the following layers, and the layers are provided in order from (1). Note that the following (1) to (5) will be described later. (1) Primer layer 30 (2) Coloring layer 40 (3) Printed pattern layer 50 (4) Transparent base material layer 20 (5) Surface protection layer 60

[0016] Note that each layer of the decorative sheet 10 is not limited to the above (1) to (5). An embossed portion 90 synchronized with the pattern of the printed pattern layer 50 may be formed on the surface side of the surface protection layer 60, or a substrate shown in FIG. 4 described later may be adhered to the side of the primer layer 30 to form a decorative board. Also, in the decorative sheet 10, the above-mentioned "(1) Primer layer 30" may be omitted. That is, if the above-mentioned "(2) Coloring layer 40" has the function of a primer layer, the primer layer 30 can be omitted. That is, the decorative sheet 10 may be such that a printed pattern layer 50 and a coloring layer 40 with a printed pattern are sequentially formed on the back side of the transparent base material layer 20 which is a single-layer film, and a surface protection layer 60 is formed on the surface side of the transparent base material. Further, the decorative sheet 10 is a decorative sheet that does not have a laminate layer formed of another film on either the surface side or the back side of the transparent base material layer 20. Furthermore, the above-mentioned "(2) Coloring layer 40" may be omitted. That is, when the coloring layer is not necessary, for example, when there is no need to impart concealment, the coloring layer 40 can be omitted.

[0017] The primer layer 30 is a layer provided to improve the adhesiveness between the decorative sheet 10 and the attachment surface such as a floor material or a wall surface to which the decorative sheet 10 is attached. The coloring layer 40 is a layer that imparts a desired color to the decorative sheet 10. The printed pattern layer 50 is a layer on which a pattern for imparting design properties to the decorative sheet 10 is printed. The transparent base layer 20 serves as a support for the cosmetic sheet 10 and is formed of a transparent olefin sheet. Although details will be described later, as shown in FIG. 1, the transparent base layer 20 is manufactured in two types and three layers in the order of a transparent skin layer 21A, a transparent core layer 22 made of transparent polypropylene, and a transparent skin layer 21B. That is, the transparent base layer 20 is composed of a transparent core layer 22 and two transparent skin layers (transparent skin layers 21A and 21B) disposed with the transparent core layer interposed therebetween. The surface protective layer 60 is provided on the uppermost surface of the cosmetic sheet 10 and is a layer provided for protecting the cosmetic sheet 10 and adjusting the gloss of the surface of the cosmetic sheet 1. The cosmetic sheet 1 according to the present embodiment may have a configuration in which at least a colored layer 40, a transparent base layer 20, and a surface protective layer 60 are laminated in this order. In the present embodiment, the surface protective layer 60 has an undercoat layer (an example of a second surface protective layer) 61 and a topcoat layer (an example of a first surface protective layer) 62. Hereinafter, each layer of the primer layer 30, the colored layer 40, the printed pattern layer 50, the surface protective layer 60, and the transparent base layer 20 will be described in detail.

[0018] (1.1.1) Configuration of the transparent base layer of the cosmetic sheet 10 As shown in FIG. 1, the transparent base layer 20 is formed of the following three layers. Note that (1) to (3) will be described later. (1) Transparent core layer 22 (2) Transparent skin layer 21A on the front side (3) Transparent skin layer 21B on the back side In the transparent base layer 20, the transparent skin layer 21B on the back side, the transparent core layer 22, and the transparent skin layer 21A on the front side are sequentially laminated.

[0019] 〔Transparent core layer 22〕 For the transparent core layer 22, a material obtained by blending a weathering agent with a polypropylene resin is used. The transparent core layer 22 is, for example, a transparent polypropylene resin film. Also, in FIG. 1, the transparent base web layer 20 is depicted such that the transparent core layer 22, the front-side transparent skin layer 21A, and the back-side transparent skin layer 21B form separate layers, but in reality, the transparent core layer 22, the front-side transparent skin layer 21A, and the back-side transparent skin layer 21B are continuous and it is a single-layer sheet (single-layer film) without an interface.

[0020] (Resin material) Examples of the resin material constituting the transparent core layer 22 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 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 resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer; or a mixture, copolymer, composite, laminate, etc. of two or more of them can be used.

[0021] 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.

[0022] In the transparent core layer 22, if necessary, for example, one or more selected from various additives such as fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss modifiers may be added.

[0023] [Surface-side transparent skin layer 21A and back-side transparent skin layer 21B] The surface-side transparent skin layer 21A and the back-side transparent skin layer 21B (hereinafter, also referred to as "transparent skin layers 21A, 21B") are formed using the same type of thermoplastic resin, for example, a transparent polypropylene-based resin, and adding a dispersant as a nano-sized additive (hereinafter, also referred to as "dispersant nano specification"). That is, in this embodiment, the transparent base film layer 20 is formed of two types and three layers. Further, for the transparent skin layers 21A, 21B, similar to the transparent core layer 22, those blended with weathering agents may also be used. Note that for the transparent base film layer 20, at least one of the surface-side transparent skin layer 21A and the back-side transparent skin layer 21B may be provided. That is, the transparent base film layer 20 may be provided with a transparent skin layer on at least one surface.

[0024] The surface-side transparent skin layer 21A is located on the surface side of the transparent core layer 21, that is, the side of the surface protection layer 60 of the transparent core layer 22. The back-side transparent skin layer 21B is located on the back side of the transparent core layer 22, that is, the side opposite to the surface-side transparent skin layer 21A across the transparent core layer 22 (the side of the printed pattern layer 50). Note that

[0025] The transparent skin layers 21A, 21A are layers containing a resin material and a nucleating agent for improving the crystallinity of the resin material, and have an uneven shape on the surface. In the present embodiment, the nucleating agent is added to the resin material in the state of a nucleating agent vesicle encapsulated by an outer membrane and vesiculated. The thickness of the transparent skin layers 21A, 21A 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 transparent skin layers 21A, 21B is 1 μm or more, the scratch resistance of the cosmetic sheet 10 becomes sufficiently high. Further, when the thickness of the transparent skin layers 21A, 21B is 50 μm or less, the bendability of the cosmetic sheet 10 does not become too high more than necessary, and the cosmetic sheet 10 can be applied in a state of being in close contact with the application surface even when the application surface to which the cosmetic sheet 1 is attached is not flat. Further, the transparent base film layer 20 is formed, for example, by coextrusion so that the thickness ratio of "front surface side transparent skin layer 21A: transparent core layer 22: back surface side transparent skin layer 21B" is "0.5: 9: 0.5".

[0026] (Resin material) Examples of the resin material constituting the transparent skin layers 21A, 21B include thermoplastic resins. There is no particular limitation on the thermoplastic resin, and the same resin material as that of the transparent core layer 22 can be used.

[0027] (Nucleating agent) The transparent skin layers 21A, 21B contain 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 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 transparent skin layers 21A, 21B may be encapsulated in a vesicle with a part of the nucleating agent exposed. Since the transparent skin layers 21A, 21B contain a nucleating agent, the crystallinity can be improved, and the scratch resistance (scratch resistance) of the cosmetic sheet 10 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.

[0028] Since the nano-sized nucleating agent has an extremely small particle size, the number and surface area of the nucleating agents 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 one 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 one nucleating agent particle, and the growth of each crystal is inhibited by the mutual inhibition of the growth of the crystal ends, and the growth of each crystal stops. Therefore, the average particle diameter of the spherulites in the crystalline part of the crystalline resin 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.

[0029] When the nucleating agent is simply added, the nucleating agent in the resin undergoes secondary aggregation, resulting in an increase in particle size. On the other hand, when the nucleating agent vesicle is 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 as compared with the case where the nucleating agent is simply added. Therefore, 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. Thus, by adding the nucleating agent vesicle, the degree of crystallinity can be further increased, and it becomes possible to better balance the improvement of the elastic modulus and processability.

[0030] The transparent skin layers 21A and 21B are formed of a resin material to which a nucleating agent is added, for example, preferably in the range of 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 the polypropylene resin as the main component. When using a nucleating agent vehicle, 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 vehicle. When the amount of the nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layers 21A and 21B may not be sufficiently improved. Further, when the amount of the nucleating agent added exceeds 0.5 parts by mass, the spherulite growth of the polypropylene may be 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 transparent skin layers 21A and 21B may not be sufficiently improved. Here, the "main component" refers to a resin material that occupies 50% by mass or more of the resin material constituting the transparent skin layers 21A and 21B.

[0031] In addition, as a method for nanosizing the nucleating agent, for example, a solid phase method in which mainly mechanical pulverization is performed on the nucleating agent to obtain nanoparticles, a liquid phase method in which nanoparticles are synthesized or crystallized in a solution in which the nucleating agent or the nucleating agent is dissolved, a gas phase method in which nanoparticles are synthesized or crystallized from a gas or vapor composed of the nucleating agent or the nucleating agent, etc. can be appropriately used. Examples of the solid phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, a jet mill, etc. Examples of the liquid phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid phase reduction method, a hydrothermal synthesis method, etc. Further, examples of the gas phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, etc.

[0032] As a method for nanosizing the nucleating agent, the supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method for producing a capsule (nanosized vehicle) encapsulating a target substance using carbon dioxide under supercritical conditions or under temperature conditions 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 conditions or pressure conditions above the critical point means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical conditions.

[0033] In addition, 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 inclusion substance, and the mixture is stirred to generate an emulsion of supercritical carbon dioxide and the aqueous phase. Next, by reducing the pressure, carbon dioxide expands and evaporates, causing a phase inversion, and generating nanocapsules (nanovesicles) in which the phospholipid covers the surface of the nucleating agent particles with a monolayer membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer membrane becomes a multi-layer membrane on the surface of the nucleating agent particles, capsules with a monolayer membrane can be easily generated, so that smaller diameter capsules can be prepared. 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, etc. Among them, the nucleating agent vesicles are preferably prepared using the supercritical reverse phase evaporation method in particular.

[0034] 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. In this specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome. Examples of the phospholipid constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and sphingomyelins such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0035] Examples of other substances that form the outer membrane of the vesicle include nonionic surfactants and dispersants such as a mixture of these with cholesterol or triacylglycerol. Among these, as the nonionic surfactant, for example, one or more of polyglycerin ether, dialkyl glycerin, 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. can be used. As the cholesterol, for example, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate or colecalciferol, etc. can be used.

[0036] Also, the outer membrane of the liposome may be formed from a mixture of phospholipid and a dispersant. In the cosmetic sheet 10 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 10, and the vesicle can be made good. The nucleating agent is not particularly limited as long as it is a substance that becomes 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. Also, for the non-melting type nucleating agent, melting type benzylidene sorbitol may be appropriately mixed and used.

[0037] As described above, in the cosmetic sheet 10 of the embodiment, the transparent base film layer 20 is formed by including a nucleating agent and a resin material (for example, a transparent olefin-based thermoplastic resin). More specifically, in the cosmetic sheet 10 of the present embodiment, the transparent skin layers 21A and 21B are formed by including a nucleating agent and a resin material (for example, an olefin-based thermoplastic resin). Further, the cosmetic sheet 10 of the present embodiment is characterized in that when forming the transparent skin layers 21A and 21B, a nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. By adding the nucleating agent in a state encapsulated in vesicles to the resin composition, the effect of dramatically improving the dispersibility of the nucleating agent in the resin material, that is, in the transparent skin layers 21A and 21B, is achieved. On the other hand, it can be said that it is difficult and unrealistic to directly identify the nucleating agent encapsulated in vesicles based on the structure and properties of the object in the state of the completed cosmetic sheet 10 depending on the situation. The reasons are as follows.

[0038] The nucleating agent added in the state of vesicles has high dispersibility and is highly dispersed in the transparent skin layers 21A and 21B even in the state of the laminate which is the precursor of the produced cosmetic sheet 10. However, in the manufacturing process of the cosmetic sheet 10, usually, various treatments such as compression treatment and curing treatment are performed on the laminate, and the outer membrane of the vesicles encapsulating the nucleating agent may be crushed or chemically reacted by such treatments.

[0039] For this reason, due to the treatment process of the cosmetic sheet 10, the state where the outer membrane of the nucleating agent in the completed cosmetic sheet 10 is crushed or chemically reacted varies, and there is also a high possibility that the nucleating agent is not encapsulated (coated) 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 is difficult to determine whether the constituent material of the crushed outer membrane is the outer membrane of the vesicles 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 10, it is assumed that it may not be practical to specify within a numerical range obtained by analyzing the structure and properties of the cosmetic sheet 10 based on measurements as to whether it is because the nucleating agent is added in the form of vesicles encapsulating the nucleating agent.

[0040] The thickness of the transparent base film layer 20 is preferably, for example, in the range of 70 μm or more and 150 μm or less, and more preferably in the range of 90 μm or more and 130 μm or less. When the thickness of the transparent base film layer 20 is 70 μm or more, suitable strength is imparted when the cosmetic sheet 10 is used as a floor material, and the scratch resistance can be improved. Further, when the thickness of the transparent base film layer 20 is 90 μm or more, the strength of the transparent base film layer 20 is further increased, and the scratch resistance can be more reliably improved. On the other hand, when the thickness of the transparent base film layer 20 is 150 μm or less, it is possible to suppress the occurrence of problems such as whitening and cracking during processing while achieving both the thinness and strength of the cosmetic sheet 10, that is, the processability can be improved. In addition, sufficient transparency can be maintained to view the pattern of the printed pattern layer from the sheet surface (the surface protective layer 60 side). Further, when the thickness of the transparent base film layer 20 is 130 μm or less, it is possible to more reliably achieve both the thinness and strength of the cosmetic sheet 10 and improve the processability.

[0041] (1.1.2) Composition of each layer of the cosmetic sheet 10 (Primer layer 30) As shown in FIG. 1, the primer layer 30 is located on the back surface side of the transparent base film layer 20 and is mainly provided for the purpose of improving adhesiveness. The primer layer 30 is formed by laminating on the back surface side of the transparent base film layer 20 with the coloring layer 40. In other words, the primer layer 30 is provided on the surface of the coloring layer 40 opposite to the printed pattern layer 50. In addition, the functions of the primer layer 30 include, in addition to improving adhesiveness, surface stabilization after surface treatment, corrosion prevention of the metal surface, imparting tackiness, preventing deterioration of the adhesive, and the like. The primer layer 30 is formed by applying a urethane resin by, for example, the gravure printing method so that the solid content is 1 g / m 2

[0042]

[0042] (Coloring layer 40) As shown in FIG. 1, the coloring layer 40 is located on the back side of the transparent base material layer 20, more specifically, on the further back side of the printed pattern layer 50, and on the surface side of the primer layer 30. It is formed using a printing method and is mainly provided for the purpose of imparting concealment. The coloring layer 40 is printed, for example, with a two-component urethane resin by the gravure printing method. The two-component urethane resin may be configured by mixing a white pigment of titanium oxide into the urethane resin.

[0043] (Printed pattern layer 50) As shown in FIG. 1, the printed pattern layer 50 is located on the surface side of the coloring layer 40, that is, on the back side of the transparent base material layer 20. It is formed using a printing method and is provided for the purpose of imparting design characteristics to the decorative sheet 10. The printed pattern layer 50 is printed with a urethane resin pattern by, for example, the gravure printing method. As an example of the printing method, the gravure printing method is exemplified, but it is not limited thereto. For example, various printing methods such as offset printing method, relief printing method, flexographic printing method, screen printing method, inkjet printing method, and electrostatic printing method are applicable.

[0044] The type of pattern of the printed pattern layer 50 is arbitrary depending on the purpose of use, the preferences of the user, etc. For example, wood grain patterns, stone grain patterns, abstract patterns, etc. are common. The type of pattern is not limited to the types exemplified above, and for example, full-surface solid printing etc. may be used. As the printing ink used in the printing method, for example, vinyl chloride-based inks (cyan, magenta, yellow) are used.

[0045] In addition, although urethane-based resins were exemplified as the printing ink, the present invention is not limited thereto. For example, coloring agents such as organic or inorganic dyes or pigments may be used, or appropriate additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, defoamers, leveling agents, surfactants, desiccants, etc., or solvents or diluents, etc., may be dispersed in a binder made of a synthetic resin or the like.

[0046] (Surface protection layer 60) The surface protection layer 60, also referred to as a top coat, is located on the surface side of the transparent base material layer 20 as shown in FIG. 1, is formed using a printing method, and is provided for the purpose of imparting functions (surface physical properties) such as abrasion resistance, water resistance, weather resistance, scratch resistance, stain resistance, and designability. The surface protection layer 60 may be a single layer or may be composed of a plurality of layers stacked as the surface protection layer 60. In the decorative sheet 10 according to the present embodiment, as shown in FIG. 1, the surface protection layer 60 is composed of a primer layer 61 applied to the surface of the transparent base material layer 20 and a top coat layer 62 applied to the surface of the primer layer 61, which has a higher gloss than the primer layer 61.

[0047] Examples of the resin material constituting the primer layer 61 include thermosetting resins. Considering scratch resistance and the like, it is preferable to use a thermosetting resin having a urethane bond such as a two-component curable urethane resin. As the two-component curable urethane resin, for example, a urethane resin having a polyol as the main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol can be used. Since the primer layer 61 formed of a thermosetting resin has a relatively low degree of crosslinking, it tends to be excellent in flexibility such as bending and following the substrate. Among these resin materials, an acrylic two-component curable urethane resin mainly composed of acrylic polyol can be preferably used for the primer layer 61.

[0048] Examples of the resin material constituting the topcoat layer 62 include radiation-curable resins. Since the topcoat layer 62 formed of a radiation-curable resin has a high degree of crosslinking after the curing reaction, it has a high hardness and tends to be excellent in scratch resistance. Examples of the radiation-curable resin include (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. Among them, an acrylic radiation-curable resin (for example, an acrylic ultraviolet-curable resin) can be preferably used as the material for the topcoat layer 62.

[0049] As the radiation used to cure the radiation-curable resin, an electromagnetic wave or a charged particle having energy capable of causing a curing reaction of molecules in the radiation-curable resin (composition) is used. Usually, ultraviolet rays or electron beams may be used, but visible light, X-rays, ion beams, etc. may also be used.

[0050] As the ultraviolet light source, for example, light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, and metal halide lamps can be used. The wavelength of the ultraviolet rays is usually preferably in the range of 190 nm or more and 380 nm or less.

[0051] As the electron beam source, for example, various electron beam accelerators such as the Cockcroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, or linear type, Dynamitron type, and high frequency type can be used. Among them, those capable of irradiating electrons having an energy in the range of 100 keV or more and 1000 keV or less are particularly preferable, and those capable of irradiating electrons having an energy of 100 keV or more and 300 keV are more preferable.

[0052] Thus, by forming the topcoat layer 62 using an acrylic radiation-curable resin in this embodiment, the decorative sheet 10 can be imparted with a hardness suitable for floor covering applications. Further, as the resin material constituting the overcoat layer 62, a mixed material obtained by mixing a radiation-curable resin and a thermosetting resin may be used. As the thermosetting resin used for the resin material of the overcoat layer 62, the same thermosetting resin as that of the undercoat layer 61 can be used. At this time, for example, in the above-described mixed material, by containing more radiation-curable resin than thermosetting resin, it is possible to satisfy scratch resistance and at the same time make it difficult for whitening or cracking to occur in the surface protection layer 60 during bending processing.

[0053] Further, the overcoat layer 62 is coated with a resin material having a higher gloss than the undercoat layer 61 and printed with a pattern synchronized with the printed pattern layer 50. That is, by applying a gloss / matte coat to the surface protection layer 60, it is possible to synchronize with the pattern and improve the designability of the decorative sheet 10.

[0054] Further, an embossed portion 90 synchronized with the pattern of the printed pattern layer 50 (for example, a wood grain conduit pattern) may be formed on the surface of the overcoat layer 62, that is, the outermost surface side of the surface protection layer 60. In the embossed portion 90, the undercoat layer 61 may be exposed. Here, when referring to an embossed portion, an image of a certain level difference is generally had. However, in the present embodiment, the level difference between the undercoat layer 61 and the overcoat layer 62 synchronized with the pattern in the embossed portion 90 is actually only on the order of several μm, which is the same meaning as the expression of synchronizing with the pattern by applying a gloss / matte coat to the surface protection layer 60. By forming the embossed portion 90, in the surface protection layer 60, by utilizing the difference in texture between the high-gloss portion (overcoat layer 62) and the low-gloss portion (undercoat layer 61), a design closer to the real thing can be reproduced. For example, when a wood grain conduit pattern is printed on the overcoat layer 6, the embossed portion 90 can impart an uneven shape imitating an actual wood grain conduit to the surface of the surface protection layer 60. Thereby, a design close to real wood can be reproduced.

[0055] Furthermore, the surface protection layer 60 may be subjected to an antiviral treatment. As an antiviral treatment, an antiviral agent is added to the surface protective layer 60. As the antiviral agent, for example, a silver-based inorganic additive (Bioside TB-B100) manufactured by Taisho Techno Co., Ltd. carrying silver ions is used. Here, since the surface protective layer 60 is composed of the undercoat layer 61 and the topcoat layer 62, the antiviral agent may be added to both the undercoat layer 61 and the topcoat layer 62, or may be attached only to the topcoat layer 62 located on the surface side of the surface protective layer 60. Although an antiviral agent is added to the surface protective layer 60, it is not limited thereto, and an antiviral agent may be applied to the surface side of the surface protective layer 60, at least to the surface of the topcoat layer 62. Further, when the surface protective layer 60 has a single-layer structure, it is sufficient that the single-layer surface protective layer 60 contains an antiviral agent (for example, a silver-based antiviral agent).

[0056] In addition, in order to impart various functions to the surface protective layer 60, each layer of the surface protective layer 60 may contain functional additives such as antibacterial agents and antifungal agents. Further, each layer of the surface protective layer 60 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-based light stabilizers.

[0057] Thus, in the cosmetic sheet 10 according to this embodiment, the surface protective layer 60 is formed of two layers, namely, a topcoat layer 62 which is the outermost layer and is formed of an ionizing radiation-curable resin (for example, an ultraviolet-curable resin), and an undercoat layer 61 provided between the topcoat layer 62 and the transparent base film layer 20. Thereby, the hardness of the surface protective layer 60 is further improved, the cosmetic sheet 10 is imparted with excellent scratch resistance performance, and the effects of the performance imparted by various additives (for example, antiviral agents, etc.) can be enhanced. Further, the undercoat layer 61 is preferably formed of a two-component curable acrylic resin. Thereby, while satisfying the scratch resistance performance of the decorative sheet 10, the processability is improved, and whitening and cracking of the surface protective layer 60 are less likely to occur during processing. When the surface protective layer 60 has a structure composed of a single layer (single-layer structure), either the undercoat layer 61 or the overcoat layer 62 may be used as the surface protective layer 60. However, from the viewpoints of improving the hardness and design of the decorative sheet 10, it is preferable to use the overcoat layer 62 containing a radiation-curable resin as the surface protective layer 60. Further, the overcoat layer 62 may be formed to contain a mixed material of a radiation-curable resin and a thermosetting resin. That is, the surface protective layer 60 only needs to be formed to contain a radiation-curable resin, and it is more preferable that the surface protective layer 60 is formed to contain an acrylic radiation-curable resin (for example, an acrylic ultraviolet-curable resin). Further, the surface protective layer 60 may be formed to contain a mixed material of a radiation-curable resin and a thermosetting resin.

[0058] (1.2) Method for manufacturing the decorative sheet 10 The decorative sheet 10 has the above-described configuration, and its manufacturing method has the following first to third configurations and is manufactured inline. Here, "inline" means that since there is no laminating process for laminating films, printing, which usually involves a plurality of processes, can be processed in one line, that is, one line. That is, the manufacturing process from printing to applying the surface protective layer 60 can be performed in one inline process.

[0059] (1) First step The first step is a step of manufacturing a transparent base film 20, which is a single-layer film obtained by extrusion molding a transparent core layer 22 made of a transparent polypropylene-based thermoplastic resin, and transparent skin layers 21A and 21B, which are respectively located on the front and back surfaces of the transparent core layer 22 and in which a dispersant as a nano-sized additive is added to the thermoplastic resin.

[0060] Specifically, 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 that becomes the transparent core layer 22. Next, a nucleating agent vesicle is mixed into a resin material such as a polypropylene resin to obtain a resin material containing a nucleating agent vesicle for the transparent skin layers 21A and 21B. Subsequently, the resin material for the transparent core layer 22 that has been heated and melted and the resin material containing a nucleating agent vesicle for the transparent skin layers 21A and 21B are simultaneously extruded from an extruder so as to be laminated in the order of, for example, the resin material containing a nucleating agent vesicle / the resin material for the core layer / the resin material containing a nucleating agent vesicle, and cooled by a cooling roll to form a laminated film. Thereby, a transparent base material layer 20 in which the skin layer 12B / the base material layer 12A / the skin layer 12B are laminated is obtained.

[0061] (2) Second step The second step is a step of sequentially forming a printed pattern layer 50, a colored layer 40, and a primer layer 30 on the back surface side of the transparent base material layer 20 manufactured in the first step. (3) Third step The third step is a step of forming a surface protective layer 60 on the front surface side of the transparent base material layer 20 manufactured in the first step after the second step or prior to the second step. The order of the above steps is two ways: the order of the first step, the second step, and the third step, and the order of the first step, the third step, and the second step. Since a conventional cosmetic sheet is multilayered, it has been difficult to achieve synchronous expression between the application of the printed pattern layer and the surface protective layer on the surface of the laminate film. In contrast, the cosmetic sheet 10 according to the present embodiment can be manufactured inline as described above. Therefore, in the cosmetic sheet 10, at the time of inline manufacturing, by applying a pattern print and an embossed portion 90 to the front and back surface sides of the transparent olefin sheet or the transparent base material layer 20, synchronous expression between the printed pattern layer 50 and the surface protective layer 60 can be easily achieved.

[0062] As described above, a cosmetic sheet of the first embodiment in which the primer layer 30, the colored layer 40, the printed pattern layer 50, the transparent base material layer 20, and the surface protective layer 60 are laminated in this order can be obtained.

[0063] (1.3) Effects of the first embodiment The cosmetic sheet 1 as described above has the following effects. (1) In the cosmetic sheet 1 of the present embodiment, a printed pattern layer 50 with a pattern printed thereon and a coloring layer 40 are sequentially formed on the back surface side of a transparent base film layer 20 which is a single-layer film, and a surface protection layer 60 is formed on the front surface side of the transparent base film layer 20. The cosmetic sheet has no laminate layer formed of another film on either the front surface side or the back surface side of the transparent base film layer 20. The transparent base film layer 20 is formed by including a nucleating agent and a transparent olefin-based thermoplastic resin, and the surface protection layer 60 is formed by including a radiation-curable resin. According to this configuration, it is possible to reduce the number of manufacturing steps, and a cosmetic sheet 10 which is a thin film but has high hardness and excellent scratch resistance can be obtained. (2) In the cosmetic sheet 10 of the present embodiment, the surface protection layer 60 may be formed by including an acrylic radiation-curable resin. According to this configuration, in the cosmetic sheet 10, the hardness suitable for the floor material can be surely improved.

[0064] (3) In the cosmetic sheet 1 of the present embodiment, the surface protection layer 60 is formed of two layers, namely, a topcoat layer 62 which is the outermost layer and is formed of a radiation-curable resin, and an undercoat layer 61 provided between the topcoat layer 62 and the transparent base film layer 20. According to this configuration, the cosmetic sheet 10 can further improve the scratch resistance and enhance the effect of the performance imparted by various additives (for example, antiviral agents). (4) In the cosmetic sheet 1 of the present embodiment, the undercoat layer 61 may be formed of a two-component curable acrylic resin. According to this configuration, while satisfying the scratch resistance performance, the processability can be improved, and a cosmetic sheet excellent in the balance between the scratch resistance performance and the processability can be obtained. (5) In the cosmetic sheet 1 of the present embodiment, an embossed portion 90 synchronized with the pattern of the printed pattern layer 50 may be formed on the outermost surface side of the surface protection layer 60 (the outermost surface of the topcoat layer 62). According to this configuration, it is possible to reduce the number of manufacturing steps, and it is possible to obtain a decorative sheet that has high hardness while being a thin film and has excellent design properties due to the coordinated expression of the printed pattern layer 50 and the surface protection layer 60. (6) In the decorative sheet 10 of the present embodiment, the thickness of the transparent base material layer 20 may be in the range of 70 μm or more and 150 μm or less. According to this configuration, it is possible to reduce the number of manufacturing steps, and it is possible to obtain a decorative sheet that more surely achieves both a thin film thickness and high hardness suitable for a floor material.

[0065] (7) In the decorative sheet 1 of the present embodiment, the transparent base material layer 20 is composed of a transparent core layer 22 and two transparent skin layers 21A and 21B disposed with the transparent core layer 22 interposed therebetween, and the two transparent skin layers 21A and 21B may be formed to contain a nucleating agent and an olefin-based thermoplastic resin. According to this configuration, it is possible to obtain a decorative sheet that can achieve both high hardness suitable for a floor material and processability. (8) The decorative sheet 10 of the present embodiment may have a primer layer 30 provided on the surface of the coloring layer 40 opposite to the printed pattern layer 50. According to this configuration, it is possible to improve the adhesion to an adhesive used for adhering the decorative sheet 10 to a floor material, a wall surface, or the like.

[0066] (1.4) Modification of the first embodiment A modification of the decorative sheet according to the present embodiment will be described with reference to FIG. 2. FIG. 2 is a cross-sectional schematic view for explaining a configuration example of a decorative sheet 10 according to a modification of the present embodiment. As shown in FIG. 2, in the decorative sheet 10, the surface protection layer 60 may have a topcoat layer 162 with a flat surface. That is, the outermost surface of the surface protection layer 60 does not have to have an embossed portion. The topcoat layer 162 has the same configuration as the topcoat layer 62 shown in FIG. 1 except that the surface is flat. Therefore, the topcoat layer 162 can be printed with a pattern that is in sync with the printed pattern layer 50. By forming the surface of the topcoat layer 162 flat, when forming the surface protection layer 60, the workload and manufacturing cost for forming an embossed portion on the topcoat layer 162 can be reduced. As a result, even when both surfaces of the decorative sheet 10 are flat, the decorative sheet 10 can have high hardness while being a thin film, and excellent scratch resistance can be sufficiently maintained.

[0067] As described above, in the decorative sheet 1 according to the modification of the present embodiment, the topcoat layer 162 in the surface protection layer 60 may have a flat surface. Thereby, the manufacturing man-hours of the decorative sheet 10 can be further reduced, and a decorative sheet having high hardness and excellent scratch resistance while being a thin film can be obtained.

[0068] 2. Second Embodiment Hereinafter, a decorative sheet according to the second 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 sheet 11 according to the second embodiment of the present disclosure. The decorative sheet 11 according to the present embodiment is a decorative sheet that is preferably applied to, for example, a wall surface or a floor material, similar to the decorative sheet 10.

[0069] The decorative sheet 11 includes a primer layer 30, a colored layer 40, a printed pattern layer 50, a transparent base material layer 120, and a surface protection layer 60. That is, the decorative sheet 110 is different from the decorative sheet 10 according to the first embodiment in that it includes a transparent base material layer 120 instead of the transparent base material layer 20.

[0070] Hereinafter, the transparent base material layer 120 will be described. Note that since each layer other than the transparent base material layer 120 (the primer layer 30, the colored layer 40, the printed pattern layer 50, and the surface protection layer 60) has the same configuration as each layer of the decorative sheet 10, the description thereof will be omitted.

[0071] (2.1) Basic Configuration of Decorative Sheet <Transparent Base Material Layer> The transparent front / back layer 120 has a transparent core layer 22 and a transparent skin layer provided on at least one surface of the transparent core layer 22. The transparent front / back layer 120 may have a transparent skin layer 121A provided on the surface of the transparent core layer 22 (the surface on the side of the surface protection layer 60), or a transparent skin layer 121B provided on the back surface of the transparent core layer 22 (the surface on the side of the coloring layer 40), or may be configured such that transparent skin layers (transparent skin layers 121A, 121B) are provided on both surfaces of the transparent core layer 22. In the present embodiment, the transparent front / back layer 120 having a configuration in which transparent skin layers are provided on both surfaces of the transparent core layer 22 (a configuration in which the transparent core layer 22 is sandwiched between the transparent skin layers 121A, 121B) will be described.

[0072] (2.1.1) Transparent core layer 22 Since the transparent core layer 22 in the present embodiment has the same configuration as the transparent core layer 22 according to the first embodiment, the description thereof will be omitted.

[0073] (2.1.2) Transparent skin layers 121A, 121B The transparent skin layers 121A, 121B are layers containing a resin material and an inorganic material. In the decorative sheet 1 according to the first embodiment, a highly crystalline high scratch-resistant resin sheet is formed of a resin material with a dispersion agent nano-specification formed by including a nucleating agent, and used as the transparent skin layers 121A, 121B. On the other hand, in the decorative sheet 11 according to the second embodiment, instead of the nucleating agent, a nano-sized inorganic filler (inorganic nanoparticles) with high hardness is added to a resin material (for example, a transparent polypropylene-based resin) to form the transparent skin layers 121A, 121B (hereinafter, also referred to as "inorganic nanoparticle specification"). Thereby, transparent skin layers 121A, 121B having high hardness are formed, and a decorative sheet 11 having high scratch resistance is obtained.

[0074] Examples of the inorganic filler include fine particles made of inorganic materials such as nano-sized silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate. The transparent skin layers 121A, 121B are formed of, for example, a resin material in which an inorganic filler 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.

[0075] The transparent base layer 120 is formed by, for example, heating and melting an inorganic particle-containing polypropylene resin containing nano-sized inorganic particles and co-extrusion molding with a resin material for the core layer, so that a transparent skin layer (transparent skin layer 121A or transparent skin layer 121B) is provided on at least one surface of the transparent core layer 22. Note that the transparent skin layers 21A and 21B may be only of an inorganic nanoparticle specification formed by including an inorganic filler, or in addition to the inorganic nanoparticle specification, a dispersant nano-specification formed by including a nucleating agent may be added. That is, the transparent skin layers 21A and 21B may be formed by adding an inorganic filler in addition to a dispersant.

[0076] (2.2) Effects of the second embodiment The decorative sheet 11 as described above has the following effects. In the decorative sheet 11 of the present embodiment, a printed pattern layer 50 with a pattern printed thereon and a coloring layer 40 are sequentially formed on the back surface side of a transparent base layer 120 which is a single-layer film, a surface protection layer 60 is formed on the front surface side of the transparent base layer 120, and it is a decorative sheet having no laminate layer formed of another film on either the front surface side or the back surface side of the transparent base layer 120. The transparent base layer 120 is formed by including an inorganic filler and a transparent olefin-based thermoplastic resin, and the surface protection layer 60 is formed of an ionizing radiation curable resin (for example, an ultraviolet curable resin). According to this configuration, similar to the first embodiment, it is possible to reduce the number of manufacturing steps, and a decorative sheet 11 which is thin but has high hardness and excellent scratch resistance can be obtained.

[0077] 3. Third embodiment Hereinafter, a decorative material according to a third embodiment of the present disclosure will be described with reference to FIG. 4. FIG. 4 is a cross-sectional view for explaining a configuration example of a decorative sheet 12 according to the second embodiment of the present disclosure. The decorative sheet 12 according to the present embodiment is a decorative sheet that is preferably applied to, for example, a wall surface or a floor material, similar to the decorative sheet 10.

[0078] The cosmetic sheet 12 includes a primer layer 30, a coloring layer 40, a printed pattern layer 50, a transparent base material layer 220, and a surface protection layer 60. That is, the cosmetic sheet 12 is different from the cosmetic sheet 10 according to the first embodiment in that it includes the transparent base material layer 220 instead of the transparent base material layer 20.

[0079] Hereinafter, the transparent base material layer 220 will be described. Note that since the layers other than the transparent base material layer 220 (the primer layer 30, the coloring layer 13, and the top coat layer 14) have the same configuration as the layers of the cosmetic sheet 10, the description thereof will be omitted.

[0080] (3.1) Basic configuration of the cosmetic sheet <Transparent base material layer> The transparent base material layer 220 is composed of a transparent core layer 222. That is, in the present embodiment, no transparent skin layer is provided on either surface of the transparent core layer 222, and the transparent base material layer 220 is a single-layer film composed only of a transparent olefin sheet, that is, only the transparent core layer 222.

[0081] (3.1.1) Transparent core layer 222 The transparent core layer 222 in the present embodiment may be a dispersant nano specification formed by adding a dispersant (for example, a nucleating agent) as a nano-sized additive to a resin material (for example, a transparent polypropylene-based resin), or an inorganic nanoparticle specification formed by adding an inorganic filler as a nano-sized additive to the resin material, or may be formed by adding an inorganic nanoparticle specification in addition to the dispersant nano specification. That is, the transparent base material layer 220 composed of one layer of the transparent core layer 222 may be formed by including at least one of a nucleating agent or an inorganic filler and a transparent olefin-based thermoplastic resin. Thereby, a transparent core layer 222 having high hardness is formed, and the cosmetic sheet 12 having high scratch resistance is obtained.

[0082] The transparent base layer 220, i.e., the transparent core layer 222, may be formed, for example, by extruding from an extruder a resin material for a base material layer obtained by mixing at least one of a nucleating agent vesicle and an inorganic filler with a resin material such as a polypropylene resin and forming it as a single-layer film. That is, in the present embodiment, by making the transparent core layer 222 at least one of a dispersant nano specification and an inorganic nanoparticle specification, the cosmetic sheet has high scratch resistance and the manufacturing man-hours of the cosmetic sheet can be further reduced.

[0083] (3.2) Effects of the third embodiment The cosmetic sheet 12 as described above has the following effects. In the cosmetic sheet 12 of the present embodiment, a printed pattern layer 50 with a pattern printed thereon and a colored layer 40 are sequentially formed on the back surface side of the transparent base layer 220 which is a single-layer film, a surface protection layer 60 is formed on the front surface side of the transparent base layer 220, and it is a cosmetic sheet having no laminate layer formed of another film on either the front surface side or the back surface side of the transparent base layer 220. The transparent base layer 220 has a transparent core layer 222, and the transparent core layer 222 is formed by including at least one of a nucleating agent or an inorganic filler and a transparent olefin-based thermoplastic resin. The surface protection layer 60 is formed of an ionizing radiation curable resin. According to this configuration, it is possible to further reduce the number of manufacturing steps, and a cosmetic sheet 12 that is thin but has high hardness and excellent scratch resistance can be obtained.

[0084] 4. Fourth embodiment Hereinafter, a decorative panel according to a fourth embodiment of the present disclosure will be described with reference to FIG. 5. FIG. 5 is a cross-sectional view for explaining a configuration example of a decorative panel 100 according to a fourth embodiment of the present disclosure. (Decorative panel) The decorative panel 100 includes a cosmetic sheet 10 and a substrate to which the cosmetic sheet 10 is bonded to at least one surface. The decorative board 100 has a colored layer 40 and a printed pattern layer 50 laminated in this order on one surface side of the transparent base material layer 20, and a surface protection layer 60 laminated on the other surface side of the transparent base material layer 20. Further, the decorative board 100 is bonded to a substrate 80 at a primer layer 30 provided on a surface of the colored layer 40 opposite to the printed pattern layer 50. That is, the decorative board 100 differs from the decorative sheet 10 according to the first embodiment in that it includes a substrate 80.

[0085] Hereinafter, the substrate 80 will be described. Note that the decorative sheet 10 has the same configuration as that in the first embodiment, and thus the description thereof will be omitted.

[0086] [Substrate] The substrate 80 constitutes the floor surface on which the user walks and is made of a hard material. The substrate 80 is made of a hard material such as a woody base material such as plywood, a composite base material in which wood powder and plastic are mixed, a polyolefin such as polyethylene (PE) or polypropylene (PP), or a resin base material such as vinyl chloride (PVC). Examples of the woody base material include South Sea plywood, particle board, medium density fiberboard (hereinafter referred to as MDF), ordinary plywood defined in Japanese Agricultural and Forestry Standards, and the like. In addition, a base material made of a wood powder-added olefin resin can also be used. Note that the substrate 80 may be a metal such as aluminum, a resin such as plastic, or a composite material thereof. By forming the substrate 80, for example, it is possible to provide a decorative board 100 that can suppress the occurrence of scratches caused by, for example, the user's walking or the placement of furniture.

[0087] Floor materials are easily scratched when furniture is placed on them. For this reason, the decorative sheet used for floor materials requires higher scratch resistance than general decorative sheets. By forming the decorative board 100 using the decorative sheet 10 which is a thin film but has high hardness and excellent scratch resistance, it is possible to obtain a decorative board with excellent scratch resistance suitable for floor materials.

[0088] In the decorative panel 100, the primer layer 30 may be provided on one surface of the substrate 80 instead of the decorative sheet 10, and the decorative sheet 10 and the substrate 80 may be bonded together via the primer layer on the substrate 80. In the present embodiment, although the substrate 80 is bonded to the decorative sheet 10, the decorative sheet 10 may be a decorative sheet 10 provided with a topcoat layer 162 having a flat outermost surface in the surface protective layer 60, or the decorative panel 100 may be formed using the decorative sheet 11 or the decorative sheet 12 instead of the decorative sheet 10.

[0089] <Effects of the Fourth Embodiment> The decorative panel 100 according to the present embodiment has the following effects in addition to the effects of the first embodiment and the second embodiment. (13) The decorative panel 100 of the present embodiment includes a decorative sheet (decorative sheets 10, 11, 12) and a substrate to which the decorative sheet 10 is bonded to at least one surface. According to this configuration, the decorative panel 100 can reduce the number of manufacturing steps, and a decorative panel using a decorative sheet that is thin but has high hardness and excellent scratch resistance can be obtained.

Examples

[0090] Hereinafter, the decorative sheet according to the present disclosure will be described with reference to examples. Note that the present disclosure is not limited to the following Examples 1 and 2. In the examples, decorative sheets having the configurations described in the following examples and comparative examples were produced and bonded onto a substrate for a flooring material to evaluate the decorative sheets.

[0091] <Example 1> Example 1 produced a decorative sheet for evaluation using the following materials and procedures. For the transparent core layer 22 (core layer) of the transparent substrate layer 20, a blend of polypropylene resin and weathering agent is used. For the surface-side transparent skin layer 21A and the back-side transparent skin layer 21B (skin layers), a transparent polypropylene resin with a formulation (dispersant nano specification) in which a dispersant as a nano-sized additive is added is used. The transparent substrate layer 20 with a total thickness of 150 μm is produced by co-extrusion so that the thickness ratio of "surface-side transparent skin layer 21A: transparent core layer 22: back-side transparent skin layer 21B" is "0.5:9:0.5".

[0092] On the back side of the transparent substrate layer 20, a pattern is printed with a urethane-based resin by the gravure printing method to provide a printed pattern layer 50. Then, in order to create a concealment, a coloring layer 40 is provided with a two-component urethane-based resin in which a white pigment of titanium oxide is mixed with urethane resin by the gravure printing method. Furthermore, by the gravure printing method, a urethane-based resin is applied so that the solid content is 1 g / m 2 and a primer layer 30 is formed. Thereafter, after corona treatment is performed on the surface side of the transparent substrate layer 20, a primer layer 61 and a topcoat layer 62 are formed as a surface protection layer 60 (topcoat layer). Specifically, a low-gloss acrylic two-component curable resin (acrylic urethane resin manufactured by DIC Graphic Co., Ltd.) is applied to a thickness of 6 μm to form the primer layer 61. Also, an acrylic ultraviolet curable resin (acrylic ultraviolet curable resin manufactured by DIC Graphic Co., Ltd.) is printed on the primer layer 61 with a pattern synchronized with the printed pattern layer 50 to form the topcoat layer 62, and a decorative sheet for evaluation is produced.

[0093] <Example 2> A decorative sheet for evaluation was produced in the same manner as in Example 1, except that the total thickness of the transparent substrate layer 20 was 90 μm.

[0094] <Example 3> In the surface protective layer 60, a glossy topcoat layer 62 was printed with a wood grain conduit pattern in synchronization with the printed pattern layer 50, and further an embossed portion 90 was formed to partially expose the undercoat layer 61. As a result, the surface of the surface protective layer 60 was made into an uneven shape imitating a wood grain conduit. Other than this, an evaluation decorative sheet was produced in the same manner as in Example 1.

[0095] <Comparative Example 1> A dispersant as a nano-sized additive was not added to the transparent polypropylene resin forming the transparent base film layer 20. Other than this, an evaluation decorative sheet was produced in the same manner as in Example 1. <Comparative Example 2> A dispersant as a nano-sized additive was not added to the transparent polypropylene resin forming the transparent base film layer 20. Other than this, an evaluation decorative sheet was produced in the same manner as in Example 2.

[0096] (Evaluation Method and Evaluation Criteria) The evaluation method of the evaluation decorative sheet produced as described above is as follows. (1) Scratch Test (2) Abrasion Hardness Test (Pencil Hardness) (3) Abrasion Resistance Test (4) Caster Resistance Test

[0097] (Scratch Test) In the scratch test, for each of the evaluation decorative sheets, a coin scratch test was conducted, and the load when no continuous scratches occurred on the surface of the evaluation decorative sheet was measured. In the scratch test, a 10-yen coin was placed on the surface of the evaluation sheet, the test was started from a load of 1 Kg, the load was gradually increased by 1 Kg, and the test was conducted up to 4 kg.

[0098] (Abrasion Hardness Test) In the abrasion hardness test, for each of the evaluation sheets, by the abrasion hardness (pencil method) test specified in JIS K5600-5-4:1999, the hardness (pencil hardness) of the hardest pencil that did not cause scratches on the surface of each evaluation decorative sheet was measured.

[0099] (Abrasion resistance test) The decorative board with each evaluation decorative sheet attached was subjected to the abrasion resistance test specified in the "Japanese Agricultural and Forestry Standards for JAS Flooring", and the number of rotations until the pattern began to disappear was confirmed. The abrasive paper was changed every 1000 rotations.

[0100] (Castor resistance test) On the decorative board with each evaluation decorative sheet attached, a load of 25 kg (about 245 N) was applied to an iron wheel (diameter 40 mm, width of one wheel 9 mm, width between two wheels 18 mm), and the castor was moved at a speed of 20 cm / second for 1000 times (one stroke is 20 cm or more). Then, the marks on the decorative board were observed. (Evaluation criteria) In the scratch test, a load of "1 Kg" or more was considered qualified, and otherwise unqualified. In the abrasion hardness test, a pencil hardness of "B" or more was considered qualified, and otherwise unqualified. In the abrasion resistance test, "1000 rotations" or more was considered qualified, and otherwise unqualified. In the castor resistance test, "when there is no significant crack" was considered qualified, and otherwise unqualified.

[0101] <Evaluation results> The composition and evaluation results of the evaluation decorative sheets are shown in Table 1.

[0102]

Table 1

[0103] (Examples 1 to 3, and Comparative Examples 1 and 2) Among the five evaluation cosmetic sheets of Examples 1 to 3 and Comparative Examples 1 and 2, the evaluation cosmetic sheets of Examples 1 to 3 all passed in (1) to (4) of the above evaluation method. That is, it was found that the evaluation cosmetic sheets of Examples 1 to 3 had high hardness while being thin films and were excellent in scratch resistance. On the other hand, among the evaluation cosmetic sheets of Comparative Examples 1 and 2, at least one of (1) to (4) of the above evaluation method was "failed". Specifically, the evaluation cosmetic sheet of Comparative Example 1 failed in the evaluation of the scratch hardness test, and the evaluation cosmetic sheet of Comparative Example 2 failed in the evaluations of the scratch test and the scratch hardness test. That is, it was found that the cosmetic sheet added with the nano-sized additive (nucleating agent (dispersant) or inorganic filler) had improved hardness and excellent scratch resistance compared to the cosmetic sheet without the nano-sized additive while being a thin film.

[0104] Also, in Examples 1, 3 and Example 2, it can be presumed that the difference in the scratch hardness test was affected by the thickness of the evaluation cosmetic sheet. That is, it can be presumed that those of Examples 1 and 3 were thicker in the thickness of the evaluation cosmetic sheet than Example 2, and being thicker was advantageous in the scratch hardness test.

[0105] Note that the cosmetic sheet and the cosmetic 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.

Explanation of Reference Numerals

[0106] 10, 11, 12 Cosmetic sheet 20, 120, 220 Transparent base material layer 100 Cosmetic board 22, 222 Transparent core layer 21A, 21B, 121A, 121B Transparent skin layer 30 Primer layer 40 Coloring layer 50 Printed pattern layer 60 Surface protection layer 61 Undercoat layer 62 Topcoat layer 80 Substrate 90 Embossed part

Claims

1. On the back side of the base film layer which is a single-layer film, a printed pattern layer with a pattern printed thereon and a coloring layer are sequentially formed, On the front side of the base film layer, a surface protection layer is formed, A decorative sheet having no laminate layer formed of another film on either the front side or the back side of the base film layer, The base film layer is formed by including either a nucleating agent or an inorganic filler and a transparent olefin-based thermoplastic resin, and is composed of a core layer and two skin layers disposed with the core layer therebetween, Only the two skin layers are formed by including either the nucleating agent or the inorganic filler and the olefin-based thermoplastic resin, The surface protection layer is formed by including a radiation-curable resin. Decorative sheet.

2. The surface protection layer is formed by including an acrylic radiation-curable resin. The decorative sheet according to Claim 1.

3. The surface protection layer is formed of two layers, a first surface protection layer which is the outermost layer and is formed of the radiation-curable resin, and a second surface protection layer provided between the first surface protection layer and the base film layer. The decorative sheet according to Claim 1 or 2.

4. The second surface protection layer is formed of a two-component curable acrylic resin. The decorative sheet according to Claim 3.

5. The decorative sheet according to any one of Claims 1 to 4, wherein an embossed portion synchronized with the pattern is formed on the outermost surface side of the surface protection layer.

6. The thickness of the base film layer is in the range of 70 μm or more and 150 μm or less. The decorative sheet according to any one of Claims 1 to 5.

7. The coloring layer has a primer layer provided on the surface opposite to the printed pattern layer. The decorative sheet according to any one of Claims 1 to 6.

8. A decorative sheet according to any one of Claims 1 to 7, A substrate to which the decorative sheet is adhered to at least one surface, A decorative board having the same.

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