decorative sheet

Abstract

To provide a decorative sheet capable of improving stain resistance.SOLUTION: A decorative sheet comprises: a base material layer 12A containing a resin material; a raw fabric layer 12 laminated on at least one surface of the base material layer 12A and having a skin layer 12B containing a resin material and a nucleating agent or inorganic particles, a top coat layer 14 laminated on the skin layer 12B, and a colored layer 13 arranged between the topcoat layer 14 and the raw fabric layer 12, wherein the topcoat layer 14 has a lower layer side topcoat 14A facing the raw fabric layer 12. and an upper layer side top coat layer 14B laminated on the lower side top coat layer 14A, at least the upper layer side top coat layer 14B of the lower layer side top coat layer 14A and the upper layer side top coat layer 14B is made using a silicone modified acrylic resin.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a cosmetic sheet.

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In view of the above problems, an object of the present invention is to provide a cosmetic sheet capable of improving stain resistance.

Means for Solving the Problems

[0006] To solve the above problems, one aspect of the present invention provides a decorative sheet comprising a base layer having a base layer containing a resin material, a skin layer laminated on at least one surface of the base layer and containing a resin material and a nucleating agent or inorganic particles, and a top coat layer laminated on the skin layer. The top coat layer is formed using a silicone-modified acrylic resin. [Effects of the Invention]

[0007] According to one aspect of the present invention, it is possible to provide a decorative sheet that can improve stain resistance. [Brief explanation of the drawing]

[0008] [Figure 1] This is a cross-sectional view showing the configuration of the decorative sheet in the first embodiment of the present invention. [Modes for carrying out the invention]

[0009] Embodiments of this technology will be described below with reference to the drawings. In the drawings, identical or similar parts are denoted by the same or similar reference numerals, and redundant explanations are omitted. Each drawing is schematic and may differ from reality. The embodiments shown below are illustrative examples of devices and methods for realizing the technical idea of ​​this technology, and the technical idea of ​​this technology is not limited to the devices and methods exemplified in the embodiments below. The technical idea of ​​this technology can be modified in various ways within the technical scope described in the claims. Furthermore, the directions "left and right" and "up and down" in the following description are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present invention. Therefore, for example, if the paper is rotated 90 degrees, "left and right" and "up and down" are swapped when read, and if the paper is rotated 180 degrees, "left" becomes "right" and "right" becomes "left," of course.

[0010] (First Embodiment) The configuration of the decorative sheet 1 will be described below with reference to Figure 1. As shown in Figure 1, the decorative sheet 1 comprises a primer layer 11, a raw material layer 12, a coloring layer 13, and a top coat layer 14.

[0011] <Primer layer> The primer layer 11 is a layer provided to improve the adhesion between the decorative sheet 1 and the surface to which it is attached (for example, the wall surface to which the decorative sheet 1 is attached). Furthermore, the primer layer 11 is laminated on the other side of the raw material layer 12 (the lower side in Figure 1). As the material for forming the primer layer 11, for example, polyester resin, polyurethane resin, or a mixture of polyester resin and polyurethane resin can be used. Furthermore, by using a two-component type material consisting of polyol and isocyanate as the material for forming the primer layer 11, it is possible to improve the adhesion between the bonding surface and the primer layer 11, as well as the cohesive force of the primer layer 11 itself.

[0012] As polyols, for example, acrylic polyols and polyester polyols can be used. As isocyanates, for example, aromatic isocyanates and aliphatic isocyanates can be used. Examples of aromatic isocyanates include tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate. Examples of aliphatic isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. Furthermore, as the material for forming the primer layer 11, aromatic polyols are preferable in terms of their rapid reactivity and heat resistance.

[0013] The thickness of the primer layer 11 is preferably 1 [μm] or more. The reason why it is preferable for the primer layer 11 to have a thickness of 1 [μm] or more is that by making the primer layer 11 thicker than 1 [μm], it is possible to prevent the adhesive from dissolving due to the solvent, which would cause the primer layer 11 to disappear and reduce adhesion. Furthermore, if the surface to which the decorative sheet 1 is to be applied has significant irregularities, it is possible to improve the adhesion between the primer layer 11 and the application surface by first sealing the surface with putty and applying a primer as needed.

[0014] <Atomic layer> The base layer 12 is the base layer of the decorative sheet 1. It absorbs unevenness and steps on the application surface to improve the finish of the decorative sheet 1, and also serves to conceal the color and pattern of the application surface. Furthermore, the base layer 12 suppresses scratches on the decorative sheet 1 and gives the decorative sheet a soft and pleasant feel. Furthermore, the base layer 12 has a base material layer 12A and a skin layer 12B. In the first embodiment, as an example, a configuration in which skin layers 12B are laminated on both sides of the base layer 12A (the lower surface and the upper surface in Figure 1) will be described.

[0015] (base material layer) The base layer 12A is a layer formed by mixing an inorganic pigment for coloring (e.g., white pigment) with a resin material (e.g., polypropylene resin). The thickness of the base layer 12A is set, for example, within the range of 50 [μm] to 200 [μm]. The reason for setting the thickness of the base layer 12A within the range of 50 [μm] to 200 [μm] is explained below. Setting the thickness of the base layer 12A to 50 [μm] or more makes it possible to fully achieve the opacity required for the decorative sheet 1. In addition, it provides sufficient strength required for the base layer 12A, making it possible to suppress deterioration of scratch resistance. On the other hand, setting the thickness of the base layer 12A to 200 [μm] or less makes it possible to suppress defects such as whitening and cracking when the decorative sheet 1 is bent. In the first embodiment, as an example, a configuration in which the thickness of the substrate layer 12A is set within the range of 80 [μm] to 160 [μm] will be described.

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

[0017] Among the above-mentioned thermoplastic resins, in view of the increasing social concern about environmental problems in recent years, it is preferable to use a non-halogen-based thermoplastic resin as the thermoplastic resin. In particular, from the aspects 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, especially a polyolefin-based resin as the non-halogen-based thermoplastic resin. For example, as the polyolefin-based resin, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

[0018] In the base material layer 12A, if necessary, for example, one or more selected from various additives such as colorants, 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 can be added. The base material layer 12A preferably has concealability to conceal the pasting surface (such as a wall surface) of the decorative sheet 1 from the surface (upper surface) of the decorative sheet 1. The base material layer 12A preferably contains a colorant. As the colorant, it is preferable to use a known inorganic pigment (for example, titanium oxide which is a white pigment for imparting concealability). When the concealability is low, the pattern formed on the pasting surface of the decorative sheet 1 is transmitted, which is not preferable. Therefore, by containing an inorganic pigment in the base material layer 12A, a decorative sheet 1 with good concealability can be obtained.

[0019] (Skin layer) The skin layer 12B is a layer containing a resin material and a nano-sized nucleating agent. The thickness of the skin layer 12B is set, for example, within the range of 1 [μm] or more and 50 [μm] or less.

[0020] The reason for setting the thickness of the skin layer 12B within the range of 1 [μm] or more and 50 [μm] or less will be explained below. When the thickness of the skin layer 12B is 1 [μm] or more, the scratch resistance of the decorative sheet 1 becomes sufficiently high. Also, when the thickness of the skin layer 12B is 50 [μm] or less, the flexibility of the decorative sheet 1 does not become excessively high, so even if the surface to which the decorative sheet 1 is attached is not flat, it is possible to install the decorative sheet 1 in close contact with the surface. In the first embodiment, as an example, a configuration in which the thickness of the skin layer 12B is set within the range of 2 [μm] to 10 [μm] will be described.

[0021] (Resin material that forms skin layer 12B) As the resin material for forming the skin layer 12B, for example, a thermoplastic resin can be used. There are no particular restrictions on the thermoplastic resin, and the same resin material as the base layer 12A can be used. However, since the base layer 12A and the skin layer 12B are formed by co-extrusion, it is preferable that the resin used as the material for the base layer 12A and the resin used as the material for the skin layer 12B are the same.

[0022] (Nucleating agent) The nucleating agent is added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated within a vesicle having a single-layer outer membrane. Alternatively, the nucleating agent may be encapsulated within the vesicle with a portion of the nucleating agent exposed. Furthermore, the nucleating agent improves the degree of crystallinity with the resin material, so the degree of crystallinity of the skin layer 12B is improved compared to when the nucleating agent is not added. For this reason, in the first embodiment, it is possible to improve the scratch resistance (scratch resistance) of the decorative sheet 1 compared to when the nucleating agent is not added. Furthermore, it is preferable that the nucleating agent has an average particle size of 1 / 2 or less of the wavelength range of visible light. Specifically, since the wavelength range of visible light is within the range of 400 nm to 750 nm, it is preferable that the nucleating agent has an average particle size wavelength range of 375 nm or less.

[0023] Furthermore, because the nucleating agent has an extremely small particle size, the number of nucleating agents per unit volume and their surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between nucleating agent particles becomes smaller. Therefore, when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the growing edge of the crystal immediately comes into contact with the edge of the growing crystal from the surface of other nucleating agent particles adjacent to that particle. This inhibits the growth of each crystal, stopping the growth of each crystal. As a result, it is possible to reduce the average particle size of spherulites in the crystalline portion of the crystalline resin, for example, to 1 [μm] or less. As a result, it is possible to make the decorative sheet 1 a high-hardness resin film with a high degree of crystallinity, and because the stress concentration between spherulites that occurs during bending is efficiently dispersed, it is possible to form a decorative sheet 1 that suppresses cracking and whitening during bending.

[0024] 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 nucleating agent vesicles are added, the dispersibility in the resin improves, so the number of crystal nuclei relative to the amount of nucleating agent added increases significantly compared to when the nucleating agent is simply added. As a result, the average particle size of spherulites in the crystalline part of the resin becomes smaller, making it possible to suppress cracking and whitening during bending of the decorative sheet 1. Therefore, by adding nucleating agent vesicles, it is possible to further increase the degree of crystallinity, making it possible to achieve both improved elastic modulus and improved processability.

[0025] The skin layer 12B is formed from a resin material to which a nucleating agent is added, for example, in an amount preferably between 0.05 parts by mass and 0.5 parts by mass, and more preferably between 0.1 parts by mass and 0.3 parts by mass, per 100 parts by mass of polypropylene resin as the main component. When using nucleating agent vesicles, the amount of nucleating agent added to the resin material is the amount added in terms of the nucleating agent in the nucleating agent vesicles. Here, "main component" refers to the resin material that accounts for 50% or more by mass of the resin material constituting the skin layer 12B.

[0026] The reason for setting the amount of nucleating agent to be within the range of 0.05 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of polypropylene resin, which is the main component, is explained below. If the amount of nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene may not improve sufficiently, and the scratch resistance of the skin layer 12B may not improve sufficiently. Conversely, if the amount of nucleating agent added exceeds 0.5 parts by mass, the excess nuclei may inhibit spherulite growth in the polypropylene, resulting in insufficient improvement in the crystallinity of the polypropylene and consequently, insufficient improvement in the scratch resistance of the skin layer 12B.

[0027] Furthermore, methods for nano-sizing the nucleating agent include, for example, solid-phase methods, liquid-phase methods, gas-phase methods, and supercritical reverse-phase evaporation methods. Supercritical reverse-phase evaporation is preferred as the method for nano-sizing the nucleating agent. The solid-phase method is a technique for obtaining nano-sized particles from a nucleating agent, primarily through mechanical grinding. Examples of solid-phase methods that can be used include ball mills, bead mills, rod mills, colloid mills, conical mills, disc mills, hammer mills, and jet mills.

[0028] Liquid-phase methods are techniques for synthesizing or crystallizing nano-sized particles in a nucleating agent or a solution containing a dissolved nucleating agent. Examples of liquid-phase methods include crystallization, coprecipitation, sol-gel, liquid-phase reduction, and hydrothermal synthesis. Gas-phase methods are techniques for synthesizing and crystallizing nano-sized particles from nucleating agents or gases and vapors formed by nucleating agents. Examples of gas-phase methods include electric furnace methods, chemical flame methods, laser methods, and thermal plasma methods.

[0029] Supercritical reverse-phase evaporation is a method for producing capsules (nano-sized vesicles) containing a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state above the critical temperature (30.98 [°C]) and critical pressure (7.3773 ± 0.0030 [MPa]), while carbon dioxide under temperature or pressure conditions above the critical point refers to carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical conditions.

[0030] Furthermore, the specific nano-processing using the supercritical reverse-phase evaporation method involves first injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipid as an outer film-forming material, and a nucleating agent as an encapsulating material, and then stirring the mixture. This generates an emulsion of supercritical carbon dioxide and the aqueous phase. Next, by reducing the pressure, the 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 single layer film. By using supercritical reverse-phase evaporation, it becomes possible to easily produce single-layer capsules, unlike conventional encapsulation methods where a multi-layer outer film forms on the surface of nucleating agent particles, thus enabling the preparation of smaller diameter capsules. Furthermore, nucleating agent vesicles can be prepared by methods such as the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse-phase evaporation method, freeze-thaw method, and supercritical reverse-phase evaporation method. Among these methods, nucleating agent vesicles are particularly preferably prepared using the supercritical reverse-phase evaporation method.

[0031] The outer membrane constituting the nucleating agent vesicle is, for example, composed of a single layer membrane. Alternatively, the outer membrane constituting the nucleating agent vesicle may be composed of a substance containing biolipids, such as phospholipids. In the following explanation, nucleating agent vesicles whose outer membrane is composed of substances containing biolipids such as phospholipids may be referred to as "nucleating agent liposomes." As phospholipids constituting the outer membrane, for example, glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soy lecithin, and hydrogenated soy lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol can be used.

[0032] Other substances that can form the outer membrane of the vesicle include, for example, nonionic surfactants or dispersants such as mixtures of nonionic surfactants with cholesterol or triacylglycerols. Nonionic surfactants can be one or more of the following: polyglycerin ether, dialkylglycerin, 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-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. Examples of cholesterol compounds that can be used include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or cholecalciferol.

[0033] Furthermore, the outer membrane of the liposome may be formed from a mixture of phospholipids and a dispersant. In the first embodiment, it is preferable that the nucleating agent vesicle be a radical scavenging liposome having an outer membrane formed using phospholipids. By forming the outer membrane of the liposome using phospholipids, it is possible to improve the compatibility between the resin material, which is the main component of the decorative sheet 1, and the vesicle. The nucleating agent is not particularly limited as long as it is a substance that acts as a starting point for crystallization when the resin crystallizes. Examples of nucleating agents that can be used include metal phosphate salts, metal benzoate salts, metal pimephosphate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, to obtain the maximum effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoate salts, metal pimephosphate salts, and metal rosin salts, which are non-melting types and are expected to have good transparency. However, if the transparency of the material itself can be achieved by the nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. In addition, molten benzylidene sorbitol may be appropriately mixed with the non-melting nucleating agent.

[0034] As described above, the decorative sheet 1 of the first embodiment contains a resin material and a nucleating agent in its skin layer 12B. Furthermore, in the decorative sheet 1 of the first embodiment, when forming the skin layer 12B, the nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. By adding the nucleating agent to the resin composition while it is encapsulated in vesicles, it is possible to dramatically improve the dispersibility of the nucleating agent in the resin material, i.e., in the skin layer 12B. On the other hand, it is conceivable that directly identifying the nucleating agent encapsulated in vesicles based on the structure and properties of the finished decorative sheet 1 may be difficult depending on the circumstances, and can be considered impractical. The reason for this is explained below.

[0035] The nucleating agent added in vesicle form exhibits high dispersibility and is dispersed even in the laminated state which is the precursor of the fabricated decorative sheet 1, remaining highly dispersed in the skin layer 12B. However, in the manufacturing process of decorative sheet 1, the laminate is usually subjected to various treatments such as compression and hardening, and these treatments may cause the outer membrane of the vesicles containing the nucleating agent to be fractured or chemical reactions to occur. Therefore, depending on the processing steps of decorative sheet 1, the degree to which the outer membrane of the nucleating agent is fractured or the state in which chemical reactions occur in the finished decorative sheet 1 may vary, and there is a high possibility that the nucleating agent is not contained (encased) by the outer membrane. Furthermore, if the nucleating agent is not contained by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself within a numerical range, and it may also be difficult to determine whether the constituent material of the fractured outer membrane is the outer membrane of the vesicles or a material added separately from the nucleating agent. Thus, although this disclosure differs from conventional methods in that the nucleating agent is formulated in a highly dispersed manner within the decorative sheet 1, it is conceivable that it may be impractical to determine, based on measurements and analysis of the structure and properties of the decorative sheet 1, whether this is due to the nucleating agent being added in the form of vesicles.

[0036] <Colored layer> The colored layer 13 is laminated on one side of the base layer 12 (the upper side in Figure 1) and is a layer that imparts the desired color, pattern (wood grain pattern, stone pattern, fabric pattern, abstract pattern, geometric pattern), letters, and symbols to the decorative sheet 1. Furthermore, the colored layer 13 is, for example, a layer containing a matrix and a coloring agent such as a dye or pigment. For the colored layer 13, it is possible to use a printing ink or coating agent in which the matrix and a coloring agent such as a dye or pigment are dissolved and dispersed in a solvent. The thickness of the colored layer 13 is preferably within the range of 3 [μm] to 20 [μm]. When the thickness of the colored layer 13 is within the range of 3 [μm] to 20 [μm], the printing can be made clearer. In addition, the printability when manufacturing the decorative sheet 1 is improved, making it possible to reduce manufacturing costs.

[0037] (matrix) As the matrix, various synthetic resins such as oily nitrate resins, two-component urethane resins, acrylic resins, styrene resins, polyester resins, urethane resins, polyvinyl resins, alkyd resins, epoxy resins, melamine resins, fluororesins, silicone resins, and rubber resins, or mixtures and copolymers thereof, can be used.

[0038] (Coloring agent) The inorganic pigment used as a coloring agent for the colored layer 13 is not particularly limited, but for example, natural inorganic pigments and synthetic inorganic pigments can be used. Natural inorganic pigments can include, for example, earth-based pigments, calcined earth, and mineral pigments. Synthetic inorganic pigments can include, for example, oxide pigments, hydroxide pigments, sulfide pigments, silicate pigments, phosphate pigments, carbonate pigments, metal powder pigments, and carbon pigments. Mixed pigments can also be used, which consist of one or more natural or synthetic inorganic pigments. More specifically, inorganic pigments that can be used include, for example, carbon black, titanium white, zinc oxide, iron oxide, yellow lead, Prussian blue, and cadmium red.

[0039] Furthermore, organic pigments may be used as colorants constituting the colored layer 13. Examples of organic pigments include carbon black, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments, or mixtures thereof. Inorganic 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.

[0040] Furthermore, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the colored layer 13 to impart various functions. Here, the colored layer 13 can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, and inkjet printing. These printing methods may be selected separately depending on the layer to be formed, but it is more efficient to select the same method and process them all at once.

[0041] <Top coat layer> The top coat layer 14 is laminated on one side of the colored layer 13 (the upper side in Figure 1) and forms the outermost surface of the decorative sheet 1. The top coat layer 14 is also provided to protect the decorative sheet 1 and to adjust the gloss generated on the surface of the decorative sheet 1. Furthermore, the top coat layer 14 has a lower top coat layer 14A and an upper top coat layer 14B. If the decorative sheet 1 is configured without a colored layer 13, a topcoat layer 14 is laminated onto the skin layer 12B.

[0042] The lower topcoat layer 14A is laminated on one side of the colored layer 13 (the upper side in Figure 1) and is the layer opposite to the raw material layer 12. The detailed composition of the lower topcoat layer 14A will be described later. The upper topcoat layer 14B is a layer laminated onto one side (the upper side in Figure 1) of the lower topcoat layer 14A. The detailed composition of the upper topcoat layer 14B will be described later.

[0043] The thickness of the topcoat layer 14 (the total thickness of the lower topcoat layer 14A and the upper topcoat layer 14B) is within the range of 4 [μm] to 12 [μm]. When the thickness of the topcoat layer 14 is 4 [μm] or more, the effect of improving scratch resistance is enhanced. Furthermore, when the thickness of the topcoat layer 14 is 12 [μm] or less, it is possible to suppress the occurrence of cracks and fractures during bending and to suppress the deterioration of the design and weather resistance of the decorative sheet 1. In the first embodiment, as an example, we will describe a case where the thickness of the top coat layer 14 is within the range of 5 [μm] to 10 [μm].

[0044] Furthermore, the topcoat layer 14 may contain a gloss adjuster for gloss adjustment. Any commercially available, known material can be used as the gloss adjuster; for example, fine particles made of inorganic materials such as silica, glass, alumina, calcium carbonate, or barium sulfate may be used. It is also possible to use fine particles made of organic materials such as acrylic as the gloss adjuster. However, when high transparency is required, it is preferable to use highly transparent fine particles of silica, glass, or acrylic as the gloss adjuster. In particular, among fine particles of silica or glass, gloss adjusters with low bulk density, which are not solid spherical particles but rather fine primary particles that have undergone secondary aggregation, exhibit a high matting effect relative to the amount added. Therefore, by using a gloss adjuster with low bulk density, it is possible to reduce the amount of gloss adjuster added.

[0045] Furthermore, it is preferable that the gloss adjuster contained in the top coat layer 14 is adjusted so that the gloss level of the decorative sheet 1 is 10 or less. As mentioned above, if the base layer 12A contains a gloss adjuster, it is necessary to adjust the gloss level of the entire decorative sheet 1 so that it is 10 or less. When the gloss level of the decorative sheet 1 is 10 or less, a decorative sheet 1 with a subdued appearance is obtained. This improves harmony with furniture and fixtures with patterns, and provides a more suitable appearance for decorative sheets used on building components that are pre-installed in the building, such as door frames, window frames, baseboards, trim, and moldings.

[0046] Furthermore, in order to impart various functions to the topcoat layer 14, the topcoat layer 14 may contain functional additives such as antibacterial agents, antiviral agents, and antifungal agents. In addition, the topcoat layer 14 may contain ultraviolet absorbers and light stabilizers as needed. As ultraviolet absorbers, for example, benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers can be used. As light stabilizers, hindered amine-based light stabilizers can be used.

[0047] (Lower topcoat layer) The lower topcoat layer 14A is a layer that provides scratch resistance to the decorative sheet 1. The thickness of the lower topcoat layer 14A is within the range of 1 [μm] to 8 [μm].

[0048] When the thickness of the lower topcoat layer 14A is 1 [μm] or more, the effect of improving stain resistance is enhanced. In the first embodiment, as an example, a case will be described in which the thickness of the lower topcoat layer 14A is within the range of 3 [μm] to 5 [μm]. When the thickness of the lower topcoat layer 14A is 3 [μm] or more, the effect of improving stain resistance is greater compared to when the thickness of the lower topcoat layer 14A is 2 [μm] or more.

[0049] The lower topcoat layer 14A is formed using a resin material. The main component of the resin material forming the lower topcoat layer 14A can be appropriately selected from, for example, polyurethane-based, acrylic silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, amino alkyd-based, and urea-based resin materials. The form of the resin material is not particularly limited, and can be aqueous, emulsion-based, solvent-based, etc. The curing method for the resin material can also be appropriately selected from one-component type, two-component type, ultraviolet curing method, thermosetting method, photocuring type, etc.

[0050] As the main component of the lower topcoat layer 14A, a urethane-based resin material using isocyanate is preferred from the viewpoint of workability, cost, and the cohesive strength of the resin itself. For the isocyanate, it is possible to appropriately select and use curing agents such as adducts, burettes, and isocyanurates, which are derivatives of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis(isocyanate-methyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc. In particular, 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, to improve surface hardness, it is preferable to use resins that harden with active energy rays such as ultraviolet light or electron beams. These resins can be used in combination with each other; for example, by using a hybrid type of thermosetting and photocuring resins, surface hardness can be improved, curing shrinkage can be suppressed, and adhesion can be improved. In the first embodiment, as an example, a case in which the lower topcoat layer 14A is formed using an acrylic urethane material will be described.

[0051] (Upper topcoat layer) The upper topcoat layer 14B is a layer that provides stain resistance to the decorative sheet 1. The thickness of the upper topcoat layer 14B is within the range of 1 [μm] to 9 [μm].

[0052] When the thickness of the upper topcoat layer 14B is 1 [μm] or more, the effect of improving stain resistance is enhanced. In the first embodiment, as an example, a case will be described in which the thickness of the upper topcoat layer 14B is within the range of 2 [μm] to 9 [μm]. When the thickness of the upper topcoat layer 14B is 2 [μm] or more, the effect of improving stain resistance is greater compared to when the thickness of the upper topcoat layer 14B is 1 [μm] or more.

[0053] The lower topcoat layer 14A is formed using a silicone-modified acrylic resin. As the silicone-modified acrylic resin, for example, a two-component curing type silicone-modified acrylic resin can be used.

[0054] <Manufacturing method for decorative sheets> The manufacturing method for decorative sheet 1 will be described below. A resin material such as polypropylene resin is melt-kneaded with inorganic pigments as needed to obtain a resin material for the base layer 12A that contains inorganic pigments. Next, nucleating agent vesicles are mixed with the resin material such as polypropylene resin to obtain a resin material containing nucleating agent vesicles for the skin layer 12B. Subsequently, the heated and melted resin material for the base layer 12A and the resin material containing nucleating agent vesicles for the skin layer 12B are simultaneously extruded from an extruder so that they are stacked in the order of, for example, nucleating agent vesicle-containing material / resin material for the base layer / nucleating agent vesicle-containing material, and cooled with a cooling roll to form a laminated film.

[0055] Next, a resin material such as urethane resin is applied to the back surface of the raw material layer 12 to form a primer layer 11. Furthermore, a resin material containing a coloring pigment is applied to the side of the raw material layer 12 facing the colored layer 13, and the applied resin material is cured to form the colored layer 13. Then, a resin material such as acrylic urethane resin is applied to the side of the colored layer 13 facing the topcoat layer 14, and the applied resin material is cured to form the lower topcoat layer 14A. Next, a silicone-modified acrylic resin is applied as a resin material to the side of the lower topcoat layer 14A facing the upper topcoat layer 14B, and the applied silicone-modified acrylic resin is cured to form the upper topcoat layer 14B. Furthermore, when forming each layer, surface treatments such as corona treatment may be applied to the coated surface. Based on the above, a decorative sheet 1 comprising a primer layer 11, a raw material layer 12, a coloring layer 13, and a topcoat layer 14 (lower topcoat layer 14A, upper topcoat layer 14B) is manufactured.

[0056] The first embodiment described above is merely one example of the present invention, and the present invention is not limited to the first embodiment described above. Various modifications can be made to forms other than this embodiment, as long as they do not depart from the technical spirit of the present invention, depending on the design and other factors.

[0057] (Effects of the first embodiment) The decorative sheet 1 of the first embodiment can achieve the effects described below. (1) The material comprises a base layer 12A containing a resin material, a skin layer 12B laminated on at least one surface of the base layer 12A and containing a resin material and a nucleating agent or inorganic particles, and a top coat layer 14 laminated on the skin layer 12B. The top coat layer 14 is formed using a silicone-modified acrylic resin. Therefore, the topcoat layer 14, which is formed using silicone-modified acrylic resin, functions as a layer to improve stain resistance. As a result, it becomes possible to provide a decorative sheet 1 that can improve stain resistance.

[0058] (2) The system further comprises a colored layer 13 positioned between the top coat layer 14 and the base layer 12. As a result, it becomes possible to impart the desired color to the decorative sheet 1.

[0059] (3) The thickness of the base layer 12A is within the range of 80 [μm] to 160 [μm]. As a result, compared to the case where the thickness of the base layer 12A is less than 80 [μm], it becomes possible to fully exhibit the opacity required for the decorative sheet 1. In addition, compared to the case where the thickness of the base layer 12A is less than 80 [μm], the structure has sufficient strength required for the base layer 12A, and it becomes possible to suppress deterioration of scratch resistance. Furthermore, compared to the case where the thickness of the base layer 12A exceeds 160 [μm], it becomes possible to suppress defects such as whitening and cracking when the decorative sheet 1 is bent.

[0060] (4) The top coat layer 14 has a lower top coat layer 14A facing the base layer 12 and an upper top coat layer 14B laminated on the lower top coat layer 14A. Furthermore, of the lower top coat layer 14A and the upper top coat layer 14B, at least the upper top coat layer 14B is formed using a silicone-modified acrylic resin. As a result, the upper topcoat layer 14B, which is formed using silicone-modified acrylic resin, functions as a layer to improve stain resistance, making it possible to provide a decorative sheet 1 that can improve stain resistance.

[0061] (5) The thickness of the lower topcoat layer 14A is within the range of 3 [μm] to 5 [μm]. As a result, it becomes possible to improve the stain resistance of the decorative sheet 1.

[0062] (6) The thickness of the upper topcoat layer 14B is within the range of 2 [μm] to 9 [μm]. As a result, it becomes possible to improve the stain resistance of the decorative sheet 1.

[0063] (7) The thickness of the top coat layer 14 is within the range of 5 [μm] to 10 [μm]. As a result, it becomes possible to improve the scratch resistance and stain resistance of the decorative sheet 1. In addition, it becomes possible to suppress the deterioration of the design and weather resistance of the decorative sheet 1. [Examples]

[0064] Referring to the first embodiment, the decorative sheets of Examples 1 to 8 and the decorative sheets of Comparative Examples 1 and 2 will be described below.

[0065] (Example 1) A single-color decorative sheet was created using the following procedure. A white polypropylene resin was mixed with a white pigment and a weather-resistant agent, melted, and kneaded to obtain a white polypropylene resin containing 30% by mass of white pigment and 1% by mass of weather-resistant agent. Next, a nucleating agent vesicle was mixed with a transparent polypropylene resin to obtain a nucleating agent vesicle-containing polypropylene resin containing 0.1% by mass of nucleating agent vesicles. Subsequently, the heated and melted white polypropylene resin and the nucleating agent vesicle-containing polypropylene resin were simultaneously extruded from an extruder in the order of nucleating agent vesicle-containing polypropylene resin / white polypropylene resin / nucleating agent-containing polypropylene resin, and cooled with a cooling roll to form a laminated film. This formed a raw material layer with a thickness of 100 μm, having a white base layer and transparent skin layers provided on both sides of the base layer. At this time, the extrusion amount of each resin was adjusted in the extruder so that the ratio of the thickness of one skin layer to the thickness of the base layer to the thickness of the other skin layer was 0.5:9:0.5.

[0066] Next, a two-component urethane resin with a solid content of 1 g / m² is applied to the other side of the raw material layer using gravure printing. 2 A primer layer was formed by coating the material in the following manner. Furthermore, after corona treatment was applied to one side of the raw material layer, a two-component acrylic curing resin (DIC Graphics Co., Ltd., acrylic urethane resin) was applied so that the thickness after curing would be 3 [μm], and the applied two-component acrylic curing resin was cured to form the lower topcoat layer. Next, a two-component silicone-modified acrylic resin was applied to the side of the lower topcoat layer opposite to the surface facing the raw material layer, so that the cured thickness would be 5 μm. The applied silicone-modified acrylic resin was then cured to form the upper topcoat layer. Based on the above, the decorative sheet of Example 1 was formed.

[0067] (Example 2) The decorative sheet of Example 2 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 5 [μm] and the thickness of the upper topcoat layer was 3 [μm]. (Example 3) The decorative sheet of Example 3 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 2 [μm] and the thickness of the upper topcoat layer was 6 [μm]. (Example 4) The decorative sheet of Example 4 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 1 [μm] and the thickness of the upper topcoat layer was 9 [μm].

[0068] (Example 5) The decorative sheet of Example 5 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 5 [μm] and the thickness of the upper topcoat layer was 2 [μm]. (Example 6) The decorative sheet of Example 6 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 6 [μm] and the thickness of the upper topcoat layer was 2 [μm]. (Example 7) The decorative sheet of Example 7 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 8 [μm] and the thickness of the upper topcoat layer was 1 [μm]. (Example 8) The decorative sheet of Example 8 was formed in the same manner as in Example 1, except that one side of the raw material layer was subjected to corona treatment, and then a two-component curable silicone-modified acrylic resin was applied to a thickness of 5 μm after curing, and the applied silicone-modified acrylic resin was cured to form a topcoat layer consisting of only one layer.

[0069] (Comparative Example 1) A decorative sheet of Comparative Example 1 was formed in the same manner as in Example 1, except that a two-component acrylic curing resin (acrylic urethane resin, manufactured by DIC Graphic Co., Ltd.) was applied to the side of the lower topcoat layer opposite to the surface facing the raw material layer, so that the cured thickness was 5 [μm], and the applied acrylic urethane resin was cured to form the upper topcoat layer. (Comparative Example 2) The decorative sheet of Comparative Example 3 was formed in the same manner as in Example 1, except that the thickness of the lower topcoat layer was 10 [μm] and the thickness of the upper topcoat layer was 0.5 [μm].

[0070] (Performance evaluation, evaluation results) The decorative materials of Examples 1 to 8 and the decorative materials of Comparative Examples 1 and 2 were subjected to a magic wipe test, scratch test, scratch hardness test, and blocking test, respectively.

[0071] <Magic Wipe Test> The stain resistance of the decorative sheet was evaluated by drawing lines and other designs on it with a felt-tip pen, wiping the marks with a cloth, and then visually observing the results. Stain resistance was evaluated as follows: "○" if there was no residue left after wiping, "△" if there was some residue left after wiping, and "×" if it could not be wiped off.

[0072] <Scratch Test> A coin scratch test was performed on the decorative sheet, and the load at which no continuous scratches appeared on the surface of the decorative sheet was measured. In the scratch test, a 10-yen coin was placed on the surface of the decorative sheet, and the test was started with a load of 1 kg, and the load was increased in increments of 1 kg up to a load of 4 kg. In the scratch test, a score of "○" was given if no continuous scratches appeared on the surface of the decorative sheet under a load of 1 [Kg] or more, and a score of "△" was given if slight scratches appeared on the surface of the decorative sheet under a load of 1 [Kg]. Furthermore, in the scratch test, a score of "×" was given if continuous scratches appeared on the surface of the decorative sheet under a load of 1 [Kg].

[0073] <Scratch hardness test> A scratch hardness (pencil method) test, as specified in "JIS K5600-5-4:1999," was performed on the decorative sheet, and the hardness of the hardest pencil (pencil hardness) in the test that did not leave a scratch on the surface of the decorative sheet was measured. In the scratch hardness test, a score of "○" was given if no scratches were left on the surface of the decorative sheet with a 2B pencil, and a score of "△" was given if slight scratches were left on the surface of the decorative sheet with a 2B pencil. Furthermore, in the scratch hardness test, a score of "×" was given if continuous scratches were left on the surface of the decorative sheet with a 2B pencil.

[0074] <Blocking Test> By folding the decorative sheet into thirds, the opposing topcoat layers and the topcoat layer and primer layer are layered on the folded decorative sheet, and 2 [Kg / cm²] 2 After placing a weight on top and leaving it in a 40°C environment for 3 days, the degree of adhesion to the contacting layers was checked. In the blocking test, a "○" was used to indicate that no blocking occurred, and a "×" was used to indicate that blocking occurred.

[0075] [Table 1]

[0076] Using the method described above, various performance tests were evaluated, and the decorative materials of Examples 1 to 8 showed excellent performance in all evaluation tests. On the other hand, the decorative materials of Comparative Examples 1 and 2 were unable to show excellent performance in all evaluation tests. [Explanation of symbols]

[0077] 1…Decorative sheet, 11…Primer layer, 12…Base layer, 12A…Base material layer, 12B…Skin layer, 13…Coloring layer, 14…Topcoat layer, 14A…Lower topcoat layer, 14B…Upper topcoat layer

Claims

1. A base layer having a base layer containing a resin material, and a skin layer laminated on at least one surface of the base layer and containing a resin material and a nucleating agent or inorganic particles, The skin layer comprises a top coat layer laminated on the skin layer, The topcoat layer comprises a lower topcoat layer facing the base material layer and an upper topcoat layer laminated on the lower topcoat layer. Of the aforementioned lower topcoat layer and upper topcoat layer, at least the upper topcoat layer is formed using a silicone-modified acrylic resin. The thickness of the aforementioned lower topcoat layer is within the range of 1 μm to 8 μm. The decorative sheet having a top coat layer thickness of 1 μm or more and 9 μm or less.

2. The decorative sheet according to claim 1, further comprising a colored layer disposed between the top coat layer and the base layer.

3. The decorative sheet according to claim 1 or claim 2, wherein the thickness of the base material layer is in the range of 50 μm or more and 200 μm or less.

4. The decorative sheet according to claim 3, wherein the thickness of the base material layer is in the range of 80 μm or more and 160 μm or less.

5. The decorative sheet according to any one of claims 1 to 4, wherein the thickness of the lower topcoat layer is in the range of 3 μm or more and 5 μm or less.

6. The decorative sheet according to any one of claims 1 to 5, wherein the thickness of the upper top coat layer is in the range of 2 μm or more and 9 μm or less.

7. The decorative sheet according to any one of claims 1 to 6, wherein the thickness of the top coat layer is in the range of 4 μm or more and 12 μm or less.

8. The decorative sheet according to claim 7, wherein the thickness of the top coat layer is in the range of 5 μm or more and 10 μm or less.

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