JP7615529B2 - Decorative sheet and method for producing the same - Google Patents

Description

This disclosure relates to decorative sheets for use on, for example, floor surfaces of buildings, and methods for manufacturing such decorative sheets.

Conventionally, flooring materials installed in spaces where people walk in shoes are prone to being damaged by hard objects such as shoe soles, shoe heels, and pebbles, unlike flooring materials installed in spaces where people do not walk in shoes, such as living rooms. For this reason, solid wood, whose surface can be repaired by polishing or painting, has traditionally been used as flooring materials.

On the other hand, in recent years, it has become difficult to obtain solid wood, and the surface repair process itself takes time and money, so it has been proposed to use a laminate with a resin surface protection layer with a specified hardness as a flooring material (Patent Document 1).

JP 2016-211367 A

However, flooring materials having a resin surface protective layer with a certain hardness may not have sufficient scratch resistance on the surface.
The present disclosure has been made in view of such problems, and an object of the present disclosure is to obtain a decorative sheet having high scratch resistance.

In order to solve the above problems, a decorative sheet according to one embodiment of the present disclosure is characterized by comprising a substrate layer made of a resin material and a highly scratch-resistant layer provided on one side of the substrate layer and containing a resin material and a nucleating agent or inorganic particles.

A method for producing a decorative sheet according to another aspect of the present disclosure is characterized in that a nucleating agent is encapsulated in a vesicle to produce a nucleating agent vesicle formed by vesiculating the nucleating agent, and a highly scratch-resistant layer is formed on one side of a substrate layer formed using a first resin material using a second resin material containing the nucleating agent vesicle.

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

FIG. 1 is a cross-sectional view showing one configuration example of a decorative sheet according to a first embodiment of the present disclosure. FIG. 2 is a cross-sectional view showing another configuration example of the decorative sheet according to the first embodiment of the present disclosure. FIG. 2 is a cross-sectional view showing one configuration example of a decorative sheet according to a second embodiment of the present disclosure. FIG. 2 is a cross-sectional view showing one configuration example of a decorative sheet according to a third embodiment of the present disclosure.

The present disclosure will be described below through embodiments, but the following embodiments do not limit the invention according to the claims. In addition, not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention. In addition, the drawings are schematic diagrams of the invention according to the claims, and the dimensions of the width, thickness, etc. of each part are different from the actual dimensions, and the ratios between these dimensions are also different from the actual dimensions.
Hereinafter, each aspect of each embodiment of the present disclosure will be described with reference to the drawings.

1. First embodiment A laminate according to a first embodiment of the present disclosure will be described. The decorative sheet 1 according to this embodiment is, for example, a decorative sheet that is applied to a floor material of a building, particularly a floor material in a space where people walk with shoes on. In the following description, the side of the decorative sheet 1 that comes into contact with shoes may be referred to as "upper" and the side of the decorative sheet 1 that comes into contact with the floor surface may be referred to as "lower".

(1.1) Basic structure of the decorative sheet Fig. 1 is a cross-sectional view for explaining one configuration example of the decorative sheet 1 according to the embodiment of the present disclosure. As shown in Fig. 1, the decorative sheet 1 includes a primer layer 11, a colored layer 12, a design layer 13, a first adhesive layer 14, a base layer 15, a second adhesive layer 16, a highly scratch-resistant layer 17, and a top coat layer 18. The decorative sheet 1 is configured by laminating the primer layer 11, the colored layer 12, the design layer 13, the first adhesive layer 14, the base layer 15, the second adhesive layer 16, the highly scratch-resistant layer 17, and the top coat layer 18 in this order.

The colored layer 12 is a layer that imparts design with a desired color to the decorative sheet 1 and conceals the color and pattern of the flooring material to which the decorative sheet 1 is attached. The pattern layer 13 is provided above the colored layer 12 and is a layer that imparts design with a desired pattern to the decorative sheet 1. The base layer 15 functions as a buffer layer and is a layer that absorbs unevenness and steps of the underlying flooring material to improve the finish of the decorative sheet 1. The high scratch resistance layer 17 is a layer that is provided on the upper surface side of the decorative sheet 1 and is a layer that suppresses scratches caused on the decorative sheet 1 by the heel of a shoe, stones, etc. The top coat layer 18 is a layer that is provided on the uppermost surface of the decorative sheet 1 that comes into contact with shoes, and is provided to protect the decorative sheet 1 and adjust the gloss of the surface of the decorative sheet 1. The first adhesive layer 14 is a layer that bonds the colored layer 12 and the pattern layer 13 to the base material layer 15, and the second adhesive layer 16 is a layer that bonds the base material layer 15 to the highly scratch-resistant layer 17.
Each of the colored layer 12, the design layer 13, the first adhesive layer 14, the base layer 15, the second adhesive layer 16, the highly scratch-resistant layer 17 and the top coat layer 18 will be described in detail below.

<Highly scratch-resistant layer>
The highly scratch-resistant layer 17 is a layer containing a resin material and a nucleating agent that improves the crystallinity of the resin material. In this embodiment, the nucleating agent is added to the resin material in the form of a nucleating agent vesicle that is encapsulated in an outer membrane and turned into a vesicle.
The thickness of the highly scratch-resistant layer 17 is preferably, for example, 70 μm to 110 μm, and more preferably 85 μm to 95 μm. When the thickness of the highly scratch-resistant layer 17 is 70 μm or more, the scratch resistance of the highly scratch-resistant layer 17 against the heels of shoes, pebbles, etc. is sufficiently high. Also, when the thickness of the highly scratch-resistant layer 17 is 110 μm or less, the bendability of the decorative sheet 1 is not too high more than necessary, and the decorative sheet 1 can be applied in a state of close contact with the floor material even if the floor material to which the decorative sheet 1 is attached is not flat.

(Resin material)
The resin material constituting the highly scratch-resistant layer 17 is, for example, a thermoplastic resin. There is no particular limitation on the thermoplastic resin, and materials similar to the thermoplastic resins used as base layers 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; and olefins 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). Examples of the resin that can be used include polyolefin 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; and mixtures, copolymers, composites, laminates, and the like of two or more of these resins.

In particular, in light of the recent growing social interest in environmental issues, it is not preferable to use thermoplastic resins containing chlorine (halogen), such as polyvinyl chloride resins, as thermoplastic resins, and it is preferable to use non-halogen thermoplastic resins. In particular, from the standpoints of various physical properties, processability, versatility, and economy, it is most preferable to use polyester resins (amorphous or biaxially oriented) or polyolefin resins, especially polyolefin resins, as non-halogen thermoplastic resins. For example, it is preferable to use polypropylene resins containing 30% by mass or more and 100% by mass or less of highly crystalline homopolypropylene resins with an isotactic pentad fraction (mmmm fraction) of 95% or more as the polyolefin resin.

The highly scratch-resistant layer 17 may contain, as necessary, one or more additives selected from various additives such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters. It is preferable that the highly scratch-resistant layer 17 has a degree of transparency (colorless transparent, colored transparent, translucent) that allows the color of the colored layer 12 and the pattern of the pattern layer 13 to be seen from the surface (top surface) of the decorative sheet 1.

(Nucleating Agent)
The highly scratch-resistant layer 17 contains a nano-sized nucleating agent. The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having a single-layer outer membrane. In this embodiment, the nucleating agent in the resin constituting the highly scratch-resistant layer 17 may be encapsulated in a vesicle with a part of the nucleating agent exposed. Since the highly scratch-resistant layer 17 contains a nucleating agent, the crystallization degree can be improved, and the scratch resistance (scratch resistance) of the decorative sheet 1 can be improved.
The nano-sized nucleating agent preferably 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 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.

Nano-sized nucleating agents have extremely small particle sizes, so the number of nucleating agents present per unit volume and their surface area increase inversely proportional to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes closer, so that when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the end from which the crystal is growing immediately comes into contact with the end of the crystal growing from the surface of another nucleating agent particle adjacent to the one nucleating agent particle, and the ends of the crystals inhibit each other's growth, stopping the growth of each crystal. Therefore, the average particle size 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 resin film with high crystallinity and high hardness can be obtained, and stress concentration between spherulites that occurs during bending processing can be efficiently dispersed, resulting in a resin film that suppresses cracking and whitening during bending processing.

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, and the number of crystal nuclei per amount of nucleating agent added increases significantly compared to when a nucleating agent is simply added. This reduces the average particle size of spherulites in the crystalline portion of the resin, making it possible to suppress cracking and whitening during bending. Therefore, the degree of crystallization can be increased by adding nucleating agent vesicles, making it possible to achieve both improved elastic modulus and processability.

The high scratch-resistant layer 17 is formed of a resin material to which a nucleating agent is added, for example, in a range of preferably 0.05 parts by mass or more and 0.5 parts by mass or less, more preferably 0.1 parts by mass or more and 0.3 parts by mass or less, relative to 100 parts by mass of polypropylene resin as the main component. When a nucleating agent vesicle is used, the amount of the nucleating agent added to the resin material is the amount converted into the nucleating agent in the nucleating agent vesicle. If the amount of the nucleating agent added is less than 0.05 parts by mass, the crystallization degree of polypropylene may not be sufficiently improved, and the scratch resistance of the high scratch-resistant layer 17 may not be sufficiently improved. In addition, if the amount of the nucleating agent added exceeds 0.5 parts by mass, the spherulite growth of polypropylene is inhibited due to an excess of crystal nuclei, and as a result, the crystallization degree of polypropylene may not be sufficiently improved, and the scratch resistance of the high scratch-resistant layer 17 may not be sufficiently improved.
Here, the term “main component” refers to a resin material that occupies 50% by mass or more of the resin material that constitutes the highly scratch-resistant layer 17 .

As a method for nano-sizing the nucleating agent, for example, a solid-phase method in which the nucleating agent is mainly mechanically pulverized to obtain nano-sized particles, a liquid-phase method in which nano-sized particles are synthesized or crystallized in a solution in which the nucleating agent or nucleating agent is dissolved, and a gas-phase method in which nano-sized particles are synthesized or crystallized from a nucleating agent or a gas or vapor containing the nucleating agent can be appropriately used. Examples of solid-phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disk mills, hammer mills, and jet mills. Examples of liquid-phase methods include crystallization methods, co-precipitation methods, sol-gel methods, liquid-phase reduction methods, and hydrothermal synthesis methods. Examples of gas-phase methods include electric furnace methods, chemical flame methods, laser methods, and thermal plasma methods.

The preferred method for nano-sizing a nucleating agent is supercritical reverse phase evaporation. Supercritical reverse phase evaporation is a method for producing capsules (nano-sized vesicles) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions above the critical point. Carbon dioxide in a supercritical state refers to carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa), and 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.

In addition, as a specific nano-processing method using the supercritical reverse phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as an outer membrane forming substance, and a nucleating agent as an encapsulating substance, and an emulsion of supercritical carbon dioxide and aqueous phase is generated by stirring. Next, the pressure is reduced, and the carbon dioxide expands and evaporates, causing a phase inversion, and nanocapsules (nanovesicles) are generated in which the phospholipids cover the surface of the nucleating agent particles with a single layer membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer membrane on the surface of the nucleating agent particles becomes multiple membranes, it is possible to easily generate capsules with a single layer membrane, and therefore to prepare capsules with a smaller diameter.
The nucleating agent vesicle is 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 these, the nucleating agent vesicle is preferably prepared by using the supercritical reverse phase evaporation method.

The outer membrane constituting the nucleating agent vesicle is, for example, composed of a monolayer membrane, and the outer membrane is composed of a substance containing a biological lipid such as a phospholipid.
Nucleating vesicles whose outer membrane is composed of materials that include biological lipids, such as phospholipids, are referred to herein as nucleating liposomes.
Examples of phospholipids constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin; and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

Other substances that form the outer membrane of the vesicle include dispersants such as nonionic surfactants and mixtures of these with cholesterols or triacylglycerols. Among these, examples of nonionic surfactants that can be used include 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 cholesterols that can be used include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, cholecalciferol, etc.

The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet 1 of this embodiment, it is preferable that the nucleating agent vesicle is a radical scavenger liposome having an outer membrane made of a phospholipid, and by forming the outer membrane from a phospholipid, 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 is the starting point of crystallization when the resin crystallizes. Examples of the nucleating agent include metal phosphate salts, metal benzoates, metal pimelate salts, metal rosin salts, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano-processing, it is preferable to use metal phosphate salts, metal benzoates, metal pimelate salts, and metal rosin salts that are non-melting and can be expected to have good transparency, but if the material itself can be made transparent by the nano-processing, colored quinacridone, cyanine blue, talc, etc. can also be used. In addition, a non-melting nucleating agent may be appropriately mixed with melting benzylidene sorbitol.

As described above, the decorative sheet 1 of this embodiment is characterized in that the highly scratch-resistant layer 17 contains a resin material and a nucleating agent. In addition, the decorative sheet 1 of this embodiment is characterized in that when the highly scratch-resistant layer 17 is formed, the nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. By adding the nucleating agent encapsulated in vesicles to the resin composition, the dispersibility of the nucleating agent in the resin material, i.e., in the highly scratch-resistant layer 17, is dramatically improved. On the other hand, it is assumed that there may be cases where it is difficult to directly identify the nucleating agent encapsulated in the vesicles based on the structure and properties of the finished decorative sheet 1, and this is impractical. The reasons for this are as follows.

The nucleating agent added in the form of a vesicle is in a dispersed state with high dispersibility, and is highly dispersed in the highly scratch-resistant layer 17 even in the laminate, which is the precursor of the produced decorative sheet 1. However, in the production process of the decorative sheet 1, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment, and such treatments may cause the outer membrane of the vesicle containing the nucleating agent to be crushed or chemically reacted. For this reason, depending on the treatment process of the decorative sheet 1, the state in which the outer membrane of the nucleating agent in the completed decorative sheet 1 is crushed or chemically reacted varies, and it is highly likely that the nucleating agent is not enclosed (enveloped) by the outer membrane. And when the nucleating agent is not enclosed by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself in 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 vesicle or a material added separately from the nucleating agent. Thus, the present disclosure differs from conventional methods in that the nucleating agent is blended into the decorative sheet 1 in a highly dispersed state, but it is anticipated that there may be cases where it is impractical to determine the structure and characteristics of the decorative sheet 1 in a numerical range based on analysis based on measurements, whether this is because the nucleating agent is added in the form of vesicles that encapsulate the nucleating agent or not.

<Colored Layer>
The colored layer 12 is a layer containing a resin material and a colorant such as a dye or a pigment.
The thickness of the colored layer 12 can be any desired thickness, but is preferably 40 μm to 70 μm, and more preferably 50 μm to 60 μm. When the thickness of the colored layer 12 is 40 μm or more, the coloring effect of the pigment can be fully exerted. When the thickness of the colored layer 12 is 70 μm or less, the colored layer 12 can be formed without using more resin material and pigment than necessary.

(Resin material)
The resin material constituting the colored layer 12 is, for example, a thermoplastic resin. There is no particular limitation on the thermoplastic resin, and materials similar to the thermoplastic resins used as colored layers in conventional decorative sheets can be used. As the thermoplastic resin, similar to that used in the high scratch-resistant layer 17, for example, polyester-based resins, polyolefin resins, polyolefin-based resins such as olefin-based copolymer resins, acrylic resins, polyamide-based resins, styrene-based resins, vinyl-based resins, fluorine-based resins, etc., or mixtures, copolymers, composites, laminates, etc. of two or more of these can be used.

Among these, it is preferable to use polypropylene resin as the resin material. The polypropylene resin used in the colored layer 12 is preferably mixed with a random polypropylene resin having an ethylene content within a specified range or a known amorphous polypropylene resin in order to facilitate dispersion of the inorganic pigment described below. In applications where an improved elastic modulus and scratch resistance are important, a highly crystalline homopolypropylene can be used, but multiple polypropylene resins can also be used in combination to adjust the elastic modulus. The elastic modulus can also be controlled by the manufacturing method.

(Coloring Agent)
The inorganic pigment used as the coloring agent constituting the colored layer 12 may be a known inorganic pigment, typically titanium oxide, for imparting hiding power. If the hiding power is low, the pattern layer 13 and the flooring material pattern will be mixed together, which is not preferable. By including an inorganic pigment, a decorative sheet 1 with good hiding power can be obtained.

The inorganic pigment is not particularly limited, but examples thereof include natural inorganic pigments and synthetic inorganic pigments. Examples of the natural inorganic pigments include earth pigments, calcined earth, and mineral pigments. Examples of the synthetic inorganic pigments include oxide pigments, hydroxide pigments, sulfide pigments, silicate pigments, phosphate pigments, carbonate pigments, metal powder pigments, and carbon pigments. In addition, a mixed pigment obtained by mixing one or more types of natural inorganic pigments and synthetic inorganic pigments may be used. An organic pigment such as carbon black may also be used in combination.
Furthermore, additives such as fatty acid metal salts may be added to improve dispersibility and extrusion suitability.

The amount of inorganic pigment mixed may be adjusted according to the desired hiding power, and is preferably within the range of 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin material. When the amount of inorganic pigment mixed is 5 parts by mass or more, sufficient hiding power can be obtained. Furthermore, when the amount of inorganic pigment mixed is 50 parts by mass or less, embrittlement of the colored layer 12 is less likely to occur.

In addition, when it is necessary to conceal color variations or defects on the surface of the flooring material to which the decorative sheet 1 is applied, it is preferable that the colored layer 12 be a layer that is colored opaquely to provide concealment. In addition, when it is necessary to make use of the texture of the flooring material surface, it is preferable that the layer be colored to a degree that allows the flooring material surface to be seen through.

When using a substrate with an inactive surface, such as an olefin-based base layer, as the colored layer 12, it is preferable to subject the front and back of the colored layer 12 to, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, dichromate treatment, etc.

<Picture layer>
The design layer 13 is formed on the upper surface of the colored layer 12, and is formed with a pattern such as a wood grain pattern, a stone grain pattern, a sand grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, or the like.
The thickness of the design layer 13 is preferably within the range of 3 μm to 20 μm. When the thickness of the design layer 13 is within this range, the printing can be made clear, the printing workability during the production of the decorative sheet 1 can be improved, and the production costs can be reduced.

The material of the pattern layer 13 is not particularly limited. For example, a printing ink or coating agent obtained by dissolving or dispersing a matrix and a coloring agent such as a dye or pigment in a solvent can be used. As the matrix, for example, various synthetic resins such as oil-based nitrocellulose resin, two-liquid urethane resin, acrylic resin, styrene resin, polyester resin, urethane resin, polyvinyl resin, alkyd resin, epoxy resin, melamine resin, fluorine resin, silicone resin, and rubber resin, or mixtures or copolymers thereof can be used. In addition, as the coloring agent, for example, inorganic pigments such as carbon black, titanium white, zinc oxide, red oxide, yellow lead, Prussian blue, and cadmium red, organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments, or mixtures thereof can be used. Examples of the solvent that can be used include toluene, xylene, ethyl acetate, butyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, water, and mixtures thereof.

In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders may be added to the design layer 13 in order to impart various functions.
Here, the design layer 13 can be formed by various printing methods, such as gravure printing, offset printing, screen printing, electrostatic printing, inkjet printing, etc. Although these printing methods may be selected separately depending on the layer to be formed, it is more efficient to select the same method and process them all at once.

A base solid ink layer (not shown) may be provided between the colored layer 12 and the pattern layer 13 depending on the level of the desired design. The base solid ink layer is provided so as to cover the entire surface of the colored layer 12. The base solid ink layer may also be multi-layered, consisting of two or more layers, depending on the required hiding power, etc. Furthermore, the pattern layer 13 may be formed by laminating as many plates as necessary to express the desired design. In this way, the pattern layer 13 and the base solid ink layer may be combined in various ways depending on the desired design, that is, the design to be expressed, but there are no particular limitations.

The base solid ink layer is preferably formed using the same material and printing method as the design layer 13. In addition, since the base solid ink layer covers the entire surface of the colored layer 12, it can also be formed by various coating methods such as roll coating, knife coating, microgravure coating, and die coating.

<Base layer>
The base layer 15 is made of a resin material, for example, a thermoplastic resin.
The thickness of the base layer 15 is preferably in the range of 160 μm to 220 μm, and more preferably 180 μm to 190 μm. When the thickness of the base layer 15 is 160 μm or more, it is possible to absorb unevenness and steps of the floor material as the base and improve the finish of the decorative sheet 1. In addition, when the thickness of the base layer 15 is 190 μm or less, the base layer 15 is not formed thicker than necessary, and the manufacturing cost of the decorative sheet 1 can be reduced.
Furthermore, the base layer 15 may contain a nucleating agent or nucleating agent vesicles, similar to the highly scratch-resistant layer 17, and may be highly crystallized.

(Resin material)
The thermoplastic resin is not particularly limited, and the same material as the thermoplastic resin used as the base layer in the conventional decorative sheet can be used. As the thermoplastic resin, for example, polyester resin, polyolefin resin, polyolefin copolymer resin, acrylic resin, polyamide resin, styrene resin, vinyl resin, fluorine resin, etc., or a mixture, copolymer, composite, laminate, etc. of two or more thereof can be used, as in the case of the highly scratch-resistant layer 17.

In particular, in light of the recent increase in social interest in environmental issues, it is not preferable to use thermoplastic resins containing chlorine (halogen), such as polyvinyl chloride resins, as thermoplastic resins, and it is preferable to use non-halogen thermoplastic resins. In particular, from the standpoints of various physical properties, processability, versatility, and economy, it is most preferable to use polyester resins (amorphous or biaxially oriented) or polyolefin resins as non-halogen thermoplastic resins, and it is even more preferable to use polyester resins. The base layer 15 needs to be formed thicker than the other layers in order to absorb the unevenness and steps of the underlying flooring material, but at the same time, it is necessary to ensure that the pattern of the pattern layer 13 is clearly expressed on the surface of the decorative sheet 1 through the base layer 15. For this reason, it is preferable that the base layer 15 is formed from a polyester resin, which is a resin material that is highly transparent and has the hardness required for a base material.

The base layer 15 may contain one or more additives selected from various additives such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters, as necessary. It is preferable that the base layer 15 has a degree of transparency (colorless transparent, colored transparent, translucent) that allows the color of the colored layer 12 and the pattern of the pattern layer 13 to be seen from the surface (top surface) of the decorative sheet 1.

<Topcoat layer>
The topcoat layer 18 is made of a resin material. The main component of the resin material constituting the topcoat layer 18 is appropriately selected from polyurethane, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and other resin materials. The form of the resin material is not particularly limited, and may be water-based, emulsion, solvent-based, or the like. The curing method of the resin material may be appropriately selected from one-liquid type, two-liquid type, ultraviolet curing method, heat curing method, photocuring type, and the like.

As the resin material used as the main component of the topcoat layer 18, a urethane-based resin using isocyanate is suitable from the viewpoints of workability, price, and the cohesive strength of the resin itself. The isocyanate can be appropriately selected from curing agents such as adducts, biurets, 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(isocyanatemethyl)cyclohexane (HXDI), and trimethylhexamethylene diisocyanate (TMDI). Among them, it is preferable to use hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI), which have a linear molecular structure, from the viewpoint of weather resistance. In addition, when trying to improve the surface hardness, it is preferable to use a resin that is cured by active energy rays such as ultraviolet rays or electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of thermosetting and photocuring, it is possible to improve the surface hardness, suppress the cure shrinkage, and improve the adhesion.

The topcoat layer 18 may contain a gloss regulator for gloss adjustment. As the gloss regulator, a commercially available known material may be used, for example, fine particles made of inorganic materials such as silica, glass, alumina, calcium carbonate, barium sulfate, etc. may be used. In addition, fine particles made of organic materials such as acrylic may be used as the gloss regulator. However, when high transparency is required, it is preferable to use fine particles of highly transparent silica, glass, acrylic, etc. as the gloss regulator. In particular, among fine particles such as silica and glass, gloss regulators with low bulk density, which are secondary aggregates of fine primary particles rather than solid spherical particles, have a high matting effect relative to the amount added. Therefore, by using a gloss regulator with low bulk density, the amount of gloss regulator added can be reduced.

In order to impart various functions to the topcoat layer 18, the topcoat layer 18 may contain functional additives such as antibacterial agents and antifungal agents. The topcoat layer 18 may also contain an ultraviolet absorber and a light stabilizer as necessary. Examples of ultraviolet absorbers include benzotriazole-based, benzoate-based, benzophenone-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers. Examples of light stabilizers include hindered amine-based light stabilizers.

The thickness of the topcoat layer 18 is preferably in the range of 3 μm to 15 μm. When the thickness of the topcoat layer 18 is 3 μm or more, the effect of improving scratch resistance is increased. Furthermore, when the thickness of the topcoat layer 18 is 15 μm or less, the occurrence of cracks and breaks during bending processing is suppressed, and deterioration of the design and weather resistance of the decorative sheet 1 can be suppressed.

<Adhesive Layer>
The first adhesive layer 14 is formed to bond the base layer 15 to the colored layer 12 and the pattern layer 13, and the second adhesive layer 16 is a layer formed to bond the base layer 15 to the highly scratch-resistant layer 17. The materials constituting the first adhesive layer 14 and the second adhesive layer 16 are not particularly limited, and known materials such as adhesives such as urethane resins, modified silicone resins, and epoxy resins, and pressure-sensitive adhesives such as polyester resins can be used appropriately in consideration of the compatibility between the layers to be bonded. Furthermore, depending on the manufacturing method of the decorative sheet 1, the first adhesive layer 14 and the second adhesive layer 16 may not be provided.

<Primer layer>
For example, polyester resin, polyurethane resin, or a mixture thereof can be used as the primer layer 11. Furthermore, by using a two-liquid type of polyol and isocyanate, the adhesion between the colored layer 12 and the primer layer 11 and the cohesive force of the primer layer 11 itself are improved. Examples of polyols include acrylic polyols and polyester polyols. Examples of isocyanates include aromatic isocyanates such as tolylene diisocyanate and 4,4' diphenylmethane diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and xylene diisocyanate. For the primer layer 11, it is preferable to use an aromatic polyol in terms of rapid reactivity and heat resistance.
The thickness of the primer layer 11 is preferably 1 μm or more. By making the thickness of the primer layer 11 1 μm or more, it is possible to prevent the adhesive from being dissolved by a solvent, causing the primer layer 11 to disappear and resulting in a decrease in adhesion.

When applying the decorative sheet 1 onto a flooring material, if the surface of the flooring material is very uneven, it is advisable to seal the unevenness with putty beforehand and apply a primer if necessary.

(1.2) Manufacturing Method of Decorative Sheet An example of the manufacturing method of the decorative sheet 1 will be described.
First, a colored film is formed to become the colored layer 12. An inorganic pigment-containing polypropylene resin, which is a polypropylene resin to which an inorganic pigment has been added, is heated and melted, and is formed into a sheet having a thickness of 40 μm to 70 μm by extrusion molding or the like to form the colored layer 12. Thereafter, a desired pattern is formed on the colored film by printing, to form the pattern layer 13.
Next, a base film is formed to become the base layer 15. The base layer 15 is formed by heating and melting a polyester resin and forming it into a sheet having a thickness of 160 μm or more and 220 μm or less by extrusion molding or the like.
Here, the colored film and the base film may be formed simultaneously or in different orders.

Then, the colored film and the base film are bonded together by dry lamination. A first adhesive is applied to the surface of the colored film on which the pattern layer 13 is formed, and dried to form a first adhesive layer 14. The base film is then pressed against the first adhesive layer 14 to form a first laminate having the colored layer 12, the pattern layer 13, the first adhesive layer 14, and the base layer 15.

Next, a nucleating agent is encapsulated in the optical vesicle to form a nucleating agent vesicle, and the nucleating agent is added to polypropylene resin to form a resin material for the highly scratch-resistant layer 17. The nucleating agent vesicle is produced, for example, by encapsulating a nucleating agent in a vesicle having a single layer membrane by supercritical reverse phase evaporation to form a vesicle.

Next, the heated and melted polypropylene resin containing nucleating agent vesicles is extruded onto the surface of the base film side of the first laminate, and formed into a sheet having a thickness of 70 μm to 110 μm by extrusion lamination to form the highly scratch-resistant layer 17. This forms a second laminate having the colored layer 12, the design layer 13, the first adhesive layer 14, the base layer 15, and the highly scratch-resistant layer 17. At this time, the cooling time from the crystallization temperature to the curing completion temperature is adjusted by a known adjustment method, so that the crystallization state of the highly scratch-resistant layer 17 can be adjusted to a state in which the desired scratch resistance is obtained.
Finally, a topcoat layer 18 is formed on the side of the highly scratch-resistant layer 17 of the second laminate.
In this manner, the decorative sheet 1 can be formed.

In the above example, dry lamination was used to form the colored layer 12, the pattern layer 13, and the base layer 15, and extrusion lamination was used to form the highly scratch-resistant layer 17, but this is not limited to the above. For example, when extruding each film, the molten resins (first adhesive and second adhesive) may be merged in a T-die or a feed block before the T-die, and the decorative sheet 1 may be formed by co-extrusion molding. Co-extrusion molding is preferred because it simplifies the formation of the decorative sheet 1 and has high productivity. Alternatively, a highly scratch-resistant film that will become the highly scratch-resistant layer 17 may be prepared in advance, and the base film and the highly scratch-resistant film may be bonded together using dry lamination.

(1.3) Modifications The decorative sheet 1 described above has a flat surface, but is not limited to this configuration. For example, as shown in Fig. 2, the decorative sheet 1 may have an uneven surface on the top coat layer 18, or on the top surface of the top coat layer 18 and the highly scratch-resistant layer 17, to enhance the design.

(1.4) Effects of the First Embodiment The decorative sheet 1 as described above has the following effects.
(1) The decorative sheet 1 of this embodiment contains a resin material and a nano-sized nucleating agent, and has a highly scratch-resistant layer 17 in which the average particle size of the spherulites in the crystalline portion of the crystalline resin is small and highly crystallized.
According to this configuration, it is possible to provide a decorative sheet 1 that has excellent scratch resistance and can suppress the occurrence of scratches caused by shoe heels or small stones during heavy walking.

(2) The decorative sheet 1 of this embodiment preferably has a highly scratch-resistant layer 17 that is highly crystallized by adding 0.05 parts by mass or more and 0.5 parts by mass or less of a nucleating agent to 100 parts by mass of the resin material constituting the highly scratch-resistant layer 17.
According to this configuration, the crystallization degree of the resin material constituting the highly scratch-resistant layer 17 is sufficiently improved, and a decorative sheet 1 having sufficient scratch resistance required under heavy foot traffic can be obtained.

(3) In the decorative sheet 1 of this embodiment, it is preferable that the highly scratch-resistant layer 17 is formed from a resin material to which nucleating agent vesicles that have been encapsulated in an outer membrane and turned into vesicles have been added.
According to this configuration, the crystallization degree of the resin material constituting the highly scratch-resistant layer 17 is sufficiently improved, and a decorative sheet 1 having sufficient scratch resistance required under heavy foot traffic can be obtained.

(4) In the decorative sheet 1 of this embodiment, the nucleating agent vesicle is preferably a nucleating agent liposome having an outer membrane made of phospholipids.
This configuration can ensure good compatibility between the resin material, which is the main component of the highly scratch-resistant layer 17, and the vesicles.
(5) In the decorative sheet 1 of this embodiment, it is preferable that a design layer 13 is provided on one surface of the colored layer 12 .
According to this configuration, the design of the decorative sheet 1 can be improved.

2. Second Embodiment Hereinafter, a decorative sheet according to a second embodiment of the present disclosure will be described with reference to FIG.
3 is a cross-sectional view for explaining one configuration example of the decorative sheet 2 according to the second embodiment of the present disclosure. The decorative sheet 2 according to this embodiment is a decorative sheet that is applied to floor materials of buildings, particularly floor materials in spaces where people walk on them with shoes on, similar to the decorative sheet 1.

The decorative sheet 2 comprises a primer layer 11, a colored layer 12, a design layer 13, a first adhesive layer 14, a base layer 15, a second adhesive layer 16, a highly scratch-resistant layer 27, and a top coat layer 18. That is, the decorative sheet 2 differs from the decorative sheet 1 according to the first embodiment in that the decorative sheet 2 comprises a highly scratch-resistant layer 27 instead of the highly scratch-resistant layer 17.
below,

The highly scratch-resistant layer 27 will be described below. Note that the layers other than the highly scratch-resistant layer 27 (primer layer 11, colored layer 12, pattern layer 13, first adhesive layer 14, substrate layer 15, second adhesive layer 16, and topcoat layer 18) have the same configuration as the layers of the decorative sheet 1, and therefore will not be described here.

(2.1) Basic structure of decorative sheet <Highly scratch-resistant layer>
The highly scratch-resistant layer 27 is a layer containing a resin material and an inorganic material. In the decorative sheet 1 according to the first embodiment, a highly scratch-resistant resin sheet having high crystallinity is formed from a resin material containing a nucleating agent to form the highly scratch-resistant layer 17. On the other hand, in the decorative sheet 2 according to the second embodiment, a highly scratch-resistant resin sheet having high hardness is formed from a resin material containing inorganic particles having high hardness to form the highly scratch-resistant layer 27, thereby obtaining a decorative sheet 2 having high scratch resistance.

Examples of inorganic particles include nano-sized fine particles made of inorganic materials such as silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.
The highly scratch-resistant layer 27 is formed from a resin material to which inorganic particles are added in an amount within the range of 0.05 parts by mass to 0.5 parts by mass with respect to 100 parts by mass of the resin material, for example.

The highly scratch-resistant layer 27 is obtained, for example, by heating and melting inorganic particle-containing polypropylene resin that contains nano-sized inorganic particles, and molding it into a sheet having a thickness of 70 μm to 110 μm by extrusion molding or the like.

(2.2) Effect of the Second Embodiment The decorative sheet 2 as described above has the following effect in addition to the effect (5) of the first embodiment.
(6) The decorative sheet 2 of this embodiment includes a highly scratch-resistant layer 27 that contains a resin material and inorganic particles and has a high hardness.
According to this configuration, it is possible to provide a decorative sheet 1 that has excellent scratch resistance and can suppress the occurrence of scratches caused by shoe heels or small stones during heavy walking.

3. Third Embodiment Hereinafter, a decorative sheet according to a third embodiment of the present disclosure will be described with reference to FIG.
4 is a cross-sectional view for explaining one configuration example of the decorative sheet 3 according to a third embodiment of the present disclosure. The decorative sheet 3 according to this embodiment is a decorative sheet that is applied to floor materials of buildings, particularly floor materials in spaces where people walk on them with shoes on, similar to the decorative sheet 1.

(3.1) Basic structure of decorative sheet Decorative sheet 3 differs from decorative sheets 1 and 2 in that decorative sheet 3 is provided with a tack layer 30 comprising a release sheet 31 and an adhesive layer 32 on the surface of decorative sheet 1 according to the first embodiment or decorative sheet 2 according to the second embodiment facing colored layer 12. That is, decorative sheet 3 is provided with release sheet 31, adhesive layer 32, primer layer 11, colored layer 12, design layer 13, first adhesive layer 14, substrate layer 15, second adhesive layer 16, highly scratch-resistant layer 17 or highly scratch-resistant layer 27, and top coat layer 18.

The tack layer 30 will be described below. Note that the layers other than the tack layer 30 (primer layer 11, colored layer 12, pattern layer 13, first adhesive layer 14, substrate layer 15, second adhesive layer 16, high scratch resistance layer 17 or 27, and top coat layer 18) have the same configuration as the layers of the decorative sheet 1, so their description will be omitted.

<Tack Layer>
(Release sheet)
The release sheet 31 may be any of various forms such as a conventionally known release film, a separator paper, a peeling film, and a release paper. For example, a release layer may be formed on one or both sides of a fine paper, a coated paper, an impregnated paper, a plastic film, etc. The release layer is not particularly limited as long as it is a material having releasability, and examples of the release layer include silicone resin, an organic resin-modified silicone resin, a fluororesin, an aminoalkyd resin, a melamine resin, an acrylic resin, and a polyester resin.

(Adhesive layer)
The adhesive layer 32 is not particularly limited as long as it is made of a material that has high affinity with both the release sheet 31 and the primer layer 11. Examples of the adhesive layer 32 include polyester-based, acrylic-based, and urethane-based adhesives, and vinyl acetate-based adhesives.
The adhesive layer 32 has an adhesion strength of the decorative sheet 3 to the attachment surface (floor material) of preferably 10 N/inch or more, more preferably 15 N/inch or more, and even more preferably 20 N/inch or more. In this embodiment, the adhesion strength of the decorative sheet 3 to the attachment surface (floor material) is indicated by the peel strength when a peel test is carried out in accordance with JIS Z0237. If it is difficult to obtain adhesion between the adhesive layer 32 and the floor material, it is preferable to apply a primer or the like that improves adhesion to the adhesive layer 32 onto the floor material before laminating the decorative sheet 3.

The thickness of the adhesive layer 32 is preferably 50 μm or more and 100 μm or less. When the thickness of the adhesive layer 32 is 50 μm or more, even if there is a foreign object or a scratch on the flooring material to which the decorative sheet 3 is attached, the unevenness of the foreign object or the scratch can be absorbed, and the adhesiveness of the decorative sheet 3 can be increased. In addition, when the thickness of the adhesive layer 32 is 50 μm or more, even when the decorative sheet 3 of this embodiment is attached on top of another decorative sheet attached on the flooring material, the decorative sheet 3 can be finished with a good finish and the construction work can be made more efficient. Furthermore, when the thickness of the adhesive layer 32 is 100 μm or less, the adhesive layer 32 does not become too thick, and the adhesive is prevented from protruding from the end face of the decorative sheet 3, which leads to reduced manufacturing costs and suppression of deterioration in construction workability.

(3.2) Advantages of the Third Embodiment The decorative sheet 3 as described above has the following advantages in addition to the advantages (1) to (5) or (5) and (6) of the first and second embodiments.
(7) The decorative sheet 3 of this embodiment has a tack layer 30 on the lower surface side of the decorative sheet 3 , which has a release sheet 31 and an adhesive layer 32 .
This configuration improves the applicability of the decorative sheet 3 to flooring, which has excellent scratch resistance and can reduce scratches caused by shoe heels or pebbles during heavy walking.

(8) The decorative sheet 3 of this embodiment may have a tack layer 30 having an adhesive layer 32 with a thickness of 50 μm or more and 100 μm or less.
This configuration absorbs unevenness due to foreign matter and scratches on the floor material and prevents the adhesive from spilling out from the end face of the decorative sheet 3, improving the finish of the decorative sheet 3 and making the installation work more efficient.

The decorative sheet according to the present disclosure will now be described with reference to examples. In the examples, a decorative sheet with a tack layer having the configuration described in the third embodiment was produced and attached to a flooring material to evaluate the decorative sheet.

Example 1
A 55 μm thick colored sheet (manufactured by RIKEN TECHNOS CORPORATION) was used as the colored layer, and a wood grain pattern was printed on one surface of the colored sheet by gravure printing using urethane ink (Lamistar manufactured by Toyo Ink Mfg. Co., Ltd.) to form a pattern layer.
Next, a transparent polyester film having a thickness of 190 μm, which is a base sheet, was attached to the side of the colored sheet on which the design layer was formed by dry lamination using an acrylic adhesive (manufactured by Toyo-Morton Co., Ltd.). After this, the colored sheet and the base sheet were firmly bonded to each other by providing a sufficient curing period.

Next, nucleating agent vesicles were mixed into the polypropylene resin, and the heated and melted polypropylene resin containing the nucleating agent vesicles was extruded into a sheet having a thickness of 90 μm onto the surface of the base sheet laminated with the colored sheet, forming a highly scratch-resistant layer by extrusion lamination.
Next, the surface of the highly scratch-resistant layer was coated with an ultraviolet-curable resin (acrylic urethane resin manufactured by DIC Graphics Co., Ltd.) to form a topcoat layer.

Finally, 60 μm of a repulsion-resistant acrylic adhesive was applied to the release paper, and the acrylic adhesive was attached to the surface of the colored sheet that had been attached to the base sheet to produce the decorative sheet of the example. In this case, the acrylic adhesive used was adhesive A, which had a value of 20 N/inch or more when a tack layer having an adhesive layer and release paper was attached to SUS and a peel test was conducted in accordance with JIS Z0237 (180° peel strength at a speed of 300 mm/min measured after leaving for 20 minutes).

Example 2
A decorative sheet of Comparative Example 1 was formed in the same manner as in Example, except that no base layer was provided.

Example 3
The decorative sheet of Comparative Example 2 was formed in the same manner as in Example 1, except that adhesive B, which had an adhesive strength of less than 10 N/inch when subjected to a peel test in accordance with JIS Z0237, was used as the acrylic adhesive.

<Comparative Example 1>
A decorative sheet of Comparative Example 1 was formed in the same manner as in Example, except that the highly scratch-resistant layer was not provided.

<Evaluation>
(a) Evaluation of scratch resistance 1 (abrasion test)
The decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2 were applied onto a vinyl floor, and it was confirmed whether or not they could pass the abrasion test A stipulated in the Japanese Agricultural Standards (JAS) for flooring 3,000 times.

(b) Evaluation of scratch resistance 2 (scratch test)
The surface of each of the decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2 was strongly scratched with a 10 yen coin to confirm whether continuous scratches were formed. In this test, the coin was used to scratch three places, and the number of scratches was confirmed.

(c) Evaluation of Adhesion to Flooring The decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2 were attached to a vinyl floor, and 30 days after attachment, the adhesion of the decorative sheet to the vinyl floor was visually confirmed.

The evaluation results of scratch resistance and adhesion to flooring materials are shown in Table 1. In Table 1, the evaluation results are listed in order of highest evaluation result with "A", "B", "C" and "D".
Here, in the abrasion tests, "A" indicates a case where the abrasion test A was passed 3000 times or more, "B" indicates a case where the abrasion test A was passed 2000 times or more, "C" indicates a case where the abrasion test A was passed 1000 times or more, and "D" indicates a case where the abrasion test A was not passed 1000 times or more.
In addition, in the scratch test, "A" indicates the case where there are 0 scratches, "B" indicates the case where there is 1 scratch, "C" indicates the case where there are 2 scratches, and "D" indicates the case where there are 3 scratches.
In terms of adhesion to flooring materials, "A" indicates a case where there is no peeling of the decorative sheet, "B" indicates a case where there is slight peeling at the edge of the decorative sheet, "C" indicates a case where there is major peeling at the edge of the decorative sheet, and "D" indicates a case where the decorative sheet has peeled off completely.

As can be seen from Table 1, the decorative sheets of Examples 1 and 3, which have both a highly scratch-resistant layer and a substrate layer, passed the abrasion test more than 3000 times, and only one scratch occurred in the scratch test. Also, Example 2, which does not have a substrate layer and has a highly scratch-resistant layer, showed a larger abrasion loss in the abrasion test than the decorative sheets of Examples 1 and 3, but passed the abrasion A test more than 1000 times, and only one scratch occurred in the scratch test.
On the other hand, the decorative sheet of Comparative Example 1 was able to pass the abrasion test of more than 2000 revolutions, but suffered three scratches in the scratch test.

As can be seen from Table 1, the decorative sheets of Examples 1 and 2 and Comparative Example 1, in which the adhesive layer was formed using Adhesive A, did not peel off from the vinyl floor at all. On the other hand, the decorative sheet of Example 3, in which the adhesive layer was formed using Adhesive B, experienced slight peeling at the edge of the sheet.

From the above evaluation results, it was confirmed that the decorative sheets of Examples 1 to 3 having a high scratch-resistant layer had higher evaluations in the scratch test than the decorative sheet of Comparative Example 1 not having a high scratch-resistant layer, and have a high effect against local scratches, etc. Also, the decorative sheets of Examples 1 and 3 having both a high scratch-resistant layer and a substrate layer had higher evaluations in the abrasion test than the decorative sheet of Example 2 having a high scratch-resistant layer and not having a substrate layer, and have a further effect against the abrasion of the entire decorative sheet. Therefore, it was confirmed that the decorative sheet for floors used in heavy foot traffic spaces in particular has high scratch resistance against shoe heels, pebbles, etc. by having a high scratch-resistant layer containing a resin material and a nano-sized nucleating agent or inorganic particles.
Furthermore, from the above evaluation results, it was confirmed that decorative sheets having an adhesive layer formed using an adhesive with a peel strength of 10 N/inch or more when subjected to a peel test conforming to JIS Z0237 have good adhesion to flooring materials even after 30 days.

The scope of the present disclosure is not limited to the exemplary embodiments shown and described, but includes all embodiments that achieve equivalent effects to those intended by the present disclosure. Furthermore, the scope of the present disclosure is not limited to the combination of inventive features defined by the claims, but may be defined by any desired combination of specific features among all the respective disclosed features.

Reference Signs List 1, 2, 3: Decorative sheet 11: Primer layer 12: Colored layer 13: Design layer 14: First adhesive layer 15: Base layer 16: Second adhesive layer 17, 27: Highly scratch-resistant layer 18: Topcoat layer 30: Tack layer 31: Release sheet 32: Adhesive layer

Claims (12)

A base layer made of a resin material and having transparency;
a highly scratch-resistant layer provided on one surface side of the base layer and containing a resin material and a nucleating agent having an average particle size of 375 nm or less ;
A pattern layer provided on the other surface of the base layer;
A colored layer is provided on a surface of the design layer opposite to the surface facing the base layer;
Equipped with
A decorative sheet in which the highly scratch-resistant layer has a thickness of 70 μm or more and 110 μm or less. The highly scratch-resistant layer includes a nucleating agent vesicle having a single-layer outer membrane and a nano-sized nucleating agent encapsulated therein.
The decorative sheet according to claim 1 . 3. The decorative sheet according to claim 2, wherein said nucleating agent vesicle is a nucleating agent liposome having an outer membrane made of phospholipids. 4. The decorative sheet according to claim 2 or 3, wherein said nucleating agent vesicle is formed by encapsulating said nucleating agent in a vesicle having a monolayer membrane by supercritical reverse phase evaporation. The decorative sheet according to claim 2 , wherein the highly scratch-resistant layer is formed from a resin material to which the nucleating agent is added in an amount within a range of 0.05 parts by mass to 0.5 parts by mass relative to 100 parts by mass of the resin material. 6. The decorative sheet according to claim 1, wherein the thickness of the substrate layer is 160 μm or more and 220 μm or less. 7. The decorative sheet according to claim 1, further comprising a topcoat layer provided on a surface of said highly scratch-resistant layer opposite to the surface facing said base layer. a primer layer provided on a surface of the color layer opposite to the surface on which the pattern layer is formed;
an adhesive layer provided on a surface of the primer layer opposite to a surface facing the colored layer;
The decorative sheet according to claim 7 , further comprising a release sheet provided on a surface of the adhesive layer opposite to the surface facing the primer layer. 9. The decorative sheet according to claim 8 , wherein the thickness of the adhesive layer is from 50 μm to 100 μm. 9. The decorative sheet according to claim 8 , wherein the adhesive layer has an adhesion strength of 10 N/inch or more. 11. The decorative sheet according to claim 1, which satisfies the standard of the abrasion test A prescribed in the Japanese Agricultural Standards for flooring 3,000 times or more. A method for producing a decorative sheet according to any one of claims 1 to 11 ,
A nucleating agent is encapsulated in the vesicle to produce a nucleating agent vesicle having an average particle size of 375 nm or less ,
a highly scratch-resistant layer having a thickness of 70 μm or more and 110 μm or less is formed on one surface of a base layer formed using a first resin material using a second resin material containing the nucleating agent vesicle;
A pattern layer is formed on the other surface of the transparent base layer;
A method for producing a decorative sheet, comprising forming a colored layer on the surface of the design layer opposite to the surface facing the base layer.

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