JP2022159907A - Decorative sheet and decorative plate - Google Patents

Abstract

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

Description

TECHNICAL FIELD The present disclosure relates to a decorative sheet and a decorative board used for surface decoration of, for example, floor materials.

Conventionally, olefin-based materials have been mainly used for decorative sheets in recent years due to the problem of gas during combustion (see Patent Documents 1 to 3).

In order to protect the pattern from abrasion of the surface, it is widely used that the decorative sheet is multi-layered and a transparent olefin sheet is pasted on the printed one on the colored olefin sheet (Patent Document 2, paragraph [0034] ] and FIG. 1, see paragraph [0059] and FIG. 1 of Patent Document 3).

JP 2006-110929 A JP 2015-199313 A JP 2016-101663 A

The conventional decorative sheet described above requires a printing process and a lamination process during manufacturing. As a result, the number of manufacturing processes for the decorative sheet increases, and the first problem is that, for example, one process cannot be in-line.

In addition, because conventional decorative sheets are multi-layered, it is not easy to reduce the thickness of the sheet. there is a problem.

Furthermore, due to limitations in the film formation of the conventional decorative sheet, the hardness of the sheet cannot be obtained when the sheet is thinned, and the sheet stretches, making it difficult to match the printing. There is a third problem of inferiority.

In view of the first to third problems described above, the present disclosure provides a decorative sheet that can reduce the number of manufacturing steps and has high hardness and excellent scratch resistance despite being a thin film, and the decorative sheet. The object is to provide a decorative board.

In order to solve the above problems, a decorative sheet according to an aspect of the present disclosure includes a printed pattern layer in which a pattern is printed and a colored layer are formed in order on the back side of a raw fabric layer that is a single-layer film, and the raw fabric A decorative sheet having a surface protective layer formed on the surface side of the layer, and having no laminate layer formed of another film on either the surface side or the back side of the raw fabric layer, wherein the raw fabric layer contains either a nucleating agent or an inorganic filler and a transparent olefinic thermoplastic resin, and the surface protective layer contains an ionizing radiation-curable resin.

A decorative board according to another aspect of the present disclosure includes the above-described decorative sheet and a substrate having the above-described decorative sheet attached to at least one surface thereof.

According to the aspect of the present disclosure, it is possible to reduce the number of manufacturing steps, and to provide a decorative sheet that is thin but has high hardness and excellent scratch resistance, and a decorative board using the decorative sheet.

1 is a cross-sectional view showing one configuration example of a decorative sheet according to a first embodiment of the present disclosure; FIG. Fig. 10 is a cross-sectional view showing one configuration example of a decorative sheet according to a modified example of 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. 10 is a cross-sectional view showing one configuration example of a decorative sheet according to a third embodiment of the present disclosure; FIG. 11 is a cross-sectional view showing a configuration example of a decorative material according to a fourth embodiment of the present disclosure;

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

A laminate according to the first embodiment of the present disclosure will be described. The decorative sheet according to the present disclosure is, for example, a decorative sheet that is applied to wall surfaces, floor materials, etc., and is a decorative sheet that is particularly preferably used for floor materials. In the following description, the side of the decorative sheet that contacts the attachment surface may be referred to as "lower", and the side opposite to the side of the decorative sheet that contacts the attachment surface (surface) may be referred to as "upper".
Hereinafter, each aspect of each embodiment of the present disclosure will be described with reference to the drawings.

1. First Embodiment (1.1) Basic Configuration of Decorative Sheet FIG. 1 is a cross section for explaining a configuration example of a decorative sheet 10 according to a first embodiment of the present disclosure (hereinafter referred to as "this embodiment"). In FIG. 1, 10 is a decorative sheet, which is not shown, but is used in a room, for example, is attached to the surface of a wall material, a floor material, etc., and the pattern of the wall material, floor material, etc. is applied to each house or room. are used together.
The decorative sheet 10 includes the following layers, and each layer is provided in order from (1).
The following (1) to (5) will be described later.
(1) Primer layer 30
(2) Colored layer 40
(3) Printed pattern layer 50
(4) Transparent raw fabric layer 20
(5) Surface protective layer 60

Each layer of the decorative sheet 10 is not limited to (1) to (5) described above, and an embossed portion 90 synchronized with the pattern of the printed pattern layer 50 may be formed on the surface side of the surface protective layer 60. Alternatively, a substrate shown in FIG. 4, which will be described later, may be adhered to the primer layer 30 side to form a decorative plate.
Further, in the decorative sheet 10, the "(1) primer layer 30" may be omitted. In other words, if the "(2) colored layer 40" has a function as a primer layer, the primer layer 30 can be omitted.
That is, in the decorative sheet 10, a printed pattern layer 50 on which a pattern is printed and a colored layer 40 are formed in order on the back side of a transparent raw fabric layer 20, which is a single-layer film, and a surface protective layer is formed on the front side of the transparent raw fabric. 60 is formed. Also, the decorative sheet 10 is a decorative sheet that does not have a laminate layer formed of another film on either the front side or the back side of the transparent raw fabric layer 20 .
Furthermore, the above "(2) colored layer 40" may be omitted. That is, the colored layer 40 can be omitted when the colored layer is not required, for example, when there is no need to impart a concealing property.

The primer layer 30 is a layer provided to improve the adhesiveness between the decorative sheet 10 and a surface to which the decorative sheet 10 is adhered, such as a flooring material or a wall surface.
The colored layer 40 is a layer that imparts a desired color to the decorative sheet 10 .
The printed pattern layer 50 is a layer printed with a pattern for imparting design to the decorative sheet 10 .
The transparent raw fabric layer 20 serves as a support for the decorative sheet 10 and is formed of a transparent olefin sheet. Although the details will be described later, as shown in FIG. 1, the transparent raw fabric layer 20 is made up of three layers of two types: a transparent skin layer 21A, a transparent core layer 22 made of transparent polypropylene, and a transparent skin layer 21B in this order. . That is, the transparent raw fabric layer 20 is composed of a transparent core layer 22 and two transparent skin layers (transparent skin layers 21A and 21B) sandwiching the transparent core layer.
The surface protective layer 60 is provided on the uppermost surface of the decorative sheet 10 to protect the decorative sheet 10 and adjust the luster of the surface of the decorative sheet 1 .
The decorative sheet 1 according to this embodiment may have at least a configuration in which a colored layer 40, a transparent raw fabric layer 20, and a surface protective layer 60 are laminated in this order.
In this embodiment, the surface protective layer 60 has an undercoat layer (an example of a second surface protective layer) 61 and a topcoat layer (an example of a first surface protective layer) 62 .
Each layer of the primer layer 30, the colored layer 40, the print pattern layer 50, the surface protective layer 60, and the transparent raw fabric layer 20 will be described in detail below.

(1.1.1) Configuration of Transparent Fabric Layer of Decorative Sheet 10 As shown in FIG. 1, the transparent fabric layer 20 is composed of the following three layers.
Note that (1) to (3) will be described later.
(1) Transparent core layer 22
(2) Front side transparent skin layer 21A
(3) Back side transparent skin layer 21B
In the transparent raw fabric layer 20, a back-side transparent skin layer 21B, a transparent core layer 22, and a front-side transparent skin layer 21A are sequentially laminated.

[Transparent core layer 22]
The transparent core layer 22 uses polypropylene resin blended with a weathering agent.
The transparent core layer 22 is, for example, a transparent polypropylene resin film. The transparent raw fabric layer 20 is represented in FIG. 1 as if the transparent core layer 22, the front side transparent skin layer 21A, and the back side transparent skin layer 21B form separate layers, but the transparent core layer is actually formed. 22. The front side transparent skin layer 21A and the back side transparent skin layer 21B are continuous single-layer sheets (single-layer films) with no interfaces.

(resin material)
Examples of the resin material forming the transparent core layer 22 include thermoplastic resins. The thermoplastic resin is not particularly limited, and materials similar to thermoplastic resins that have been used as base layers and the like in conventional decorative sheets can be used.
Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymers, ethylene-α-olefin copolymers, and propylene-α-olefin copolymers, polyethylene terephthalate, Polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymer polyethylene terephthalate, polyarylate, polyester resins such as polycarbonate, ethylene-vinyl acetate copolymer ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralized product (ionomer), etc. Polyolefin resins, acrylic resins such as poly(meth)acrylonitrile, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polybutyl(meth)acrylate, polyacrylamide, 6-nylon, 6,6-nylon, 6,10- Polyamide resins such as nylon, styrene resins such as polystyrene, AS resin, ABS resin, vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene fluoride, Polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer and other fluororesins, or mixtures, copolymers, composites, laminates, etc. of two or more thereof Available.

Above all, in view of the recent heightened social interest in environmental issues, it is not preferable to use thermoplastic resins containing chlorine (halogen) such as polyvinyl chloride resins as thermoplastic resins. It is preferred to use thermoplastic resins.
In particular, polyester resins (amorphous or biaxially oriented) or polyolefin resins, especially polyolefin resins, are used as non-halogen thermoplastic resins in terms of physical properties, processability, versatility, and economy. most preferably. For example, as the polyolefin resin, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

The transparent core layer 22 may optionally contain fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, and reducing agents. One or more selected from various additives such as abrasives, light scattering agents and gloss modifiers may be added.

[Front-Side Transparent Skin Layer 21A and Back-Side Transparent Skin Layer 21B]
The front side transparent skin layer 21A and the back side transparent skin layer 21B (hereinafter also referred to as "transparent skin layers 21A and 21B") are made of the same kind of thermoplastic resin, for example, a transparent polypropylene-based resin, and nano-sized additives are added. (hereinafter also referred to as "dispersant nano specification").
That is, in this embodiment, the transparent raw fabric layer 20 is formed of three layers of two types.
As with the transparent core layer 22, the transparent skin layers 21A and 21B may be blended with a weather resistant agent. At least one of the front-side transparent skin layer 21A and the back-side transparent skin layer 21B may be provided on the transparent raw fabric layer 20 . In other words, the transparent raw fabric layer 20 may be provided with a transparent skin layer on at least one surface.

The surface-side transparent skin layer 21A is located on the surface side of the transparent core layer 21, that is, on the surface of the transparent core layer 22 on the surface protection layer 60 side. The back side transparent skin layer 21B is located on the back side of the transparent core layer 22, that is, on the side opposite to the front side transparent skin layer 21A with the transparent core layer 22 interposed therebetween (the side on the printed pattern layer 50 side). . note that,

The transparent skin layers 21A, 21A are layers containing a resin material and a nucleating agent that improves the crystallinity of the resin material, and have uneven surfaces. In this embodiment, the nucleating agent is added to the resin material in the form of nucleating agent vesicles that are encapsulated in the outer membrane and formed into vesicles.
The thickness of the transparent skin layers 21A, 21A is, for example, preferably 1 μm or more and 50 μm or less, more preferably 2 μm or more and 10 μm or less. When the transparent skin layers 21A and 21B have a thickness of 1 μm or more, the scratch resistance of the decorative sheet 10 is sufficiently high. In addition, when the thickness of the transparent skin layers 21A and 21B is 50 μm or less, the bendability of the decorative sheet 10 does not become excessively high, and the decorative sheet 10 can be applied even when the attachment surface to which the decorative sheet 1 is attached is not flat. Construction can be performed in a state in which 10 is in close contact with the attachment surface.
In addition, the transparent raw fabric layer 20 is formed so that, for example, "front side transparent skin layer 21A: transparent core layer 22: back side transparent skin layer 21B" has a thickness ratio of "0.5:9:0.5". It is formed by co-extrusion.

(resin material)
Examples of the resin material forming the transparent skin layers 21A and 21B include thermoplastic resins. The thermoplastic resin is not particularly limited, and the same resin material as that for the transparent core layer 22 can be used.

(Nucleating agent)
The transparent skin layers 21A, 21B contain nano-sized nucleating agents. The nano-sized nucleating agent is preferably used by being added to the polypropylene resin in the form of nucleating agent vesicles enclosed in vesicles having a single-layer outer membrane. Further, in the present embodiment, the nucleating agent in the resin forming the transparent skin layers 21A and 21B may be encapsulated in the vesicle with a portion of the nucleating agent exposed. Since the transparent skin layers 21A and 21B contain a nucleating agent, the degree of crystallinity can be improved, and the abrasion resistance (scratch resistance) of the decorative sheet 10 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, is preferably 375 nm or less.

Since nano-sized nucleating agents have extremely small particle sizes, the number of nucleating agents present per unit volume and the surface area increase in inverse proportion to the cube of the particle diameter. As a result, since the distance between each nucleating agent particle becomes short, when crystal growth occurs from the surface of one nucleating agent particle added to the resin, the edge where the crystal is growing immediately becomes one. contact with the edges of crystals growing from the surface of other nucleating agent particles adjacent to the nucleating agent particles, the edges of the crystals hinder the growth of each crystal, and the growth of each crystal stops. Therefore, the average grain size of the spherulites in the crystal portion 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 generated during bending is efficiently dispersed, so that cracking and whitening during bending are suppressed. film can be realized.

When the 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 a nucleating agent vesicle is added, the dispersibility in the resin is improved, so the number of crystal nuclei with respect to the amount of the nucleating agent added is greatly increased compared to the case where the nucleating agent is simply added. do.
As a result, the average grain size of the spherulites in the crystal part of the resin becomes small, and the occurrence of cracking and whitening during bending can be suppressed. Therefore, by adding a nucleating agent vesicle, the degree of crystallinity can be further increased, and it becomes possible to achieve both improvement in elastic modulus and workability.

The transparent skin layers 21A and 21B are, for example, 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 with respect to 100 parts by mass of the polypropylene resin as the main component. It is formed of a resin material to which a nucleating agent is added within the range of 1 part or less.
When the nucleating agent vesicle is used, the amount of the nucleating agent added to the resin material is the amount added in terms of the nucleating agent in the nucleating agent vesicle. If the amount of the nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layers 21A and 21B may not be sufficiently improved. If the amount of the nucleating agent added exceeds 0.5 parts by mass, the spherulite growth of polypropylene is hindered due to excessive crystal nuclei, and as a result, the crystallinity of polypropylene is not sufficiently improved. The scratch resistance of the transparent skin layers 21A and 21B may not be sufficiently improved.
Here, the "main component" indicates a resin material that accounts for 50% by mass or more of the resin material that constitutes the transparent skin layers 21A and 21B.

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

A supercritical reversed-phase evaporation method is preferable as a method for nano-izing the nucleating agent. The supercritical reverse-phase evaporation method is a method of producing capsules (nano-sized vesicles) encapsulating a target substance using carbon dioxide in a supercritical state or under temperature or pressure conditions equal to or higher than the critical point.
Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state with a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, under conditions of temperature above the critical point or Carbon dioxide under pressure conditions means carbon dioxide under conditions where only temperature or only pressure exceeds critical conditions.

In addition, as a specific nano-processing by the supercritical reverse phase evaporation method, first, the water phase is injected into a mixed fluid of supercritical carbon dioxide, phospholipids as outer membrane forming substances, and nucleating agents as inclusion substances. and stirring to generate an emulsion of supercritical carbon dioxide and an aqueous phase.
Next, when the pressure is reduced, the carbon dioxide expands and evaporates, phase inversion occurs, and nanocapsules (nanovesicles) are formed in which the surface of the nucleating agent particles is covered with a monolayer film of the phospholipid.
By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer film is a multi-layered film on the surface of the nucleating agent particle, it is possible to easily produce a single-layer film capsule. Small diameter capsules can be prepared.
Nucleating agent vesicles are prepared by, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, supercritical reverse phase evaporation method, and the like. Among them, the nucleating agent vesicle is preferably prepared using a supercritical reversed-phase evaporation method.

The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane. In addition, the outer membrane is composed of, for example, a substance containing biological lipids such as phospholipids.
Nucleogenic vesicles whose outer membrane is composed of a substance containing biological lipids such as phospholipids are referred to herein as nucleogenic liposomes.
Phospholipids constituting the outer membrane include, for example, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and the like. and sphingolipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

Other substances that form the outer membrane of vesicles include, for example, nonionic surfactants and dispersing agents such as mixtures of these with cholesterols or triacylglycerols.
Among these, nonionic surfactants include, for example, 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. 1 type or 2 types or more can be used. Examples of cholesterols that can be used include cholesterol, α-cholestanol, β-cholestanol, cholestan, desmosterol (5,24-cholestadien-3β-ol), sodium cholate and cholecalciferol.

Alternatively, the liposome outer membrane may be formed from a mixture of a phospholipid and a dispersant.
In the decorative sheet 10 of the present embodiment, the nucleating agent vesicle is preferably a radical scavenger liposome having a phospholipid outer membrane. The compatibility between the resin material, which is the main component, and the vesicle can be improved.
The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Nucleating agents include, for example, phosphate metal salts, benzoate metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc. In particular, in order to maximize the effect of the nano-processing, it is preferable to use phosphate ester metal salts, benzoate metal salts, pimelic acid metal salts, and rosin metal salts that are non-melting and can be expected to have good transparency. Colored quinacridone, cyanine blue, talc, etc. can also be used when the material itself can be made transparent by nano-processing. Further, a melting type benzylidene sorbitol may be appropriately mixed with a non-melting type nucleating agent.

As described above, in the decorative sheet 10 of the embodiment, the transparent raw fabric layer 20 is formed containing a nucleating agent and a resin material (for example, a transparent olefinic thermoplastic resin). More specifically, in the decorative sheet 10 of this embodiment, the transparent skin layers 21A and 21B are formed containing a nucleating agent and a resin material (for example, an olefinic thermoplastic resin).
Further, the decorative sheet 10 of the present embodiment is characterized in that, when forming the transparent skin layers 21A and 21B, a nucleating agent contained in vesicles is added to the resin material to crystallize the resin material. have. By adding the nucleating agent in a vesicle-encapsulated state to the resin composition, there is an effect of dramatically improving the dispersibility of the nucleating agent in the resin material, that is, in the transparent skin layers 21A and 21B. . On the other hand, it may be difficult to directly identify the nucleating agent contained in the vesicles from the structure and characteristics of the finished decorative sheet 10 depending on the situation, and it can be said to be impractical. . The reason is as follows.

The nucleating agent added in the form of vesicles is in a dispersed state with high dispersibility, and the transparent skin layers 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21E, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, 21A, and 12E are also formed into transparent skin layers 21A, 21A, 21A, 21A, 21A, 21A, 21A, and 21D in the form of vesicles. 21B are highly dispersed.
However, in the manufacturing process of the decorative sheet 10, the laminate is usually subjected to various treatments such as compression treatment and hardening treatment. may react.

For this reason, depending on the process of processing the decorative sheet 10, the outer film of the nucleating agent in the finished decorative sheet 10 is crushed, or the state of chemical reaction varies, and the nucleating agent is enclosed (wrapped) by the outer film. Most likely not.
When the nucleating agent is not contained in the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself in the numerical range, and whether the crushed outer membrane is composed of the outer membrane of the vesicle. It may be difficult to determine whether the material is added separately from the nucleating agent.
As described above, the present disclosure differs from the conventional art in that the nucleating agent is blended in a highly dispersed manner with respect to the decorative sheet 10, but the nucleating agent is added in the form of vesicles containing the nucleating agent. In some cases, it may be impractical to specify the structure and characteristics of the decorative sheet 10 in terms of numerical ranges analyzed based on measurements.

The thickness of the transparent raw fabric layer 20 is, for example, preferably in the range of 70 μm or more and 150 μm or less, and more preferably in the range of 90 μm or more and 130 μm or less.
When the thickness of the transparent raw fabric layer 20 is 70 μm or more, suitable strength is imparted when the decorative sheet 10 is used as a floor material, and scratch resistance can be improved. Further, when the thickness of the transparent raw fabric layer 20 is 90 μm or more, the strength of the transparent raw fabric layer 20 is further increased, and the scratch resistance can be improved more reliably.
On the other hand, when the thickness of the transparent raw fabric layer 20 is 150 μm or less, the thin film thickness and strength of the decorative sheet 10 are compatible while suppressing defects such as whitening and cracking during processing. Aptitude can be improved. In addition, sufficient transparency can be maintained so that the pattern of the printed pattern layer can be seen from the sheet surface (surface protective layer 60 side). Further, when the thickness of the transparent raw fabric layer 20 is 130 μm or less, it is possible to achieve both thin film thickness and strength of the decorative sheet 10 more reliably, and to improve workability.

(1.1.2) Structure of Each Layer of Decorative Sheet 10 (Primer Layer 30)
As shown in FIG. 1, the primer layer 30 is positioned on the back side of the transparent raw fabric layer 20 and is provided mainly for the purpose of improving adhesion. The primer layer 30 is laminated on the colored layer 40 on the back side of the transparent raw fabric layer 20 . In other words, the primer layer 30 is provided on the surface of the colored layer 40 opposite to the printed pattern layer 50 .
The functions of the primer layer 30 include, in addition to improving adhesiveness, surface stabilization after surface treatment, anticorrosion of metal surfaces, provision of adhesiveness, prevention of deterioration of adhesives, and the like.
The primer layer 30 is formed by applying a urethane-based resin to a solid content of 1 g/m ² by gravure printing, for example.

(Colored layer 40)
The colored layer 40 is positioned on the back side of the transparent raw fabric layer 20 as shown in FIG. It is formed with the mask and is provided mainly for the purpose of imparting concealability.
The colored layer 40 is printed with a two-liquid urethane resin by, for example, gravure printing. The two-liquid urethane-based resin may have a structure in which a urethane resin is mixed with a titanium oxide white pigment.

(Printed picture layer 50)
As shown in FIG. 1, the printed pattern layer 50 is positioned on the front side of the colored layer 40, that is, on the back side of the transparent raw fabric layer 20, is formed using a printing method, and imparts design to the decorative sheet 10. It is provided for the purpose.
The printed pattern layer 50 is formed by printing a pattern with a urethane-based resin, for example, by gravure printing.
Examples of the printing method include gravure printing, but are not limited thereto, and various printing methods such as offset printing, letterpress printing, flexographic printing, screen printing, inkjet printing, and electrostatic printing. method is applicable.

The type of pattern of the printed pattern layer 50 is arbitrary depending on the purpose of use, user's preference, etc. For example, a wood grain pattern, a stone grain pattern, an abstract pattern, and the like are common. The type of pattern is not limited to the types exemplified above, and may be, for example, solid printing on the entire surface.
As the printing ink used in the printing method, for example, vinyl chloride acetate-based ink (cyan, magenta, yellow) is used.

As the printing ink, a urethane-based resin was exemplified, but it is not limited to this. Appropriate additives such as stabilizers, dispersants, antifoaming agents, leveling agents, surfactants, and desiccants, as well as solvents or diluents, are dispersed in a binder made of synthetic resin or the like. be.

(Surface protective layer 60)
The surface protective layer 60, also called a top coat, is positioned on the surface side of the transparent raw fabric layer 20 as shown in FIG. It is provided for the purpose of imparting functions (surface physical properties) such as durability, stain resistance, and design.
The surface protective layer 60 may be a single layer, or may be formed by stacking a plurality of layers. In the decorative sheet 10 according to this embodiment, as shown in FIG. It is composed of a topcoat layer 62 with a higher gloss than the above.

Examples of the resin material forming the undercoat layer 61 include thermosetting resins. As the thermosetting resin, it is preferable to use a thermosetting resin having a urethane bond, such as a two-component curable urethane resin, in consideration of scratch resistance and the like. As the two-liquid curable urethane resin, for example, a urethane resin containing polyol as a main component and isocyanate as a cross-linking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol can be used.
The undercoat layer 61 formed of a thermosetting resin has a relatively low degree of cross-linking, and therefore tends to be excellent in flexibility such as bending and conformability to the base material.
For the undercoat layer 61, among these resin materials, an acrylic two-liquid curing type urethane resin containing acrylic polyol as a main component can be suitably used.

Examples of the resin material forming the topcoat layer 62 include ionizing radiation-curable resins. The topcoat layer 62 formed of an ionizing radiation curable resin has a high degree of cross-linking after the curing reaction, and thus has a high degree of hardness and tends to be excellent in scratch resistance. As ionizing radiation curable resins, for example, (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins can be used. Among them, acrylic ionizing radiation-curable resins (for example, acrylic UV-curable resins) can be preferably used as the material of the topcoat layer 62 .

As the ionizing radiation used for curing the ionizing radiation-curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation-curable resin (composition) are used. Usually, ultraviolet rays or electron beams may be used, but visible rays, X-rays, ion beams, etc. may also be used.

Ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, and the like can be used as ultraviolet light sources. The wavelength of ultraviolet rays is preferably in the range of 190 nm or more and 380 nm or less.

As the electron beam source, for example, various electron beam accelerators such as Cockcroft-Walton type, Vandegraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used. Among them, those capable of irradiating electrons having an energy in the range of 100 keV to 1000 keV are particularly preferable, and those capable of irradiating electrons having an energy of 100 keV to 300 keV are more preferable.

Thus, in the present embodiment, by forming the topcoat layer 62 using an acrylic ionizing radiation-curable resin, the decorative sheet 10 can be given hardness suitable for use as a flooring material.
As the resin material forming the topcoat layer 62, a mixed material in which an ionizing radiation-curable resin and a thermosetting resin are mixed may be used. As the thermosetting resin used for the resin material of the topcoat layer 62, the same thermosetting resin as that for the undercoat layer 61 can be used. At this time, for example, by containing more ionizing radiation-curable resin than thermosetting resin in the above mixed material, scratch resistance is satisfied, and whitening and cracking of the surface protective layer 60 are prevented during bending. can be made less likely to occur.

The topcoat layer 62 is coated with a resin material having a higher luster than the undercoat layer 61 and is printed with a pattern synchronized with the printed pattern layer 50 .
That is, by applying a gloss/matte coat to the surface protective layer 60, it can be synchronized with the pattern and the design of the decorative sheet 10 can be improved.

Also, on the surface of the topcoat layer 62, that is, on the outermost surface side of the surface protective layer 60, an embossed portion 90 that is in sync with the pattern of the printed pattern layer 50 (for example, a wood grain pattern) may be formed.
In the embossed portion 90, the undercoat layer 61 may be exposed.
Here, the embossed portion has an image of a certain difference in height, but in the present embodiment, the difference in height between the undercoat layer 61 and the overcoat layer 62 in sync with the pattern in the embossed portion 90 is actually on the order of several μm. This has the same meaning as the expression that the surface protective layer 60 is coated with a gloss/matte coat to synchronize with the pattern. By forming the embossed portion 90, the surface protective layer 60 utilizes the difference in texture between the high-gloss portion (topcoat layer 62) and the low-gloss portion (undercoat layer 61) to create a more realistic design. can be reproduced. For example, when a wood grain pattern is printed on the topcoat layer 6 , the embossed portion 90 can give the surface of the surface protective layer 60 an uneven shape imitating an actual wood grain pipe. This makes it possible to reproduce a design that is close to real wood.

Furthermore, the surface protective layer 60 may be subjected to antiviral treatment.
As an antiviral treatment, an antiviral agent is added to the surface protective layer 60 . As the antiviral agent, for example, a silver-based inorganic additive (Biocide TB-B100) made by Taisho Technos Co., Ltd. carrying silver ions is used.
Here, since the surface protective layer 60 is composed of the undercoat layer 61 and the topcoat layer 62, the antiviral agent may be added to both the undercoat layer 61 and the topcoat layer 62. Alternatively, it may be attached only to the overcoat layer 62 located on the surface side of the surface protective layer 60 .
Although the antiviral agent is added to the surface protective layer 60 , it is not limited to this, and the antiviral agent may be applied to the surface side of the surface protective layer 60 , at least the surface of the topcoat layer 62 .
Moreover, when the surface protective layer 60 has a single-layer structure, the single-layer surface protective layer 60 may contain an antiviral agent (for example, a silver-based antiviral agent).

Further, each layer of the surface protective layer 60 may contain functional additives such as an antibacterial agent and an antifungal agent in order to impart various functions to the surface protective layer 60 . Moreover, each layer of the surface protective layer 60 may contain an ultraviolet absorber and a light stabilizer as needed. Examples of UV absorbers include benzotriazole, benzoate, benzophenone, triazine, and cyanoacrylate UV absorbers. Further, the light stabilizer includes a hindered amine light stabilizer.

As described above, in the decorative sheet 10 according to the present embodiment, the surface protective layer 60 includes the top coat layer 62 which is the outermost layer and is formed of an ionizing radiation curable resin (for example, an ultraviolet curable resin), and the top coat layer 62 . and an undercoat layer 61 provided between the transparent raw fabric layer 20 . As a result, the hardness of the surface protective layer 60 is further improved, the decorative sheet 10 is imparted with excellent scratch resistance, and the effect of performance imparted by various additives (for example, antiviral agents, etc.) can be enhanced. can.
In addition, the undercoat layer 61 is preferably made of a two-liquid curing acrylic resin. This satisfies the scratch resistance of the decorative sheet 10 and at the same time improves the workability, and makes it difficult for the surface protective layer 60 to whiten or crack during processing.
When the surface protective layer 60 has a single-layer structure (single-layer structure), either the undercoat layer 61 or the topcoat layer 62 may be used as the surface protective layer 60, but the hardness of the decorative sheet 10 is improved and the designability is improved. From the viewpoint of making the surface protective layer 60, it is preferable to use the topcoat layer 62 containing an ionizing radiation-curable resin. Moreover, the topcoat layer 62 may be formed including a mixed material of an ionizing radiation-curable resin and a thermosetting resin.
That is, the surface protective layer 60 may be formed containing an ionizing radiation-curable resin, and is more preferably formed containing an acrylic ionizing radiation-curable resin (for example, an acrylic UV-curable resin). preferable. Moreover, the surface protective layer 60 may be formed including a mixed material of an ionizing radiation-curable resin and a thermosetting resin.

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

(1) First step In the first step, the transparent core layer 22 using a transparent polypropylene-based thermoplastic resin and the front and back surfaces of the transparent core layer 22 are respectively positioned. This is a step of manufacturing the transparent raw fabric layer 20, which is a single-layer film obtained by extruding the transparent skin layers 21A and 21B to which a dispersing agent is added as an additive.

Specifically, an inorganic pigment or the like is added to a resin material such as a polypropylene resin as necessary, and the mixture is melted and kneaded to obtain a resin material for the base material layer containing the inorganic pigment or the like to be the transparent core layer 22 . Next, a nucleating agent vesicle is mixed with a resin material such as polypropylene resin to obtain a nucleating agent vesicle-containing resin material for the transparent skin layers 21A and 21B. Subsequently, the heated and melted resin material for the transparent core layer 22 and the resin material containing the nucleating agent vesicles for the transparent skin layers 21A and 21B are mixed, for example, with a resin material containing the nucleating agent vesicle/resin material for the core layer/nucleating agent. The vesicle-containing resin materials were simultaneously extruded from an extruder so as to be laminated in order, and cooled with a cooling roll to form a laminated film. Thereby, the transparent raw fabric layer 20 in which the skin layer 12B/base material layer 12A/skin layer 12B is laminated is obtained.

(2) Second step The second step is a step of sequentially forming a printed pattern layer 50, a colored layer 40, and a primer layer 30 on the back side of the transparent raw fabric layer 20 produced in the first step. is.
(3) Third step In the third step, after the second step or prior to the second step, the surface protective layer 60 is applied to the surface side of the transparent raw fabric layer 20 produced in the first step. It is a step of forming
The order of the above-described steps is two types: the order of the first step, the second step, and the third step, and the order of the first step, the third step, and the second step.
Since conventional decorative sheets are multi-layered, it is difficult to provide a printed picture layer and a surface protective layer on the surface of the laminate film in harmony with each other. In contrast, the decorative sheet 10 according to this embodiment can be manufactured in-line as described above. For this reason, in the decorative sheet 10, when the decorative sheet 10 is manufactured in-line, the printed pattern layer 50 and the surface protective layer 60 are provided on the front and back sides of the transparent raw fabric layer 20, which is the transparent olefin sheet. Synchronization expression with can be easily done.

As described above, the decorative sheet of the first embodiment in which the primer layer 30, the colored layer 40, the printed pattern layer 50, the transparent raw fabric layer 20 and the surface protective layer 60 are laminated in this order can be obtained.

(1.3) Effects of First Embodiment The decorative sheet 1 as described above has the following effects.
(1) In the decorative sheet 1 of the present embodiment, a printed pattern layer 50 on which a pattern is printed and a colored layer 40 are formed in order on the back side of a transparent raw fabric layer 20 that is a single-layer film. A decorative sheet having a surface protective layer 60 formed on the surface side and having no laminate layer formed of another film on either the surface side or the back side of the transparent raw fabric layer 20, wherein the transparent raw fabric layer 20 is formed containing a nucleating agent and a transparent olefinic thermoplastic resin, and the surface protective layer 60 is formed containing an ionizing radiation curable resin.
According to this configuration, it is possible to reduce the number of manufacturing processes, and it is possible to obtain the decorative sheet 10 that is thin but has high hardness and excellent scratch resistance.
(2) In the decorative sheet 10 of the present embodiment, the surface protective layer 60 may be formed containing an acrylic ionizing radiation-curable resin.
According to this configuration, it is possible to reliably improve the hardness suitable for flooring in the decorative sheet 10 .

(3) In the decorative sheet 1 of the present embodiment, the surface protective layer 60 comprises a topcoat layer 62 which is the outermost layer and is formed of an ionizing radiation-curable resin, and between the topcoat layer 62 and the transparent raw fabric layer 20. It is formed of two layers including the provided undercoat layer 61 .
According to this configuration, the decorative sheet 10 can further improve the scratch resistance and enhance the effect of the performance imparted by various additives (for example, antiviral agent).
(4) In the decorative sheet 1 of the present embodiment, the undercoat layer 61 may be made of a two-liquid curing acrylic resin.
According to this configuration, it is possible to obtain a decorative sheet that satisfies the scratch resistance performance and at the same time has improved processability, and has an excellent balance between the scratch resistance performance and the processability.
(5) In the decorative sheet 1 of the present embodiment, the outermost surface of the surface protective layer 60 (the outermost surface of the topcoat layer 62) may be formed with an embossed portion 90 that is aligned with the pattern of the printed pattern layer 50. good.
According to this configuration, it is possible to reduce the number of manufacturing steps, and obtain a decorative sheet having high hardness in spite of being a thin film and excellent in design by the synchronized expression of the printed pattern layer 50 and the surface protective layer 60. - 特許庁be able to.
(6) In the decorative sheet 10 of the present embodiment, the thickness of the transparent raw fabric layer 20 may be in the range of 70 μm or more and 150 μm or less.
According to this configuration, it is possible to reduce the number of manufacturing processes, and obtain a decorative sheet that more reliably achieves both a thin film thickness and a high hardness suitable for floor materials.

(7) In the decorative sheet 1 of the present embodiment, the transparent raw fabric layer 20 is composed of a transparent core layer 22 and two transparent skin layers 21A and 21B sandwiching the transparent core layer 22, The two transparent skin layers 21A and 21B may be formed containing a nucleating agent and an olefinic thermoplastic resin.
According to this configuration, it is possible to obtain a decorative sheet that can achieve both high hardness suitable for floor materials and workability.
(8) The decorative sheet 10 of the present embodiment may have the primer layer 30 provided on the surface of the colored layer 40 opposite to the printed pattern layer 50 .
According to this configuration, it is possible to improve the adhesiveness between the decorative sheet 10 and the adhesive used for bonding the floor material, the wall surface, or the like.

(1.4) Modification of First Embodiment A modification of the decorative sheet according to this embodiment will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view for explaining one configuration example of the decorative sheet 10 according to a modification of the present embodiment. As shown in FIG. 2, in the decorative sheet 10, the surface protective layer 60 may have a topcoat layer 162 having a flat surface. That is, the outermost surface of the surface protective layer 60 does not have to have embossed portions. Topcoat layer 162 has the same configuration as topcoat layer 62 shown in FIG. 1, except that the surface is flat. Therefore, the overcoat layer 162 can be printed with a pattern that is in sync with the printed pattern layer 50 .
By forming the surface of the topcoat layer 162 flat, it is possible to reduce the work load and manufacturing cost for forming the embossed portions in the topcoat layer 162 when forming the surface protective layer 60, and as a result, the cosmetic Even when both surfaces of the sheet 10 are made flat, the decorative sheet 10 is thin but has high hardness, and can sufficiently maintain excellent scratch resistance.

As described above, in the decorative sheet 1 according to the modified example of the present embodiment, the topcoat layer 162 in the surface protective layer 60 may have a flat surface.
As a result, the number of steps for manufacturing the decorative sheet 10 can be further reduced, and a decorative sheet having high hardness and excellent scratch resistance despite being a thin film can be obtained.

2. Second Embodiment A decorative sheet according to a second embodiment of the present disclosure will be described below with reference to FIG.
FIG. 3 is a cross-sectional view for explaining one configuration example of the decorative sheet 11 according to the second embodiment of the present disclosure. Like the decorative sheet 10, the decorative sheet 11 according to the present embodiment is a decorative sheet that is preferably applied, for example, to a wall surface, a floor material, or the like.

The decorative sheet 11 includes a primer layer 30 , a colored layer 40 , a print pattern layer 50 , a transparent raw fabric layer 120 and a surface protective layer 60 . That is, the decorative sheet 110 differs from the decorative sheet 10 according to the first embodiment in that the transparent raw fabric layer 120 is provided instead of the transparent raw fabric layer 20 .

The transparent raw fabric layer 120 will be described below. The layers other than the transparent raw fabric layer 120 (primer layer 30, colored layer 40, printed pattern layer 50, and surface protective layer 60) have the same structure as the layers of the decorative sheet 10, so description thereof is omitted.

(2.1) Basic composition of decorative sheet <transparent raw fabric layer>
The transparent raw fabric layer 120 has a transparent core layer 22 and a transparent skin layer provided on at least one surface of the transparent core layer 22 . The transparent raw fabric layer 120 may be provided with a transparent skin layer 121A on the surface of the transparent core layer 22 (surface on the surface protective layer 60 side), or on the back surface of the transparent core layer 22 (surface on the colored layer 40 side). A transparent skin layer 121B may be provided on the transparent core layer 22, or a configuration in which transparent skin layers (transparent skin layers 121A and 121B) are provided on both sides of the transparent core layer 22 may be used. In this embodiment, a transparent raw fabric layer 120 having a configuration in which transparent skin layers are provided on both sides of a transparent core layer 22 (a configuration in which the transparent core layer 22 is sandwiched between transparent skin layers 121A and 121B) will be described.

(2.1.1) Transparent core layer 22
The transparent core layer 22 in this embodiment has the same structure as that of the transparent core layer 22 in the first embodiment, so the description thereof is omitted.

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

Examples of inorganic fillers include fine particles made of inorganic materials such as nano-sized silica, glass, alumina, titania, zirconia, calcium carbonate, and barium sulfate.
The transparent skin layers 121A and 121B are made of, for example, a resin material to which an inorganic filler is added in an amount of 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the resin material.

The transparent raw fabric layer 120 is formed by, for example, heating and melting an inorganic particle-containing polypropylene resin containing nano-sized inorganic particles and co-extrusion molding it together with the core layer resin material, so that at least one surface of the transparent core layer 22 is transparent. A skin layer (transparent skin layer 121A or transparent skin layer 121B) is provided and formed.
The transparent skin layers 21A and 21B may be made of inorganic nanoparticles containing an inorganic filler, or may be made of dispersant nanoparticles containing a nucleating agent in addition to the inorganic nanoparticles. can be That is, the transparent skin layers 21A and 21B may be formed by adding an inorganic filler in addition to the dispersant.

(2.2) Effects of Second Embodiment The decorative sheet 11 as described above has the following effects.
In the decorative sheet 11 of the present embodiment, a printed pattern layer 50 on which a pattern is printed and a colored layer 40 are formed in this order on the back side of a transparent raw fabric layer 120, which is a single-layer film. , A decorative sheet on which a surface protective layer 60 is formed and which does not have a laminate layer formed of another film on either the front side or the back side of the transparent raw fabric layer 120, wherein the transparent raw fabric layer 120 is The surface protection layer 60 is made of an ionizing radiation-curable resin (for example, an ultraviolet-curable resin) containing an inorganic filler and a transparent olefinic thermoplastic resin.
According to this configuration, similarly to the first embodiment, the number of manufacturing steps can be reduced, and the decorative sheet 11 having high hardness and excellent scratch resistance despite being a thin film can be obtained.

3. Third Embodiment A decorative material according to a third embodiment of the present disclosure will be described below with reference to FIG.
FIG. 4 is a cross-sectional view for explaining one configuration example of the decorative sheet 12 according to the second embodiment of the present disclosure. Like the decorative sheet 10, the decorative sheet 12 according to the present embodiment is a decorative sheet that is preferably applied, for example, to a wall surface, a floor material, or the like.

The decorative sheet 12 includes a primer layer 30 , a colored layer 40 , a print pattern layer 50 , a transparent raw fabric layer 220 and a surface protective layer 60 . That is, the decorative sheet 12 differs from the decorative sheet 10 according to the first embodiment in that the transparent raw fabric layer 220 is provided instead of the transparent raw fabric layer 20 .

The transparent raw fabric layer 220 will be described below. The layers (the primer layer 30, the colored layer 13 and the top coat layer 14) other than the transparent raw fabric layer 220 have the same structure as the layers of the decorative sheet 10, so the description thereof is omitted.

(3.1) Basic composition of decorative sheet <transparent raw fabric layer>
The transparent raw fabric layer 220 is composed of a transparent core layer 222 . That is, in the present embodiment, the transparent core layer 222 is not provided with a transparent skin layer on either side, and the transparent raw fabric layer 220 is composed only of the transparent olefin sheet, that is, the transparent core layer 222 only. It is a single layer film.

(3.1.1) Transparent core layer 222
The transparent core layer 222 in the present embodiment may be a dispersant nano specification formed by adding a dispersant (e.g., nucleating agent) as a nano-sized additive to a resin material (e.g., transparent polypropylene resin). Inorganic nanoparticle specifications formed by adding an inorganic filler as a nano-sized additive to a resin material may be used, or inorganic nanoparticle specifications may be added in addition to dispersant nanospecifications.
That is, the transparent raw fabric layer 220 composed of one layer of the transparent core layer 222 may contain at least one of the nucleating agent and the inorganic filler, and a transparent olefinic thermoplastic resin.
As a result, the transparent core layer 222 having high hardness is formed, and the decorative sheet 12 having high scratch resistance is obtained.

The transparent raw fabric layer 220, that is, the transparent core layer 222, is obtained by, for example, mixing at least one of a nucleating agent vesicle and an inorganic filler into a resin material such as polypropylene resin, and extruding a base layer resin material from an extruder, It may be formed as a single layer film.
In other words, in the present embodiment, the transparent core layer 222 is made to have at least one of dispersant nano-specifications and inorganic nanoparticle specifications, so that the decorative sheet has high scratch resistance and further reduces the manufacturing man-hours of the decorative sheet. can be done.

(3.2) Effects of Third Embodiment The decorative sheet 12 as described above has the following effects.
In the decorative sheet 12 of the present embodiment, a printed pattern layer 50 having a pattern printed thereon and a colored layer 40 are formed in this order on the back side of a transparent raw fabric layer 220, which is a single-layer film. , a surface protective layer 60 is formed, and a decorative sheet that does not have a laminate layer formed of another film on either the front side or the back side of the transparent raw fabric layer 220, and the transparent raw fabric layer 220 is transparent It has a core layer 222, and the transparent core layer 222 is formed containing at least one of a nucleating agent and an inorganic filler, and a transparent olefinic thermoplastic resin. It is made of mold resin.
According to this configuration, it is possible to further reduce the number of manufacturing steps, and it is possible to obtain the decorative sheet 12 that is thin but has high hardness and excellent scratch resistance.

4. Fourth Embodiment Hereinafter, a decorative panel according to a fourth embodiment of the present disclosure will be described with reference to FIG.
FIG. 5 is a cross-sectional view for explaining one configuration example of the decorative board 100 according to the fourth embodiment of the present disclosure.
(decorative board)
The decorative plate 100 includes a decorative sheet 10 and a substrate having the decorative sheet 10 attached to at least one surface thereof.
The decorative board 100 has a colored layer 40 and a printed pattern layer 50 laminated in this order on one side of a transparent raw fabric layer 20, and a surface protective layer 60 on the other side of the transparent raw fabric layer 20. Laminated. Also, the decorative board 100 is bonded to the substrate 80 at the primer layer 30 provided on the surface of the colored layer 40 opposite to the printed pattern layer 50 .
That is, the decorative plate 100 differs from the decorative sheet 10 according to the first embodiment in that the substrate 80 is provided.

The substrate 80 will be described below. Note that the decorative sheet 10 has the same configuration as that of the first embodiment, and thus the description thereof is omitted.

[substrate]
The substrate 80 constitutes the floor on which the user walks, and is made of a hard material. The substrate 80 is made of a rigid material such as a wood base material such as plywood, a composite base material obtained by mixing wood flour and plastic, a polyolefin such as polyethylene (PE) or polypropylene (PP), or a resin base material such as vinyl chloride (PVC). made of material. As the wood base material, for example, plywood made of tropical timber, particle board, medium density fiberboard (hereinafter referred to as MDF), ordinary plywood defined by Japanese Agricultural Standards, etc. can be used. Also, a base material made of wood powder-added olefinic resin can be used. The substrate 80 may be made of metal such as aluminum, resin such as plastic, or a composite material thereof. By forming the substrate 80, it is possible to provide the decorative panel 100 capable of suppressing the generation of scratches caused by, for example, walking of the user or installation of furniture.

The floor material is easily damaged by placing furniture on it. For this reason, the decorative sheet used for flooring is required to have higher scratch resistance than general decorative sheets. By forming the decorative sheet 100 using the decorative sheet 10 which is thin but has high hardness and excellent scratch resistance, it is possible to obtain a decorative board suitable for a floor material and excellent in scratch resistance.

Further, in the decorative sheet 100, the primer layer 30 may be provided on one surface of the substrate 80 instead of the decorative sheet 10, and the decorative sheet 10 and the substrate 80 may be bonded via the primer layer on the substrate 80. In the present embodiment, the substrate 80 is attached to the decorative sheet 10, but the decorative sheet 10 is the decorative sheet 10 provided with the topcoat layer 162 having a flat outermost surface in the surface protective layer 60. Alternatively, the decorative sheet 11 or the decorative sheet 12 may be used instead of the decorative sheet 10 to form the decorative plate 100 .

<Effects of the fourth embodiment>
The decorative board 100 according to this embodiment has the following effects in addition to the effects of the first and second embodiments.
(13) The decorative board 100 of the present embodiment includes decorative sheets (decorative sheets 10, 11, 12) and a substrate having the decorative sheet 10 bonded to at least one surface. can reduce the number of manufacturing processes, and can obtain a decorative board using a decorative sheet that is thin but has high hardness and excellent scratch resistance.

Hereinafter, the decorative sheet according to the present disclosure will be described with reference to Examples. The present disclosure is not limited to Examples 1 and 2 below.
In the examples, decorative sheets having the configurations described in the following examples and comparative examples were prepared and laminated on substrates for flooring materials to evaluate the decorative sheets.

<Example 1>
In Example 1, a decorative sheet for evaluation was produced using the following materials and procedures.
For the transparent core layer 22 (core layer) of the transparent raw fabric layer 20, a blend of polypropylene resin and a weather-resistant agent is used. A transparent polypropylene resin having a prescription (nano-specification of a dispersant) to which a dispersant is added as a size additive is used, and "front side transparent skin layer 21A: transparent core layer 22: back side transparent skin layer 21B" is "0. 5:9:0.5″ thickness ratio to produce a transparent raw fabric layer 20 with a total thickness of 150 μm.

On the back side of the transparent raw fabric layer 20, a pattern is printed with a urethane-based resin by gravure printing, and a printed pattern layer 50 is applied. A colored layer 40 was applied using a two-liquid urethane resin mixed with a pigment.
Furthermore, a primer layer 30 was formed by applying a urethane-based resin to a solid content of 1 g/m ² by gravure printing.
After that, the surface side of the transparent raw fabric layer 20 was subjected to corona treatment, and then an undercoat layer 61 and a topcoat layer 62 were formed as a surface protective layer 60 (topcoat layer). Specifically, the undercoat layer 61 was formed by applying a low-gloss acrylic two-component curing type resin (acrylic urethane resin manufactured by DIC Graphic Co., Ltd.) to a thickness of 6 μm. In addition, an acrylic ultraviolet curable resin (acrylic ultraviolet curable resin manufactured by DIC Graphic Co., Ltd.) is printed on the undercoat layer 61 in a pattern synchronized with the printed pattern layer 50 to form a topcoat layer 62, and a decorative sheet for evaluation is prepared. made.

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

<Example 3>
In the surface protective layer 60, a highly glossy topcoat layer 62 is printed with a wood grain pattern that matches the printed pattern layer 50, and an embossed portion 90 is formed to partially expose the undercoat layer 61. - 特許庁As a result, the surface of the surface protective layer 60 is formed into an uneven shape that imitates a wood grain conduit. A decorative sheet for evaluation was produced in the same manner as in Example 1 except for this.

<Comparative Example 1>
No dispersing agent as a nano-sized additive was added to the transparent polypropylene resin forming the transparent raw fabric layer 20 . A decorative sheet for evaluation was produced in the same manner as in Example 1 except for this.
<Comparative Example 2>
No dispersing agent as a nano-sized additive was added to the transparent polypropylene resin forming the transparent raw fabric layer 20 . A decorative sheet for evaluation was produced in the same manner as in Example 2 except for this.

(Evaluation method and evaluation criteria)
The evaluation method of the decorative sheet for evaluation produced above is as follows.
(1) Scratch test (2) Scratch hardness test (pencil hardness)
(3) Abrasion resistance test (4) Caster resistance test

(Scratch test)
In the scratch test, a coin scratch test was performed on each of the decorative sheets for evaluation, and the load was measured when continuous scars were not generated on the surface of the decorative sheet for evaluation.
In the scratch test, a 10-yen coin was applied to the surface of the evaluation sheet, and the test was started with a load of 1 kg, and the load was gradually increased by 1 kg until the test reached 4 kg.

(Scratch hardness test)
The scratch hardness test was performed on each evaluation sheet by the scratch hardness (pencil method) test specified in JISK5600-5-4: 1999. Hardness (pencil hardness) was measured.

(Abrasion resistance test)
The decorative board to which each decorative sheet for evaluation was attached was subjected to an abrasion resistance test specified in "JAS Flooring Japanese Agricultural Standards", and the number of rotations until the pattern started to disappear was confirmed. The worn paper was replaced every 1000 revolutions.

(Caster resistance test)
On the decorative board to which each decorative sheet for evaluation was pasted, a load of 25 kg was applied to the iron wheel (40 mm in diameter, 9 mm in width of one wheel, 18 mm in width between two wheels) with a weight of 25 kg (about 245 N), and 1000 times (1 stroke 20 cm) above), the caster was moved at a speed of 20 cm/sec. After that, the marks on the decorative plate were observed.
(Evaluation criteria)
In the scratch test, a load of "1 kg" or more was regarded as passed, and other than that was regarded as unsuccessful.
In the scratch hardness test, the hardness of the pencil (pencil hardness) of "B" or higher was regarded as acceptable, and the others were regarded as unacceptable.
In the abrasion resistance test, "1000 rotations" or more was regarded as a pass, and other than that was regarded as a failure.
In the caster resistance test, "no significant cracks" were judged to be acceptable, and other cases were judged to be unacceptable.

<Evaluation results>
Table 1 shows the composition of the decorative sheet for evaluation and the evaluation results.

(Examples 1 to 3 and Comparative Examples 1 and 2)
Of the total of five decorative sheets for evaluation of Examples 1 to 3 and Comparative Examples 1 and 2, the decorative sheets for evaluation of Examples 1 to 3 had all of (1) to (4) of the above evaluation methods. It was "passed". That is, it was found that the decorative sheets for evaluation of Examples 1 to 3 had high hardness and excellent scratch resistance despite being thin films. On the other hand, the decorative sheets for evaluation of Comparative Examples 1 and 2 were "failed" in at least one of the above evaluation methods (1) to (4). Specifically, the evaluation decorative sheet for evaluation of Comparative Example 1 was evaluated as "failed" in the scratch hardness test, and the evaluation decorative sheet for evaluation of Comparative Example 2 was evaluated as "failed" in the scratch test and the scratch hardness test. "Met. In other words, the decorative sheet to which a nano-sized additive (nucleating agent (dispersant) or inorganic filler) is added has a lower hardness than a decorative sheet to which no nano-sized additive is added, even though it is a thin film. It was found to be improved and to have excellent scratch resistance.

Moreover, it can be inferred that the difference in the scratch hardness test between Examples 1 and 3 and Example 2 is influenced by the thickness of the decorative sheet for evaluation. That is, in Examples 1 and 3, the decorative sheet for evaluation is thicker than in Example 2, and it can be assumed that the thicker one is advantageous in the scratch hardness test.

It should be noted that the decorative sheet and decorative material of the present disclosure are not limited to the above embodiments and examples, and various modifications are possible without impairing the characteristics of the invention.

10, 11, 12 Decorative Sheets 20, 120, 220 Transparent Raw Fabric Layer 100 Decorative Boards 22, 222 Transparent Core Layers 21A, 21B, 121A, 121B Transparent Skin Layer 30 Primer Layer 40 Colored Layer 50 Printed Pattern Layer 60 Surface Protective Layer 61 Undercoat layer 62 Topcoat layer 80 Substrate 90 Embossed portion

Claims (9)

A printed pattern layer on which a pattern is printed and a colored layer are formed in order on the back side of the original fabric layer, which is a single-layer film,
A surface protective layer is formed on the surface side of the raw fabric layer,
A decorative sheet that does not have a laminate layer formed of another film on either the front side or the back side of the raw fabric layer,
The raw fabric layer is formed containing either a nucleating agent or an inorganic filler and a transparent olefinic thermoplastic resin,
The decorative sheet, wherein the surface protective layer contains an ionizing radiation-curable resin. The decorative sheet according to claim 1, wherein the surface protective layer is formed containing an acrylic ionizing radiation-curable resin. The surface protective layer includes a first surface protective layer, which is the outermost layer and is formed of the ionizing radiation-curable resin, and a second surface protective layer provided between the first surface protective layer and the raw fabric layer. The decorative sheet according to claim 1 or 2, which is formed of two layers. The decorative sheet according to claim 3, wherein the second surface protective layer is made of a two-liquid curing acrylic resin. 5. The decorative sheet according to any one of claims 1 to 4, wherein an embossed portion synchronized with the pattern is formed on the outermost surface side of the surface protective layer. The decorative sheet according to any one of Claims 1 to 5, wherein the raw fabric layer has a thickness in the range of 70 µm or more and 150 µm or less. The raw fabric layer is composed of a core layer and two skin layers sandwiching the core layer,
7. The cosmetic according to any one of claims 1 to 6, wherein the two skin layers contain either one of the nucleating agent or the inorganic filler and the olefinic thermoplastic resin. sheet. The decorative sheet according to any one of claims 1 to 7, wherein the colored layer has a primer layer provided on a surface opposite to the printed pattern layer. The decorative sheet according to any one of claims 1 to 8;
a substrate having the decorative sheet attached to at least one surface;
A veneer having a

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