Decorative sheet and decorative material

Abstract

To provide a decorative sheet and a decorative material that can reduce an emission amount of carbon dioxide.SOLUTION: A decorative material 10 comprises a decorative sheet 1 and a substrate 7, where the decorative sheet 1 comprises: a pattern layer 2 including a coloring agent; a sealer layer 3 which is laminated on one surface of the pattern layer 2 and includes a sealer agent; a transparent polypropylene layer 4 which is laminated on one surface of the sealer layer 3 and is formed by using a transparent polypropylene resin; and a surface protective layer 5 which is laminated on one surface of the transparent polypropylene layer 4, and a radical scavenger is added to the transparent polypropylene layer 4.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a decorative sheet and a decorative material. [Background technology]

[0002] Patent Document 1 discloses, for example, a technology relating to a sheet (such as a decorative sheet) intended to reduce carbon dioxide emissions. In the technology disclosed in Patent Document 1, liposomes formed by supercritical reverse phase evaporation so as to encapsulate a carbon dioxide absorbent and a crystal nucleating agent for a polyolefin-based resin are added to a polyolefin-based resin to produce a resin composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6060451 Summary of the Invention [Problem to be solved by the invention]

[0004] In decorative sheets formed by conventional techniques, including the technique disclosed in Patent Document 1, for example, when incinerated at the time of disposal, heat is transferred from an ignition source to the resin, and when the temperature of the resin rises, the polymer is decomposed and becomes a low-molecular gas containing radicals, which diffuses into the atmosphere. When the diffused gas approaches an ignition source, a rapid and complex chain reaction occurs, in which an oxidation reaction is dominated by the reaction of radicals with oxygen, and carbon dioxide is generated as the final product of the reaction of radicals with oxygen.

[0005] In view of the above-mentioned problems, an object of the present invention is to provide a decorative sheet and a decorative material that are capable of reducing carbon dioxide emissions. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, one aspect of the present invention is a decorative sheet comprising a design layer, a sealer layer, a transparent polypropylene layer, and a surface protective layer. The design layer is a layer containing a colorant. The sealer layer is a layer laminated on one side of the design layer and containing a sealing agent. The transparent polypropylene layer is a layer laminated on one side of the sealer layer and formed using a transparent polypropylene resin. The surface protective layer is a layer laminated on one side of the transparent polypropylene layer. In addition, a radical scavenger is added to the transparent polypropylene layer.

[0007] In order to solve the above-mentioned problems, one aspect of the present invention is a decorative material comprising a substrate and a decorative sheet laminated on at least one surface of the substrate. Effect of the Invention

[0008] According to one aspect of the present invention, it is possible to provide a decorative sheet and a decorative material that are capable of reducing carbon dioxide emissions. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a configuration of a decorative sheet in a first embodiment. [Diagram 2] 1 is a cross-sectional view showing the configuration of a decorative material in a first embodiment. [Diagram 3] FIG. 11 is a cross-sectional view showing the configuration of a decorative sheet in a modified example. [Figure 4] FIG. 11 is a cross-sectional view showing the configuration of a decorative material in a modified example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present technology will be described with reference to the drawings. In the description of the drawings, the same or similar parts are denoted with the same or similar reference numerals, and duplicated descriptions are omitted. Each drawing is schematic and may differ from the actual one. The embodiments shown below are examples of devices and methods for embodying the technical idea of ​​the present technology, and the technical idea of ​​the present technology is not limited to the devices and methods exemplified in the following embodiments. The technical idea of ​​the present technology can be modified in various ways within the technical scope described in the claims. In addition, the directions of "left and right" and "up and down" in the following description are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present invention. Therefore, for example, if the paper is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and of course, if the paper is rotated 180 degrees, "left" becomes "right" and "right" becomes "left".

[0011] First embodiment Hereinafter, the configuration of a decorative sheet 1 in a first embodiment will be described with reference to FIG. As shown in FIG. 1, the decorative sheet 1 comprises a design layer 2, a sealer layer 3, a transparent polypropylene layer 4, a surface protective layer 5, and a primer layer 6.

[0012] <Pattern layer> The pattern layer 2 is a layer for adding a pattern to impart design to the decorative sheet 1. The design layer 2 is formed using printing ink, paint, etc. The printing ink, paint, etc. that forms the design layer 2 is formed, for example, by dissolving or dispersing a colorant such as a dye or pigment together with a suitable binder resin in a suitable dilution solvent.

[0013] The printing ink or paint forming the design layer 2 is applied by using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating. The weight of the pattern layer 2 after drying is preferably 0.1 [g / m 2 ] or more than 15[g / m 2 ] or less, more preferably 3 [g / m2 ] or more than 10[g / m 2 ] or less, more preferably 6 [g / m 2 ] or more than 9 [g / m 2 ] is within the following range.

[0014] Any pattern can be used as the pattern of the pattern layer 2, for example, a wood grain pattern, a stone pattern, a fabric pattern, an abstract pattern, a geometric pattern, letters, symbols, a solid color, or a combination of these.

[0015] In addition, the pattern layer 2 may be configured to have, for example, a solid colored base material layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer for adding a pattern to impart design appeal. The thickness of the pattern layer 2 is set within the range of 1 μm to 10 μm, preferably 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm, and even more preferably 0.7 μm to 3 μm. This is because when the thickness of the pattern layer 2 is 1 μm or more, it is possible to make the printing clear. Also, when the thickness of the pattern layer 2 is 10 μm or less, it is possible to improve the printing workability when manufacturing the decorative sheet 1 and to suppress the manufacturing cost.

[0016] In addition, in order to impart various functions to the design layer 2, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, hardeners, hardening accelerators, and hardening retarders may be added. In addition, the pattern layer 2 may be configured to have, for example, a solid colored base fabric layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer for adding a pattern to impart design appeal.

[0017] <Sealer layer> The sealer layer 3 is laminated on one surface (the upper surface in FIG. 1) of the design layer 2, and is a layer containing a sealant. The content of the sealant in the sealer layer 3 is, for example, 5 g / m2 in terms of solid matter. 2 ] below.

[0018] <Transparent polypropylene layer> The transparent polypropylene layer 4 is composed of a single layer (single-layer structure) and is a layer laminated on one surface (the upper surface in FIG. 1) of the sealer layer 3, and is made of a transparent polypropylene resin. As the transparent polypropylene resin, for example, homopolypropylene is used. Moreover, the transparent polypropylene layer 4 preferably has a degree of transparency (colorless transparent, colored transparent, translucent) that allows the pattern of the pattern layer 2 to be seen from the surface (upper surface) of the decorative sheet 1.

[0019] The thickness of the transparent polypropylene layer 4 is, for example, in the range of 10 μm to 200 μm, in the range of 30 μm to 150 μm, preferably in the range of 55 μm to 100 μm, and more preferably in the range of 60 μm to 80 μm. This is because when the thickness of the transparent polypropylene layer 4 is 10 μm or more, it is possible to absorb unevenness and steps of the underlying flooring material and the like, thereby improving the finish of the application of the decorative sheet 1. Also, when the thickness of the transparent polypropylene layer 4 is 150 μm or less, the transparent polypropylene layer 4 is not formed thicker than necessary, and the manufacturing costs of the decorative sheet 1 can be reduced.

[0020] The method for producing the transparent polypropylene layer 4 is not particularly limited, and a conventionally known method can be used. In the first embodiment, the case where the transparent polypropylene layer 4 is formed by extrusion molding will be described. Moreover, the extrusion molding is preferably performed by a T-die method or an inflation method.

[0021] Moreover, the transparent polypropylene layer 4 contains a nano-sized additive and a radical scavenger. A nano-sized additive is an additive that has been made into nano-sized particles by a technique for nano-sizing the additive (nanofiber processing). As the nano-processing, for example, a solid phase method, a liquid phase method, a gas phase method, or the like can be used.

[0022] The solid phase method is a method in which additives are mainly mechanically pulverized to obtain nano-sized particles. For the solid phase method, a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, a jet mill, etc. can be used. The liquid phase method is a method for synthesizing or crystallizing nano-sized particles in an additive or a solution in which the additive is dissolved, and examples of the liquid phase method that can be used include a crystallization method, a co-precipitation method, a sol-gel method, a liquid phase reduction method, and a hydrothermal synthesis method. The gas phase method is a method for synthesizing or crystallizing nano-sized particles from additives or gas or vapor of the additives. Examples of the gas phase method that can be used include an electric furnace method, a chemical flame method, a laser method, and a thermal plasma method.

[0023] A more specific method for the nano-processing will be described below. In a specific example of the solid phase method, for example, a mixture of 100 g of isopropyl alcohol and 50 g of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate is milled in a bead mill for 60 minutes using 30 μm stabilized zirconia beads to obtain nano-sized nucleating agent particles with an average particle size of approximately 100 nm to 150 nm.

[0024] In a specific example of the crystallization method, for example, a solution obtained by dissolving 50[g] of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate in a mixed solvent of 96[g] of xylene, 72[g] of isopropyl alcohol, and 24[g] of water is brought into contact with a poor solvent such as ethanol in a microreactor to precipitate nano-sized nucleating agent particles with an average particle size of 1[nm] to 150[nm]. The additive-encapsulating vesicle is a vesicle-like capsule having a membrane structure closed in a spherical shell shape, and particularly, one containing a liquid phase inside is called an additive-encapsulating vesicle. In the present invention, the case where an additive is contained in the liquid phase will be described.

[0025] In addition, the additive-encapsulating vesicles have extremely high dispersibility and do not cause aggregation of particles due to the mutual repulsion of the outer membranes of the vesicles, and the mutual repulsion of the outer membranes of the vesicles makes it possible to uniformly disperse the additive in the resin composition constituting each resin layer. Among the nano-processing methods, methods for obtaining nano-sized additives as additive-encapsulating vesicles (vesicle processing) that can be used include, for example, the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-thaw method, and supercritical reverse phase evaporation method.

[0026] The vesicle formation process will now be described. The Bangham method involves putting chloroform or a chloroform / methanol mixed solvent into a flask or other container, then adding and dissolving phospholipids. The solvent is then removed using an evaporator to form a thin film containing lipids, and after adding a dispersion of additives, the mixture is hydrated and dispersed in a vortex mixer to obtain vesicles.

[0027] The extrusion method is a method for obtaining vesicles by preparing a thin film of phospholipid solution and passing it through a filter instead of a mixer used as an external perturbation in the Bangham method. The hydration method is a preparation method similar to the Bangham method, but in this method, vesicles are obtained by dispersing the particles by gentle stirring without using a mixer.

[0028] The reverse phase evaporation method involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as an external perturbation, and is a method for obtaining vesicles by repeating cooling and heating. In particular, a method for obtaining an additive-encapsulating vesicle having a unilamellar outer membrane includes supercritical reverse phase evaporation.

[0029] The supercritical reverse phase evaporation method is a method for producing capsules containing 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±0.0030MPa). Carbon dioxide under temperature or pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions.

[0030] In the specific vesicle formation process using the supercritical reverse phase evaporation method, an emulsion of supercritical carbon dioxide and aqueous phase is generated by injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipids as a dispersant, and additives as encapsulated substances, and stirring the mixture. When the pressure is then reduced, the carbon dioxide expands and evaporates, causing phase inversion, and nanocapsules are generated in which the phospholipids cover the surface of the additive particles with a monolayer membrane. By using the supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the dispersant forms multiple layers on the surface of the additive particles, it is possible to easily produce capsules with a single layer, making it possible to prepare capsules with a smaller diameter.

[0031] Furthermore, if a multi-membrane capsule is desired, it can be easily produced by injecting supercritical carbon dioxide into a mixed fluid of phospholipids, additives, and an aqueous phase. Examples of phospholipids used in preparing the additive-encapsulating vesicle include glycerophospholipids such as phosphatidylcholine, phosphatidiethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol. Furthermore, the additive-encapsulating vesicle can achieve excellent compatibility with resin materials by being provided with an outer membrane of phospholipids.

[0032] The additive-encapsulating vesicle may also have an outer membrane containing a dispersant, such as a polymeric surfactant, a fatty acid metal salt, a silane coupling agent, a titanate coupling agent, silicone, wax, or a modified resin. Examples of polymer surfactants include aliphatic polyvalent polycarboxylic acids, polycarboxylate alkylamines, polyacrylic acids, polymethacrylic acids, polyoxyethylene alkyl ethers, and sorbitan fatty acid esters.

[0033] Examples of fatty acid metal salts include those in which stearic acid, lauric acid, 12-hydroxystearic acid, montanic acid, behenic acid, ricinoleic acid, myristic acid, or the like is combined with lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, or the like. Examples of the silane coupling agent include 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0034] Titanate coupling agents include tetrakis[2,2-bis(allyloxymethyl)butoxy]titanium(IV), di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, isopropyl titanium triisostearate, di-n-butoxy bis(triethanolaminato)titanium, tetrakis(2-ethylhexyloxy)titanium, and di-i-propoxy bis(acetylacetonato)titanium. Examples of silicones include those obtained by polymerizing olefins or pyrolyzing polyolefins, such as dimethylsilicone oil, methylphenylsilicone oil, methylhydrogensilicone oil, cyclic dimethylsilicone oil, alkyl-modified silicone oil, long-chain alkyl-modified silicone oil, and higher fatty acid-modified silicone oil, and further oxidizing or modifying them with maleic acid, sulfonic acid, carboxylic acid, rosin acid, or the like. Examples of the resin include polyolefins modified with maleic acid, sulfonic acid, carboxylic acid, rosin acid, and the like.

[0035] As a result, a nano-processed nucleating agent is added to the transparent polypropylene layer 4. That is, the transparent polypropylene layer 4 is formed using a smart nano-formulated transparent polypropylene resin. The nucleating agent added to the transparent polypropylene layer 4 includes, for example, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphonate.

[0036] The radical scavenger contains a constituent material that has the function of suppressing autoxidation by capturing radicals that occur when the dye undergoes oxidative deterioration, thereby suppressing deterioration (fading) of the dye. As the radical scavenger, for example, Chimassorb (registered trademark) 2020FDL, Chimassorb (registered trademark) 944FDL, Tinuvin (registered trademark) 622 manufactured by BASF, LA-63P manufactured by ADEKA, etc. can be used.

[0037] In the first embodiment, a case will be described in which a hindered amine-based photoradical scavenger is used as the radical scavenger. As the hindered amine-based photoradical scavenger, for example, a NOR-type hindered amine light stabilizer or the like can be used.

[0038] Furthermore, in the first embodiment, a case will be described in which the hindered amine-based photoradical scavenger used as the radical scavenger is a hindered amine-based photoradical scavenger having a molecular weight of 2000 or more. This is because a high color fading suppression effect can be obtained by using a hindered amine-based photoradical scavenger with a molecular weight of 2000 or more as the radical scavenger. However, a radical scavenger with a low molecular weight is easily volatile, so that fewer molecules remain in the transparent polypropylene layer 4, making it difficult to obtain a sufficient color fading suppression effect.

[0039] The radical scavenger is added in an amount within the range of 0.3% to 10.0% relative to 100% of the polypropylene resin that forms the transparent polypropylene layer 4. In the first embodiment, a case will be described in which the radical scavenger is added in a range of 0.5% to 3.0% with respect to 100% of the polypropylene resin forming the transparent polypropylene layer 4.

[0040] Moreover, the transparent polypropylene layer 4 contains a light stabilizer. As the light stabilizer, for example, a NOR type hindered amine light stabilizer or the like can be used.

[0041] <Surface protective layer> The surface protective layer 5 is laminated on one side of the transparent polypropylene layer 4 (the upper side in Figure 1), and is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1. The surface protective layer 5 also plays an important role in determining the superiority or inferiority of bending workability, weather resistance, scratch resistance, and cleanability. The surface protective layer 5 is mainly composed of a curable resin. In other words, it is preferable that the resin component is substantially composed of a curable resin. "Substantially" refers to, for example, 80 parts by mass or more when the entire resin is taken as 100 parts by mass.

[0042] The weight of the surface protective layer 5 after drying is preferably 0.1 [g / m 2 ] or more than 15[g / m 2 ] or less, more preferably 3 [g / m 2 ] or more than 10[g / m 2 ] or less, more preferably 6 [g / m 2 ] or more than 9 [g / m 2 ] is within the following range. The thickness of the surface protection layer 5 is preferably in the range of 0.1 μm to 10 μm, more preferably in the range of 3 μm to 10 μm, and even more preferably in the range of 6 μm to 9 μm.

[0043] The surface protective layer 5 may contain various additives such as weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scatterers, colorants, light scattering agents, and gloss adjusters, etc. The surface protective layer 5 may contain functional additives such as antibacterial agents and antifungal agents, etc., as necessary. The surface protective layer 5 may be formed of a single layer or a plurality of layers stacked on top of each other.

[0044] In the first embodiment, as shown in FIG. 1, a case will be described in which the surface protective layer 5 has a structure (multi-layer structure) constituted by two layers, a first surface protective layer 5a and a second surface protective layer 5b. When forming the surface protective layer 5 having the first surface protective layer 5a and the second surface protective layer 5b, application and curing of the coating film are performed using known equipment such as a coating device, a heat drying device, an ultraviolet irradiation device, etc., depending on the type of curable resin used as the main component of the first surface protective layer 5a.

[0045] [First surface protective layer] The first surface protective layer 5a is the layer (outermost layer) located on the outermost surface (outermost surface) of the layers constituting the surface protective layer 5. In other words, the first surface protective layer 5a is a layer that forms the surface of the decorative sheet 1. The hardness of the first surface protective layer 5a, measured by a pencil hardness test according to JIS K 5600, is within the range of 4B or more and 2H or less, and more preferably within the range of 3B or more and 3H or less.

[0046] This is because, if the hardness of the first surface protective layer 5a is within the range of 4B or more and 2H or less, when the embossment 7 described below is formed on the surface protective layer 5, it is possible to suppress coating cracking of the surface protective layer 5 and cracks that occur in the coating of the surface protective layer 5 when the embossment 7 is formed. The first surface protective layer 5a contains at least one of a thermosetting resin containing an antiviral agent, an ultraviolet curing resin, and an electron beam curing resin. In the following description, the electron beam curing resin and the ultraviolet curing resin may be collectively referred to as an ionizing radiation curing resin.

[0047] The first surface protective layer 5a can generally be formed by a method in which a coating film is formed by coating a reactive resin, and then the coating film is cured by heating or exposure to ionizing radiation. The thickness of the first surface protective layer 5a is preferably within a range of 3 μm to 15 μm. This is because when the thickness of the first surface protective layer 5a is 3 μm or more, various resistances such as scratch resistance, abrasion resistance, weather resistance, etc. are improved. In addition, when the thickness of the first surface protective layer 5a is 15 μm or less, there is no need to use a resin material in an amount greater than necessary, which makes it possible to reduce costs.

[0048] In addition, the first surface protective layer 5a has different characteristics depending on the curing method. For example, the first surface protective layer 5a formed of an ionizing radiation curable resin generally has a high degree of crosslinking after the curing reaction, and therefore has high hardness and tends to have excellent scratch resistance. On the other hand, the first surface protective layer 5a formed of a thermosetting resin has a relatively low degree of crosslinking, and therefore has low hardness and tends to have excellent flexibility in terms of bending and conforming to a substrate. The first surface protective layer 5a may mainly contain any one of a thermosetting resin, an ultraviolet curing resin, and an electron beam curing resin. In other words, the main component of the first surface protective layer 5a may be a thermosetting resin alone, or may be an ultraviolet curing resin or an ionizing radiation curing resin alone.

[0049] For example, when the decorative sheet 1 is used as a component of a fitting, which often has a complex shape, flexibility (e.g., suitability for processing) is often required. For this reason, for example, in the decorative sheet 1 used for fittings, it is preferable to use a thermosetting resin as the main component of the first surface protective layer 5a. Also, when scratch resistance is required rather than flexibility in the decorative sheet 1, it is preferable to use an ionizing radiation curable resin as the main component of the first surface protective layer 5a. The main component of the first surface protective layer 5a may be a mixture of a thermosetting resin, an ultraviolet curing resin, and an electron beam curing resin. When the main component is a mixture, the ratio of the thermosetting resin, the ultraviolet curing resin, and the electron beam curing resin in the first surface protective layer 5a can be controlled depending on the application of the decorative sheet 1, thereby making it possible to use the decorative sheet 1 in a manner suited to the requirements of various applications.

[0050] [Second surface protective layer] The second surface protective layer 5b is a layer (inner layer) formed between the first surface protective layer 5a and the pattern layer 2, among the layers (first surface protective layer 5a, second surface protective layer 5b) that constitute the surface protective layer 5. The second surface protective layer 5b contains at least one of a thermosetting resin, an ultraviolet curing resin, and an electron beam curing resin, similar to the first surface protective layer 5a. Note that the thermosetting resin, the ultraviolet curing resin, and the electron beam curing resin are the same as the curing resin contained in the first surface protective layer 5a, and therefore the explanation thereof will be omitted.

[0051] The total thickness of the first surface protective layer 5a and the second surface protective layer 5b is, for example, within the range of 3 μm to 15 μm.

[0052] <Primer layer> The primer layer 6 is a layer formed by applying a primer (undercoat) to the other surface of the pattern layer 2 (the lower surface in Figure 1) and laminating it on the other surface of the pattern layer 2.

[0053] <Decorative materials> The configuration of the decorative material 10 will be described with reference to FIG. As shown in FIG. 2, the decorative material 10 is formed, for example, in a plate shape, and includes a decorative sheet 1, a substrate 7, and an adhesive layer 8.

[0054] <Substrate> The substrate 7 is disposed on the other surface (the lower surface in FIG. 2) of the primer layer 6 of the decorative sheet 1, with an adhesive layer 8 sandwiched therebetween. The substrate 7 is made of a wood-based material or a metal-based material.

[0055] Examples of wood-based materials that can be used include wooden veneer, plywood, laminated lumber, particle board, medium density fiberboard, and hard fiberboard. As the metallic material, a steel plate, a brass plate, an aluminum plate, a duralumin plate, a stainless steel plate, or the like can be used.

[0056] Furthermore, the substrate 7 has a folded structure or a three-dimensional structure. When the decorative sheet 1 is laminated onto the substrate 7, it may be laminated via an appropriately selected adhesive as necessary, or it may be laminated directly without an adhesive or the like.

[0057] The decorative sheet 1 can be laminated and bonded to the substrate 7 by a method of contacting a metal plate and pressing it with a flat pressure, or a continuous lamination method using a circular pressure system. In particular, the continuous lamination method using an endless metal belt makes it possible to continuously produce a high-quality decorative material 10 at high speed without surface warping or waviness, with good interlayer adhesion and dense hardened integration.

[0058] <Adhesive layer> The adhesive layer 8 is laminated on one surface of the substrate 7 by, for example, applying a primer (undercoat agent) to one surface of the substrate 7 (the upper surface in FIG. 2). A primer layer 6 is laminated on one surface of the adhesive layer 8 (the upper surface in FIG. 2).

[0059] The above-described first embodiment is one example of the present invention, and the present invention is not limited to the above-described first embodiment. Various modifications can be made depending on the design, etc., even if the modifications are in a form other than the first embodiment, as long as they do not deviate from the technical idea of ​​the present invention.

[0060] (Effects of the First Embodiment) The decorative sheet 1 of the first embodiment can achieve the effects described below. (1) The film comprises a design layer 2 containing a colorant, a sealer layer 3 laminated on one side of the design layer 2 and containing a sealing agent, and a transparent polypropylene layer 4 laminated on one side of the sealer layer 3 and formed using a transparent polypropylene resin. In addition, the film comprises a surface protection layer 5 laminated on one side of the transparent polypropylene layer 4. A radical scavenger is added to the transparent polypropylene layer 4. As a result, it is possible to provide a decorative sheet 1 that is capable of reducing carbon dioxide emissions.

[0061] The decorative sheet 1 of the first embodiment is used, for example, for decorating the surface of buildings such as houses. Decorative sheets used indoors are applied to the surfaces of fittings (interior doors, entrance storage) and construction materials (trimmings, moldings, baseboards, window frames, door frames, etc.) Generally, decorative sheets are multi-layered sheets (multi-layer sheets) made by laminating a transparent olefin sheet to a colored olefin sheet to protect the pattern from surface wear. For this reason, the manufacturing of decorative sheets requires printing and lamination processes. In contrast, the decorative sheet 1 of the first embodiment does not require a lamination process in its production because it is a decorative sheet (single layer sheet) made of a single layer film in which the pattern layer 2 is formed on the transparent polypropylene layer 4. Therefore, the production process of the decorative sheet 1 can be carried out in a single in-line process.

[0062] Furthermore, conventional decorative sheets have a multi-layer structure, and therefore have problems in that there is a limit to the film formation and the hardness is insufficient in order to make the decorative sheet thinner. In contrast, the decorative sheet 1 of the first embodiment has a single-layer structure and is therefore easy to make thin. Furthermore, compared with decorative sheets with a multi-layer structure, the single-layer sheet of the present invention requires less resin and fewer steps in production, and can be made thinner relatively easily, making it possible to reduce carbon dioxide emissions compared to conventional decorative sheets.

[0063] Here, the reason why the amount of carbon dioxide emissions is reduced for decorative sheets formed using resin materials will be explained. In recent years, it has become widely recognized that the cause of global warming is greenhouse gases, primarily carbon dioxide, emitted by human activities, and efforts to reduce carbon dioxide emissions on a global scale have accelerated. On the other hand, resin materials are needed in a wide range of fields, from daily life to industrial applications, such as films, sheets, and bottle containers, due to their ease of molding and light weight, but their widespread use in large quantities has caused various problems, such as the emission of carbon dioxide when incinerated at the time of disposal. To address this problem, compounds that suppress carbon dioxide generation can be added to the resin material. Common additives include calcium carbonate, calcium hydroxide, and zeolite.

[0064] The deterioration of resin and the generation of carbon dioxide due to the combustion of a resin material will be described below. The mechanism by which resin materials burn is as follows: first, heat is transferred from the ignition source to the resin material, causing the temperature of the resin material to rise. As the temperature of the resin material rises, the polymer decomposes, becoming a low-molecular-weight gas containing radicals, which diffuses into the atmosphere. When the diffused gas approaches the vicinity of the ignition source, it reacts violently with oxygen (oxidation reaction). The reaction between oxygen and gas is a rapid and complex chain reaction, with the reaction between radicals and oxygen being predominant. Therefore, carbon dioxide is produced as the final product of the reaction between radicals and oxygen.

[0065] The deterioration of resin and the generation of carbon dioxide due to ultraviolet rays and light will be explained below. Radicals are generated by various factors other than combustion. For example, radicals are generated by light energy such as ultraviolet rays and sunlight. When this happens, a chain reaction between the organic polymer and the radicals progresses, leading to deterioration of the resin and, in the case of decorative sheets, quality problems such as discoloration.

[0066] Here, a common point between the deterioration of resin and the generation of carbon dioxide due to the combustion of resin materials and the deterioration of resin and the generation of carbon dioxide due to ultraviolet rays or light is that the combustion and deterioration of resin progresses due to radicals generated by heat or ultraviolet and light energy. Therefore, in the first embodiment, a radical scavenger is added to the resin material (the transparent polypropylene resin that forms the transparent polypropylene layer 4) to inactivate the generated radicals and suppress combustion and deterioration, thereby improving flame retardancy and weather resistance.

[0067] (2) A nano-processed nucleating agent is added to the transparent polypropylene layer 4. As a result, it is possible to reduce the amount of carbon dioxide emissions compared to a configuration in which a nano-processed nucleating agent is not added to the transparent polypropylene layer 4. Also, it is easier to make the decorative sheet 1 thinner than when a nano-processed nucleating agent is not added to the transparent polypropylene layer 4. In addition, it is possible to increase the hardness of the decorative sheet 1. Furthermore, it is easier to add a radical scavenger.

[0068] (3) The transparent polypropylene layer 4 is formed as a single layer. As a result, it is possible to reduce the amount of carbon dioxide emissions compared to a configuration in which the transparent polypropylene layer 4 is formed in multiple layers.

[0069] (4) The radical scavenger is added in an amount ranging from 0.5% to 3.0% based on 100% of polypropylene resin. As a result, it is possible to reduce the amount of carbon dioxide emitted when the decorative sheet 1 is burned. In addition, it is possible to improve the weather resistance of the decorative sheet 1.

[0070] (5) The radical scavenger is a hindered amine-based photoradical scavenger. As a result, it is possible to reduce the amount of carbon dioxide emitted when the decorative sheet 1 is burned.

[0071] (6) The molecular weight of the photoradical scavenger is 2000 or more. As a result, a high effect of suppressing discoloration can be obtained.

[0072] (7) The transparent polypropylene layer 4 contains a light stabilizer. As a result, it is possible to reduce the amount of carbon dioxide emitted when the decorative sheet 1 is burned.

[0073] Furthermore, the decorative material 10 in the first embodiment can achieve the effects described below. (8) The device comprises a substrate 7 and a decorative sheet 1 laminated on at least one surface of the substrate 7. As a result, it is possible to provide a decorative material 10 that can reduce carbon dioxide emissions.

[0074] <Modification of the first embodiment> (1) In the first embodiment, the surface protective layer 5 has a multi-layer structure. However, the present invention is not limited to this, and the surface protective layer 5 may have a single-layer structure.

[0075] (2) In the first embodiment, the radical scavenger is added in an amount ranging from 0.5% to 3.0% relative to 100% of the polypropylene resin that forms the transparent polypropylene layer 4, but this is not limited to this. That is, the radical scavenger may be added in a range of 0.3% to 4.9% with respect to 100% of the polypropylene resin forming the transparent polypropylene layer 4. Even in this case, it is possible to reduce the amount of carbon dioxide emitted when the decorative sheet 1 is burned. The radical scavenger may be added in an amount ranging from 0.3% to 10.0% relative to 100% of the polypropylene resin that forms the transparent polypropylene layer 4. Even in this case, it is possible to reduce the amount of carbon dioxide emitted when the decorative sheet 1 is burned.

[0076] (3) In the first embodiment, the transparent polypropylene layer 4 has a single-layer structure. However, this is not limited to this. For example, as shown in FIGS. 3 and 4, the transparent polypropylene layer 4 may have a multi-layer structure. Specifically, the transparent polypropylene layer 4 may be configured to include a first skin layer 4a, a core layer 4b, and a second skin layer 4c.

[0077] The first skin layer 4a is a layer laminated on one side of the sealer layer 3, and is a layer formed using a transparent polypropylene resin to which a nano-processed nucleating agent has been added. The core layer 4b is a layer laminated on the surface of the first skin layer 4a opposite to the surface facing the sealer layer 3, and is a layer formed by adding a radical scavenger to a transparent polypropylene resin. The second skin layer 4c is a layer laminated on the surface of the core layer 4b opposite to the surface facing the first skin layer 4a, and is a layer formed using a transparent polypropylene resin to which a nano-treated nucleating agent has been added.

[0078] (4) In the first embodiment, a hindered amine-based photoradical scavenger is used as the radical scavenger. However, the present invention is not limited to this. For example, a phenol-based antioxidant may be used as the radical scavenger. EXAMPLES

[0079] With reference to the first embodiment, the decorative sheets of Examples 1 to 6 and the decorative sheets of Comparative Examples 1 and 2 will be described below.

[0080] Example 1 The transparent polypropylene layer was formed as a multi-layer structure including a first skin layer, a core layer, and a second skin layer. The core layer was formed by adding 3.0% of a radical scavenger to 100% transparent polypropylene resin.

[0081] The first and second skin layers were formed using a transparent polypropylene resin containing a nano-processed nucleating agent. Then, by simultaneously extruding the layers so that the thickness ratio of the first skin layer, the core layer, and the second skin layer was 0.5:9:0.5, a transparent polypropylene layer with a thickness of 50 μm was formed.

[0082] The design layer was formed by applying a corona treatment to the other surface of the transparent polypropylene layer to form a sealer layer, and then printing a design using a urethane resin. The first surface protective layer was formed by subjecting one side of a transparent polypropylene layer to corona treatment and then applying a low-gloss acrylic two-component curing resin (acrylic urethane resin manufactured by DIC Graphics) to a thickness of 6 μm.

[0083] The second surface protective layer is formed on the surface of the first surface protective layer opposite to the surface facing the transparent polypropylene layer by printing an acrylic two-component curing resin having a higher gloss than the acrylic two-component curing resin forming the first surface protective layer with a pattern that matches the pattern layer. The primer layer was formed by applying a primer to the other surface of the design layer. In this manner, the decorative sheet of Example 1 was formed.

[0084] Example 2 The decorative sheet of Example 2 was formed in the same manner as in Example 1, except that the transparent polypropylene layer was made to have a single layer structure of transparent polypropylene resin to which a nano-processed nucleating agent had been added.

[0085] Example 3 The decorative sheet of Example 3 was formed in the same manner as in Example 1, except that the core layer was formed by adding 0.5% of a radical scavenger to 100% transparent polypropylene resin.

[0086] Example 4 The decorative sheet of Example 4 was formed in the same manner as in Example 1, except that the core layer was formed by adding 1.5% of a radical scavenger to 100% of the transparent polypropylene resin.

[0087] Example 5 The decorative sheet of Example 5 was formed in the same manner as in Example 1, except that the core layer was formed by adding 5.0% of a radical scavenger to 100% of transparent polypropylene resin.

[0088] Example 6 The decorative sheet of Example 6 was formed in the same manner as in Example 1, except that the core layer was formed by adding 10.0% of the radical scavenger to 100% of the transparent polypropylene resin.

[0089] Comparative Example 1 A decorative sheet of Comparative Example 1 was formed in the same manner as in Example 1, except that the core layer was configured by using a transparent polypropylene resin to which no radical scavenger was added.

[0090] Comparative Example 2 The decorative sheet of Comparative Example 2 was formed in the same manner as in Example 1, except that, instead of the pattern layer, sealer layer, and transparent polypropylene layer, a multi-layer structure layer was formed by laminating a colored olefin sheet on which a pattern was printed with transparent polypropylene resin.

[0091] (Performance evaluation) The decorative sheets of Examples 1 to 6 and Comparative Examples 1 and 2 were each evaluated for fire resistance, weather resistance, and carbon dioxide emissions. The evaluation methods used were as described below.

[0092] <Fire resistance> A combustion test was carried out on the decorative sheets of the examples and the decorative sheets of the comparative examples to evaluate their fire resistance. Combustion tests were conducted according to the fire resistance test method based on Article 2, Paragraph 9 of the Building Standards Act and Article 108, Paragraph 2 of the Enforcement Order of the Building Standards Act, and heat generation tests using a cone calorimeter tester in accordance with the performance evaluation standard.

[0093] <Fire resistance evaluation> For decorative sheets that underwent fire resistance and heat generation tests, those that satisfied all of the criteria A through C were rated as "O", and those that did not satisfy even one of the criteria A through C were rated as "X". Criterion A: The total heat generated 20 minutes after the start of heating is 8 [MJ / m 2 ]below. Criterion B: The maximum heat generation rate continues for 10 seconds or more within 20 minutes after the start of heating [200KW / m 2 ] is less than. Criterion C: No cracks or holes harmful to fire protection are present within 20 minutes after heating begins.

[0094] <Weather resistance> A weather resistance test was carried out on the decorative sheets of the examples and the decorative sheets of the comparative examples to evaluate their weather resistance. The weather resistance test was conducted using an ultra-accelerated weather resistance tester (metal halide lamp weather meter) under the following conditions: UV irradiation mode (20 hours) and condensation mode (4 hours). A combination of one UV irradiation mode and one condensation mode was counted as one cycle (24 hours), and 25 cycles (600 hours) of weather resistance test were conducted.

[0095] UV irradiation mode ·Illuminance: 65[mW / cm 2 ] Black panel temperature: 53[℃] Relative humidity: 50%

[0096] Condensation Mode ·Environmental temperature: 30[℃] Relative humidity 98% When switching between the ultraviolet irradiation mode and the condensation mode, a shower spray was performed for 10 seconds.

[0097] <Weather resistance evaluation> The appearance of the decorative sheets that underwent the weather resistance test was visually inspected, and those that did not show any significant discoloration, fading, or peeling were rated as "○", those that showed significant discoloration, fading, or peeling were rated as "△", and those that showed significant discoloration, fading, or peeling were rated as "×". In addition, for weather resistance, decorative sheets that were rated as "○" were deemed to have passed the test.

[0098] <Carbon dioxide emissions> The amount of carbon dioxide emission was measured for the decorative sheet of the example and the decorative sheet of the comparative example, and the amount of carbon dioxide emission was evaluated. The amount of carbon dioxide emissions was measured using a plastic combustion tester (manufactured by Sugiyamagen Co., Ltd.). Specifically, a test piece weighing 0.1 g was taken from each of the decorative sheets of the examples and the comparative examples, and the 0.1 g sample was burned for 10 minutes under conditions of a gas supply rate of 0.5 L / min and a set temperature of 750°C. The total amount of carbon dioxide emitted during combustion was then measured. The total amount of carbon dioxide emitted was measured three times for each of the decorative sheets of Examples 1 to 6 and the decorative sheets of Comparative Examples 1 and 2, and the average value was used as the measured value. [Table 1]

[0099] (Evaluation Results) As a result of evaluating various performances using the above-mentioned methods, the decorative sheets of Examples 1 to 6 showed excellent performance in the evaluation tests of fire resistance and carbon dioxide emission. In particular, it was confirmed that the decorative sheets of Examples 4 to 6 had half the carbon dioxide emission compared to the decorative sheets of Comparative Examples 1 and 2. It was also confirmed that the decorative sheets of Examples 1 to 4 had excellent weather resistance in addition to fire resistance and carbon dioxide emission. On the other hand, the decorative sheets of Comparative Examples 1 and 2 were unable to demonstrate excellent performance in all of the evaluation tests.

[0100] The present technology can be configured as follows. (1) A design layer including a colorant; a sealer layer laminated on one surface of the design layer and containing a sealer agent; a transparent polypropylene layer laminated on one surface of the sealer layer and formed using a transparent polypropylene resin; A surface protective layer is laminated on one surface of the transparent polypropylene layer, A decorative sheet, wherein a radical scavenger is added to the transparent polypropylene layer. (2) A decorative sheet according to (1) above, wherein a nano-processed nucleating agent is added to the transparent polypropylene layer. (3) The decorative sheet according to (1) or (2) above, wherein the transparent polypropylene layer is formed as a single layer. (4) The decorative sheet according to any one of (1) to (3) above, wherein the radical scavenger is added in an amount within the range of 0.3% to 10.0% based on 100% of the polypropylene resin. (5) The decorative sheet according to (4) above, wherein the radical scavenger is added in an amount within the range of 0.3% to 4.9% based on 100% of the polypropylene resin. (6) The decorative sheet according to (5) above, wherein the radical scavenger is added in an amount of 0.5% to 3.0% based on 100% of the polypropylene resin. (7) The decorative sheet according to any one of (1) to (6) above, wherein the radical scavenger is a hindered amine-based photoradical scavenger. (8) The decorative sheet according to (7) above, wherein the molecular weight of the photoradical scavenger is 2000 or more. (9) The decorative sheet according to any one of (1) to (8) above, wherein a light stabilizer is added to the transparent polypropylene layer. (10) The decorative sheet according to any one of (1) to (9) above, further comprising a primer layer laminated on the other side of the design layer. (11) A substrate; A decorative material comprising: a decorative sheet according to any one of (1) to (10) above, laminated on at least one surface of the substrate. [Explanation of symbols]

[0101] 1...decorative sheet, 2...picture layer, 3...sealer layer, 4...transparent polypropylene layer, 4a...first skin layer, 4b...core layer, 4c...second skin layer, 5...surface protective layer, 5a...first surface protective layer, 5b...second surface protective layer, 6...primer layer, 7...substrate, 8...adhesive layer, 10...decorative material

Claims

1. A design layer including a colorant; a sealer layer laminated on one surface of the design layer and containing a sealer agent; a transparent polypropylene layer laminated on one surface of the sealer layer and formed using a transparent polypropylene resin; A surface protective layer is laminated on one surface of the transparent polypropylene layer, A decorative sheet, wherein a radical scavenger is added to the transparent polypropylene layer.

2. 2. The decorative sheet according to claim 1, wherein a nano-processed nucleating agent is added to said transparent polypropylene layer.

3. 3. The decorative sheet according to claim 2, wherein said transparent polypropylene layer is formed as a single layer.

4. 2. The decorative sheet according to claim 1, wherein the radical scavenger is added in an amount within the range of 0.3% to 10.0% based on 100% of the polypropylene resin.

5. 5. The decorative sheet according to claim 4, wherein the radical scavenger is added in an amount within the range of 0.3% to 4.9% based on 100% of the polypropylene resin.

6. 6. The decorative sheet according to claim 5, wherein the radical scavenger is added in an amount within the range of 0.5% to 3.0% based on 100% of the polypropylene resin.

7. 2. The decorative sheet according to claim 1, wherein the radical scavenger is a hindered amine-based photoradical scavenger.

8. 8. The decorative sheet according to claim 7, wherein the molecular weight of said photoradical scavenger is 2,000 or more.

9. 2. The decorative sheet according to claim 1, wherein said transparent polypropylene layer contains a light stabilizer.

10. 2. A decorative sheet according to claim 1, further comprising a primer layer laminated on the other side of said design layer.

11. A substrate; A decorative material comprising: a decorative sheet according to any one of claims 1 to 10 laminated on at least one surface of the substrate.

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