Decorative sheets and floor coverings

Abstract

To provide a decorative sheet that maintains anti-allergen properties while exhibiting excellent scratch resistance and sliding properties. [Solution] The decorative sheet 1 comprises at least a colored layer 2 and a surface protective layer 7, the surface protective layer 7 having, for example, an upper layer 7a and a lower layer 7b, the upper layer 7a which is the outermost layer of the surface protective layer 7 contains a mixed composition of a thermosetting resin and an ionizing radiation curing resin, the weight ratio of the thermosetting resin in the mixed composition is in the range of 3% by weight or more and 30% by weight or less. The upper layer 7a further contains an anti-allergen composition, the weight ratio of the allergen composition in the upper layer 7a is in the range of 3% by weight or more and 30% by weight or less.

Description

[Technical Field]

[0001] This invention relates to decorative sheets and decorative materials for floors. [Background technology]

[0002] Conventionally, decorative sheets have been proposed that possess anti-allergen properties by applying an anti-allergen agent to the surface of wood materials or wood-based materials such as plywood, or by incorporating an anti-allergen agent into the resin used as a surface protective layer of the decorative sheet (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-098170 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In order to exhibit anti-allergen properties by incorporating an anti-allergen composition into the surface protective layer, the anti-allergen composition must be placed on the outermost surface of the surface protective layer. However, anti-allergen compositions are not necessarily designed with hardness as a primary consideration. Therefore, for example, in the case of decorative flooring sheets, if the anti-allergen composition is placed on the outermost surface of the surface protective layer, the anti-allergen composition may be damaged by people walking on the sheets every day, or the anti-allergen composition may be worn away by friction between the surfaces of the decorative sheets during transportation of the flooring material, resulting in problems in terms of scratch resistance and sliding properties.

[0005] This invention has been made in view of the above points, and aims to provide decorative sheets and floor coverings that have excellent scratch resistance and sliding properties while maintaining anti-allergen performance. [Means for solving the problem]

[0006] According to one aspect of the present invention, a decorative sheet is provided comprising at least a sheet substrate and a surface protection layer laminated on one side of the sheet substrate, wherein the surface protection layer has one or more layers, the outermost layer of the surface protection layer contains a mixed composition of a thermosetting resin and an ionizing radiation-curable resin, the weight ratio of the thermosetting resin in the mixed composition is in the range of 3% by weight or more and 30% by weight or less, and the outermost layer further contains an anti-allergen composition, the weight ratio of the anti-allergen composition in the outermost layer is in the range of 3% by weight or more and 30% by weight or less. Furthermore, according to another aspect of the present invention, a floor decorative material is provided comprising a floor base material and a decorative sheet according to the above-described aspect provided on one side of the floor base material. [Effects of the Invention]

[0007] According to one embodiment of the present invention, decorative sheets and floor coverings that are excellent in scratch resistance and sliding properties and can maintain anti-allergen performance can be easily obtained. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet and floor covering material according to one embodiment of the present invention. [Modes for carrying out the invention]

[0009] The embodiments of this technology will be described below with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Within the scope of this disclosure, the layers do not necessarily have to be stacked in the order shown in the drawings. Furthermore, additional layers not shown in these drawings may be added. Also, the embodiments described below are illustrative of configurations for embodying the technical concept of this disclosure, and the technical concept of this disclosure is not limited to the materials, shapes, and structures of the components described below. The technical concept of this disclosure can be modified in various ways within the technical scope defined by the claims described in the patent claims. Furthermore, the terms "left / right" and "up / down" in the following explanation are merely definitions for the sake of explanation and do not limit the technical concept of this disclosure. Therefore, for example, if the page is rotated 90 degrees, "left / right" and "up / down" will be swapped when read, and if the page is rotated 180 degrees, "left" will become "right" and "right" will become "left".

[0010] [Decorative sheet 1] A decorative sheet 1 according to one embodiment of the present invention is constructed by laminating, for example, a colored layer 2 as a sheet substrate made of a colored thermoplastic resin layer, a pattern layer 3, a transparent adhesive layer 4, a transparent adhesive resin layer 5, a transparent resin layer 6, and a surface protection layer 7 in this order, as shown in Figure 1. Furthermore, in order to provide anti-allergen properties, an anti-allergen composition is added to the surface protection layer 7 of the decorative sheet 1 according to this embodiment. Note that the decorative sheet 1 only needs to include at least a colored layer 2 as a sheet substrate and a surface protection layer 7. As shown in Figure 1, the decorative sheet 1 of this embodiment is constructed as a floor decorative material 11 by bonding a floor base material 10 to the other side of the colored layer 2 via a back primer layer 8 and a floor wood adhesive 9. As the floor base material 10, for example, wood-based boards, inorganic boards, metal plates, etc., can be used.

[0011] <Colored layer 2> The colored layer 2 is a colored thermoplastic resin layer that serves as the sheet base material for the decorative sheet 1. As the colored layer 2, vinyl chloride resin, acrylic resin, polyolefin-based polypropylene resin or polyethylene resin, and polyester-based, acrylic-based, PVC, etc., can be used. Among these, colored thermoplastic polyolefin-based resins are preferred due to their environmental compatibility, processability, and cost. The resin grade and composition can also be selected considering ease of sheeting, printability, and suitability for bending.

[0012] As colored thermoplastic polyolefin resins, for example, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer, as well as olefin copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, and ethylene-unsaturated carboxylic acid copolymer metal neutralization products (ionomers), can be used individually or as mixtures of two or more, copolymers, composites, laminates, etc.

[0013] As for polyolefin resins, they can be appropriately selected and used from these many types depending on the intended use of the decorative sheet 1. In particular, polypropylene resins, i.e., polypropylene alone or copolymers, are most suitable for general use. For example, homopolypropylene resins, random polypropylene resins, block polypropylene resins, etc., can be used alone or in appropriate combinations, or resins to which atactic polypropylene can be appropriately added can be used. Furthermore, copolymers containing olefin monomers other than propylene may also be used. For example, a propylene-α-olefin copolymer having a polypropylene crystalline portion and containing 15 mol% or more of one or more carbon-2 to carbon-20 α-olefins other than propylene, preferably ethylene, butene-1, 4-methylpentene-1, hexene-1, or octene-1 comonomers. Furthermore, modifiers such as low-density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, styrene-butadiene copolymer, or hydrogenated versions thereof, which are commonly used to soften polypropylene resins, can be added as appropriate.

[0014] The colored layer 2 may optionally contain one or more additives selected from a variety of additives, such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters. The thickness of the coloring layer 2 is preferably in the range of 40 μm or more and 150 μm or less, and more preferably 50 μm or more and 130 μm or less. When the thickness of the coloring layer 2 is 40 μm or more, unevenness and steps of the floor material or the like serving as the base can be absorbed, and the finished application of the decorative sheet 1 can be improved. Further, when the thickness of the coloring layer 2 is 150 μm or less, the coloring layer 2 is not formed thicker than necessary, and the manufacturing cost of the decorative sheet 1 can be reduced. Coloring of the coloring layer 2 can conceal the base material to which the decorative sheet 1 is bonded and select a hue as the base color of the pattern layer 3. For example, when seating a thermoplastic resin to be the coloring layer 2, coloring can be achieved by mixing and kneading a colorant such as a pigment. Alternatively, before providing the pattern layer 3, as a solid ink layer, a coloring layer can be provided under the pattern layer 3 using a coating or printing method.

[0015] <Pattern layer 3> The pattern layer 3 is formed on the coloring layer 2 and is a layer for adding a pattern for imparting design characteristics, and is provided as necessary. The pattern layer 3 can be omitted when it can be substituted by the coloring of the coloring layer 2. The pattern layer 3 is formed using a printing ink or paint or the like obtained by dissolving or dispersing a colorant such as a dye or a pigment together with a suitable binder resin in a suitable diluting solvent. The printing ink or paint or the like is applied by various known printing methods such as a gravure printing method or an offset printing method, or various coating methods such as a gravure coating method or a roll coating method. Further, as the binder resin, for example, a urethane resin, an acrylic resin, a vinyl chloride acetate resin, a polyimide resin, nitrocellulose, or the like, or a mixture thereof can be used, but of course, it is not limited thereto.

[0016] In addition, as the pattern, any pattern can be used. For example, wood grain patterns, stone grain patterns, cloth grain patterns, abstract patterns, geometric patterns, characters, symbols, solid colors without patterns, etc., or combinations thereof can be used. The pattern can be any pattern considering the design property as a flooring material. In the case of a woody pattern, various wood grains are often preferably used. In addition to wood grains, cork can also be used as a pattern. For example, if it is an image of a floor made of a stone material such as marble, it may be used as a pattern such as the grain of marble. In addition to the pattern of natural materials, artificial pattern motifs based on them or artificial pattern motifs such as geometric patterns can also be used.

[0017] In addition, in order to improve the concealment of the decorative sheet 1, a concealment layer made of an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide and iron oxide may be provided between the pattern layer 3 and the coloring layer 2. The thickness of the pattern layer 3 is preferably in the range of 1 μm or more and 10 μm or less. When the thickness of the pattern layer 3 is 1 μm or more, printing can be made clear. When the thickness of the pattern layer 3 is 10 μm or less, the printing workability when manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.

[0018] In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, curing agents, curing accelerators, and curing retarders may be added to the pattern layer 3 in order to impart various functions. In addition, the pattern layer 3 may have, for example, a solid-colored coating layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached and a pattern layer for adding a pattern for imparting design property. Regarding the printing ink, there is no particular limitation, but an ink corresponding to the printing method can be appropriately selected. It is preferably selected in consideration of the adhesion to the coloring layer 2, the printing suitability, and the weather resistance as a flooring material.

[0019] <Transparent adhesive layer 4> The transparent adhesive layer 4 is provided to strengthen the adhesion between the colored layer 2 or patterned layer 3 and the transparent resin layer 6. This strong adhesion allows the decorative sheet 1 to be bend to conform to curved and right-angled surfaces. Note that the transparent adhesive layer 4 is not necessarily required.

[0020] <Transparent adhesive resin layer 5> The transparent adhesive resin layer 5 is a layer provided on the pattern layer 3 for the purpose of improving the adhesion between the pattern layer 3, the transparent adhesive layer 4, and the transparent resin layer 6, and is provided as needed. The resin used for the transparent adhesive resin layer 5 is not particularly limited, but for example, a two-component curing urethane resin can be used, and it can be provided using, for example, a coating apparatus or a gravure printing apparatus.

[0021] <Transparent resin layer 6> As the resin material for the transparent resin layer 6, a thermoplastic polyolefin resin is preferably used. As the polyolefin resin, the thermoplastic polyolefin resin used for the colored layer 2 can be used. As with the colored layer 2, as with the polyolefin resin, a variety of types can be appropriately selected and used depending on the intended use of the decorative sheet 1, and in particular, polypropylene resin, i.e., a single or copolymer mainly composed of propylene, is most suitable for general use. By providing the transparent resin layer 6, the decorative sheet 1 has the effect of having thickness and depth in terms of design, and the weather resistance and abrasion resistance of the decorative sheet 1 can be improved.

[0022] The transparent resin layer 6 may contain, as needed, one or more additives selected from various sources such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters. Preferably, the transparent resin layer 6 has a transparency (colorless, colored, or semi-transparent) such that the pattern of the pattern layer 3 can be seen through the surface (top surface) of the decorative sheet 1. The transparent resin layer 6 may be provided as needed. The thickness of the transparent resin layer 6 shall be, for example, within the range of 20 μm to 200 μm. The transparent resin layer 6 may have an embossed pattern (not shown) formed on the surface facing the protective surface layer 7 to provide aesthetic appeal. Typically, the uneven pattern is formed by embossing. The embossing method is not particularly limited. Examples of uneven shapes for the embossed pattern include wood grain grooves, surface irregularities of a right-hand panel (such as granite cleavage surfaces), fabric surface textures, pearlescent finishes, sand textures, hairline finishes, and fine grooves.

[0023] <Surface protective layer 7> The surface protection layer 7 is a layer formed on the transparent resin layer 6 and is provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1. The surface protection layer 7 includes a lower layer 7b laminated on the transparent resin layer 6 and an upper layer 7a laminated on the lower layer 7b. Each layer is formed by coating and curing the coating film using a known coating device, heat drying device, and ultraviolet irradiation device, depending on the type of curable resin. The surface protection layer 7 may consist of one layer, but it is preferable to consist of two or more layers from the viewpoint of adhesion. The surface protection layer 7 plays a crucial role in determining the quality of the material in terms of bendability, weather resistance, scratch resistance, and ease of cleaning. The surface protection layer 7 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 means, for example, 80 parts by mass or more when the total resin is 100 parts by mass.

[0024] As curable resins, ionizing radiation-curable resins and thermosetting resins are preferably used. As ionizing radiation-curable resins, known materials such as various monomers and commercially available oligomers can be used. For example, polyfunctional monomers such as pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4A), trimethylolpropane triacrylate (TMPTA), and dipentaerythritol hexaacrylate (DPHA), or polyfunctional oligomers such as Shiko UV-1700B (manufactured by Nippon Synthetic Chemical Co., Ltd.), or mixtures thereof are preferably used.

[0025] The ionizing radiation-curable resin used preferably contains four or more functional groups per molecule. If the number of functional groups per molecule is less than four, the hardness of the cured product may be insufficient, and sufficient scratch resistance may not be obtained. Furthermore, the number of functional groups is preferably 20 or less. If the number of functional groups is greater than 20, the versatility of the material may be low and the cost may be high. In addition, the mass-average molecular weight is preferably in the range of 500 to 5,000. If the mass-average molecular weight is less than 500, the crosslinking density will be high, which may reduce crack resistance. Furthermore, if the mass-average molecular weight exceeds 5,000, the solubility may decrease, which may result in poor design properties. Thermosetting resins are formed, for example, by curing a polymer (polyol) containing hydroxyl groups and an isocyanate compound by heat, as described below.

[0026] The polyol compounds mentioned above are not particularly limited, but may be used to impart mechanical properties such as molecular structure extension. They can be appropriately selected from, for example, various acrylic polyols, various polyester polyols, various polyether polyols, various polycarbonate polyols, and various caprolactone diols. As mentioned above, there are no particular limitations on the isocyanate compounds, but examples include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), and isophorone diisocyanate (IPDI).

[0027] The surface protective layer 7 may contain various additives as needed, such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, UV absorbers, heat stabilizers, light stabilizers, antiblocking agents, catalyst scavengers, colorants, light scattering agents, and gloss modifiers. It may also contain functional additives such as antibacterial agents and antifungal agents.

[0028] [Upper layer 7a] The upper layer 7a of the surface protective layer 7 is a resin layer with a thickness in the range of 5 μm to 10 μm. If the thickness of the upper layer 7a is 5 μm or more, various resistances such as scratch resistance, abrasion resistance, and weather resistance are improved. If the thickness of the upper layer 7a is 10 μm or less, it is not necessary to use an unnecessarily large amount of resin material, and costs can be reduced. Furthermore, by applying the coating liquid for the upper layer 7a so that the amount of coating after drying is within the range of 5 μm to 10 μm, the thickness of the upper layer 7a can be set within the range of 5 μm to 10 μm. However, if the thickness of the upper layer 7a is greater than 10 μm, there is a possibility of poor curing, which is undesirable. Also, if the thickness of the upper layer 7a is less than 5 μm, the scratch resistance will decrease, which is undesirable.

[0029] The main material of the resin component constituting the upper layer 7a is preferably an ionizing radiation-curable resin from the viewpoint of ensuring hardness and scratch resistance, but a mixed composition of an ionizing radiation-curable resin and a thermosetting resin may also be used from the viewpoint of ensuring weather resistance in addition to hardness and scratch resistance. In that case, it is preferable that the upper layer 7a contains, as the main component, a mixed composition of an ionizing radiation-curable resin and a thermosetting resin in an amount of 50% by weight or more relative to the total weight of the upper layer 7a. Furthermore, it is preferable that the weight ratio of the thermosetting resin in the mixed composition in the upper layer 7a is 3% by weight or more and 30% by weight or less, and more preferably 5% by weight or more and 20% by weight or less. Furthermore, the upper layer 7a contains an anti-allergen composition that is solid at room temperature. The anti-allergen composition consists of either an organic or an inorganic anti-allergen composition, or a combination of these organic and inorganic anti-allergen compositions. By using an anti-allergen composition that is solid at room temperature, it is possible to improve scratch resistance and obtain the effect of being less prone to bleeding.

[0030] The anti-allergen composition preferably has an average particle size of 1 μm to 10 μm in its solid state. If the average particle size of the anti-allergen composition is large, the film-forming properties will be poor. Also, whether the average particle size of the anti-allergen composition is large or small, the allergen composition that protrudes from the surface of the upper layer 7a is prone to falling off due to sliding, etc. Furthermore, in order to exhibit anti-allergen properties, it is necessary for the anti-allergen composition to protrude from the surface of the upper layer 7a, but if the average particle size of the anti-allergen composition is small, the portion embedded in the surface of the upper layer 7a becomes small, and the fixing force that holds the anti-allergen composition decreases. Also, if the average particle size exceeds 10 μm, the anti-allergen composition becomes larger than the thickness of the coating film of the upper layer 7a, so the portion embedded in the coating film of the anti-allergen composition becomes small and it becomes prone to falling off. The upper layer 7a contains an anti-allergen composition in an amount of 3% to 30% by weight relative to the upper layer 7a. Examples of anti-allergen compositions include organic anti-allergen compositions such as a composite of an anion-modified organic compound and a carrier. The composite exerts an allergen reduction effect by chemically adsorbing to the proteins of the allergen substance.

[0031] Examples of anionically modified organic compounds include anionically modified linear alkanes and anionically modified polyvinyl alcohol. Specifically, anionically modified linear alkanes include linear alkanes modified with acidic anionic groups such as carboxyl groups, phosphate groups, and sulfonic acid groups. Examples of counterions for acidic anionic groups include sodium ions and potassium ions. Examples of anionically modified polyvinyl alcohol include polyvinyl alcohol modified with acidic anionic groups such as carboxyl groups and sulfonic acid groups. Examples of carriers include inorganic particles or organic particles, such as acrylic particles such as base-modified acrylic particles, styrene particles such as base-modified styrene particles, and silver oxide particles. Examples of inorganic anti-allergen compositions include alkaline earth metal salt compounds, rare earth metal salt compounds, zirconium salt compounds, aluminum salt compounds, and ceramic compounds. Furthermore, in the decorative sheet 1 according to this embodiment, for example, as a measure to improve stain resistance, a silicone-based component (e.g., silicone resin) or a fluorine-based component (e.g., fluororesin) may be provided on the outermost surface (upper layer 7a) of the decorative sheet 1.

[0032] [Silicone resin] When using a silicone resin, it is preferable to use a modified silicone due to issues of adhesion and compatibility with the surrounding material. When the curable resin constituting the upper layer 7a is formed from an ultraviolet-curable resin or an electron beam-curable resin, the modified silicone is preferably an ionizing radiation-reactive modified silicone resin. When the curable resin constituting the upper layer 7a is formed from a thermosetting resin, the modified silicone is preferably a thermally reactive modified silicone resin. Furthermore, when the curable resin constituting the upper layer 7a is formed from a mixture of an ionizing radiation-curable resin and a thermosetting resin, the modified silicone is preferably a modified silicone resin having at least one of ionizing radiation reactivity and thermal reactivity.

[0033] Modified silicon can be classified into reactive and non-reactive types. Examples of heat-reactive modified silicon include monoamine-modified silicon, diamine-modified silicon, epoxy-modified silicon, carbinol-modified silicon, carboxy-modified silicon, mercapto-modified silicon, silanol-modified silicon, alcohol-modified silicon, and diol-modified silicon. Examples of ionizing radiation-reactive modified silicon include acrylic-modified silicon and methacrylic-modified silicon. Examples of non-reactive modified silicon include polyether-modified silicon, aralkyl-modified silicon, long-chain alkyl-modified silicon, and higher fatty acid ester-modified silicon. Manufacturers of these modified silicon include Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Japan LLC, and Asahi Kasei Wacker Silicone Co., Ltd.

[0034] [Fluororesin] Fluororesins are widely known to exhibit the lowest level of surface tension and are suitable as stain-resistant materials. Examples of fluororesins contained in the upper layer 7a include tetrafluoroethylene resin, tetrafluoroethylene-ethylene copolymer, and polyvinylidene fluoride, and many other derivatives can also be used. Manufacturers of these fluororesins include Daikin Industries, Ltd. and Mitsui DuPont Fluorochemicals Co., Ltd. The amount of fluororesin contained in the upper layer 7a is preferably 10 parts by mass or more and 100 parts by mass or less. More preferably 20 parts by mass or more. Here, the fluororesin itself may be a curable resin. That is, a part of the fluororesin may also serve as a part of the curable resin that is the main component of the surface protection layer 7 (upper layer 7a, lower layer 7b). For example, the entire resin component of the lower layer 7b may be fluororesin. Thus, in the decorative sheet 1 according to this embodiment, the outermost layer of the surface protective layer 7, i.e., the upper layer 7a, may contain at least one of a silicone-based component or a fluorine-based component. This improves the stain resistance of the decorative sheet 1.

[0035] [Lower layer 7b] The lower layer 7b of the surface protective layer 7 is a resin layer with a thickness in the range of 5 μm to 15 μm, preferably 5 μm to 10 μm. The thickness of the lower layer 7b is preferably greater than or equal to the thickness of the upper layer 7a. Ionizing radiation-curable resin or thermosetting resin can be used as the main material of the resin component constituting the lower layer 7b. However, since thermosetting resin has better adhesion to the transparent resin layer 6 than ionizing radiation-curable resin, thermosetting resin is preferred as the main material of the resin component constituting the lower layer 7b.

[0036] When the main material of the resin component constituting the lower layer 7b is a thermosetting resin, it is preferable that the thermosetting resin be composed of a polymer (polyol) containing hydroxyl groups and an isocyanate curing agent. In this case, it is particularly preferable to use an acrylic polyol as the polymer (polyol) containing hydroxyl groups. The mixing ratio of the acrylic polyol and the isocyanate curing agent is determined by the NCO / OH ratio, which is the molar ratio of the hydroxyl groups (OH groups) of the acrylic polyol to the isocyanate groups (NCO groups) of the isocyanate curing agent. The NCO / OH ratio is preferably in the range of 1 to 5. More preferably, it is in the range of 1 to 3.

[0037] When the thermosetting resin constituting the lower layer 7b is composed of an acrylic polyol and an isocyanate curing agent, it is preferable that the glass transition temperature (Tg) of the thermosetting resin is 50°C or higher, and the mass-average molecular weight of the acrylic polyol used is in the range of 20,000 to 200,000. If the glass transition temperature (Tg) of the thermosetting resin is below 50°C, coating during sheet fabrication may become difficult. Furthermore, it is preferable that the glass transition temperature (Tg) is 105°C or lower. If the glass transition temperature (Tg) is higher than 105°C, the versatility of the material may be reduced and the cost may increase. If the mass-average molecular weight of the acrylic polyol is less than 20,000, coating during sheet fabrication may become difficult. Furthermore, if the mass-average molecular weight exceeds 200,000, solubility may decrease, potentially resulting in poor aesthetic appeal.

[0038] Furthermore, by applying the coating liquid for the lower layer 7b such that the amount of coating after drying is within the range of 5 μm to 15 μm, preferably within the range of 5 μm to 10 μm, the thickness of the lower layer 7b can be set to within the range of 5 μm to 15 μm, preferably within the range of 5 μm to 10 μm. Note that if the thickness of the lower layer 7b is less than 5 μm, the scratch resistance will decrease, which is undesirable. Furthermore, in order to improve the adhesive strength of each layer of the decorative sheet 1, an adhesive layer containing a two-component curing urethane adhesive using an isocyanate-based curing agent may be provided between the transparent resin layer 6 and the lower layer 7b of the surface protective layer 7.

[0039] <Primer layer on the back surface 8> The back surface primer layer 8 is a layer provided between the colored layer 2 and the adhesive 9 for the floor substrate for facilitating adhesion of the floor substrate 10, and is provided as needed. The back surface primer layer 8 is formed by applying a known primer to the side of the colored layer 2 opposite to the pattern layer 3. Examples of primers include urethane resin-based primers made of acrylic-modified urethane resin, and primers made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrated cotton).

[0040] The amount of primer to be applied is not particularly limited, but is usually 0.1 g / m². 2 More than 100g / m 2 Preferably, it is within the following range: 0.1 g / m 2 More than 50g / m 2 It is more preferable that the range be within the following: The thickness of the back surface primer layer 8 is not particularly limited, but is usually preferably in the range of 0.01 μm to 10 μm, and more preferably in the range of 0.1 μm to 1 μm.

[0041] <Adhesive for flooring materials 9> A floor adhesive 9 is formed between the colored layer 2 and the floor substrate 10. The floor adhesive 9 may be formed by applying a composition for forming the floor adhesive 9 onto the floor substrate 10, or by applying a composition for forming the floor adhesive 9 onto the colored layer 2. The adhesive included in the floor adhesive 9 can be arbitrarily selected from, for example, urethane-based, acrylic-based, polyester-based, etc., depending on the combination with the thermoplastic resin included in the colored layer 2.

[0042] The amount of composition to be applied to form the adhesive 9 for floor substrates is 3 g / m². 2 More than 20g / m 2 The following range is preferable: The amount of the composition for forming the adhesive 9 for floor substrates is 3 g / m². 2As a result, the adhesion between the colored layer 2 and the floor substrate 10 is improved. Also, the amount of composition to be applied to form the floor substrate adhesive 9 is 20 g / m². 2 The following conditions result in a uniform coating of the composition for forming the adhesive 9 for the floor substrate, and uniform adhesion between the colored layer 2 and the floor substrate 10.

[0043] <Floor base material 10> For example, the material used for the floor base material 10 can be wood veneer, wood plywood, laminated wood, particleboard, medium-density fiberboard, or rigid fiberboard.

[0044] [Effects of this embodiment] (1) According to the decorative sheet 1 of this embodiment, the upper layer 7a of the surface protective layer 7 is composed of a mixed composition of a thermosetting resin and an ionizing radiation curing resin, the weight ratio of the thermosetting resin in this mixed composition is in the range of 3% by weight or more and 30% by weight or less, and the upper layer 7a contains an anti-allergen composition in the range of 3% by weight or more and 30% by weight or less relative to the upper layer 7a, so that the anti-allergen composition is not damaged or scraped, and a decorative sheet 1 with excellent scratch resistance and sliding properties can be obtained while maintaining anti-allergen properties. (2) By using an anti-allergen composition that is solid at room temperature and has an average particle size in the range of 1 μm to 10 μm, the anti-allergen composition can be maintained in a state that protrudes appropriately from the surface of the upper layer 7a, and a decorative sheet 1 with superior scratch resistance and sliding properties can be obtained. (3) Furthermore, by forming a floor covering 11 using such a decorative sheet 1, a floor covering 11 can be obtained that maintains anti-allergen properties while having excellent scratch resistance and sliding properties. [Examples]

[0045] The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples. (Preparation of decorative sheets for the examples and comparative examples) The decorative sheets in Examples 1-15 and Comparative Examples 1-4 were prepared using the following material composition and procedure. (Example 1) Colored layer 2: Colored polyethylene resin was used, with a thickness of 55 μm. Transparent adhesive layer 4: A polyester resin and an HDI-based isocyanate curing agent were used, with a thickness of 1 μm. Transparent resin layer 6: Polypropylene resin was used, with a thickness of 90 μm. Surface protection layer 7: It has a two-layer structure consisting of an upper layer 7a which is the outermost layer and a lower layer 7b on the transparent resin layer 6 side. The lower layer 7b uses a thermosetting resin and has a thickness of 3 μm. The upper layer 7a was made using a mixed composition of a thermosetting resin and an ionizing radiation-curable resin, with a thickness of 6 μm. In the upper layer 7a, the weight ratio of the thermoplastic resin in the mixed composition of the thermosetting resin and the ionizing radiation-curable resin was 10% by weight.

[0046] In the upper layer 7a, a mixture of an acrylic polyol resin and an HDI-based isocyanate curing agent was used as the thermosetting resin, and an ultraviolet-curable polyfunctional urethane acrylate resin was used as the ionizing radiation-curable resin. An anti-allergen composition was also added to the upper layer 7a. As the anti-allergen composition, an organic anti-allergen composition, a composite of the sodium salt of an acid anionic group-modified linear alkane and styrene particles ("Allerbuster BV," manufactured by Sekisui Material Solutions Co., Ltd.), was used, and 10% by weight of the anti-allergen composition was added to the upper layer 7a. The anti-allergen composition was solid at room temperature, and its average particle size was 5 μm.

[0047] In the lower layer 7b, a mixture of an acrylic polyol resin and an HDI-based isocyanate curing agent was used as the thermosetting resin. A colored layer 2, a transparent adhesive layer 4, and a resin that will become a transparent resin layer 6 are laminated in this order. A thermosetting resin that will become the lower layer 7b is applied to the side of the transparent resin layer 6 opposite to the transparent adhesive layer 4, and a mixed composition of thermosetting resin and ionizing radiation-curable resin that will become the upper layer 7a is applied on top of the lower layer 7b. Subsequently, ultraviolet irradiation is performed to cure the ionizing radiation-curable resin of the upper layer 7a, and then a heat load is applied to cure the thermosetting resins of the upper layer 7a and the lower layer 7b, thereby obtaining a decorative sheet 1.

[0048] (Example 2) The decorative sheet of Example 1 is identical to that of Example 1, except that an inorganic anti-allergen composition, a zirconium phosphate compound ("AllerRemove", manufactured by Toagosei Co., Ltd.), was used as the anti-allergen composition. (Example 3) The decorative sheet of Example 1 is identical to that of Example 1, except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the ionizing radiation-curable resin in the upper layer 7a is 3% by weight. (Example 4) The decorative sheet of Example 1 is identical to that of Example 1, except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the ionizing radiation-curable resin in the upper layer 7a is 5% by weight.

[0049] (Example 5) The decorative sheet of Example 1 is identical to that of Example 1, except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the ionizing radiation-curable resin in the upper layer 7a is 20% by weight. (Example 6) The decorative sheet of Example 1 is identical to that of Example 1, except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the ionizing radiation-curable resin in the upper layer 7a is 30% by weight. (Example 7) The decorative sheet of Example 1 is identical to that of Example 1, except that the amount of inorganic anti-allergen composition added was 3% by weight relative to the upper layer 7a.

[0050] (Example 8) The decorative sheet of Example 1 is identical to that of Example 1, except that the amount of inorganic anti-allergen composition added was 5% by weight relative to the upper layer 7a. (Example 9) The decorative sheet of Example 1 is identical to that of Example 1, except that the amount of inorganic anti-allergen composition added was 15% by weight relative to the upper layer 7a. (Example 10) The decorative sheet of Example 1 is identical to that of Example 1, except that the amount of inorganic anti-allergen composition added was 20% by weight relative to the upper layer 7a.

[0051] (Example 11) The decorative sheet of Example 1 is identical to that of Example 1, except that the amount of inorganic anti-allergen composition added was 30% by weight relative to the upper layer 7a. (Example 12) The decorative sheet of Example 1 is identical to that of Example 1, except that the average particle size of the organic anti-allergen composition used as the anti-allergen composition was set to 1 μm. (Example 13) The decorative sheet of Example 1 is identical to that of Example 1, except that the average particle size of the organic anti-allergen composition used as the anti-allergen composition was set to 10 μm.

[0052] (Example 14) The decorative sheet of Example 1 is identical to that of Example 1, except that the average particle size of the organic anti-allergen composition used as the anti-allergen composition was set to 0.5 μm. (Example 15) The decorative sheet of Example 1 is identical to that of Example 1, except that the average particle size of the organic anti-allergen composition used as the anti-allergen composition was set to 15 μm.

[0053] (Comparative Example 1) In the cosmetic sheet of Example 1, it is the same as the cosmetic sheet of Example 1 except that no anti-allergen composition is added. (Comparative Example 2) In the cosmetic sheet of Example 1, it is the same as the cosmetic sheet of Example 1 except that the addition amount of the organic anti-allergen composition is 40% by weight based on the upper layer 7a.

[0054] (Comparative Example 3) In the cosmetic sheet of Example 1, it is the same as the cosmetic sheet of Example 1 except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the radiation-curable resin in the upper layer 7a is 2% by weight. (Comparative Example 4) In the cosmetic sheet of Example 1, it is the same as the cosmetic sheet of Example 1 except that the weight ratio of the thermosetting resin in the mixed composition of the thermosetting resin and the radiation-curable resin in the upper layer 7a is 40% by weight.

[0055] [Evaluation] For the cosmetic sheets of Examples 1 to 15 and Comparative Examples 1 to 4, evaluations of anti-allergenicity, scratch resistance, and sliding resistance were conducted. The evaluation methods are as follows. (Evaluation of anti-allergenicity) The cosmetic sheet was cut into small pieces, and after being immersed in a mite allergen aqueous solution for 1 day, the amount of allergen was visually confirmed by horizontal development chromatography (Mighty Checker, manufactured by Sumika Environmental Science Co., Ltd.). The evaluation criteria were as follows according to the degree of color development of the Mighty Checker. ○ or ◎ was regarded as non-compliance. ×: "++: Clear line" ○: "+: Can be confirmed as a line" ◎: "+-: Slightly colored" "-: Not colored at all"

[0056] (Scratch resistance) For each cosmetic sheet, its surface was rubbed with #0000 steel wool (Bonser #0000, manufactured by Nippon Steel Wool Co., Ltd.) at 100 g / cm 2The surface was rubbed back and forth 10 times while applying a load. Afterwards, the surface of the decorative sheet was visually inspected for any scratches. The evaluation criteria were as follows: ◎ or ○ was considered a pass. ◎: No scratches were found on the surface. ○: Slight scratches can be seen on the surface. ×: Scratches can be easily seen on the surface.

[0057] (Sliding resistance) Each decorative sheet is layered with its surfaces facing each other at 340g / cm². 2 The sheet was rubbed back and forth 1000 times under a load, and then the surface of the decorative sheet was visually inspected for any scratches. The evaluation criteria were as follows: ◎ or ○ was considered a pass. ◎: No scratches were found on the surface. ○: Slight scratches can be seen on the surface. ×: Scratches can be easily seen on the surface. The evaluation results are shown in Table 1.

[0058] [Table 1]

[0059] As shown in Table 1, the decorative sheets of Examples 1 to 15 showed good results in all evaluation items, with no failures (×). Furthermore, it was confirmed that the decorative sheets of Examples 1 to 13, in which the average particle size of the anti-allergen composition that is solid at room temperature is in the range of 1 μm to 10 μm, obtained better scratch resistance and sliding resistance compared to Example 14, in which the average particle size is 0.5 μm, and Example 15, in which the average particle size is 15 μm. On the other hand, in the mixed composition of thermosetting resin and ionizing radiation-curable resin constituting the upper layer 7a, the decorative sheets of Comparative Examples 3 and 4, in which the weight ratio of the thermosetting resin was 2% by weight or 40% by weight, had anti-allergenic properties, but lacked sufficient scratch resistance or abrasion resistance. Furthermore, when the content of the anti-allergenic composition in the upper layer 7a was 40% by weight, anti-allergenic properties were obtained, but scratch resistance was insufficient.

[0060] Furthermore, the present invention can take the following configuration, for example. (1) At least a sheet substrate, The sheet substrate comprises a surface protective layer laminated on one side of the sheet substrate, The surface protective layer comprises one or more layers. The outermost layer of the surface protective layer mainly contains a mixed composition of a thermosetting resin and an ionizing radiation-curable resin, and the weight ratio of the thermosetting resin in the mixed composition is in the range of 3% by weight or more and 30% by weight or less. The decorative sheet is characterized in that the outermost layer further contains an anti-allergen composition, and the weight ratio of the anti-allergen composition in the outermost layer is within the range of 3% by weight or more and 30% by weight or less. (2) The decorative sheet according to (1) above, characterized in that the anti-allergen composition is solid at room temperature and its average particle size is within the range of 1 μm to 10 μm. (3) The decorative sheet according to (1) or (2) above, characterized in that the weight ratio of the mixed composition in the outermost layer is 50% by weight or more. (4) The cosmetic sheet according to any one of (1) to (3) above, characterized in that the anti-allergen composition is an organic anti-allergen composition, an inorganic anti-allergen composition, or a combination of organic and inorganic anti-allergen compositions. (5) The decorative sheet according to any one of (1) to (4) above, characterized in that the weight ratio of the thermosetting resin in the mixed composition is within the range of 5% by weight or more and 20% by weight or less. (6) Flooring base material and A decorative flooring material characterized by comprising a decorative sheet according to any one of the above items (1) to (5) provided on one side of the flooring base material. [Explanation of Symbols]

[0061] 1 Decorative sheet 2 colored layer 3 Pattern Layers 4 Transparent adhesive layer 5 Transparent adhesive resin layer 6 Transparent resin layer 7 Surface protective layer 7a upper layer 7b Lower layer 8. Primer layer on the back side 9. Flooring wood adhesive 10 Base material for flooring 11 Floor covering materials

Claims

1. At least a sheet substrate, The sheet substrate comprises a surface protective layer laminated on one side of the sheet substrate, The surface protective layer has one or more layers, The outermost layer of the surface protective layer mainly contains a mixed composition of a thermosetting resin and an ionizing radiation-curable resin, and the weight ratio of the thermosetting resin in the mixed composition is in the range of 3% by weight or more and 30% by weight or less. The decorative sheet is characterized in that the outermost layer further contains an anti-allergen composition, and the weight ratio of the anti-allergen composition in the outermost layer is within the range of 3% by weight or more and 30% by weight or less.

2. The decorative sheet according to claim 1, characterized in that the anti-allergen composition is solid at room temperature and its average particle size is within the range of 1 μm to 10 μm.

3. The decorative sheet according to claim 1 or 2, characterized in that the weight ratio of the mixed composition in the outermost layer is 50% by weight or more.

4. The cosmetic sheet according to claim 1 or 2, characterized in that the anti-allergen composition is an organic anti-allergen composition, an inorganic anti-allergen composition, or a combination of organic and inorganic anti-allergen compositions.

5. The decorative sheet according to claim 1 or 2, characterized in that the weight ratio of the thermosetting resin in the mixed composition is within the range of 5% by weight or more and 20% by weight or less.

6. Flooring base material and A decorative flooring material comprising a decorative sheet according to claim 1 or claim 2 provided on one side of the flooring base material.

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