Decorative sheet and decorative plate

Abstract

The present invention relates to a decorative sheet having excellent adhesion between a surface protective layer and a lower layer, excellent surface hardness and scratch resistance, and excellent processability. Provided is a decorative sheet characterized by having at least a surface protective layer, the surface protective layer containing a cross-linked and curable resin, the ratio of the peak height of A to the peak height of B ((A / B) * 100 (%)) being 105%-400%, where A is the peak height appearing at 855-1325 cm <-1 > and B is the peak height appearing at 1650-1800 cm <-1 > in infrared spectroscopy measurement of the surface protective layer. When C is the peak height appearing at 3200-3500 cm <-1 > in infrared spectroscopy measurement of the surface protection layer, the peak height ratio of B to C ((B / C) * 100 (%)) is 1000% or more and 6000% or less.

Description

Technical Field

[0001] The present invention relates to a decorative sheet and a decorative board. Background Art

[0002] The decorative sheet is used by being adhered to the surface of a wooden board, a plastic board, etc. for the purpose of surface protection, decoration, etc. Further, the decorative board thus obtained is used for various purposes such as ornaments, building materials, furniture, etc.

[0003] The decorative sheet used for the above uses needs to exhibit the adhesion of the surface protective layer to the lower layer. In particular, since a film having a small number of polar groups is sometimes used for the surface of the lower layer, the surface protective layer of the decorative sheet needs to exhibit adhesion to such a film.

[0004] As a decorative sheet having a surface protective layer that exhibits adhesion to a film, a hard coat film in which at least one surface of a base film is provided with a hard coat has been proposed (see Patent Document 1).

[0005] However, in the hard coat film provided with a hard coat in Patent Document 1, the adhesion between the base film and the hard coat film when used for various purposes is insufficient, and there is room for improvement.

[0006] In addition, since the decorative sheet is used by being adhered to the surface of a wooden board, a plastic board, etc., it sometimes collides with an object. For this reason, the surface of the decorative sheet needs to have surface hardness and scratch resistance.

[0007] Furthermore, since the decorative sheet is used by being adhered to the surface of an article for decorative purposes, it needs to conform to the shape of the article. Therefore, the decorative sheet needs to have processability capable of being processed to conform to the shape of the article. The hard coat film described in Patent Document 1 has not been studied for processability and has a problem of poor processability.

[0008] Therefore, it is desired to develop a decorative sheet having excellent adhesion to the lower layer, excellent surface hardness and scratch resistance, and excellent processability.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2017-177667 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] An object of the present invention is to provide a decorative sheet having excellent adhesion between a surface protective layer and a lower layer, excellent surface hardness and scratch resistance, and excellent processability.

[0014] Technical solution for solving the problem

[0015] The inventors of the present invention conducted repeated and in-depth research and found that the above object can be achieved by using the following decorative sheet material, thus completing the present invention. The decorative sheet material has at least a surface protective layer, and the surface protective layer contains a crosslinked and cured resin. In the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 855-1325 cm ﹣1 is set as A and the peak height appearing at 1650-1800 cm ﹣1 is set as B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less. In the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 3200-3500 cm ﹣1 is set as C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less.

[0016] That is, the present invention relates to the following decorative sheet material and decorative board.

[0017] 1. A decorative sheet material, characterized in that the decorative sheet material has at least a surface protective layer, the surface protective layer contains a crosslinked and cured resin, and in the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 855-1325 cm ﹣1 is set as A and the peak height appearing at 1650-1800 cm ﹣1 is set as B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less,

[0018] and in the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 3200-3500 cm ﹣1 is set as C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less.

[0019] 2. The decorative sheet material according to item 1, wherein the peak height ratio of A to B is 110% or more and 300% or less, and the peak height ratio of B to C is 1300% or more and 5500% or less.

[0020] 3. The decorative sheet material according to item 1 or item 2, wherein the crosslinked and cured resin contains a radiation-curable resin.

[0021] 4. The decorative sheet material according to item 3, wherein the radiation-curable resin contains an acrylate resin having a (meth)acryloyl group.

[0022] 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface protective layer contains at least one selected from an antibacterial agent, an antiviral agent, and an anti-allergen agent.

[0023] 6. The decorative sheet according to any one of Items 1 to 5, wherein a pattern layer, a transparent resin layer, and the surface protective layer are sequentially provided on the base sheet.

[0024] 7. The decorative sheet according to Item 6, wherein at least one layer selected from the base sheet and the transparent resin layer contains a flame retardant.

[0025] 8. The decorative sheet according to Item 6 or 7, wherein at least one layer selected from the base sheet, the pattern layer, the transparent resin layer, and the surface protective layer contains a biomass-derived component.

[0026] 9. A decorative board, wherein the decorative sheet according to any one of Items 1 to 8 is provided on a base material.

[0027] Advantages of the Invention

[0028] The surface protective layer of the decorative sheet of the present invention has excellent adhesion to the lower layer, excellent surface hardness and scratch resistance, and excellent processability. Therefore, the decorative board laminated with the decorative sheet of the present invention can be used for various building materials, furniture, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram showing an example of the infrared spectrum measurement result of the surface protective layer of the decorative sheet of the present invention.

[0030] Figure 2 It is a schematic diagram for explaining a method for determining the peak height in the infrared spectrum measurement of the surface protective layer of the decorative sheet of the present invention.

[0031] Figure 3 It is a schematic diagram for explaining a method for determining the peak height in the infrared spectrum measurement of the surface protective layer of the decorative sheet of the present invention.

[0032] Figure 4 It is a schematic diagram showing an example of the layer structure of the decorative sheet of the present invention.

[0033] Figure 5 It is a schematic diagram showing an example of the layer structure of the decorative board of the present invention.

[0034] Figure 6 It is a schematic diagram showing an example of the intermolecular hydrogen bond of a crosslinking and curing type resin.

[0035] Figure 7 It is a schematic diagram of a method for testing the difficulty of fire spread.

[0036] Figure 8 Schematic diagram of the method for testing the difficulty of fire spread Detailed implementation mode

[0037] 1. Decorative sheet

[0038] The decorative sheet of the present invention is characterized in that the decorative sheet has at least a surface protective layer, the surface protective layer contains a crosslinked and cured resin, and in the infrared spectrum measurement of the surface protective layer, the peak height appearing at 855-1325 cm ﹣1 is set as A, and when the peak height appearing at 1650-1800 cm ﹣1 is set as B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less. In the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 3200-3500 cm ﹣1 is set as C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less. Due to the above characteristics, the surface protective layer of the decorative sheet of the present invention has excellent adhesion to the lower layer, excellent surface hardness and scratch resistance, and excellent processability. Therefore, the decorative board laminated with the decorative sheet of the present invention can be used for various applications such as various building materials and furniture.

[0039] As described above, for the decorative sheet of the present invention, when the peak height appearing at 855-1325 cm ﹣1 is set as A and the peak height appearing at 1650-1800 cm ﹣1 is set as B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less, and in the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 3200-3500 cm ﹣1 is set as C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less. Hereinafter, it will be described with reference to the drawings.

[0040] Figure 1 Schematic diagram of an example of the infrared spectrum (hereinafter also simply referred to as "IR") measurement result of the surface protective layer of the decorative sheet of the present invention. In Figure 1 , A represents the peak of the ether bond, B represents the peak of the ester bond, and C represents the peak of the urethane bond.

[0041] It should be noted that in this specification, the peak height of each peak is measured as follows. That is, as Figure 2 shown, two base points b1 and b2 of each peak are taken, and a baseline bL connecting the base points with a straight line is drawn. Then, a perpendicular line is drawn vertically downward from the peak top position p to determine the intersection point bp with the baseline bL. The length h between p and bp is set as the peak height of the peak.

[0042] In addition, as Figure 3 shown, when the A peak appears as multiple peaks, the peak height is measured as described below. That is, as Figure 3 shown, when there are two adjacent peaks, when the heights h1-1 and h2-1 from the peak valley between the two peaks to the peak top are above 0.10 Abs, the sum of the peak heights h1 and h2 of the two peaks is set as the peak height. It should be noted that in Figure 3 , there are adjacent peaks on both sides of the peak with the peak top p2, and there are two heights h2-1 and h2-2 from the peak valley between the two peaks to the peak top. In this case, the shorter height h2-1 is used to determine whether it is above 0.10 Abs.

[0043] In this specification, the infrared spectrum measurement of the surface protective layer can be carried out by a commercially available measurement device for infrared spectrum measurement.

[0044] In the decorative sheet material of the present invention, in the infrared spectrum measurement of the surface protective layer, when the peak height appearing at 855-1325 cm ﹣1 is set as A and the peak height appearing at 1650-1800 cm ﹣1 is set as B, the peak height ratio of A to B ((A / B)×100 (%)) is above 105% and below 400%. When the peak height ratio of A to B is less than 105%, there are too many ester bonds in the surface protective layer, the surface protective layer becomes too hard, and the processability of the decorative sheet material becomes lower. When the peak height ratio of A to B exceeds 400%, there are too many ether bonds, the surface protective layer becomes too soft, and the surface hardness and scratch resistance of the decorative sheet material become lower. The peak height ratio of A to B is preferably above 110% and below 300%, and more preferably above 150% and below 250%.

[0045] In the decorative sheet material of the present invention, when the peak height appearing at 3200-3500 cm ﹣1 in the infrared spectrum measurement of the surface protective layer is set as C, the peak height ratio of B to C ((B / C)×100 (%)) is above 1000% and below 6000%. When the peak height ratio of B and C is less than 1000%, there are too many urethane bonds in the surface protective layer, as Figure 6 shown, the hydrogen bond between the -N-H group and the -C=O group in the urethane bond increases excessively, the surface protective layer becomes too hard, and the processability of the decorative sheet material becomes lower. When the peak height ratio of B to C exceeds 6000%, there are too few urethane bonds in the surface protective layer, the surface protective layer becomes too soft, and the surface hardness and scratch resistance of the decorative sheet material become lower. The peak height ratio of B and C is preferably above 1300% and below 5500%, and more preferably above 1500% and below 5200%.

[0046] As a method for adjusting the peak height ratio of A to B and the peak height ratio of B to C to the above ranges, a method for adjusting the composition ratio of the crosslinkable and curable resin used to form the surface protective layer can be cited. In the case of a composition ratio in which the crosslinkable and curable resin contains a large amount of ether bonds and a small amount of ester bonds, the peak height ratio of A to B increases. Conversely, in the case of a composition ratio in which the crosslinkable and curable resin contains a small amount of ether bonds and a large amount of ester bonds, the peak height ratio of A to B decreases. In addition, in the case of a composition ratio in which the crosslinkable and curable resin contains a large amount of ester bonds and a small amount of urethane bonds, the peak height ratio of B to C increases. Conversely, in the case of a composition ratio in which the crosslinkable and curable resin contains a small amount of ester bonds and a large amount of urethane bonds, the peak height ratio of B to C decreases.

[0047] The respective layers of the decorative sheet of the present invention will be described in detail below. It should be noted that in the decorative sheet of the present invention, the surface refers to the so-called "front surface layer". When the decorative sheet of the present invention is used by being laminated on a substrate or the like, the surface is the layer on the opposite side to the layer in contact with the substrate, and is the visible layer after lamination. In addition, in the present specification, the direction of the above-mentioned surface of the decorative sheet of the present invention is sometimes referred to as "front" or "upper", and the opposite side thereof is sometimes referred to as "back" or "lower". In addition, in the following description, the lower limit and the upper limit of the numerical range represented by "~" mean "above... and below..." (for example, "α~β" means above α and below β).

[0048] In addition, the layer thickness in the present specification is a measured value of a portion of the decorative sheet where there are no embossments, protruding fine particles, or other uneven shapes.

[0049] (Layer structure of the decorative sheet of the present invention)

[0050] The decorative sheet of the present invention only needs to have at least a surface protective layer, and preferably has the above-mentioned surface protective layer on the outermost surface of the decorative sheet. The specific structure can be appropriately set according to the use of the decorative sheet and the like. For example, a layer structure having a base sheet 11, a pattern layer 12 (solid color coating layer and / or pattern coating layer), an adhesive layer (not shown), a transparent resin layer 13, and a surface protective layer 14 in this order as shown in Figure 4 can be cited. Hereinafter, a decorative sheet having such a layer structure will be described as a representative example.

[0051] (Surface protective layer)

[0052] The decorative sheet of the present invention has at least a surface protective layer. In the present specification, the surface protective layer contains a crosslinkable and curable resin.

[0053] Examples of crosslinking and curing type resins include thermosetting resins, radiation-curable resins (e.g., electron beam-curable resins), etc. In particular, from the perspectives of scratch resistance brought by high surface hardness, excellent shape retention, productivity, etc., the surface protective layer preferably contains a radiation-curable resin, and more preferably, the resin constituting the surface protective layer is a radiation-curable resin.

[0054] Examples of thermosetting resins include, for example, unsaturated polyester resins, polyurethane resins (including two-component curing type polyurethanes), epoxy resins, amino alkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanidine resins, melamine-urea co-condensation resins, silicone resins, polysiloxane resins, etc.

[0055] Curing agents such as crosslinking agents and polymerization initiators, and polymerization accelerators, etc. can be added to the above resins. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide, free radical initiators such as azobisisobutyronitrile can be added to unsaturated polyester resins.

[0056] Examples of the method of forming a surface protective layer with a thermosetting resin include a method of coating a thermosetting resin solution by coating methods such as roll coating method, gravure coating method, etc. and then drying and curing.

[0057] The radiation-curable resin is not limited as long as it can initiate a crosslinking polymerization reaction by irradiating ionizing radiation and change into a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiating ionizing radiation in the molecule can be used. For example, acrylate resins such as polyurethane acrylate, polyester acrylate, epoxy acrylate, etc.; silicone resins such as siloxane; polyester resins; epoxy resins, etc. can be cited.

[0058] The radiation-curable resin preferably contains an acrylate resin having a (meth)acryloyl group. By making the radiation-curable resin contain an acrylate resin having a (meth)acryloyl group, hydrogen bonds are generated between the molecules of the radiation-curable resin, so that the surface hardness and scratch resistance of the surface protective layer can be further improved.

[0059] Ionizing radiation includes visible light, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, ion beams, etc., and among them, ultraviolet rays and / or electron beams are preferred.

[0060] As the ultraviolet light source, light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, metal halide lamps, etc. can be used. As the wavelength of the ultraviolet light, it is about 190 to 380 nm.

[0061] As the electron beam source, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaft type, resonant transformer type, insulated core transformer type, linear type, dynamic electron type, high frequency type, etc. can be used. As the energy of the electron beam, it is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation dose of the electron beam is preferably about 2 to 15 Mrad.

[0062] The ionizing radiation curable resin can be sufficiently cured after irradiating with an electron beam, but when curing by irradiating with ultraviolet light, it is preferable to add a photoinitiator (sensitizer).

[0063] In the case of a resin system containing a radically polymerizable unsaturated group, as the photoinitiator, at least one of, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl benzimidazole, isopropyl-N,N-dimethylaminobenzoate, etc. can be used. In addition, in the case of a resin system having a cationically polymerizable functional group, at least one of, for example, aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonate esters, radical oxosulfonium diallyl iodide salts, etc. can be used.

[0064] The addition amount of the photoinitiator is usually but not particularly limited to about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

[0065] In addition, in recent years, the use of biomass-derived resins with a small environmental load has been studied from various aspects, and the resin forming the surface protective layer of the decorative sheet of the present invention may also contain biomass-derived components, and specifically, biomass polyolefins, etc. can be used.

[0066] The surface protective layer may be one layer or two or more layers. In the present invention, when the surface protective layer is multiple layers, each layer contains a crosslinkable curable resin. In addition, when the surface protective layer is multiple layers, the infrared spectrum measurement of the surface protective layer is to measure the infrared spectrum of the laminated surface protective layer from the surface protective layer side of the outermost surface.

[0067] The thickness of the surface protective layer is not particularly limited as long as it is within the range that does not hinder the effects of the present invention, and is preferably 1 to 200 μm, more preferably 1 to 100 μm, further preferably 3 to 50 μm, and particularly preferably 4 to 40 μm.

[0068] The surface protective layer may contain fine particles. Examples of the fine particles include inorganic fillers such as silica, alumina, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconia, chromium oxide, iron oxide, boron nitride, diamond, emery, glass fiber, etc.; organic material powders or beads such as acryloyl, crosslinked alkyl, crosslinked styrene, benzoguanamine resin, urea-formaldehyde resin, phenolic resin, polyethylene, nylon, etc. One or more of the above fine particles can be used.

[0069] The average particle size of the fine particles is preferably equal to or greater than the thickness of the surface protective layer, and in order to exhibit scratch resistance, it is preferably less than "the thickness of the surface protective layer + 40 μm", more preferably "the thickness of the surface protective layer + 30 μm" or less.

[0070] The average particle size of the fine particles can be measured by known methods such as laser diffraction method, Coulter counter method, sedimentation method, etc. It should be noted that the above average particle size refers to the most frequent particle size.

[0071] The content of the fine particles in the surface protective layer is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the resin component forming the surface protective layer.

[0072] Silicone can be added to the surface protective layer. When adding silicone to the surface protective layer, from the perspective of having both easy erasability and non-slip properties, the addition amount of silicone is preferably 0.1 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, based on 100 parts by mass of the resin (resin component) constituting the surface protective layer.

[0073] Solvents, dyes, pigments and other colorants, inorganic fillers and other fillers, various additives such as defoamers, leveling agents, thixotropy imparting agents (thixotropic agents), flame retardants, antibacterial agents, antiviral agents, anti-allergy agents, etc. can also be added to the surface protective layer as needed.

[0074] As the inorganic filler, by making the surface protective layer contain inorganic fillers with a size larger than the layer thickness of the surface protective layer, it can be used as a means to endow the surface protective layer with a set surface property. In addition, the inorganic filler can also be used as a matting agent, and by making the surface protective layer contain the inorganic filler, it is expected to achieve the effect of suppressing the curing shrinkage of the surface protective layer. Therefore, in the present invention, the inorganic filler is preferably a filler that has been surface-treated (hydrophobized). In addition, since the effects are easily achieved, it is particularly preferred that at least one selected from antibacterial agents, antiviral agents and anti-allergen agents is contained in the surface protective layer of the outermost surface layer among these additives.

[0075] Examples of the inorganic filler include silica, alumina, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, emery, glass fiber, etc.

[0076] The method for surface treatment (hydrophobization treatment) of the inorganic filler is not particularly limited and can be carried out by known methods. For example, a method of hydrophobizing the inorganic filler with a silicone oil-based treatment agent can be cited; a method of treating the inorganic filler with an alkylsilazane-based treatment agent, a trimethylsilylating agent, and / or an alkoxysilane and then hydrophobizing the inorganic filler with the above silicone oil-based treatment agent; a method of hydrophobizing the inorganic filler with a silicone oil-based treatment agent and then treating it with a trimethylsilylating agent or an alkylsilazane-based treatment agent; a method of hydrophobizing the inorganic filler with an alkoxysilane; a method of treating the inorganic filler with an alkoxysilane and then treating it with a silicone oil-based treatment agent or a combination of a silicone oil-based treatment agent and an alkoxysilane; a method of treating the inorganic filler with a dimethyl ether siloxane and / or trimethylsilanol or a cyclic siloxane, etc. In addition, as the hydrophobization treatment method, not only the above hydrophobization treatment methods can be cited, but also methods of treating with various coupling agents such as silane coupling agents, titanate-based coupling agents, and aluminate-based coupling agents; surfactants such as phosphoric acid-based and fatty acid-based surfactants; oils, stearic acid, etc. Hereinafter, the above-mentioned various products (for example, treatment agents such as silicone oil-based treatment agents, all products such as silane coupling agents and surfactants) used for hydrophobizing the untreated inorganic filler are collectively referred to as hydrophobization treatment agents.

[0077] The method for hydrophobizing the inorganic filler with a hydrophobization treatment agent is not particularly limited and can be carried out by known methods. For example, a method of adding (for example, spraying) the hydrophobization treatment agent stock solution or a dilution of the hydrophobization treatment agent diluted with water or an organic solvent to the untreated inorganic filler (dry treatment method); a method of treating (for example, impregnating) the untreated inorganic filler with the hydrophobization treatment agent stock solution, an aqueous solution containing the hydrophobization treatment agent, or an organic solvent containing the hydrophobization treatment agent and then drying it (wet treatment method), etc. Through such treatment, the surface of part or all of the inorganic filler is (a) coated with the hydrophobization treatment agent, or (b) adsorbed with the hydrophobization treatment agent, or (c) coated with the hydrophobization treatment agent and adsorbed with the hydrophobization treatment agent (a combination of (a) and (b)), etc. As a result, the hydrophobized inorganic filler is obtained. It should be noted that the hydrophobization treatment agent can be used alone or in combination of two or more.

[0078] As the above-mentioned antibacterial agents, there are inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are generally safer, and have better durability and heat resistance than organic antibacterial agents, and thus are preferred. Inorganic antibacterial agents refer to products in which antibacterial metals such as copper and zinc represented by silver are carried on various inorganic carriers. When the antibacterial agent is contained in the surface protective layer, its addition amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer, and the details can be appropriately adjusted according to the type of antibacterial agent.

[0079] As the above-mentioned antiviral agents, they can generally be roughly classified into organic and inorganic types. As organic antiviral agents, there are quaternary ammonium salts, quaternary phosphonium salts, pyridine-based, pyrithione-based, benzimidazole-based, organic iodonium-based, isothiazoline-based, anionic-based, ether-based, etc. As inorganic antiviral agents, there are products in which metal ions such as silver, copper, and zinc are carried on carriers such as zeolite, apatite, zircon, glass, and molybdenum oxide. When the antiviral agent is contained in the surface protective layer, its addition amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer, and the details can be appropriately adjusted according to the type of antiviral agent.

[0080] Among the above-mentioned organic antiviral agents, it is particularly suitable to use benzimidazole-based antiviral agents, anionic-based antiviral agents, or ether-based antiviral agents that maintain the particle shape. Among them, maintaining the particle shape means that the preparation does not dissolve in the composition (coating before curing) of the curable resin that forms the surface protective layer and exists in a particulate state. Therefore, during the formation of the surface protective layer, imidazole-based compound particles, anionic-based compound particles, or ether-based compound particles tend to float, so that imidazole-based compound particles, anionic-based compounds, or ether-based compound particles tend to segregate on the outermost surface side of the surface protective layer. Moreover, by segregating imidazole-based compound particles, anionic-based compound particles, or ether-based compound particles on the outermost surface side of the surface protective layer, it is possible to suppress the addition amount of the antiviral agent required to obtain the set antiviral performance, and it is easy to suppress the reduction of the scratch resistance of the surface protective layer.

[0081] As the above-mentioned anionic-based antiviral agent, a preparation containing, for example, a styrene resin, a styrene polymer derivative compound, and an unsaturated carboxylic acid derivative compound is preferred. In addition, the above-mentioned styrene polymer derivative compound and unsaturated carboxylic acid derivative compound preferably contain at least one structure among the structures of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all the structures. This is because based on the presence or absence of an envelope, there are generally two types of viruses, and the structures of antiviral agents that can effectively inhibit the activity of each virus are different. For this reason, for example, if it is expected to be effective only against the influenza virus, a non-enveloped virus, it may be sufficient to contain only the styrene polymer derivative compound, and in some cases, sufficient effects can be achieved by containing only the styrene resin monomer.

[0082] As the above-mentioned inorganic antiviral agent, from the perspective of having no biological toxicity and good safety, a silver-based antiviral agent is preferably used. Among them, since a phosphoric acid-based glass-silver supported compound, a silver zeolite compound, and a silver molybdenum oxide double salt compound can exhibit antiviral performance even in small amounts and the addition amount can be controlled, they are more preferred.

[0083] When the above-mentioned silver-based antiviral agent is contained in the surface protective layer, it will change color along with the surface protective layer (in the case of changing color due to heat / light based on the state of the added coating, or changing color due to heat / light after the surface protective layer is formed). However, in this case, it can be improved by adding an ultraviolet inhibitor, a light stabilizer, etc. in a timely manner. For example, when using a benzotriazole-based compound relative to the above-mentioned silver molybdenum oxide double salt compound, an effect of improving color change is expected.

[0084] The above-mentioned anti-allergen agent contains either an inorganic compound or an organic compound, and each compound can be used alone, or two or more different types can be mixed and used. As the inorganic compound, a material formed by supporting a metal is preferably used. When contained in the surface protective layer, the addition amount of the anti-allergen agent is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the resin component of the surface protective layer, and the details can be appropriately adjusted according to the type of the anti-allergen agent.

[0085] As a method for forming a surface protective layer containing a radiation-curable resin, for example, a solution (a resin composition for forming a surface protective layer) containing (1) a resin such as a radiation-curable resin and (2) other resins, fine particles, an ultraviolet absorber, an antibacterial agent, and the above various additives as needed is coated by a coating method such as a gravure coating method or a roll coating method, and then the radiation-curable resin is cured to form a surface protective layer.

[0086] (Substrate sheet)

[0087] A pattern layer, etc. are laminated in sequence on the surface (the surface layer) of the substrate sheet.

[0088] As the base material sheet, a sheet (film) formed of, for example, a thermoplastic resin is applicable. Specifically, examples thereof include olefin resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylate copolymer; polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ionomer, acrylate polymer, methacrylate polymer, etc. In addition, in recent years, the use of biomass-derived resins with a small environmental load has been studied from various aspects, and the resin for the base material sheet forming the decorative sheet of the present invention may also contain biomass-derived components. Specifically, biomass polyolefin, etc. can be used. The base material sheet can be formed by using these resins alone or in combination of two or more resins.

[0089] It should be noted that in this specification, "(meth)acrylic acid" means acrylic acid and / or methacrylic acid, and the same applies to other parts described as (meth).

[0090] The base material sheet can be colored. In this case, it can be colored by adding a colorant (pigment or dye) to the thermoplastic resin as described above. As the colorant, in addition to inorganic pigments such as titanium dioxide, carbon black, and iron oxide, and organic pigments such as phthalocyanine blue, various dyes can also be used. They can be selected from one or more known or commercially available ones. In addition, the addition amount of the coloring material can also be appropriately set according to the required hue, etc.

[0091] The base material sheet can contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers as needed.

[0092] In the base material sheet, the above-mentioned ultraviolet absorber, light stabilizer, and flame retardant are the same as those used for the transparent resin layer described later and are used in the same addition amount.

[0093] The thickness of the base material sheet can be appropriately set according to the use and usage method of the final product, etc., and is usually preferably 20 to 300 μm.

[0094] The base material sheet can be subjected to corona discharge treatment on the surface (front surface) as needed to improve the adhesion of the coating for forming the pattern layer. The method and conditions of the corona discharge treatment can be carried out according to known methods. In addition, as needed, the back surface of the base material sheet can be subjected to corona discharge treatment or a back primer layer can be formed.

[0095] (Pattern layer)

[0096] The decorative sheet material of the present invention may have a pattern layer.

[0097] The pattern layer imparts the required pattern (design) to the decorative sheet material, and the types of patterns are not limited. Examples include wood grain patterns, leather grain patterns, stone grain patterns, sand grain patterns, tile patterns, brick patterns, cloth patterns, geometric figures, characters, symbols, abstract patterns, etc.

[0098] The method for forming the pattern layer is not particularly limited. For example, it can be formed on the surface of the base sheet material by a printing method using a coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) and a binder resin in a solvent (or dispersion medium). As the coating, from the perspective of reducing the VOC of the decorative sheet material, an aqueous composition can also be used.

[0099] Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc flower, red oxide, Prussian blue, cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments; metallic powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxychloride; fluorescent pigments; luminous pigments, etc. These colorants can be used alone or in combination of two or more. These colorants can be used together with fillers such as silica, extender pigments such as organic microspheres, neutralizing agents, surfactants, etc.

[0100] As the binder resin, in addition to the polyester-based polyurethane resin treated by hydrophilic treatment, it can also be used in combination with polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, styrene-acrylate copolymer, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymer, cellulose-based resins, etc. More specifically, for example, polyacrylamide-based resins, poly(meth)acrylic acid-based resins, polyethylene oxide-based resins, poly-N-vinylpyrrolidone-based resins, water-soluble polyester-based resins, water-soluble polyamide-based resins, water-soluble amino-based resins, water-soluble phenolic-based resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, etc. can be used. In addition, for example, modified products of natural rubber, synthetic rubber, polyvinyl acetate-based resins, (meth)acryloyl-based resins, polyvinyl chloride-based resins, polyurethane-polyacrylamide-based resins, etc., mixtures of the above natural rubbers, etc., and other resins can also be used. The above binder resins can be used alone or in combination of two or more.

[0101] As the solvent (or dispersion medium), examples thereof include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, butanone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

[0102] In addition, in recent years, the use of biomass-derived resins with a small environmental impact has been studied from multiple aspects, and the binder resin forming the pattern layer of the decorative sheet of the present invention may also contain biomass-derived components. For example, biomass-derived urethane (meth)acrylate, etc. can be used. Specifically, at least urethane (meth)acrylate containing polyol, isocyanate compound, and hydroxy (meth)acrylate can be cited, and a binder resin in which at least one of the above polyol, isocyanate compound, and hydroxy (meth)acrylate contains a biomass-derived component.

[0103] As the printing method for forming the pattern layer, examples thereof include gravure printing method, offset printing method, screen printing method, flexographic printing method, electrophotographic printing method, inkjet printing method, etc. In addition, when forming a solid-print-like pattern layer, various coating methods such as roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma roll coating method, kiss coating method, flow coating method, and dip coating method can be cited. In addition, a hand-painting method, ink flow method, photographic method, transfer method, laser beam lithography method, electron beam lithography method, local vapor deposition method of metal, etc., or etching method, etc. can also be used, or combined with other forming methods.

[0104] The thickness of the pattern layer is not particularly limited and can be appropriately set according to the product performance, and is about 0.1 to 10 μm in layer thickness.

[0105] (Color masking layer)

[0106] In the decorative sheet of the present invention, a color masking layer can be further formed between the base sheet and the pattern layer.

[0107] The color masking layer only needs to be able to mask the base color of the covered object member after the decorative sheet is joined to the covered object member, and is usually formed in a manner of covering the base sheet.

[0108] The color shielding layer can be formed by using the above-known printing method. In addition, the coating material used in the formation of the above pattern layer can be directly used.

[0109] The coating amount is preferably in the range of 2 to 30 g / m 2 . The thickness of the color shielding layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

[0110] (Adhesive layer)

[0111] In order to enhance the adhesion between the transparent resin layer and the pattern layer described later, an adhesive layer can also be formed on the pattern layer. The adhesive layer is preferably a transparent adhesive layer, and as this transparent adhesive layer, any one of colorless transparent, colored transparent, translucent, etc. is included.

[0112] There is no particular limitation on the adhesive, and known adhesives in the field of decorative sheets can be used.

[0113] As known adhesives in the field of decorative sheets, for example, thermoplastic resins such as polyamide resin, acrylate resin, and vinyl acetate resin, and thermosetting resins such as urethane resins can be cited. These colorants can be used alone or in combination of two or more. In addition, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be used.

[0114] The above-known printing method can be adopted when forming the transparent adhesive layer.

[0115] The thickness of the transparent adhesive layer is not particularly limited, and the thickness after drying is about 0.1 to 30 μm, preferably about 1 to 20 μm.

[0116] (Transparent resin layer)

[0117] The floor decorative sheet of the present invention can have a transparent resin layer.

[0118] The transparent resin layer is not particularly limited as long as it is transparent, including any one of colorless transparent, colored transparent, translucent, etc. As the resin constituting the above transparent resin layer, for example, polypropylene such as polyethylene, ethylene-α-olefin copolymer, homopolypropylene, atactic polypropylene; polyolefin resins such as polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, olefin-based elastomer; polyethylene terephthalate, polybutylene terephthalate, polyamide, ionomer, acrylate-based polymer, methacrylate-based polymer, polycarbonate, cellulose triacetate, etc. In addition, in recent years, the use of biomass-derived resins with a small environmental load has been studied from various aspects, and the resin forming the transparent resin layer of the decorative sheet of the present invention may also contain biomass-derived components. Specifically, biomass polyolefin, etc. can be used. In the case of the transparent resin layer, these resins can be used alone or in combination of two or more.

[0119] The transparent resin layer is preferably a transparent thermoplastic resin layer, more preferably contains an olefin-based resin represented by a polypropylene resin or a polyethylene resin, and the resin constituting the transparent resin layer is further preferably the above olefin-based resin or ionomer resin.

[0120] It should be noted that the transparent resin layer can be colored as long as it has transparency, and it is particularly preferably not mixed with a colorant.

[0121] According to needs, the transparent resin layer may further contain various additives. For example, lubricants such as silicone resin, wax, fluororesin; colorants such as dyes, pigments; antioxidants; ultraviolet absorbers; light stabilizers; flame retardants, etc. The content of the above additives is not particularly limited. For example, based on the transparent resin layer being 100% by mass, the content of the above additives is 0.1% by mass or more and 10% by mass or less.

[0122] From the perspective of achieving weather resistance, the transparent resin layer preferably contains an ultraviolet absorber.

[0123] As the ultraviolet absorber, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers can be cited. Among them, triazine-based ultraviolet absorbers are preferred. One kind of ultraviolet absorber can be used, or two or more kinds can be used.

[0124] Among triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers in which three organic groups selected from among hydroxyphenyl groups, alkoxyphenyl groups, and organic groups containing these groups are linked to the triazine ring are more preferable, and hydroxyphenyltriazine-based ultraviolet absorbers represented by the following general formula (A) are further preferable. Since hydroxyphenyltriazine-based ultraviolet absorbers have a branched structure, it is expected to achieve the property of being less likely to bleed from the transparent resin layer, and excellent weather resistance over a longer period can be achieved.

[0125]

[0126] In the general formula (A), R 11 is a divalent organic group, and R 12 is an ester group represented by -C(=O)OR 15 , and R 13 , R 14 and R 15 are each independently a monovalent organic group, and n 11 and n 12 are each independently an integer of 1 to 5.

[0127] Examples of the divalent organic group for R 11 include aliphatic hydrocarbon groups such as alkylene groups and alkenyl groups. From the viewpoint of weather resistance, an alkylene group is preferable, and the number of carbon atoms thereof is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 8 or less, and particularly preferably 1 or more and 4 or less. The alkylene group and the alkenyl group may be any of linear, branched, and cyclic shapes, and linear and branched shapes are preferable.

[0128] Examples of the alkylene group having 1 or more and 20 or less carbon atoms include various propylene groups such as methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, and 2,2-propylene (the following "various" means groups including linear, branched, and their isomers). Various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups, and various eicosylene groups.

[0129] Examples of the monovalent organic groups R 13 and R 14 include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, etc. Aromatic groups such as aryl groups or aralkyl groups are preferable, and aryl groups are preferable. Among them, as the monovalent organic groups R 13 and R 14 , a phenyl group is preferable.

[0130] As the aryl group, it is preferably an aryl group having 6 or more and 20 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms, and still more preferably 6 or more and 10 or less carbon atoms, such as phenyl, various methylphenyls, various ethylphenyls, various dimethylphenyls, various propylphenyls, various trimethylphenyls, various butylphenyls, various naphthyls, etc. As the aralkyl group, it is preferably an aralkyl group having 7 or more and 20 or less carbon atoms, more preferably 7 or more and 12 or less carbon atoms, and still more preferably 7 or more and 10 or less carbon atoms. For example, benzyl, phenethyl, various phenylpropyls, various phenylbutyls, various methylbenzyls, various ethylbenzyls, various propylbenzyls, various butylbenzyls, various hexylbenzyls, etc. can be cited.

[0131] As the monovalent organic group R 15 , alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, etc. can be cited. It is preferably an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, and more preferably an alkyl group. That is, as R 12 , an alkyl ester group or an alkenyl ester group is preferred, and an alkyl ester group is more preferred.

[0132] As the alkyl group, it is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably 2 or more and 16 or less carbon atoms, and still more preferably 6 or more and 12 or less carbon atoms. For example, methyl, ethyl, various propyls, various butyls, various pentyls, various hexyls, various octyls, various nonyls, various decyls, various undecyls, various dodecyls, various tridecyls, various tetradecyls, various pentadecyls, various hexadecyls, various heptadecyls, various octadecyls, various nonadecyls, various icosyls can be cited.

[0133] As the alkenyl group, it is preferably an alkenyl group having 2 or more and 20 or less carbon atoms, more preferably 3 or more and 16 or less carbon atoms, and still more preferably 6 or more and 12 or less carbon atoms. For example, vinyl, various propenyls, various butenyls, various pentenyls, various hexenyls, various octenyls, various nonenyls, various decenyls, various undecenyls, various dodecenyls, various tridecenyls, various tetradecenyls, various pentadecenyls, various hexadecenyls, various heptadecenyls, various octadecenyls, various nonadecenyls, various icosenyls can be cited.

[0134] As the hydroxybenzotriazine compound represented by the general formula (A), more specifically, it is preferred that R 11 is an alkylene group having 1 or more and 20 or less carbon atoms, R 12 and R 15 are alkyl ester groups of an alkyl group having 1 or more and 20 or less carbon atoms, R 13 and R 14 are aryl groups having 6 or more and 20 or less carbon atoms, n11 and n 12 is a hydroxytriazine compound of 1. More preferably, R 11 is an alkylene group having 1 or more and 12 or less carbon atoms, R 12 and R 15 is an alkyl ester group of an alkyl group having 2 or more and 16 or less carbon atoms, R 13 and R 14 is an aryl group having 6 or more and 12 or less carbon atoms, n 11 and n 12 is a hydroxytriazine compound of 1. Further preferably, R 11 is an alkylene group having 1 or more and 8 or less carbon atoms, R 12 is R 15 and an alkyl ester group of an alkyl group having 6 or more and 12 or less carbon atoms, R 13 and R 14 is an aryl group having 6 or more and 10 or less carbon atoms, n 11 and n 12 is a hydroxytriazine compound of 1. Particularly preferably, R 11 is an alkylene group having 1 or more and 4 or less carbon atoms, R 12 and R 15 is an ester group of an alkyl group having 8 carbon atoms, R 13 and R 14 is a phenyl group, n 11 and n 12 is a hydroxytriazine compound of 1.

[0135] Examples of the above-mentioned hydroxyphenyltriazine compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethylhexanoic acid 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)1-3-5-triazine, 2,4-bis(2-hydroxy-4-butyl oxyphenyl)-6-(2,4-bis-butyl oxyphenyl)-1,3,5-triazine, and the like, as well as their mixtures, modified products, polymers, derivatives, and the like.

[0136] The content of the ultraviolet absorber is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and still more preferably 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer.

[0137] Examples of the light stabilizer include aromatic compounds, amine compounds, organic acid compounds, catechin compounds, and hindered amine compounds, among which hindered amine compounds are preferred. The hindered amine compounds refer to compounds having a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

[0138] The content of the light stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8.0 parts by mass, and still more preferably 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the resin component constituting the transparent resin layer. It should be noted that as the light stabilizer, hindered amine compounds are preferably included in the above range.

[0139] Examples of the above-mentioned flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, aluminum-based flame retardants, antimony-based flame retardants, magnesium-based flame retardants, boron-based flame retardants, zirconium-based flame retardants, etc. From an environmental perspective, it is more preferable to use halogen-free flame retardants. The above-mentioned flame retardants can be used alone or in combination of two or more.

[0140] Examples of the phosphorus-based flame retardants include metal hypophosphite flame retardants and phosphazene flame retardants. In addition, regardless of the type of the flame retardant, its content relative to 100 parts by mass of the resin component constituting the transparent resin layer is preferably 3 parts by mass or more and 30 parts by mass or less. By maintaining within the above range, not only can the flame retardancy of the decorative sheet be improved, but also the hindrance to the required properties originally possessed by the decorative sheet can be suppressed.

[0141] The thickness of the transparent resin layer is usually about 20 to 200 μm, and can also exceed the above range depending on the use of the floor decorative sheet, etc.

[0142] (Primer layer)

[0143] A primer layer can be provided on the transparent resin layer. The primer layer can be formed by coating a known primer agent on the surface of the transparent resin layer. Examples of the primer agent include polyurethane resin-based primer agents such as acryloyl-modified polyurethane resin (acryloyl polyurethane resin), primer agents containing polyurethane-cellulose resin (for example, a resin formed by adding hexamethylene diisocyanate to a mixture of urethane and nitrocellulose), resin-based primer agents containing a block copolymer of an acryloyl compound and a urethane, etc. Additives can be blended according to needs as the primer agent. Examples of the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, etc. The mixing amount of the additives can be appropriately set according to the product performance.

[0144] The coating amount of the primer agent is not particularly limited, and is usually 0.1 to 100 g / m 2 , preferably 0.1 to 50 g / m 2 or so.

[0145] The thickness of the primer layer is not particularly limited, and is usually 0.01 to 10 μm, preferably about 0.1 to 1 μm.

[0146] (Back primer layer)

[0147] The back surface of the base material sheet (the surface opposite to the surface laminated with the pattern layer) can be provided with a primer layer as needed. This is effective, for example, when preparing a decorative board by laminating a decorative sheet and a base material (coated object member).

[0148] The back primer layer can be formed by coating a known primer agent on the substrate sheet. As the primer agent, for example, polyurethane resin-based primer agents such as acrylate compound-modified polyurethane resin (acrylate polyurethane resin), primer agents containing polyurethane-cellulose resin (for example, a resin formed by adding hexamethylene diisocyanate to a mixture of urethane and nitrocellulose), resin-based primer agents containing a block copolymer of acrylate compound and urethane, etc. can be cited. If necessary, additives can be incorporated into the primer agent. As the additives, for example, fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, etc. can be cited. The blending amount of the additives can be appropriately set according to the product performance.

[0149] The coating amount of the primer agent is not particularly limited, and is usually 0.1 to 100 g / m 2 , preferably 0.1 to 50 g / m 2 or so.

[0150] The thickness of the back primer layer is not particularly limited, and is usually 0.01 to 10 μm, preferably about 0.1 to 1 μm.

[0151] (Synthetic resin back lining layer)

[0152] A synthetic resin back lining layer (hereinafter also simply referred to as "back lining layer". It is a synthetic resin layer for improving scratch resistance or reducing the impact on the substrate (coated object member)) can be provided on the back of the substrate sheet. It should be noted that the above-mentioned scratch resistance particularly refers to the dent resistance after a load is locally applied. Although the decorative sheet of the present invention has sufficient scratch resistance even without providing a back lining layer, various properties such as scratch resistance can be further improved by providing a back lining layer.

[0153] As a method for forming the back lining layer, melt resin extrusion molding is preferably adopted, for example, extrusion molding using a T-die is preferably adopted.

[0154] As a method for joining the back of the substrate sheet and the back lining layer, a joining method of heat-fusing the substrate sheet and the back lining layer obtained by melt resin extrusion molding, and a joining method of providing an adhesive layer (and a primer layer if necessary) between the substrate sheet and the back lining layer, etc. can be cited.

[0155] The resin constituting the backing layer is not limited, and examples thereof include thermoplastic resins such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate (A-PET), highly heat-resistant polyethylene terephthalate glycol (e.g., polyethylene terephthalate in which part of ethylene glycol is replaced by 1,4-cyclohexanedimethanol or diethylene glycol, etc., namely the so-called trade name PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene (naphthalate / isophthalate) glycol copolymer, polyimide, polystyrene, polyamide, ABS (acrylonitrile-butadiene-styrene copolymer), etc. In addition, in recent years, the use of biomass-derived resins with a small environmental load has been studied from various aspects, and the resin forming the backing layer of the decorative sheet of the present invention may also contain biomass-derived components, and specifically, biomass polyolefins, etc. can be used. These resins can be used alone or in combination of two or more.

[0156] The thickness of the backing layer can be appropriately set according to the use, usage method, etc. of the final product, and is usually preferably 100 to 800 μm. Among them, more preferably 100 to 600 μm.

[0157] If necessary, known joining surface treatments such as corona discharge treatment, plasma treatment, degreasing treatment, and surface roughening treatment can also be performed on the backing layer. In addition, considering the joining property with the member to be coated, a primer layer can be further provided on the back surface. (Vesiculation of various additives contained in each layer of the decorative sheet)

[0158] The various additives added to the above-mentioned layers of the decorative sheet of the present invention (inorganic fillers, etc. added in the primer layer, surface protection layer, etc.) are preferably subjected to vesiculation treatment for the various additives. The method for vesiculating the various additives is not particularly limited, and known methods can be used to form vesicles, and among them, the supercritical reverse phase evaporation method is preferred.

[0159] As vesiculation methods, in addition to the supercritical reverse phase evaporation method, the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, the freeze-thaw method, etc. can also be cited. Briefly speaking, the Bangham method is a method in which a chloroform or chloroform / methanol mixed solvent is added to a container such as a flask, phospholipids are added and dissolved, and then the solvent is removed using an evaporator to form a lipid-containing film. After adding a dispersion liquid containing additives, it is hydrated and dispersed using a vortex mixer to obtain vesicles; the extrusion method is a method in which a phospholipid solution for preparing a film is used, and the mixer used as an external perturbation in the Bangham method is replaced by a filter to obtain vesicles; the hydration method is almost the same as the preparation method of the Bangham method, except that it is a method in which dispersion is carried out by gently stirring without using a mixer to obtain vesicles; the reverse phase evaporation method is a method in which phospholipids are dissolved in ether or chloroform, etc., a solution containing additives is added to make a W / O emulsion, and after removing the organic solvent from this emulsion under reduced pressure, vesicles are obtained by adding water; the freeze-thaw method is a method in which cooling / heating is used as an external perturbation, and vesicles are obtained by repeatedly performing this cooling / heating.

[0160] Hereinafter, the supercritical reverse phase evaporation method will be described in detail. The supercritical reverse phase evaporation method is a method in which an aqueous phase of various additives as water-soluble or hydrophilic encapsulants is added to a mixture obtained by uniformly dissolving a substance forming an outer membrane of vesicles in carbon dioxide under supercritical state or temperature or pressure conditions above the supercritical point, to form a capsule-shaped vesicle containing various additives as encapsulants with a single-layer membrane. It should be noted that carbon dioxide in the supercritical state refers to carbon dioxide in the supercritical state above the critical temperature (30.98 °C) and critical pressure (7.3773 ± 0.0030 MPa), and carbon dioxide under temperature or pressure conditions above the critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, single-layered vesicles with a diameter of 50 to 800 nm can be obtained. Generally, vesicles are a general term for small vesicles with a membrane structure closed in a spherical shell shape and containing a liquid phase inside, and in particular, vesicles whose outer membrane is formed of biological lipids such as phospholipids are collectively referred to as liposomes.

[0161] As the above-mentioned phospholipids, glycerolipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc., and sphingomyelins such as sphingomyelin, amide phosphoethanolamine, and ceramide phosphoglycerol can be cited.

[0162] As the substance constituting the outer membrane, a dispersant such as a nonionic surfactant or a mixture thereof with cholesterols or triacylglycerols can also be used.

[0163] As the above nonionic surfactant, one or more of polyglycerol ethers, dialkyl glycerols, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene-polyoxypropylene copolymers, polybutadiene-polyoxyethylene copolymers, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymers, polyoxyethylene-polyethyl ethylene copolymers, polyoxyethylene-polycaprolactam copolymers, etc. can be used.

[0164] As the above cholesterols, one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol, etc. can be used.

[0165] The outer membrane of the above liposome can be formed of a mixture of phospholipids and a dispersant. In the decorative sheet of the present invention, by making the outer membrane a liposome formed of phospholipids, the compatibility between the resin composition as the main component of each layer and various additives can be improved.

[0166] (Manufacturing method of decorative sheet)

[0167] The decorative sheet of the present invention is obtained by forming at least a surface protective layer on the outermost surface. For example, it can be obtained by laminating a pattern layer, a transparent adhesive layer, a transparent resin layer, and a primer layer on a base sheet and then forming a surface protective layer on the outermost surface.

[0168] In addition, when embossing is applied to the decorative sheet, it can be either after forming the surface protective layer or before forming the surface protective layer. For example, as a specific embodiment, it can be: 1) After sequentially forming a pattern layer, a transparent resin layer, and a primer layer on a base sheet, forming a surface protective layer, and finally performing embossing; or as another specific embodiment, it can also be: 2) After sequentially forming a pattern layer, a transparent resin layer, and a primer layer on a base sheet, performing embossing, and finally forming a surface protective layer; additionally, as yet another specific embodiment, it can be: 3) After sequentially forming a pattern layer and a transparent resin layer on a base sheet, then performing embossing, then setting a primer layer, and finally forming a surface protective layer. When adjusting the Sm, Rz, and the area ratio of the portion from the surface to a depth of 30 μm of the surface protective layer by embossing, it is preferable to perform embossing after forming the surface protective layer.

[0169] Embossing can transfer an uneven pattern to the patterned printing surface side of the decorative sheet at a sheet temperature of 120°C to 160°C and a pressure of 10 to 40 kg / cm 2 of pressure.

[0170] 2. Decorative board

[0171] The decorative panel of the present invention is a decorative panel having the above-mentioned decorative sheet on a base material. As long as the decorative sheet can be laminated on the base material so that the surface protective layer of the decorative sheet is the outermost surface layer.

[0172] The base material (coated object member) is not limited, and the same base materials as those of known decorative panels can be used. For example, wood materials, metals, ceramics, plastics, glass, etc. can be cited. The decorative sheet of the present invention can be particularly suitable for wood materials. As wood materials, specifically, various materials such as cypress, hinoki, beech, pine, lauan, teak, white lauan, etc. can be cited to make raised panels, wood veneers, plywood, fiberboard, particle board, medium density fiberboard (MDF), etc.

[0173] The lamination method can be but is not limited to, for example, a method of bonding the decorative sheet to the base material using an adhesive, etc. The adhesive can be appropriately selected from known adhesives according to the type of the base material, etc. For example, in addition to polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, etc., butadiene / acrylonitrile rubber, chloroprene rubber, natural rubber, etc. can also be cited. These adhesives can be used alone, or two or more of them can be used in combination.

[0174] The decorative panel manufactured in this way can be used for, for example, interior building materials such as walls, ceilings, and floors, surface decorative panels for building components such as window frames, doors, and handrails, surface decorative panels for furniture or cabinets of weak current and OA equipment, etc. In particular, the decorative panel of the present invention can be suitably used as a decorative material for floors.

[0175] Examples

[0176] Examples and comparative examples are given below to more specifically illustrate the present invention. However, the present invention is not limited to the examples.

[0177] Example 1

[0178] (Preparation of Decorative Sheet)

[0179] A primer layer (back primer layer) was provided on the back of a 60-μm-thick colored polypropylene film base material sheet. Subsequently, a pattern layer was formed on the surface of the base material sheet by printing, and then an adhesive layer was formed on the pattern layer. A transparent polypropylene-based resin (transparent random polypropylene-based resin) sheet was laminated on the adhesive layer by extrusion lamination to form a 80-μm-thick transparent resin layer. Subsequently, after corona discharge treatment was performed on the surface of the transparent random polypropylene-based resin sheet on the adhesive layer, a primer layer was formed by coating a two-component curable polyurethane resin.

[0180] An ionizing radiation-curable resin containing a polyurethane acrylate oligomer was used. By means of gravure coating, it was coated on the surface of the above primer layer at a coating amount of 15 μm over the entire surface. Then, in an environment with an oxygen concentration of 200 ppm or less, an electron beam was irradiated using an electron irradiation device under the conditions of an acceleration voltage of 165 keV and 5 Mrad, thereby forming a surface protective layer. Subsequently, the side of the surface protective layer was heated with an infrared non-contact heater to soften the base sheet and the transparent resin layer, and then embossing was performed using hot pressing.

[0181] It should be noted that as the polyurethane acrylate oligomer contained in the ionizing radiation-curable resin for forming the surface protective layer, a product in which the following polyurethane acrylate oligomers were mixed in the following ratio was used.

[0182] · Bifunctional polyurethane acrylate oligomer A (polyol component is polyester diol, Tg: 25 °C, molecular weight 1500)

[0183] · Hexafunctional aliphatic polyurethane acrylate oligomer B (Tg: 200 °C or higher, molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.)

[0184] Ratio (mass ratio) A:B = 80:20

[0185] (Preparation of decorative board)

[0186] On a medium-density fiberboard (MDF) with a thickness of 2.5 mm, an aqueous emulsion binder (BA-10L (main agent): BA-11B (curing agent) = 100:2.5 (mass ratio) manufactured by Japan Coating Resin Co., Ltd.) was uniformly coated at a dosage of 80 g / m 2 and pasted on the side of the back primer layer of the above-obtained decorative sheet, and cured at room temperature for 3 days to prepare a decorative board.

[0187] Example 2

[0188] (Nanometer treatment of nucleating agent using supercritical reverse phase evaporation method)

[0189] The nanosizing treatment of the nucleating agent using the supercritical inverse phase evaporation method was carried out as follows. First, 100 parts by mass of methanol, 82 parts by mass of a metal salt of phosphoric acid ester-based nucleating agent (ADEKASTAB NA-11, manufactured by ADEKA Corporation), and 5 parts by mass of phosphatidylcholine were added to a high-pressure stainless steel container maintained at a temperature of 60 °C and sealed. Carbon dioxide was injected until the pressure reached 20 MPa to form a supercritical state. Then, 100 parts by mass of ion-exchanged water was injected under a state of vigorous stirring and mixing, and stirred for 15 minutes while maintaining the temperature and pressure inside the container. Then, carbon dioxide was discharged to return to atmospheric pressure, and a nucleating agent vesicle having a phospholipid outer membrane encapsulating the nucleating agent was obtained.

[0190] (Formation of the transparent resin layer, the pattern layer, and the color masking layer)

[0191] The polypropylene-based resin (transparent random polypropylene resin) containing the nucleating agent vesicles obtained as described above was extrusion molded into a thickness of 80 μm to form a transparent resin layer. A pattern was printed on one surface of the transparent resin layer using a two-component curable polyurethane coating (V351, manufactured by Toyo T&I Co., Ltd.) to form a pattern layer. Then, a two-component curable polyurethane coating having a masking property (V351, manufactured by Toyo T&I Co., Ltd.) was applied on top of the pattern layer at a coating amount of 6 g / m 2 to form a color masking layer.

[0192] (Formation of the primer layer)

[0193] A two-component curable polyurethane coating (PET-E, reducer, manufactured by Dainichi Seika Co., Ltd.) as a primer was applied on top of the color masking layer at a coating amount of 1 g / m 2 to form a back primer layer.

[0194] (Formation of the embossed pattern)

[0195] Subsequently, an embossed pattern was formed by embossing on the other surface of the transparent resin layer using an embossing die roll.

[0196] (Formation of the surface protective layer)

[0197] A surface protective layer including a surface protective layer 1 (lower layer) and a surface protective layer 2 (upper layer) was formed by sequentially laminating the following surface protective layer forming composition 1 (coating amount after drying (described by film thickness after drying), the same below) 5 μm) and surface protective layer forming composition 2 (coating amount after drying 10 μm) on the surface of the embossed pattern.

[0198] [Surface protective layer forming composition 1]

[0199] Add the following additives in the following amounts relative to 100 parts by mass of the main agent to prepare Composition 1 for forming a surface protective layer.

[0200] · Main agent: Acryloyl polyol (acryloyl polyol containing a urethane bond), curing agent (forming a urethane bond by bonding with an isocyanate containing an N-H group) (glass transition temperature of about 100 °C, weight average molecular weight Mw of about 40,000, hydroxyl value of 12)

[0201] (Additive)

[0202] · UV absorber: Tinuvin 479 (manufactured by BASF Corporation) 5 parts by mass

[0203] · Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 3 parts by mass

[0204] · Dilution solvent: Ethyl acetate 50 parts by mass

[0205] · Gloss modifier: Inorganic filler L-121 (manufactured by AGC Si-Tech Corporation) 15 parts by mass

[0206] · Curing agent: Duranate TAP-100 (manufactured by Asahi Kasei Corporation) 5 parts by mass

[0207] [Composition 2 for forming a surface protective layer]

[0208] Mix the following resins in a ratio of A:B:C = 40:40:20 (by mass) to prepare a mixed resin. Add the following additives in the following amounts relative to 100 parts by mass of the mixed resin to prepare Composition 2 for forming a surface protective layer.

[0209] · Resin A: Polyfunctional polyurethane acrylate oligomer having 3 to 15 functional groups

[0210] · Resin B: Polyfunctional polyurethane acrylate oligomer having 2 to 9 functional groups

[0211] · Resin C: 5 parts by mass of curing agent DURANATE TAP-100 (manufactured by Asahi Kasei Corporation) relative to 100 parts by mass of acryloyl polyol having a glass transition temperature of about 100 °C, a weight average molecular weight Mw of about 50,000, and a hydroxyl value of 15

[0212] (Additive)

[0213] · UV absorber: Tinuvin 479 (manufactured by BASF Corporation) 5 parts by mass

[0214] · Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 3 parts by mass

[0215] · Dilution Dilution solvent: 50 parts by mass of ethyl acetate (for the preparation of decorative boards)

[0216] On a medium-density fiberboard (MDF) with a thickness of 2.5 mm, a water-based emulsion binder was uniformly coated at a dosage of 80 g / m 2 (BA-10L (main agent) : BA-11B (curing agent) = 100 : 2.5 (mass ratio)) manufactured by Japan Coating Resin Co., Ltd., pasted on the side of the back primer layer of the above-mentioned obtained decorative sheet, and cured at room temperature for 3 days to produce a decorative board.

[0217] Example 3

[0218] Except that the polyurethane acrylate oligomer contained in the ionizing radiation-curable resin forming the surface protective layer was a mixture of the following polyurethane acrylate oligomers according to the following ratio, the same procedures as in Example 1 were carried out to produce the decorative sheet and decorative board of Example 3.

[0219] · Bifunctional polyurethane acrylate oligomer A (polyol component is polyester diol, Tg: 25 °C, molecular weight 1500)

[0220] · Bifunctional polyurethane acrylate oligomer B (polyol component is polyether diol, Tg: -55 °C, molecular weight 5000)

[0221] · Hexafunctional polyurethane acrylate oligomer C (Tg: 200 °C or higher, molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.)

[0222] Ratio (mass ratio) A : B : C = 60 : 10 : 30

[0223] Example 4

[0224] Except that the polyurethane acrylate oligomer contained in the ionizing radiation-curable resin forming the surface protective layer was a mixture of the following polyurethane acrylate oligomers according to the following ratio, the same procedures as in Example 1 were carried out to produce decorative sheets and decorative boards.

[0225] · Bifunctional polyurethane acrylate oligomer A (polyol component is polyester diol, Tg: 25 °C, molecular weight 1500)

[0226] · Hexafunctional polyurethane acrylate oligomer C (Tg: 200 °C or higher, molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.)

[0227] · Ratio (mass ratio) A : B = 65 : 35

[0228] Comparative Example 1

[0229] As the resin for forming the surface protective layer, the polyurethane acrylate-based ultraviolet curable resin composition "TOMAX FA-3246" (solid content: 40%, manufactured by Nippon Chemical Coating Co., Ltd.) and the polyurethane acrylate-based ultraviolet curable resin "ART RESIN UN-904" (solid content: 100%, number of (meth)acryloyloxy groups: 10, manufactured by Negami Kogyo Co., Ltd.) were used as the main components, and TOMAX FA-3246 and UN-904 were mixed at a solid component ratio (mass ratio) of 80 / 20. After adding IRGACURE 184 (photoinitiator, manufactured by BASF Co., Ltd.) at a dosage of 3 parts by mass relative to the solid components of the resin composition, it was diluted with butyl acetate until the solid component concentration in the coating for forming the surface protective layer reached 30%, and it was sufficiently stirred to prepare the coating for forming the surface protective layer. On the surface of the primer layer, the prepared coating for forming the surface protective layer was coated with a doctor blade coater and hot air dried in a drying oven at 80°C for 1 minute to form a coating with a film thickness of 5.0 μm. Subsequently, a UV irradiation device installed at a height 60 mm higher than the coating application surface was used to perform UV irradiation under the condition of a UV irradiation dose of 250 mJ / cm 2 and the surface protective layer was cured and formed. In addition, the decorative sheet and decorative board of Comparative Example 1 were prepared in the same manner as in Example 1.

[0230] The following measurements were carried out using the decorative sheets prepared in the examples and comparative examples.

[0231] [IR peak height ratio]

[0232] The infrared spectrum of the surface of the surface protective layer of the decorative sheet was measured using an infrared spectrometer (IR Affinity-1A, manufactured by Shimadzu Corporation). When the peak height appearing in the wavenumber range of 855 - 1325 cm ﹣1 is set as A, the peak height appearing in the wavenumber range of 1650 - 1800 cm ﹣1 is set as B, and the peak height appearing in the wavenumber range of 3200 - 3500 cm ﹣1 is set as C, the ratios (A / B)×100 and (B / C)×100 are defined as the peak height ratios.

[0233] As the method for measuring the peak height, a baseline was drawn in each wavelength range, and the length connecting from the peak apex parallel to the vertical axis to the baseline was measured. It should be noted that when there are multiple peaks in each wavelength range, if the difference between the peak apex and valley of adjacent peaks is 0.010 Abs or more, they are regarded as "two peaks", and the sum of the heights of each peak is regarded as the "peak height".

[0234] [Adhesion]

[0235] According to the test method of JIS-K5600-5-6, under the conditions of 25°C and 50% RH in a JIS environment, a cross-cut peel test was conducted on the surface protective layer of the decorative sheet. Specifically, a cutter was used to make scratches on the surface protective layer of the decorative sheet at intervals of 1 mm, forming a cross-cut pattern with 11 vertical and 11 horizontal scratches, creating 100 square cross-cuts. On this, tape No. 252 manufactured by Sekisui Chemical Co., Ltd. was pasted, and after evenly pressing it with a spatula, peeling was carried out along the 60° direction. After 5 times of pressing and peeling at the same position, the number of remaining surface protective layers (cross-cuts) was measured and evaluated according to the following evaluation criteria. It should be noted that in the case of evaluating adhesion after environmental testing, after placing the decorative sheet in a damp heat environment of 60°C and 90% RH for 3 weeks, the above-mentioned adhesion evaluation was carried out at an environment of 25°C. It should be noted that the longitudinal direction of the decorative sheet refers to the winding direction of the raw material roll of the decorative sheet (MD direction of the manufacturing device), and the transverse direction of the decorative sheet refers to the width direction of the raw material roll of the decorative sheet (TD direction of the manufacturing device).

[0236] (Evaluation criteria)

[0237] ++: 100

[0238] +: More than 95 and less than 99

[0239] -: More than 80 and less than 94

[0240] ――: 79 or less

[0241] [Scratch resistance]

[0242] Steel wool (No. 0000 manufactured by BON STAR) was brought into contact with the surface protective layer of the decorative sheet and a load of 300 g / m 2 was applied, and a friction test was carried out under the condition of reciprocating 300 times. According to the test method of JIS-K5600-5-10, steel wool (No. 0000 manufactured by BON STAR) was used to reciprocate 100 times with a load of 1 kg on the surface of one side of the surface protective layer of the decorative sheet, and the evaluation of the scratch situation was carried out according to the following evaluation criteria.

[0243] (Evaluation criteria)

[0244] ++: No scratches appeared

[0245] +: A small number of scratches appeared

[0246] -: A large number of scratches appeared

[0247] [Pencil hardness]

[0248] The pencil hardness was measured according to the test method of JIS K5600-5-4. The hardness at which no scratch appeared on the surface was taken as the pencil hardness.

[0249] [Bending whitening]

[0250] The decorative sheet was cut into a test piece of 10 cm × 10 cm. This test piece was sharply bent 180 degrees in the longitudinal and transverse directions (both vertical and horizontal directions) in such a way that the surface protective layer side bulged into a mountain shape, and evaluation was carried out according to the following evaluation criteria. It should be noted that the longitudinal direction of the decorative sheet refers to the winding direction of the raw material roll of the decorative sheet (MD direction of the manufacturing apparatus), and the transverse direction of the decorative sheet refers to the width direction of the raw material roll of the decorative sheet (TD direction of the manufacturing apparatus).

[0251] Evaluation criteria

[0252] ++: No whitening appeared at all

[0253] +: Although there was some whitening, it was not obvious

[0254] -: Whitening and obvious

[0255] The results are shown in Table 1.

[0256] [Table 1]

[0257]

[0258] From the results in Table 1, it can be seen that: since the peak height ratios of A to B in Examples 1 and 2 were 221 and 116, and there were appropriate amounts of ester bonds, the surface protective layer had moderate hardness, excellent evaluation in scratch resistance, pencil hardness, and bending whitening, and these properties were excellent at the same time. Moreover, since the peak height ratios of B to C in Examples 1 and 2 were 1723 and 5057, and there were appropriate amounts of urethane bonds, the inventors believe that as Figure 6 shown, ester bonds and hydrogen bonds were formed in the surface protective layer, the adhesion reached the ++ rating, and since hydrolysis was inhibited, the adhesion after the environmental test reached the ++ rating.

[0259] In addition, based on the results in Table 1, it can be seen that: compared with the surface protective layers of Examples 1 and 2, the surface protective layer of Example 3 was a relatively soft surface protective layer. That is, since the peak height ratio of A to B in it increased relative to Examples 1 and 2 and there were fewer ester bonds, the surface protective layer was softer, and the scratch resistance and pencil hardness were slightly inferior to those of Examples 1 and 2, but the bending whitening was further inhibited. In addition, in Example 3, since the peak height ratio of B to C in it increased relative to Examples 1 and 2 and there were fewer urethane bonds, the adhesion was slightly inferior to that of Examples 1 and 2, and it was more prone to hydrolysis, so the adhesion after the environmental test was slightly inferior.

[0260] Moreover, it can be seen that in Table 1, compared with the surface protective layers of Examples 1 and 2, the surface protective layer of Example 4 becomes a relatively harder and more brittle surface protective layer. That is, since the peak height ratio of A to B is smaller than that of Examples 1 and 2 and there are more ester bonds, the surface protective layer is harder, with a pencil hardness rating of H, but the bending whitening rating is +. In addition, in Example 4, since the peak height ratio of B to C is smaller than that of Examples 1 and 2 and there are more urethane bonds, as Figure 6 shown, ester bonds and hydrogen bonds are formed in the surface protective layer, the adhesion reaches a ++ rating, and due to the inhibition of hydrolysis, the adhesion after environmental testing reaches a ++ rating.

[0261] Example 5

[0262] Except that 3 parts by mass of a phosphoric acid-based glass silver carrier compound (PG-711 manufactured by Koa Glass Co., Ltd.), which is an antiviral agent, was added to 100 parts by mass of the radiation-curable resin for forming the surface protective layer, the same procedures as in Example 1 were carried out to produce a decorative sheet and a decorative board. It should be noted that the peak height ratio of A to B and the peak height ratio of B to C in the surface protective layer are the same as those in Example 1.

[0263] The following evaluations were carried out using the decorative sheets prepared according to Example 1 and Example 5.

[0264] [Antiviral performance]

[0265] [Evaluation method]

[0266] According to the method described in the antiviral test method (ISO21702), the antiviral performance of the decorative sheets prepared according to Example 1 and Example 5 was tested, the antiviral activity value against influenza virus was calculated, and the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 2. It should be noted that when the rating is +, it is evaluated that there will be no problems in actual use. In addition, the antiviral agent (parts by mass) in Table 2 refers to the amount of the antiviral agent (parts by mass) relative to 100 parts by mass of the radiation-curable resin.

[0267] [Evaluation criteria]

[0268] +: The antiviral activity value is 2.0 or more

[0269] -: The antiviral activity value is less than 2.0

[0270] The results are shown in Table 2.

[0271] [Table 2]

[0272]

[0273] Example 6

[0274] Except that the following resin composition was heated, melt-extruded, and laminated as a transparent polypropylene resin (transparent random polypropylene resin) to form a 80-μm transparent resin layer, the same procedures as in Example 1 were carried out to prepare a decorative sheet and a decorative board. It should be noted that the peak height ratios of surface protective layers A to B and B to C were the same as those in Example 1.

[0275] (Resin composition)

[0276] Transparent polypropylene resin: 100 parts by mass

[0277] Metal salt phosphonate flame retardant (product name: Pekoflam STC (manufactured by Archroma): aluminum phosphonate): 10 parts by mass.

[0278] The following evaluations were carried out using the decorative sheets prepared in Examples 1 and 6.

[0279] [Flammability evaluation]

[0280] The decorative boards prepared in Example 1 and Example 6 were cut into a size of 9 cm × 30 cm as test pieces. As Figure 7 and Figure 8 shown, a metal rectangular placing table 103 was placed on the placing table 102 of a commercially available household heater 101 (ZAIGLE handsome SJ-100 (trade name)), and the test piece 105 was placed in a metal frame 104 provided on the placing table. The difficulty of fire spread was tested under the conditions of a heating angle of 45° and a heater power dial of 4. Specifically, the test piece was preheated with the above household heater for 2 minutes, and then as Figure 7 shown, the end 106 on the heater side in the length direction of the test piece was heated with a lighter 107 for 1 minute and ignited, and the fire spread along the length direction of the test piece 105 as Figure 8 shown. Then, the state of fire spread was observed with the naked eye, and the burning distance (L1) and burning duration were evaluated as follows. Thus, the horizontal combustion performance (difficulty of fire spread) was evaluated.

[0281] (Burning distance (L1))

[0282] The fire spread distance after the flame of the lighter was removed from the test piece after ignition was measured as the fire spread distance (L1), and the evaluation was carried out according to the following evaluation criteria. It should be noted that when the rating is + or above, it is evaluated that there will be no problem in actual use.

[0283] ++: L1 is less than 5 cm

[0284] + : L1 is more than 5 cm and less than 10 cm

[0285] - : L1 is 10 cm or more (burning duration)

[0286] The burning duration from the start of burning to self - extinction after removing the flame of the igniter after igniting the test piece was measured and evaluated according to the following evaluation criteria. It should be noted that when the rating is + or above, it is evaluated that there will be no problem in actual use.

[0287] +++ : The burning duration is less than 100 seconds or does not catch fire

[0288] ++ : The burning duration is 100 seconds or more and less than 300 seconds

[0289] + : The burning duration is 300 seconds or more and less than 600 seconds

[0290] - : The burning duration is 600 seconds or more (not self - extinguished at 600 seconds)

[0291] The results are shown in Table 3.

[0292] [Table 3]

[0293]

[0294] Symbol Explanation

[0295] 1. Decorative sheet; 11. Substrate sheet; 12. Pattern layer; 13. Transparent resin layer; 14. Surface protective layer; 2. Substrate; 101. Household heater; 102. Household heater storage table; 103. Rectangular metal storage table; 104. Metal frame; 105. Test piece; 106. End of the test piece on the heater side in the length direction; 107. Igniter; L1. Burning distance.

Claims

1. A decorative sheet, characterized in that: The decorative sheet at least has a surface protection layer, The surface protection layer contains a cross-linking curing resin, In the infrared spectrum measurement of the surface protective layer, the ﹣1 The peak height is set as A, appearing at 1650-1800cm ﹣1 When the peak height of A is set as B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less, In the infrared spectrum measurement of the surface protective layer, the ﹣1 When the peak height of B is defined as C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less.

2. The decorative sheet according to claim 1, characterized in that: The peak height ratio of A to B is greater than 110% and less than 300%, and the peak height ratio of B to C is greater than 1300% and less than 5500%.

3. The decorative sheet according to claim 1, characterized in that: The crosslinking curable resin includes an ionizing radiation curable resin.

4. The decorative sheet according to claim 3, characterized in that: The ionizing radiation curable resin includes an acrylic resin having a (meth)acryloyl group.

5. The decorative sheet according to claim 1, characterized in that: The surface protection layer contains at least one selected from antibacterial agents, antiviral agents and antiallergenic agents.

6. The decorative sheet according to claim 1, characterized in that: On the base sheet, there are a pattern layer, a transparent resin layer and the surface protection layer in sequence.

7. The decorative sheet according to claim 6, characterized in that: At least one layer selected from the base sheet and the transparent resin layer contains a flame retardant.

8. The decorative sheet according to claim 6, characterized in that: At least one layer selected from the base sheet, the pattern layer, the transparent resin layer, and the surface protection layer contains a biomass-derived component.

9. A decorative board, characterized in that: The decorative sheet according to any one of claims 1 to 8 is provided on a substrate.

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