Decorative sheet, coating agent, method for producing decorative sheet, and transfer film

Abstract

To provide a decorative sheet or the like capable of suppressing the lowering of productivity at the time of embossing even if a surface protective layer containing a biomass-derived component is formed and excellent in weatherability.SOLUTION: A decorative sheet comprising at least a transparent resin layer and a surface-protecting layer, wherein the surface-protecting layer contains a cross-linked curable resin, the cross-linked curable resin contains at least one biomass-derived component, the cross-linked curable resin is formed from a composition containing a urethane (meth) acrylate and at least one (meth) acrylic monomer, the (meth) acrylic monomer has a molecular weight of more than 300 and less than 1000, and the decorative sheet has an irregular shape on a surface provided with the surface-protecting layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet, a coating agent, a method for producing a decorative sheet, and a transfer film. [Background technology]

[0002] BACKGROUND ART Decorative sheets with designs are used to decorate building materials, furniture, home appliances, and the like.

[0003] Plastic is often used as the main component of decorative sheets, and although petroleum-derived plastics are commonly used, they are not desirable from the perspective of reducing environmental impact.

[0004] Therefore, biomass-derived plastics, which are made from renewable biological resources, are being considered for use in decorative sheets as a material that has a lower environmental impact than petroleum-derived plastics.

[0005] For example, Patent Document 1 discloses a decorative sheet comprising, in this order, a colored thermoplastic resin layer, an adhesive resin layer, a transparent thermoplastic resin layer, and a surface protective layer, wherein the colored thermoplastic resin layer and the transparent thermoplastic resin layer are each resin layers formed from a resin composition containing a biomass-derived polyolefin, and the surface protective layer contains a biomass-derived component. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2023-122232 Summary of the Invention [Problem to be solved by the invention]

[0007] In order to impart design to the decorative sheet, the surface (the surface having the surface protective layer) may be provided with an uneven shape by embossing.

[0008] In Patent Document 1, the surface protection layer contains a biomass-derived component, but depending on the type of monomer that constitutes the surface protection layer, there is a problem that the embossing plate may be contaminated by the influence of the monomer component when embossing the surface, resulting in reduced productivity.

[0009] Furthermore, there has been a problem in that it is not possible to impart sufficient weather resistance depending on the selection of the cross-linking curable resin that constitutes the surface protective layer.

[0010] Therefore, an object of the present invention is to provide a decorative sheet that can suppress a decrease in productivity during embossing and has excellent weather resistance, even when a surface protective layer containing a biomass-derived component is formed. [Means for solving the problem]

[0011] The inventors focused on the composition of the resin component that forms the surface protective layer and discovered that by including urethane (meth)acrylate and at least one (meth)acrylic monomer of a specific molecular weight, even if a surface protective layer containing a biomass-derived component is formed, it is possible to suppress a decrease in productivity during embossing and to obtain a decorative sheet with excellent weather resistance, thereby completing the present invention.

[0012] That is, the present invention provides a decorative sheet comprising at least a transparent resin layer and a surface protective layer, wherein the surface protective layer comprises a cross-linked curable resin, the cross-linked curable resin comprises at least one biomass-derived component, and is formed from a composition comprising a urethane (meth)acrylate and at least one (meth)acrylic monomer, the (meth)acrylic monomer having a molecular weight of more than 300 and less than 1000, and the side comprising the surface protective layer has an uneven shape.

[0013] In the decorative sheet of the present invention, the cross-linked curable resin preferably has a biomass content of 10% or more. The surface protective layer preferably contains a weathering agent. The surface protective layer preferably contains an inorganic filler. The surface protection layer preferably has a thickness of 3 μm or more and 30 μm or less. It is also preferable that an adhesive layer, a design layer, and a base sheet are provided in this order on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided. It is also preferable that at least one layer of the transparent resin layer, the adhesive layer, and the base sheet contains a biomass-derived component. The present invention also relates to a coating agent that contains at least one biomass-derived component, and also contains a urethane (meth)acrylate and at least one (meth)acrylic monomer, wherein the (meth)acrylic monomer has a molecular weight of more than 300 and less than 1,000. The present invention also provides a method for producing a decorative sheet, comprising the steps of applying the coating agent of the present invention onto a transparent resin layer and curing it to form a surface protective layer, and embossing the surface having the surface protective layer. The present invention also provides a transfer film comprising the decorative sheet of the present invention as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided. [Effects of the Invention]

[0014] The present invention provides a decorative sheet that can suppress a decrease in productivity during embossing and has excellent weather resistance, even when a surface protective layer containing a biomass-derived component is formed. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a cross-sectional view that schematically illustrates a preferred example of the decorative sheet of the present invention. [Figure 2] FIG. 2 is a cross-sectional view for explaining a schematic view of another preferred example of the decorative sheet of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] <Decorative sheet> The decorative sheet of the present invention comprises at least a transparent resin layer and a surface protective layer, the surface protective layer comprising a cross-linked curable resin, the cross-linked curable resin comprising at least one biomass-derived component, and formed from a composition comprising a urethane (meth)acrylate and at least one (meth)acrylic monomer, the (meth)acrylic monomer having a molecular weight of more than 300 and less than 1000, and having an uneven shape on the side comprising the surface protective layer.

[0017] FIG. 1 is a cross-sectional view that schematically illustrates one example of the decorative sheet of the present invention. As shown in Figure 1, the decorative sheet 10 comprises a transparent resin layer 3 and a surface protective layer 4, and comprises a pattern layer 2 and a base sheet 1 on the side of the transparent resin layer 3 opposite to the side on which the surface protective layer 4 is provided. The decorative sheet 10 also has an uneven shape 5 on the side on which the surface protective layer 4 is provided.

[0018] FIG. 2 is a cross-sectional view for explaining a schematic view of another preferred example of the decorative sheet of the present invention. As shown in FIG. 2, the decorative sheet 10 is formed by laminating a transparent resin layer 3 and a surface protective layer 4 via an adhesive auxiliary layer 8 (also referred to as a surface adhesive auxiliary layer). In addition, on the side of the transparent resin layer 3 opposite to the side having the surface protective layer 4, an adhesive layer 7, a pattern layer 2, an adhesive auxiliary layer 6 (also called a pattern auxiliary layer), a base sheet 1, and an adhesive auxiliary layer 9 (also called a back surface adhesive auxiliary layer) are laminated in this order. The decorative sheet 10 also has an uneven shape 5 on the side on which the surface protective layer 4 is provided. Each component of the decorative sheet of the present invention will be described in detail below.

[0019] (Surface protective layer) The decorative sheet of the present invention is provided with a surface protective layer.

[0020] The surface protective layer contains a cross-linked curable resin. The cross-linking curable resin is formed from a composition containing a urethane (meth)acrylate and at least one (meth)acrylic monomer. In this specification, (meth)acrylate means acrylate and / or methacrylate, and (meth)acrylic means acrylic and / or methacrylic.

[0021] The cross-linked curable resin contains at least one biomass-derived component. The urethane (meth)acrylate may contain a biomass-derived component, and the (meth)acrylic monomer may contain a biomass-derived component.

[0022] From the viewpoint of suitably reducing the environmental load, the cross-linking curable resin preferably has a biomass content of 10% or more. The biomass degree is more preferably 15% or more, further preferably 30% or more, and particularly preferably 40% or more. The upper limit of the biomass content is, for example, 70%.

[0023] In this specification, "biomass content" refers to a value measured by radiocarbon (C14) measurement to determine the content of carbon derived from biomass. Atmospheric carbon dioxide contains a certain proportion of C14 (105.5 pMC), and it is known that the C14 content in plants that grow by absorbing atmospheric carbon dioxide, such as corn, is also about 105.5 pMC. On the other hand, it is also known that fossil fuels contain almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in the total carbon atoms in the layer of the base sheet of the present invention (or in the transparent resin layer described below). That is, the content of C14 in the crosslinked curable resin (or in the resin components constituting the transparent resin layer or the substrate sheet) is P C14 The content of biomass-derived carbon in this case is P bio can be found as follows: P bio (%)=(PC14 / 105.5)×100

[0024] The urethane (meth)acrylate is preferably one obtained by reacting a polyol, an isocyanate, and a hydroxy (meth)acrylate.

[0025] Examples of polyols include polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols.

[0026] Polyester polyols are the reaction products of polyfunctional alcohols and polyfunctional carboxylic acids, polyether polyols are the reaction products of polyfunctional alcohols and polyfunctional isocyanates, and polycarbonate polyols are the reaction products of polyfunctional alcohols and carbonates. Polycaprolactone polyols can be obtained by ring-opening polymerization of ε-caprolactone with polyfunctional alcohols. The polyfunctional alcohols, polyfunctional carboxylic acids, polyfunctional isocyanates, and carbonates may be known petroleum-derived materials, but the polyfunctional alcohols, polyfunctional carboxylic acids, and polyfunctional isocyanates may also be biomass-derived materials.

[0027] Examples of biomass-derived alcohols include aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, cassava, and sago palm, and examples thereof include polypropylene glycol, neopentyl glycol, ethylene glycol, diethylene glycol, butylene glycol, and hexamethylene glycol.

[0028] Examples of biomass-derived carboxylic acids that can be used include aliphatic polyfunctional carboxylic acids obtained from plant raw materials such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and examples thereof include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid.

[0029] As the biomass-derived isocyanate, polyfunctional isocyanates obtained from plant raw materials can be used, and examples thereof include dimer acid diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate.

[0030] As the hydroxy(meth)acrylate, a known hydroxy(meth)acrylate having two or more functional groups may be used.

[0031] The urethane (meth)acrylate preferably has 2 or more and 6 or less functional groups, more preferably 2 or more and 4 or less, from the viewpoint of suitably imparting scratch resistance and weather resistance to the surface protective layer. Furthermore, from the viewpoint of suitably imparting weather resistance, it is preferable to use a caprolactone-based urethane (meth)acrylate obtained by reacting polycaprolactone polyol with isocyanate and hydroxy (meth)acrylate.

[0032] The urethane (meth)acrylate preferably has a biomass degree of 40 or more. By ensuring that the biomass degree is within the above range, the biomass degree of the cross-linked curable resin can be suitably increased.

[0033] The urethane (meth)acrylate preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 2,000 or more. In this specification, the term "weight average molecular weight (Mw)" refers to an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0034] From the viewpoint of providing suitable weather resistance, the content of the urethane (meth)acrylate in the composition forming the cross-linked curable resin is preferably 30% by mass or more, more preferably 60% by mass or more, and from the viewpoint of solvent resistance, the content of the urethane (meth)acrylate in the composition forming the cross-linked curable resin is preferably 90% by mass or less, more preferably 70% by mass or less.

[0035] The (meth)acrylic monomer has a molecular weight of more than 300 and less than 1,000. By ensuring that the molecular weight is within the above range, it is possible to suppress a decrease in productivity during embossing. The (meth)acrylic monomer preferably has a molecular weight of 320 or more, more preferably 340 or more. The molecular weight of the (meth)acrylic monomer means the molecular weight calculated from the chemical formula.

[0036] As the (meth)acrylic monomer, a petroleum-derived (meth)acrylic monomer can be used, but it is preferable to use a biomass-derived (meth)acrylic monomer.

[0037] Biomass-derived (meth)acrylic monomers include glycerin di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate. , trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

[0038] As the petroleum-derived (meth)acrylic monomer, a difunctional or higher monomer (a compound having two or more ethylenically unsaturated bonds) can be used, for example, the following known compounds having two or more ethylenically unsaturated bonds. Specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl 2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-Dimethyl-2,5-hexanediol di(meth)acrylate, 2-Methyl-1,8-octanediol di(meth)acrylate, 2-Butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-Diethyl-1,5-pentanediol di(meth)acrylate, 1,2-Hexanediol di(meth)acrylate, 1,5-Hexanediol di(meth)acrylate, 2,5-Hexanediol di(meth)acrylate, 1,7-Heptanediol Diol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate Decanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol Di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-Pentanediol di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, tricyclodecanedimethylol dicaprolactonate di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di( Bifunctional monomers such as di(meth)acrylates of polyhydric alcohols such as glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, etc.; trifunctional monomers such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; Trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactonate tetra(meth)acrylate, diglycerin tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexa Examples of suitable monomers include tetrafunctional or higher monomers such as tetramethylolpropane tetra(meth)acrylate, ditrimethylol octane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and tripentaerythritol polyalkylene oxide hepta(meth)acrylate. Among these, examples include trimethylolpropane triacrylate (TMPTA; trifunctional), ditrimethylolpropane tetraacrylate (DITMPTA; tetrafunctional), dipentaerythritol hexaacrylate (DPHA; hexafunctional), and hexanediol diacrylate (HDDA; bifunctional).

[0039] The (meth)acrylic monomer preferably has 2 or more and 6 or less functional groups, from the viewpoint of suitably imparting scratch resistance and weather resistance to the surface protective layer.

[0040] The (meth)acrylic monomer preferably has a biomass degree of 35 or more. By ensuring that the biomass degree is within the above range, the biomass degree of the cross-linked curable resin can be suitably increased.

[0041] From the viewpoint of solvent resistance, the content of the (meth)acrylic monomer in the composition forming the cross-linked curable resin is preferably 10% by mass or more, more preferably 20% by mass or more, and from the viewpoint of weather resistance, the content of the (meth)acrylic monomer in the composition forming the cross-linked curable resin is preferably 40% by mass or less, more preferably 30% by mass or less. In addition, from the viewpoint of preventing a decrease in productivity during embossing, it is preferable that the composition does not contain a (meth)acrylic monomer having a molecular weight of 300 or less.

[0042] The surface protective layer preferably contains a weathering agent from the viewpoint of imparting weather resistance to the surface protective layer.

[0043] Examples of weatherproofing agents include ultraviolet absorbers and light stabilizers.

[0044] Examples of the ultraviolet absorber include organic ultraviolet absorbers such as triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyano(meth)acrylate-based ultraviolet absorbers; and inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based ultraviolet absorbers are preferred from the viewpoint of providing suitable weather resistance.

[0045] Examples of the light stabilizer include hindered amine light stabilizers.

[0046] The content of the weather resistance agent is preferably 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the cross-linking curable resin.

[0047] The surface protective layer preferably contains an inorganic filler. By including an inorganic filler, the gloss of the decorative sheet can be adjusted, and a more luxurious design can be imparted.

[0048] Examples of inorganic fillers include silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, and synthetic silicates.

[0049] The inorganic filler preferably has a particle size of 1 μm or more and 20 μm or less. The particle size is the 50% particle size (d50: median size) when the particle size distribution measured by a dynamic light scattering method is expressed as a volume cumulative distribution.

[0050] The content of the weather resistance agent is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the cross-linking curable resin.

[0051] The cross-linking curable resin may contain a known photopolymerization initiator, if necessary. The amount of the photopolymerization initiator added is preferably, for example, 0.1% by mass or more and 10% by mass or less based on the mass of the crosslinking curable resin.

[0052] The surface protective layer may contain various additives such as colorants such as dyes and pigments, antifoaming agents, leveling agents, thixotropy-imparting agents, flame retardants, antibacterial agents, antiviral agents, antiallergens, etc. The amounts of the additives to be added may be appropriately selected depending on the properties of each additive.

[0053] The surface protection layer preferably has a thickness of 3 μm or more and 30 μm or less. When the thickness of the surface protective layer is within the above range, scratch resistance and weather resistance can be suitably imparted. The surface protective layer preferably has a thickness of 5 μm or more and 20 μm or less. In addition, when the uneven shape described below is formed, the thickness of the surface protection layer is defined as the length from the part of the surface of the surface protection layer where the uneven shape is not formed to the surface of the surface protection layer on the transparent resin layer side.

[0054] The surface protective layer preferably comprises at least one biomass-derived component, and is formed from a coating agent (composition) comprising a urethane (meth)acrylate and at least one (meth)acrylic monomer, the (meth)acrylic monomer having a molecular weight of more than 300 and less than 1,000. The urethane (meth)acrylate and (meth)acrylic monomer (also referred to as resin component) contained in the coating agent can be those described above. If necessary, the coating agent may also contain the weathering agent and inorganic filler described above. Such coating agents are also included in the present invention.

[0055] The surface protective layer may be formed by applying a coating agent by a known method and curing it with ionizing radiation. The term "ionizing radiation" refers to electromagnetic waves or charged particles that have enough energy to polymerize or crosslink molecules, and generally refers to electron beams (EB) or ultraviolet rays (UV).

[0056] (Transparent resin layer) The decorative sheet of the present invention comprises a transparent resin layer. The above-mentioned "transparency" may be semi-transparent or colored, as long as the design layer is visible.

[0057] The transparent resin layer may be made of, for example, an ester-based resin, an olefin-based resin, an acrylic-based resin, a carbonate-based resin, a urethane-based resin, a styrene-based resin, a vinyl chloride-based resin, a vinyl acetate-based resin, a vinyl chloride-vinyl acetate copolymer resin, etc. From the viewpoint of improving moldability and scratch resistance, an ester-based resin or an olefin-based resin such as polypropylene or polyester is preferred.

[0058] The transparent resin layer may contain a biomass-derived component. When the transparent resin layer contains a biomass-derived component, the environmental load can be suitably reduced. In this case, biomass-derived polyolefin (biomass-derived polyethylene, polypropylene, etc.) may be used as the resin constituting the transparent resin layer.

[0059] The transparent resin layer may further contain various additives as needed. Examples include antioxidants, ultraviolet absorbers, light stabilizers, lubricants, nucleating agents, colorants such as dyes and pigments, etc. The amount of the additives to be added may be appropriately selected depending on the properties of each additive.

[0060] The thickness of the transparent resin layer is preferably 40 μm or more and 150 μm or less. By ensuring that the thickness of the transparent resin layer is within the above range, the scratch resistance of the decorative sheet can be suitably improved.

[0061] The method for laminating the transparent resin layer is not limited as long as it is a common method, and examples thereof include a dry lamination method and an extrusion lamination method in which a molten resin is extruded using a T-die to perform lamination. A T-die or the like capable of extruding molten resin can be used as the extrusion mechanism described above.

[0062] The transparent resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, ultraviolet (UV) treatment, and flame treatment.

[0063] (Picture layer) The decorative sheet of the present invention preferably has a pattern layer on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided.

[0064] The pattern layer is used to impart a desired pattern (design) to the decorative sheet, and the type of pattern is not limited, etc. Examples include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-grained patterns, geometric figures, letters, symbols, abstract patterns, etc.

[0065] The ink used to form the design layer contains a colorant component, a resin component, and a liquid component. The ink may also contain an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, etc.

[0066] Examples of colorant components that can be used include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; scaly foil metal pigments such as aluminum and brass; and scaly foil pearlescent pigments such as titanium dioxide-coated mica and basic lead carbonate. The resin component is not particularly limited and can be any resin selected from the group consisting of urethane resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, nitrocellulose (nitrocellulose) resins, cellulose acetate resins, acrylic-urethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, and chlorinated polypropylene resins, either alone or in combination. As the liquid component, for example, organic solvents such as methyl ethyl ketone, toluene, cyclohexanone, ethyl acetate alcohol, ethanol, and methanol, or water can be used.

[0067] The design layer can be formed by partially printing an ink containing a colorant component, a resin component, and a liquid component using a gravure printing method using an intaglio roll. The design layer may also be formed by partially printing inks of the same or different compositions in different regions and / or by overlapping the same region multiple times.

[0068] The thickness of the design layer is preferably, for example, 0.1 μm or more and 5 μm or less.

[0069] (Base sheet) The decorative sheet of the present invention preferably has a substrate sheet on the side opposite to the side on which the transparent resin layer of the design layer is provided.

[0070] Examples of resins that constitute the substrate sheet include ester-based resins, olefin-based resins, urethane-based resins, acrylic-based resins, polycarbonate-based resins, polystyrene-based resins; vinyl chloride-based resins, vinyl acetate-based resins, and vinyl chloride-vinyl acetate copolymer resins. Of these, ester-based resins and olefin-based resins are preferred, and polyethylene and polypropylene are more preferred.

[0071] The base sheet may contain a biomass-derived component. When the base sheet contains a biomass-derived component, the environmental load can be suitably reduced. In this case, biomass-derived polyolefin (biomass-derived polyethylene, polypropylene, etc.) may be used as the resin constituting the base sheet.

[0072] The substrate sheet may be colored as necessary. The surface may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer, which is a base coating material, to improve adhesion to adjacent layers.

[0073] The substrate sheet may contain various additives, as needed, such as colorants, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, ultraviolet absorbers, antioxidants, light stabilizers, etc. The amounts of the additives to be added may be appropriately selected depending on the properties of each additive.

[0074] The substrate sheet may be colored as necessary. The surface may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer, which is a base coating material, to improve adhesion to adjacent layers.

[0075] The thickness of the substrate sheet is, for example, preferably 50 μm or more and less than 100 μm, and more preferably 60 μm or more and 80 μm or less.

[0076] The specific method for forming a film (sheeting) of the substrate sheet is not particularly limited, and examples include the T-die method in which molten resin is extruded and laminated using a T-die, the calendar method, and the circular die method (inflation method, tubular method). Among these, the T-die method is preferred when improving production efficiency (production speed) and alleviating internal stress during sheeting. The calendar method is preferred when making the thickness of the substrate sheet uniform and reducing foreign matter defects.

[0077] (adhesive layer) The decorative sheet of the present invention may have an adhesive layer between the design layer and the transparent resin layer. The adhesive layer is preferably transparent.

[0078] The adhesive that can be used to form the adhesive layer includes, for example, urethane adhesives such as ester urethane and acrylic urethane, acrylic adhesives, epoxy adhesives, and rubber adhesives.

[0079] The adhesive layer may include a biomass-derived component. As the biomass-derived component, for example, the above-mentioned urethane-based adhesive using biomass-derived isocyanate may be used.

[0080] The thickness of the adhesive layer is, for example, 0.1 μm or more and 30 μm or less. The method for forming the adhesive layer is not particularly limited, and any known method may be appropriately selected.

[0081] (adhesion auxiliary layer) If necessary, the decorative sheet of the present invention may have an adhesive auxiliary layer (pattern auxiliary layer) between the base sheet and the pattern layer, an adhesive auxiliary layer (surface adhesive auxiliary layer) between the transparent resin layer and the surface protective layer, or an adhesive auxiliary layer (back surface adhesive auxiliary layer) on the back surface of the base sheet (the side opposite to the side having the pattern layer). The adhesion auxiliary layer functions as a primer layer or an easy-adhesion layer.

[0082] The adhesive auxiliary layer can be formed using, for example, an ester-based resin, a urethane-based resin, an acrylic-based resin, a polycarbonate-based resin, a vinyl chloride-vinyl acetate copolymer, a polyvinyl butyral-based resin, a nitrocellulose-based resin, etc., and one or more of these resins can be used.

[0083] The thickness of the adhesion auxiliary layer is preferably 0.1 μm or more and 30 μm or less, from the viewpoint of suitably suppressing poor adhesion between layers. The method for forming the adhesive auxiliary layer is not particularly limited, and any known method may be appropriately selected.

[0084] The adhesive layer or the adhesive auxiliary layer may contain additives as required. Examples of the additives include lubricants such as silicone resins, waxes, and fluororesins, colorants such as dyes and pigments, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, flame retardants, deodorizers, antibacterial agents, antiviral agents, antiallergens, and antifungal agents. The amount of additive to be added may be appropriately selected depending on the properties of each additive.

[0085] (Uneven shape) The decorative sheet of the present invention has an uneven shape on the side having the surface protective layer, from the viewpoint of providing a suitable design.

[0086] The uneven shape may reach the transparent resin layer or the adhesive auxiliary layer (adhesive auxiliary layer 6 in FIG. 2), or may be a flat shape (finely uneven shape).

[0087] The maximum height Rz of the uneven shape is preferably, for example, 10 μm or more and 60 μm or less. By setting the maximum height Rz of the uneven shape within the above range, it is possible to suitably impart an excellent design that gives a three-dimensional feel not only visually but also tactilely (to the touch). The "maximum height Rz" means the maximum height Rz specified in JIS B 0601 (2001).

[0088] The method for forming the uneven shape is not particularly limited, and examples thereof include a method of embossing with heat, and a method of transferring the uneven shape using a shaping sheet. Examples of heat embossing include a method of embossing using a well-known sheet-type or rotary embossing machine. Examples of embossed patterns include sand grain, hairline, matte finish, wood grain vessel grooves, uneven stone surface, cloth surface texture, and linear grooves.

[0089] (others) The decorative sheet of the present invention may, if necessary, have a backer layer on the side of the substrate sheet opposite the design layer. By providing a backer layer, impact resistance can be more suitably imparted.

[0090] The backer layer can be produced by molding the resin composition into a sheet (film) by a calendering method, an inflation method, a T-die extrusion method, or the like.

[0091] The resin forming the backer layer is preferably a thermoplastic resin, such as polypropylene (PP), polyethylene (PE), ethylene-propylene copolymer, acrylic, polyurethane, polyvinyl chloride, polymethylene, polymethylpentene, polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, ABS, etc.

[0092] The thickness of the backer layer is preferably, for example, 100 μm or more and 400 μm or less.

[0093] <Manufacturing method of decorative sheet> The method for producing the decorative sheet of the present invention includes a step of applying the coating agent of the present invention onto a transparent resin layer and curing it to form a surface protective layer, and a step of embossing from the side having the surface protective layer. In the decorative sheet manufacturing method of the present invention, the coating agent contains urethane (meth)acrylate and a (meth)acrylic monomer of a specific molecular weight, so that even if a surface protective layer containing biomass-derived components is formed, a decrease in productivity during embossing can be suppressed.

[0094] In the method for producing a decorative sheet of the present invention, the order in which the layers are formed is not particularly important. For example, an adhesive auxiliary layer (pattern auxiliary layer), a pattern layer, an adhesive layer, a transparent resin layer, an adhesive auxiliary layer (surface adhesive auxiliary layer), and a surface protective layer may be formed in this order on one side of the base sheet. Furthermore, the steps of forming each layer do not need to proceed consecutively, and other steps or treatments may be carried out between these steps. Each layer may also be laminated on a releasable support, which will be described later.

[0095] <Release film> The release film of the present invention comprises the decorative sheet of the present invention as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided.

[0096] Examples of the releasable support include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins.

[0097] The thickness of the releasable support may be, for example, 10 μm or more and 200 μm or less.

[0098] (decorative panels) The decorative sheet of the present invention may have an adherend laminated on the side of the base sheet opposite to the side having the pattern layer.

[0099] Examples of the adherend include wood boards, gypsum boards, cement boards, ceramic boards, metal boards, resin boards, and fiber-reinforced plastic boards. As a method for laminating the adherend, for example, the adherend may be laminated on the side of the base sheet opposite to the side having the pattern layer via the adhesive layer described above.

[0100] The present specification discloses the following:

[0101] The present disclosure (1) is a decorative sheet comprising at least a transparent resin layer and a surface protective layer, the surface protective layer comprising a cross-linked curable resin, the cross-linked curable resin comprising at least one biomass-derived component, and formed from a composition comprising a urethane (meth)acrylate and at least one (meth)acrylic monomer, the (meth)acrylic monomer having a molecular weight of more than 300 and less than 1000, and having an uneven shape on the side comprising the surface protective layer. The present disclosure (2) is the decorative sheet according to the present disclosure (1), wherein the cross-linked curable resin has a biomass content of 10% or more. The present disclosure (3) is the decorative sheet according to the present disclosure (1) or (2), wherein the surface protective layer contains a weathering agent. The present disclosure (4) is the decorative sheet according to any one of the present disclosures (1) to (3), wherein the surface protective layer contains an inorganic filler. The present disclosure (5) is the decorative sheet according to any one of the present disclosures (1) to (4), wherein the surface protective layer has a thickness of 3 μm or more and 30 μm or less. The present disclosure (6) is a decorative sheet according to any one of the present disclosures (1) to (5), which has an adhesive layer, a pattern layer, and a base sheet in this order on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided. The present disclosure (7) is the decorative sheet according to the present disclosure (6), wherein at least one layer of the transparent resin layer, the adhesive layer, and the base sheet contains a biomass-derived component. The present disclosure (8) is a coating agent comprising a cross-linking curable resin, the cross-linking curable resin comprising at least one biomass-derived component, and comprising a urethane (meth)acrylate and at least one (meth)acrylic monomer, the (meth)acrylic monomer having a molecular weight of more than 300 and less than 1,000. The present disclosure (9) is a method for producing a decorative sheet, which includes a step of applying the coating agent described in the present disclosure (8) onto a transparent resin layer, curing the coating agent to form a surface protective layer, and a step of embossing the surface having the surface protective layer. The present disclosure (10) is a transfer film comprising a decorative sheet according to any one of the present disclosures (1) to (7) as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided. [Example]

[0102] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0103] Example 1 A colored substrate layer formed of a resin composition containing a biomass-derived polyolefin was prepared, and used as a substrate sheet. A back adhesive auxiliary layer (containing 53% by mass of ester-based polyurethane resin and 3% by mass of soluble nitrocellulose) was formed on one side of the base sheet so as to cover the entire surface by solid printing with an ink containing an organic solvent using a gravure printing method with an intaglio roll. On the other side of the base sheet, a 2 μm thick pattern auxiliary layer mainly composed of an acrylic-urethane resin was formed by solid printing with an ink containing an organic solvent using a gravure printing method with an intaglio roll so as to cover the entire surface, and then a 2 μm thick pattern layer (wood grain pattern) mainly composed of an acrylic-urethane resin was formed by partial printing with an ink containing a colorant and an organic solvent using a gravure printing method with an intaglio roll. An ester-based polyurethane was applied to the side of the pattern layer opposite the pattern auxiliary layer to form a 10 μm thick adhesive layer, and a 60 μm thick transparent olefin sheet was dry laminated onto the adhesive layer to form a transparent resin layer. Furthermore, a surface adhesion auxiliary layer made of an acrylic-urethane copolymer resin having a thickness of 2 μm was formed on the side of the transparent resin layer opposite the adhesive layer, and a coating agent was applied onto the surface adhesion auxiliary layer by gravure coating. After that, the coating agent was cured by irradiating it with ionizing radiation to form a surface protection layer having a thickness of 5 μm. Finally, the surface having the surface protective layer was embossed by heat and pressure to form a concave-convex shape, thereby producing a decorative sheet. The coating agent used to form the surface protective layer consisted of 40 parts by mass of biomass-derived glycerin triacrylate "Aronix M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.) and 60 parts by mass of petrochemically derived bifunctional urethane acrylate "RECRYL 270" (weight-average molecular weight: 3000, manufactured by Daicel-Allnex Corporation). Additionally, 20 parts by mass of matte silica was added per 100 parts by mass of the resin component, and 2 parts by mass each of a UV absorber (TINUVIN 400, manufactured by BASF) and a light stabilizer (SANOL LS-3410, manufactured by Nippon Nyukazai Co., Ltd.) were added as weather resistance agents per 100 parts by mass of the resin component.

[0104] Example 2 A decorative sheet was produced in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of biomass-derived glycerin triacrylate "Aronix M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.) and 60 parts by mass of biomass-derived bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight average molecular weight: 4000, manufactured by Negami Chemical Industrial Co., Ltd.).

[0105] Example 3 A decorative sheet was produced in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of petrochemically derived polyethylene glycol diacrylate "PEG600 diacrylate" (molecular weight: 700, manufactured by Daicel-Allnex Corporation) and 60 parts by mass of biomass-derived bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight average molecular weight: 4000, manufactured by Negami Chemical Industrial Co., Ltd.).

[0106] Example 4 A decorative sheet was produced in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of biomass-derived glycerin triacrylate "Aronix M-930" (molecular weight: 348, manufactured by Toagosei Co., Ltd.), 50 parts by mass of biomass-derived bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight average molecular weight: 4000, manufactured by Negami Chemical Industrial Co., Ltd.), and 10 parts by mass of pentafunctional tripentaerythritol acrylate "Viscoat #802" (molecular weight: 804, manufactured by Osaka Organic Chemical Industry Ltd.).

[0107] Example 5 A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the surface protective layer was set to 30 μm.

[0108] (Comparative Example 1) A decorative sheet was manufactured in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of petrochemically derived polyethylene glycol diacrylate "PEG200 diacrylate" (molecular weight: 300, manufactured by Daicel-Allnex Corporation) and 60 parts by mass of bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight average molecular weight: 4000, manufactured by Negami Chemical Industrial Co., Ltd.).

[0109] (Comparative Example 2) A decorative sheet was manufactured in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of biomass-derived glycerin diacrylate (molecular weight: 254, manufactured by Toa Gosei Co., Ltd.) and 60 parts by mass of bifunctional urethane acrylate "ART RESIN STQI-037PR" (weight average molecular weight: 4000, manufactured by Negami Chemical Industrial Co., Ltd.).

[0110] (Comparative Example 3) A decorative sheet was manufactured in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of biomass-derived glycerin diacrylate (molecular weight: 254, manufactured by Toa Gosei Co., Ltd.) and 60 parts by mass of petrochemically derived bifunctional urethane acrylate "RECRYL 270" (weight average molecular weight: 3000, manufactured by Daicel-Allnex Corporation).

[0111] Comparative Example 4 A decorative sheet was manufactured in the same manner as in Example 1, except that the resin components of the coating agent used to form the surface protective layer were changed to 40 parts by mass of biomass-derived glycerin diacrylate (molecular weight: 254, manufactured by Toa Gosei Co., Ltd.) and 60 parts by mass of biomass-derived glycerin triacrylate "Aronix M-930" (molecular weight: 348, manufactured by Toa Gosei Co., Ltd.).

[0112] <Evaluation method>

[0113] (1) Productivity Decorative sheets of Examples and Comparative Examples were prepared before embossing. The temperature of the sheet is 120℃ to 160℃ and the pressure is 20kg / cm from the surface protection layer side of the decorative sheet. 2 Embossing was carried out under the conditions above, and after 3,000 m of the embossed plate was continuously produced, the appearance of the embossed plate was checked for dirt. The staining of the embossed plate was visually observed from a position 1 m away from the embossed plate before and after the run, and was evaluated according to the following criteria. The sheet temperature is the temperature obtained by measuring the decorative sheet during production (on the conveyor before embossing) using a non-contact thermometer (IT2-60, manufactured by KEYENCE Corporation). +: There was little dirt on the embossed plate. -: The embossing plate was dirty with white spots. A "+" rating was considered a pass, and a "-" rating was considered a fail.

[0114] (2) Weather resistance The surface protection layer side of the decorative sheet was tested using an Eye Super UV Tester (model number: SUV-W261, manufactured by Iwasaki Electric Co., Ltd.) at a back panel temperature of 63°C, humidity of 50% RH, and ultraviolet irradiance of 60 mW / cm. 2 After 20 hours of irradiation under the above conditions, a 4-hour condensation cycle was repeated, and after 9 cycles (216 hours) the appearance change was visually confirmed from a distance of 30 cm and evaluated according to the following criteria. ++: No change in appearance +: There was a change in appearance, but it was minor. -: Significant change in appearance In the above test, a "++" or "+" rating was considered a pass, and a "-" rating was considered a fail.

[0115] [Table 1] TIFF2026028473000003.tif439

[0116] From Table 1, it was confirmed that by forming the cross-linked curable resin constituting the surface protective layer from a coating agent containing urethane (meth)acrylate and a (meth)acrylic monomer having a molecular weight of more than 300 and less than 1000, even if a surface protective layer containing biomass-derived components is formed, it is possible to suppress a decrease in productivity during embossing, and a decorative sheet with excellent weather resistance can be obtained. [Explanation of symbols]

[0117] 1 Base sheet 2. Picture layer 3 Transparent resin layer 4 Surface protective layer 5 Uneven shape 6 Adhesive auxiliary layer (pattern auxiliary layer) 7 Adhesive layer 8 Adhesion auxiliary layer (surface adhesion auxiliary layer) 9 Adhesion auxiliary layer (back side adhesion auxiliary layer) 10 Decorative Sheet

Claims

1. The film comprises at least a transparent resin layer and a surface protective layer, the surface protection layer contains a cross-linked curable resin, the cross-linked curable resin contains at least one biomass-derived component and is formed from a composition containing a urethane (meth)acrylate and at least one (meth)acrylic monomer; the (meth)acrylic monomer has a molecular weight of more than 300 and less than 1,000; A decorative sheet having an uneven shape on the surface having the surface protective layer.

2. 2. The decorative sheet according to claim 1, wherein the cross-linked curable resin has a biomass content of 10% or more.

3. The decorative sheet according to claim 1 or 2, wherein the surface protective layer contains a weathering agent.

4. The decorative sheet according to claim 1 or 2, wherein the surface protective layer contains an inorganic filler.

5. 3. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 3 μm or more and 30 μm or less.

6. 3. The decorative sheet according to claim 1, further comprising an adhesive layer, a design layer, and a base sheet in this order on the side of the transparent resin layer opposite to the side on which the surface protective layer is provided.

7. The decorative sheet according to claim 6 , wherein at least one of the transparent resin layer, the adhesive layer, and the base sheet contains a biomass-derived component.

8. The composition contains at least one biomass-derived component, and also contains a urethane (meth)acrylate and at least one (meth)acrylic monomer; The (meth)acrylic monomer has a molecular weight of more than 300 but less than 1,000.

9. a step of applying the coating agent according to claim 8 onto the transparent resin layer and curing the coating agent to form a surface protective layer; and A method for producing a decorative sheet, comprising a step of embossing the surface having the surface protective layer.

10. A transfer film comprising the decorative sheet according to claim 1 or 2 as a transfer layer, and a releasable support on the side of the surface protective layer opposite to the side on which the transparent resin layer is provided.

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