Decorative sheets, transfer sheets and decorative moldings

Abstract

To provide a decorative sheet which improves smooth touch feeling on a sheet surface.MEANS FOR SOLVING THE PROBLEM: A decorative sheet has a design layer, and a surface resin layer provided on the design layer, where the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a decorative sheet, a transfer sheet, and a decorated molded article. [Background technology]

[0002] Conventionally, decorative sheets have been known in which a wood grain pattern (wood grain pattern) identical to that of natural wood is printed on a base layer. For example, studies have been conducted to improve the tactile feel by incorporating particles into the surface resin layer of the decorative sheet to create unevenness on the surface (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-159507 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional decorative sheets having a surface resin layer containing particles and having an uneven texture exhibit a rough texture and are not sufficiently smooth. One object of the present disclosure is to provide a decorative sheet having an improved smooth texture on the sheet surface. Another object of the present disclosure is to provide a transfer sheet capable of transferring a transfer layer exhibiting the above-mentioned texture to an adherend. Another object of the present disclosure is to provide a decorated molded product exhibiting the above-mentioned texture. [Means for solving the problem]

[0005] The decorative sheet of the present disclosure has a design layer and a surface resin layer provided on the design layer. The surface resin layer may contain a polymer-based lubricant and an organic particle-based lubricant. The transfer sheet of the present disclosure has a releasable support and a transfer layer. The transfer layer may have a design layer and a surface resin layer provided on the design layer. The surface resin layer may contain a polymer-based lubricant and an organic particle-based lubricant. The releasable support may be disposed on the surface resin layer of the transfer layer. The decorated molded article of the present disclosure includes a molded article, a design layer provided on at least a partial region of the molded article, and a surface resin layer provided on the design layer. The surface resin layer may contain a polymer-based lubricant and an organic particle-based lubricant. [Effects of the Invention]

[0006] According to the present disclosure, a decorative sheet having an improved smooth feel on the sheet surface can be provided. According to the present disclosure, a transfer sheet capable of transferring a transfer layer exhibiting the above-mentioned feel to an adherend can be provided. According to the present disclosure, a decorated molded article exhibiting the above-mentioned feel can be provided. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic cross-sectional view of a decorative sheet of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view of the transfer sheet of the present disclosure. [Figure 3] FIG. 3 is a schematic cross-sectional view of a decorated molded product of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure can be implemented in many different forms, and should not be construed as being limited to the description of the embodiments exemplified below. For clarity of explanation, the drawings may show the width, thickness, shape, etc. of each layer more schematically than in the embodiments, but these are merely examples and do not limit the interpretation of the present disclosure. In this specification and each drawing, elements similar to those already described with reference to the previous drawings are designated by the same reference numerals, and detailed description may be omitted as appropriate.

[0009] In the following description, each of the components (for example, resin components, various resins, particles, colorants, and additives) that appear may be used either alone or in combination of two or more.

[0010] The decorative sheet of the present disclosure comprises: A design layer and a surface resin layer provided on the design layer; It has. In one embodiment, the decorative sheet of the present disclosure further comprises a substrate layer. In this embodiment, the design layer may be provided between the substrate layer and the surface resin layer.

[0011] Films and sheets are often referred to as films and sheets in the order of their relative thickness, however, in the present disclosure, unless otherwise specified, sheets encompass films.

[0012] FIG. 1 shows a schematic cross-sectional view of one embodiment of a decorative sheet according to the present disclosure. The decorative sheet 1 comprises a substrate layer 10 including a first surface 11 and a second surface 12 opposite the first surface 11, a design layer 20 provided on the first surface 11 of the substrate layer 10, and a surface resin layer 30 provided on the design layer 20, in this order in the thickness direction. That is, the substrate layer 10, the design layer 20, and the surface resin layer 30 are stacked in the thickness direction, which is the vertical direction in the plane of FIG. 1. The surface resin layer 30 contains an organic particle-based lubricant, as described below, but these particles are not shown in FIG. 1. Particles are also not shown in other drawings. The decorative sheet 1 may further comprise an adhesive layer (not shown) on the second surface 12 of the substrate layer 10.

[0013] Examples of the substrate layer include a paper substrate, a resin substrate, a nonwoven fabric, and a woven fabric. Examples of paper substrates include kraft paper, titanium paper, linter paper, coated paper, art paper, glassine paper, parchment paper, paraffin paper, parchment paper, tissue paper, wood-free paper, Japanese paper, and resin-impregnated paper.

[0014] Examples of resin components constituting the resin substrate include thermoplastic resins. Examples of thermoplastic resins include polyolefins such as polyethylene, polypropylene, and polymethylpentene; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers; (meth)acrylic resins such as polymethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and ethylene glycol-terephthalic acid-isophthalic acid copolymers; polycarbonates; polyamides; polyimides; cellulose resins; and ionomer resins. The resin substrate may be composed of a single resin layer or two or more resin layers of the same or different types. (Meth)acrylate refers to acrylate or methacrylate. (Meth)acrylic refers to acrylic or methacrylic.

[0015] Nonwoven or woven fabrics are made of, for example, inorganic and / or organic fibers. Examples of inorganic fibers include glass fibers, alumina fibers, silica fibers, and carbon fibers. Examples of organic fibers include synthetic fibers such as polyolefin fibers, polyester fibers, and (meth)acrylic fibers, as well as natural fibers such as silk, cotton, and linen.

[0016] The substrate layer may have one of the above substrates alone or in combination. For example, the substrate layer may have multiple paper substrates, a paper substrate and a nonwoven fabric or a woven fabric, a paper substrate and a resin substrate, a resin substrate and a nonwoven fabric or a woven fabric, or a paper substrate, a nonwoven fabric or a woven fabric, and a resin substrate.

[0017] The substrate layer may contain additives. Examples of additives include ultraviolet absorbers, light stabilizers, antioxidants, fillers, foaming agents, flame retardants, plasticizers, lubricants, and colorants. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. Examples of light stabilizers include hindered amine-based light stabilizers such as piperidinyl sebacate-based light stabilizers.

[0018] The base layer may contain a colorant. For example, when the surface hue of the adherend to which the decorative sheet is attached varies, and it is desired to conceal the surface hue and improve the stability of the color tone of the design layer, the base layer may contain an inorganic pigment such as a white pigment.

[0019] The thickness of the substrate layer is preferably 20 μm or more and 1,000 μm or less, more preferably 30 μm or more and 500 μm or less, and even more preferably 50 μm or more and 200 μm or less. In the case of a paper substrate, nonwoven fabric, or woven fabric, the basis weight is preferably 20 g / m 2 More than 150g / m 2 Less than 30 g / m, more preferably 2 More than 100g / m 2 The following is the result.

[0020] One or both surfaces of the substrate layer may be subjected to a surface treatment. Examples of the surface treatment include physical surface treatments such as oxidation and roughening, as well as chemical surface treatments. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of the roughening method include sandblasting and solvent treatment. The substrate layer may have an easy-adhesion layer on one or both surfaces. This can improve, for example, the interlayer adhesion between the substrate layer and other layers.

[0021] The decorative sheet of the present disclosure has a design layer. In one embodiment, the decorative layer is provided on the substrate layer. In other words, in this embodiment, the decorative sheet has a decorative layer overlapped with the substrate layer in the thickness direction. The substrate layer and the decorative layer may be in contact with each other, or another layer may be present between the substrate layer and the decorative layer.

[0022] The decorative sheet of the present disclosure, which has a design layer and a surface resin layer, has excellent tactile feel and design. In one embodiment, the design layer is provided between the substrate layer and the surface resin layer for the purpose of imparting decorativeness to the decorative sheet. The design layer is provided to display the design expressed by the decorative sheet. In other words, the design layer displays the design.

[0023] The design layer has, for example, a pattern. Examples of patterns include wood grain patterns that imitate tree rings or vessel grooves on the surface of a wooden board, stone grain patterns that imitate the surface of rocks such as marble and granite, fabric patterns that imitate cloth grain or cloth-like patterns, leather grain patterns that imitate the surface of leather, pear-skin patterns, tile patterns, brickwork patterns, geometric patterns, and abstract patterns such as letters, figures, symbols, polka dots, and floral patterns. The pattern may be a single, solid color (a so-called solid image). The pattern may also be a composite pattern containing two or more of these. The design layer may have two or more layers. For example, the design layer may have a colored first layer and a second layer that is provided on the first layer to form the pattern.

[0024] Among these, wood grain patterns that imitate annual rings or vessel grooves on the surface of a wooden board are preferred. Examples of wood grain patterns include wood grain patterns that include vessel sections. The vessel sections are patterns that imitate the vessel grooves of the wood grain pattern. In the above wood grain patterns, the pattern area other than the vessel sections is, for example, a grain surface section. The grain surface section is a pattern that imitates the wood fibers of the wood grain pattern. Examples of wood grain patterns include wood grain patterns that include early wood and late wood sections.

[0025] The design layer can be formed, for example, by a printing method or a coating method. Examples of printing methods include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing. Examples of coating methods include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, and reverse roll coating. Each layer described below can also be formed, for example, by these methods.

[0026] In one embodiment, the design layer contains a resin component and a colorant. Examples of the resin component include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane-(meth)acrylic copolymer, (meth)acrylic resin, polystyrene, polyurethane, polyester, polyamide, butyral resin, nitrocellulose, and cellulose acetate.

[0027] Examples of colorants include pigments and dyes. Specific examples include inorganic pigments such as carbon black, 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, phthalocyanine blue, azomethine azo black, and nickel azo complexes; metal pigments consisting of scaly flakes such as aluminum and brass; and pearlescent pigments consisting of scaly flakes such as titanium dioxide-coated mica and basic lead carbonate.

[0028] The content of colorant in the design layer is preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 30 parts by mass or more and 300 parts by mass or less, and even more preferably 50 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of the resin component contained in the design layer.

[0029] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, antioxidants, fillers, antifoaming agents, flame retardants, plasticizers, and lubricants.

[0030] The thickness of the design layer is preferably 0.5 μm to 20 μm, more preferably 1 μm to 15 μm, and even more preferably 2 μm to 10 μm, which can improve the design of the decorative sheet, for example.

[0031] The design layer may have a metal thin film. Examples of metals constituting the metal thin film include tin, indium, chromium, aluminum, nickel, iron, cobalt, copper, silver, gold, platinum, and zinc, as well as alloys containing at least one selected from these metals. Examples of alloys include brass, bronze, and stainless steel. Examples of methods for forming the metal thin film include vacuum deposition, sputtering, and ion plating. The thickness of the metal thin film is, for example, 0.1 μm or more and 1 μm or less.

[0032] The decorative sheet of the present disclosure may have a concealing layer between the substrate layer and the design layer. By providing the concealing layer, for example, it is possible to prevent the substrate layer from adversely affecting the color tone or pattern of the decorative sheet.

[0033] The hiding layer may be an opaque color layer. In one embodiment, the hiding layer contains a resin component and a colorant. The resin component and colorant in the hiding layer can be appropriately selected from the resin component and colorant in the design layer, respectively, and therefore, description thereof will be omitted here. The hiding layer may contain the above-mentioned additives. The thickness of the hiding layer is, for example, 1 μm or more and 20 μm or less.

[0034] The decorative sheet of the present disclosure has a surface resin layer. In one embodiment, the surface resin layer is provided on the entire surface of the design layer. The surface resin layer is superimposed on the design layer in the thickness direction. By providing the surface resin layer, for example, the heat resistance, scratch resistance, and contamination resistance of the decorative sheet can be improved. The surface resin layer constitutes the outermost layer on one side of the decorative sheet.

[0035] The surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant. This can, for example, impart a smooth feel and a textured surface to the decorative sheet. For example, the organic particle-based lubricant creates texture on the surface of the surface resin layer. This texture is based on the organic particle-based lubricant, and therefore exhibits a smooth feel. Furthermore, the polymer-based lubricant further improves the smooth feel across the entire surface of the surface resin layer. In this way, by using a polymer-based lubricant and an organic particle-based lubricant in combination, a decorative sheet can be obtained that combines a textured surface and a smooth feel. In one embodiment, a decorative sheet having such a surface resin layer exhibits a texture similar to that of wood that has been subjected to a soap finish treatment.

[0036] Soap finish treatment is a process in which soap bubbles are applied to the surface of wood to form a coating film. This treatment is carried out, for example, to improve the smooth feel while maintaining the texture of the wood. The coating film formed by soap finish treatment tends to have low heat resistance, scratch resistance, and stain resistance. On the other hand, the surface resin layer of the decorative sheet of the present disclosure excels in these physical properties. For example, by applying the decorative sheet of the present disclosure to the surface of recycled wood, the feel of wood can be reproduced, thereby reducing the amount of natural wood used.

[0037] Examples of polymer-based lubricants include organic polymer-based lubricants such as silicone polymers, fluororesins, and synthetic polyethylene waxes. Among these, silicone polymers are preferred. In the present disclosure, organic polymer-based lubricants also include organic-inorganic hybrid polymers such as silicone polymers.

[0038] Examples of silicone polymers include silicone resins, modified silicone resins, silicone oils, modified silicone oils, and silicone-modified polymers. The silicone polymers may be linear, branched, or have a three-dimensional structure.

[0039] Examples of silicone resins include straight silicone resins such as methyl silicone resins and methylphenyl silicone resins. Examples of modified silicone resins include alkyd-modified silicone resins, epoxy-modified silicone resins, (meth)acrylic-modified silicone resins, and polyester-modified silicone resins.

[0040] Examples of silicone oils include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil. Examples of modified silicone oils include polyether-modified silicone oils (such as polyether-modified dimethyl silicone oil), alkyl-modified silicone oils (such as alkyl-modified dimethyl silicone oil), aralkyl-modified silicone oils (such as aralkyl-modified dimethyl silicone oil), higher fatty acid ester-modified silicone oils (such as higher fatty acid ester-modified dimethyl silicone oil), and fluoroalkyl-modified silicone oils (such as fluoroalkyl-modified dimethyl silicone oil).

[0041] Examples of silicone-modified polymers include silicone-modified (meth)acrylic resins, silicone-modified polyesters, silicone-modified polyethers, and silicone-modified polyurethanes.

[0042] Examples of fluororesins include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, vinylidene fluoride polymer, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and vinyl fluoride polymer.

[0043] The polymer-based lubricant may be, for example, a non-reactive lubricant or a reactive lubricant having a crosslinkable functional group or a polymerizable functional group. Reactive lubricants are preferred because they are less likely to fall off the surface resin layer and can prevent the excellent tactile feel from deteriorating over time.

[0044] Specific examples of reactive lubricants include polymers of the silicone polymers or fluororesins described above that have crosslinkable or polymerizable functional groups. Examples of crosslinkable or polymerizable functional groups include functional groups (ethylenically unsaturated groups) having an ethylenic double bond, such as (meth)acryloyl groups, vinyl groups, and allyl groups, as well as hydroxyl groups, mercapto groups, isocyanate groups, and epoxy groups. Among these, ethylenically unsaturated groups are preferred. In the reactive lubricant, the number of functional groups per molecule is, for example, 1 to 3.

[0045] The reactive lubricant having an ethylenically unsaturated group can react with an ionizing radiation-curable compound described below when irradiated with ionizing radiation such as electron beams and ultraviolet rays. This can prevent the reactive lubricant from falling off. When the reactive lubricant is incorporated into the curing system of the surface resin layer, the content of the reactive lubricant (including the reactive lubricant incorporated into the curing system) can be calculated, for example, from the solids ratio of the reactive lubricant in the resin composition that forms the surface resin layer.

[0046] In one embodiment, the content of the polymer-based lubricant in the surface resin layer is preferably 2% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, relative to 100% by mass of the resin component. When the content is equal to or less than the upper limit, for example, a decrease in the surface hardness of the surface resin layer can be suppressed. When the content is equal to or more than the lower limit, the smooth feel of the surface resin layer can be improved. The resin component also includes the polymer-based lubricant.

[0047] Examples of organic particle-based lubricants include silicone particles and fluororesin particles. Among these, silicone particles are preferred. In the present disclosure, organic particle-based lubricants also include organic-inorganic hybrid particles such as silicone particles.

[0048] The average particle size of the organic particle-based lubricant is preferably 0.5 μm or more and 15 μm or less, more preferably 1 μm or more and 12 μm or less, and even more preferably 2 μm or more and 10 μm or less, which can improve, for example, the uneven feel and smooth feel of the surface resin layer.

[0049] In the present disclosure, the average particle size refers to the average particle size (arithmetic mean diameter) measured for 100 randomly selected non-aggregated particles when a cross section of each layer in the thickness direction is observed with a scanning electron microscope (SEM).

[0050] In one embodiment, the content of the organic particle-based lubricant in the surface resin layer is preferably 10 to 50 parts by mass, more preferably 12 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, per 100 parts by mass of the resin components contained in the surface resin layer. When the content is equal to or greater than the lower limit, for example, the smooth feel of the surface resin layer can be improved. When the content is equal to or less than the upper limit, for example, the content of inorganic particles described below in the surface resin layer can be ensured, thereby achieving a high matte feel. The resin components also include polymer-based lubricants.

[0051] The surface resin layer may further contain an organic lubricant component other than the polymer-based lubricant and the organic particle-based lubricant, such as a hydrocarbon-based lubricant, a fatty acid-based lubricant, a higher alcohol-based lubricant, a fatty acid ester-based lubricant, a fatty acid amide-based lubricant, a phosphate ester-based lubricant, and a metal soap-based lubricant.

[0052] Examples of hydrocarbon-based lubricants include liquid paraffin, paraffin wax, and microcrystalline wax. Examples of fatty acid-based lubricants include stearic acid and montanic acid. Examples of higher alcohol-based lubricants include stearyl alcohol. Examples of fatty acid ester-based lubricants include stearic acid ester-based lubricants such as stearic acid monoglyceride and stearyl stearate. Examples of fatty acid amide-based lubricants include stearic acid amide, oleic acid amide, erucic acid amide, methylene bisstearic acid amide, and ethylene bisstearic acid amide. Examples of phosphate-based lubricants include polyoxyethylene tridecyl ether phosphate ester. Examples of metal soap-based lubricants include lead stearate, zinc stearate, calcium stearate, and magnesium stearate.

[0053] Lubricant components include, for example, waxes of animal origin such as beeswax, spermaceti, and wool wax; and waxes of plant origin such as carnauba wax, candelilla wax, rice wax, and Japan wax.

[0054] In one embodiment, the surface resin layer contains at least one selected from a silicone polymer and a fluororesin, and at least one selected from silicone particles and fluororesin particles, preferably a silicone polymer and silicone particles. These lubricant components have excellent compatibility with the resin components that may constitute the surface protective layer. This configuration makes it easier to achieve a smooth feel similar to that of wood that has been subjected to the above-mentioned soap finish treatment.

[0055] In one embodiment, the surface resin layer contains an additional resin component other than the polymer-based lubricant. For example, from the viewpoint of further improving the heat resistance, scratch resistance, and contamination resistance of the surface resin layer, the surface resin layer preferably contains an additional resin component.

[0056] The resin component functions, for example, as a binder in the surface resin layer. Examples of the resin component include a thermoplastic resin and a cured product of a curable compound. Examples of the cured product of a curable compound include a cured product of an ionizing radiation curable compound and a cured product of a thermosetting resin. The surface resin layer may contain two or more of these resin components.

[0057] Examples of thermoplastic resins include polyolefins, vinyl chloride resins, styrene resins, (meth)acrylic resins, polyesters, polycarbonates, polyamides, and polyimides.

[0058] Examples of thermosetting resins include unsaturated group-containing (meth)acrylic resins, unsaturated polyesters, urethane resins, epoxy resins, phenolic resins, aminoalkyd resins, urea resins, melamine resins, melamine-urea co-condensation resins, guanamine resins, diallyl phthalate resins, and silicone resins.

[0059] A curing agent is used together with the thermosetting resin as needed. In the case of unsaturated group-containing (meth)acrylic resin and unsaturated polyester, for example, a peroxide such as methyl ethyl ketone peroxide or a radical initiator such as azoisobutylnitrile is used. In the case of urethane resin, for example, an isocyanate-based curing agent is used. In the case of epoxy resin, for example, an organic amine-based curing agent is used.

[0060] Examples of thermosetting resins include two-component curing urethane resins that use a polyol as a base resin and an isocyanate compound as a curing agent. Examples of polyols include (meth)acrylic polyols, polyether polyols, polyester polyols, polyethylene glycols, and polypropylene glycols. The isocyanate compounds are polyvalent isocyanates having two or more isocyanate groups, such as aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; and aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0061] The ionizing radiation-curable compound refers to a compound that crosslinks and cures upon exposure to ionizing radiation and has an ionizing radiation-curable functional group. The ionizing radiation-curable functional group is a group that crosslinks upon exposure to ionizing radiation, and examples thereof include functional groups (ethylenically unsaturated groups) having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. The ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV), as well as electromagnetic waves such as X-rays and gamma rays; and charged particle beams such as alpha rays and ion beams.

[0062] Examples of the ionizing radiation curable compound include polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable compounds. The polymerizable monomer is preferably a (meth)acrylate monomer having a (meth)acryloyl group in the molecule, more preferably a polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups in the molecule. The number of (meth)acryloyl groups in the polyfunctional (meth)acrylate monomer is 2 or more, preferably 8 or less, more preferably 6 or less.

[0063] Examples of the polymerizable monomer include bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A tetraethoxy di(meth)acrylate, and bisphenol A tetrapropoxy di(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Examples of the (meth)acrylate include tri- or higher functional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and ethylene oxide-modified, propylene oxide-modified, caprolactone-modified, isocyanuric acid-modified, or propionic acid-modified products of these (meth)acrylates.

[0064] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule. Examples of the (meth)acrylate oligomer include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, polycaprolactone urethane (meth)acrylate, and polycaprolactone diol urethane (meth)acrylate. The number of (meth)acryloyl groups in the polymerizable oligomer is two or more, preferably eight or less, and more preferably six or less.

[0065] The weight-average molecular weight of the polymerizable oligomer is preferably from 500 to 100,000, more preferably from 1,000 to 50,000. The weight-average molecular weight is an average molecular weight measured by gel permeation chromatography (GPC) analysis and converted into standard polystyrene.

[0066] As the ionizing radiation-curable compound, a monofunctional (meth)acrylate may be appropriately used in combination with a polyfunctional (meth)acrylate for the purpose of reducing viscosity, etc. Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isobornyl (meth)acrylate.

[0067] When the ionizing radiation curable compound is an ultraviolet curable compound, it is preferable to use at least one selected from a photopolymerization initiator and a photopolymerization accelerator together with the ultraviolet curable compound.

[0068] From the viewpoint of achieving excellent heat resistance, scratch resistance, and contamination resistance, the surface resin layer preferably contains a cured product of a curable compound, and more preferably contains a cured product of an ionizing radiation curable compound. Among ionizing radiation curable compounds, electron beam curable compounds are preferred as components for forming the surface resin layer because they can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing properties. Among ionizing radiation curable compounds, polymerizable oligomers are preferred, (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule are more preferred, and urethane (meth)acrylates are even more preferred.

[0069] In one embodiment, the content of the resin component in the surface resin layer is preferably 60% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 80% by mass or less. The content of the resin component includes the content of the polymer-based lubricant. This can improve, for example, the heat resistance, scratch resistance, and stain resistance of the decorative sheet.

[0070] In one embodiment, the surface resin layer further contains inorganic particles. By containing inorganic particles in the surface protective layer together with a polymer-based lubricant and an organic particle-based lubricant, for example, the decorative sheet can be given a matte feel in addition to a smooth feel. For example, a decorative sheet can be obtained that has the matte feel of a wood grain pattern and the smooth feel of soap-finished wood.

[0071] Examples of inorganic particles include silica, alumina, kaolinite, clay, aluminosilicate, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, barium sulfate, and calcium silicate. Among these, silica particles are preferred from the viewpoint of improving the matte finish. The shape of the inorganic particles is, for example, spherical, polyhedral, or scaly.

[0072] The average particle size of the inorganic particles is preferably 0.5 μm to 15 μm, more preferably 1 μm to 12 μm, and even more preferably 2 μm to 10 μm, which can improve the matte finish of the decorative sheet, for example.

[0073] In one embodiment, the content of inorganic particles in the surface resin layer is preferably 10 to 250 parts by weight, more preferably 30 to 200 parts by weight, and even more preferably 50 to 150 parts by weight, per 100 parts by weight of the organic particle-based lubricant. This can, for example, further improve the balance between the smooth textured surface and the matte finish of the decorative sheet. The resin component also includes a polymer-based lubricant.

[0074] The surface resin layer may contain additives, such as ultraviolet absorbers, light stabilizers, antioxidants, abrasion resistance improvers, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy-imparting agents, coupling agents, antifoaming agents, flame retardants, plasticizers, and antiblocking agents. Among these, ultraviolet absorbers and light stabilizers are preferred.

[0075] In one embodiment, the surface resin layer can be formed by preparing a curable composition, applying the composition to the design layer to form an uncured resin layer, and crosslinking and curing the uncured resin layer. The crosslinking and curing is performed by heat treatment when a thermosetting resin is used, or by irradiation with ionizing radiation such as electron beams or ultraviolet rays when an ionizing radiation-curable compound is used.

[0076] When an electron beam is used as the ionizing radiation, the exposure dose is, for example, 5 kGy to 300 kGy (0.5 Mrad to 30 Mrad), preferably 10 kGy to 100 kGy (1 Mrad to 10 Mrad). When ultraviolet light is used as the ionizing radiation, light containing ultraviolet light with a wavelength of 190 nm to 380 nm may be emitted.

[0077] The average thickness of the surface resin layer is preferably 1 μm or more and 10 μm or less, more preferably 1.5 μm or more and 9 μm or less, and even more preferably 2 μm or more and 8 μm or less. When the average thickness is equal to or greater than the lower limit, for example, it is possible to suppress the falling off of particles and improve scratch resistance. When the average thickness is equal to or less than the upper limit, for example, it is possible to improve the above-mentioned tactile sensation.

[0078] The average thickness of the surface resin layer is a value calculated by observing the cross section of the decorative sheet with a scanning electron microscope (SEM) and averaging the measured values. The average thickness of the surface resin layer can be calculated, for example, by the following steps (X1) and (X2). (X1) Prepare 10 cross-sectional photographs of the decorative sheet in a width range of 500 μm to 1500 μm. In each cross-sectional photograph, measure the thickness of the surface resin layer every 5 μm in the width direction of the decorative sheet. For example, if the width of the decorative sheet in each cross-sectional photograph is 500 μm, measure the thickness of the surface resin layer at 100 points in each cross-sectional photograph. (X2) The average thickness of the surface resin layer is calculated from the measured total height data.

[0079] The ratio of the average particle size of the particles contained in the surface resin layer to the average thickness of the surface resin layer (average particle size / average thickness) is preferably 1.0 or more and 2.5 or less, more preferably 1.2 or more and 2.3 or less, and even more preferably 1.3 or more and 2.0 or less. The particles contained in the surface resin layer are, for example, organic particle-based lubricants and inorganic particles. This can further improve the tactile feel provided by the organic particle-based lubricants, or further improve the above-mentioned effects provided by the inorganic particles.

[0080] The decorative sheet of the present disclosure may have a primer layer between the design layer and the surface resin layer. The primer layer is provided as needed for purposes such as improving the adhesion of the surface resin layer.

[0081] In one embodiment, the primer layer contains a resin component. Examples of the resin component include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane-(meth)acrylic copolymer, (meth)acrylic resin, polystyrene, polyurethane, polyester, polyamide, butyral resin, nitrocellulose, and cellulose acetate. The resin component may be a crosslinked cured product of these resins using a curing agent. The resin component may be, for example, a cured product of the two-component curing urethane resin described above.

[0082] The primer layer may contain the above-mentioned additives. The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and even more preferably 1 μm or more and 6 μm or less.

[0083] The decorative sheet of the present disclosure may have an adhesive layer on the surface of the base layer opposite to the surface resin layer side. The adhesive layer is provided as needed for the purpose of improving adhesion to the adherend (molded article) in the decorated molded article.

[0084] The adhesive layer is composed of, for example, an adhesive. Examples of adhesives include (meth)acrylic resins, (meth)acrylic-modified polyolefins, chlorinated polyolefins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-(meth)acrylic copolymers, polyesters, polyurethanes, and polyamides. Two-component curing polyurethane adhesives or polyester adhesives using an isocyanate compound or the like as a curing agent may also be used. Examples of adhesives include (meth)acrylic, urethane, silicone, or rubber-based pressure-sensitive adhesives.

[0085] From the viewpoint of obtaining excellent adhesiveness, the thickness of the adhesive layer is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and even more preferably 10 μm or more and 30 μm or less.

[0086] The transfer sheet of the present disclosure has a releasable support and a transfer layer. The transfer layer is provided so as to be releasable from the releasable support. The transfer layer has a design layer and a surface resin layer provided on the design layer. The surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant.

[0087] The transfer layer may have a primer layer between the design layer and the surface resin layer. The transfer layer may have a masking layer on the surface of the design layer opposite to the surface of the surface resin layer.

[0088] The design layer, surface resin layer, hiding layer and primer layer in the transfer layer are similar to the design layer, surface resin layer, hiding layer and primer layer in the decorative sheet, respectively, and therefore will not be described here.

[0089] The releasable support is disposed on the surface resin layer of the transfer layer. The releasable support may be the above-mentioned resin substrate. If necessary, the surface of the releasable support on the transfer layer side may be subjected to a known release treatment, or a release layer such as a silicone resin may be provided. This can improve the releasability between the releasable support and the transfer layer when transferring the transfer layer to the surface of the adherend (molded product).

[0090] In one embodiment, the transfer layer further has an adhesive layer on the surface of the design layer opposite to the surface resin layer side. This improves the adhesion of the transfer layer to the adherend. The adhesive layer in the transfer layer is the same as the adhesive layer in the decorative sheet, so a description thereof will be omitted here. In one embodiment, the transfer layer further includes a substrate layer between the adhesive layer and the design layer. The substrate layer in the transfer layer is the same as the substrate layer in the decorative sheet, and therefore a description thereof will be omitted here.

[0091] 2 shows a schematic cross-sectional view of one embodiment of the transfer sheet of the present disclosure. Transfer sheet 2 has a releasable support 40 and a transfer layer 42. Transfer layer 42 has, in this order in the thickness direction, an adhesive layer 50, a design layer 20, and a surface resin layer 30 provided on design layer 20.

[0092] The decorated molded article of the present disclosure includes a molded article, a design layer provided on at least a partial region of the molded article, and a surface resin layer provided on the design layer.

[0093] The decorated molded article may have a primer layer between the design layer and the surface resin layer. The decorated molded article may have a concealing layer on the surface of the design layer opposite to the surface resin layer side. The decorated molded article may have a substrate layer between the molded article and the design layer. The decorated molded article may have an adhesive layer between the molded article and the substrate layer.

[0094] The base layer, design layer, surface resin layer, concealing layer, primer layer and adhesive layer in the decorated molded product are similar to the base layer, design layer, surface resin layer, concealing layer, primer layer and adhesive layer in the decorative sheet, respectively, and therefore will not be described here.

[0095] Examples of molded articles include resin members, wood members, and inorganic members. Examples of resin members include sheets, plates, and three-dimensional articles made of polyolefin, vinyl chloride resin, styrene resin, (meth)acrylic resin, polyester, polycarbonate, polyamide, polyimide, cellulose resin, phenolic resin, rubber, etc.

[0096] Examples of the wooden member include boards or three-dimensional articles made of wood fiberboards such as wood veneer, wood plywood, particle board, medium density fiberboard (MDF), and laminated wood. In one embodiment, the decorative molded product is a decorative board in which the molded product is a wooden member.

[0097] Examples of inorganic members include metal members and other inorganic members. Metal members include sheets, plates, and three-dimensional articles made of iron, aluminum, copper, tin, titanium, and alloys containing at least one of these metals (e.g., carbon steel, stainless steel, duralumin, brass, and bronze). Other inorganic members include plates and three-dimensional articles made of glass, ceramics such as porcelain, non-cement ceramic materials such as gypsum, and lightweight aerated concrete (ALC) plates.

[0098] The decorative molded products of the present disclosure can be used, for example, for furniture such as desks, chairs, cupboards, and chests of drawers; interior components such as walls, ceilings, and floors in buildings; exterior components such as exterior walls, roofs, eaves ceilings, fences, and gates in buildings; fittings or fixtures such as various doors such as entrance doors, handrails, baseboards, moldings, window frames, door frames, and moldings; housings for home appliances or office equipment, and surface decorative panels for kitchen equipment or kitchen furniture; and interior or exterior components for vehicles.

[0099] A schematic cross-sectional view of one embodiment of the decorated molded product of the present disclosure is shown in Figure 3. The decorated molded product 3 has, in this order in the thickness direction, a molded product 60, an adhesive layer 50, a base layer 10, a design layer 20 provided on the base layer 10, and a surface resin layer 30 provided on the design layer 20.

[0100] The decorated molded article of the present disclosure can be obtained, for example, by placing the decorative sheet of the present disclosure on the surface of an adherend (molded article).The decorated molded article of the present disclosure can be obtained, for example, by using the transfer sheet of the present disclosure to transfer the transfer layer of the transfer sheet to the surface of the adherend (molded article).

[0101] In one embodiment, the decorative sheet of the present disclosure is attached to at least a portion of the surface of the adherend (molded article) so that the substrate layer or adhesive layer of the sheet contacts the surface of the adherend. In one embodiment, the transfer sheet of the present disclosure is attached to at least a portion of the surface of the adherend (molded article) so that the adhesive layer of the transfer sheet contacts the surface of the adherend. Next, the releasable support of the transfer sheet is peeled off. In this way, a decorated molded article is obtained. The attachment may be performed under heat and pressure. For example, known roll transfer or press transfer can be used for the transfer.

[0102] The decorated molded article of the present disclosure may be produced, for example, by various injection molding methods such as insert molding and simultaneous injection molding and decoration using the decorative sheet or transfer sheet of the present disclosure.

[0103] The present disclosure relates to, for example, the following [1] to

[15] . [1] A decorative sheet having a design layer and a surface resin layer provided on the design layer, the surface resin layer containing a polymer-based lubricant and an organic particle-based lubricant. [2] The decorative sheet according to [1] above, wherein the polymer-based lubricant is at least one selected from silicone polymers and fluororesins, and the organic particle-based lubricant is at least one selected from silicone particles and fluororesin particles. [3] The decorative sheet according to [2] above, wherein the surface resin layer contains a silicone polymer and silicone particles. [4] The decorative sheet according to any one of the above [1] to [3], wherein the ratio of the average particle size of the organic particle-based lubricant contained in the surface resin layer to the average thickness of the surface resin layer (average particle size / average thickness) is 1.0 or more and 2.5 or less. [5] The decorative sheet according to any one of [1] to [4] above, wherein the content of the organic particle-based lubricant is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin component contained in the surface resin layer. [6] The decorative sheet according to any one of the above [1] to [5], wherein the surface resin layer further contains inorganic particles. [7] The decorative sheet according to [6] above, wherein the ratio of the average particle size of the inorganic particles contained in the surface resin layer to the average thickness of the surface resin layer (average particle size / average thickness) is 1.0 or more and 2.5 or less. [8] The decorative sheet according to [6] or [7] above, wherein the content of the inorganic particles is 10 parts by mass or more and 250 parts by mass or less per 100 parts by mass of the organic particle-based lubricant. [9] The decorative sheet according to any one of the above [1] to [8], wherein the average thickness of the surface resin layer is 1 μm or more and 10 μm or less.

[10] The decorative sheet according to any one of the above [1] to [9], wherein the design layer has a wood grain pattern.

[11] The decorative sheet according to any one of the above [1] to

[10] , further comprising a substrate layer, and a design layer located between the substrate layer and the surface resin layer.

[12] The decorative sheet according to the above

[11] , further comprising an adhesive layer on the surface of the substrate layer opposite to the surface resin layer side.

[13] A transfer sheet having a releasable support and a transfer layer, wherein the transfer layer has a design layer and a surface resin layer provided on the design layer, the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, and the releasable support is disposed on the surface resin layer of the transfer layer.

[14] The transfer sheet according to the above

[13] , wherein the transfer layer further has an adhesive layer on the surface of the design layer opposite to the surface resin layer side.

[15] A decorated molded article having a molded article, a design layer provided on at least a partial region of the molded article, and a surface resin layer provided on the design layer, wherein the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant. [Example]

[0104] The decorative sheet of the present disclosure will be explained in more detail below based on examples, but the decorative sheet of the present disclosure is not limited to these examples. In the following description, "parts by mass" will simply be expressed as "parts".

[0105] [Example 1] The base material is colored base paper for building materials ("CHPS45 (model number)", basis weight: 45 g / m 2 A resin sheet (manufactured by Tenma Tokushu Paper Co., Ltd.) was prepared. Resin composition (1) was applied by gravure printing to the surface of the substrate that had been treated for easy adhesion, forming a first design layer with a thickness of 5 μm. Resin composition (1) contains a binder consisting of a mixed resin of (meth)acrylic resin and polyurethane, and a colorant containing titanium white, red iron oxide, and yellow lead. A second design layer with a wood grain pattern was formed on the first design layer using resin composition (2). Resin composition (2) contains a binder consisting of nitrocellulose and a colorant whose main component is red iron oxide. The wood grain pattern has duct portions.

[0106] A primer layer resin composition containing a two-component curing resin (main component: (meth)acrylic polyol, curing agent: hexamethylene diisocyanate) was applied to the entire surface of the design layer and dried to form a primer layer with a thickness of 2 μm.

[0107] An uncured resin layer was formed on the primer layer by roll coating using a resin composition for the surface resin layer having the following composition. The uncured resin layer was cured by irradiating it with an electron beam (3 Mrad (30 kGy)) to form a surface resin layer with an average thickness of 4 μm. The resulting layer was then heat-cured at 70°C for 24 hours. In this manner, a decorative sheet was obtained.

[0108] <Resin composition for surface resin layer> Urethane (meth)acrylate: 80 parts Reactive silicone polymer: 20 parts Silica particles: 15 parts (average particle size: 6 μm) Silicone particles: 15 parts (average particle size: 6 μm)

[0109] [Example 2, Comparative Example 1 and Comparative Example 2] A decorative sheet was obtained in the same manner as in Example 1, except that the blending composition of the resin composition in the surface resin layer was changed as shown in Table 1.

[0110] [Evaluation of the texture of decorative sheets] The surface of the surface resin layer of the resulting decorative sheet was touched with the fingers of a hand and evaluated for tactile sensation according to the following criteria. The evaluation results are shown in Table 1. A: It has particularly high smoothness, It has a smooth feel like soap-finished wood. B: Smooth to the touch. C: Low smoothness.

[0111] [Evaluation of the matte feel of decorative sheets] The surface of the surface resin layer of the resulting decorative sheet was visually observed and evaluated for matte feel. The evaluation was carried out under fluorescent lighting indoors with external light blocked. The evaluation results are shown in Table 1. A: It is matte. B: Glossy finish.

[0112] [Table 1] [Explanation of symbols]

[0113] 1. Decorative sheet 2. Transfer sheet 3. Decorative molding products 10...Base material layer 20. Design layer 30...Surface resin layer 40...Releasable support 42···Written layer 50...then the layers 60··· Covered body (molded product)

Claims

1. A design layer and a surface resin layer provided on the design layer; and the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, the polymer-based lubricant is a silicone polymer, and the organic particle-based lubricant is silicone particles; the surface resin layer further contains inorganic particles, a ratio of an average particle diameter of the inorganic particles contained in the surface resin layer to an average thickness of the surface resin layer (average particle diameter / average thickness) is 1.0 or more and 2.5 or less; Decorative sheet.

2. A design layer, a surface resin layer provided on the design layer; and the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, the polymer-based lubricant is a silicone polymer, and the organic particle-based lubricant is silicone particles; The surface resin layer is in direct contact with the design layer. Decorative sheet.

3. 3. The decorative sheet according to claim 1, wherein the ratio of the average particle diameter of the organic particle-based lubricant contained in the surface resin layer to the average thickness of the surface resin layer (average particle diameter / average thickness) is 1.0 or more and 2.5 or less.

4. The decorative sheet according to any one of claims 1 to 3, wherein the content of the organic particle-based lubricant is 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin component contained in the surface resin layer.

5. The decorative sheet according to claim 2 , wherein the surface resin layer further contains inorganic particles.

6. 6. The decorative sheet according to claim 1, wherein the content of said inorganic particles is 10 parts by mass or more and 250 parts by mass or less per 100 parts by mass of said organic particle-based lubricant.

7. The decorative sheet according to any one of claims 1 to 6, wherein the surface resin layer has an average thickness of 1 µm or more and 10 µm or less.

8. The decorative sheet according to any one of claims 1 to 7, wherein the design layer has a wood grain pattern.

9. The decorative sheet according to any one of claims 1 to 8, wherein the decorative sheet further comprises a substrate layer, and the design layer is located between the substrate layer and the surface resin layer.

10. 10. The decorative sheet according to claim 9, further comprising an adhesive layer on the surface of said base layer opposite to the surface on which said surface resin layer is formed.

11. The coating further includes a primer layer located between the design layer and the surface resin layer, The decorative sheet according to claim 1 , wherein the primer layer contains a thermosetting resin as a resin component.

12. A transfer sheet having a releasable support and a transfer layer, The transfer layer is A design layer and a surface resin layer provided on the design layer; and the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, the polymer-based lubricant is a silicone polymer, and the organic particle-based lubricant is silicone particles; the releasable support is disposed on the surface resin layer of the transfer layer; Transfer sheet.

13. The transfer sheet according to claim 12 , wherein the transfer layer further comprises an adhesive layer on the surface of the design layer opposite to the surface resin layer side.

14. the transfer layer further has a primer layer located between the design layer and the surface resin layer, The transfer sheet according to claim 12 , wherein the primer layer contains a thermosetting resin as a resin component.

15. a molded article; A design layer provided on at least a partial region of the molded article; a surface resin layer provided on the design layer; and the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, the polymer-based lubricant is a silicone polymer, and the organic particle-based lubricant is silicone particles; the surface resin layer further contains inorganic particles, a ratio of an average particle diameter of the inorganic particles contained in the surface resin layer to an average thickness of the surface resin layer (average particle diameter / average thickness) is 1.0 or more and 2.5 or less; Decorative moldings.

16. A molded article; A design layer provided on at least a partial region of the molded article; a surface resin layer provided on the design layer; and the surface resin layer contains a polymer-based lubricant and an organic particle-based lubricant, the polymer-based lubricant is a silicone polymer, and the organic particle-based lubricant is silicone particles; The surface resin layer is in direct contact with the design layer. Decorative moldings.

17. The coating further includes a primer layer located between the design layer and the surface resin layer, The decorated molded product according to claim 15 or 16, wherein the primer layer contains a thermosetting resin as a resin component.

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