JP2017065261A - Decorative sheet, decorative laminate and decorative resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having high designability and exhibiting an excellent tactile feeling.SOLUTION: A decorative sheet includes: a first resin layer containing a matting agent; a second resin layer partially arranged on the first resin layer; and a projecting part containing a resin and an organic particle and arranged on the second resin layer in this order on a base material sheet.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet, a decorative board, and a decorative resin molded product.

  Conventionally, decorative sheets have been laminated on the surfaces of various articles in order to impart design properties. For example, decorative sheets are laminated and used on the surfaces of wall coverings used for building walls, floor decorative materials used for floors, furniture, and the like.

  The decorative sheet laminated on the surface of the article as described above is required to exhibit a three-dimensional design. As a decorative sheet showing such a three-dimensional design, a pattern printing layer is provided on a substrate, a resin layer containing a matting agent is provided on the entire surface, and a resin layer is further provided on the substrate as a pattern printing layer. A decorative sheet partially provided so as to be synchronized has been proposed (see, for example, Patent Document 1). Such a decorative sheet is visually excellent and has a three-dimensional appearance due to the contrast between the high gloss (gloss) part and the low gloss (matte) part, but the surface is almost flat. Even when touched by hand, a three-dimensional effect was not obtained.

  On the other hand, as a decorative sheet that gives a three-dimensional effect when touched by the hand, that is, exhibits an excellent tactile sensation, a pattern printing layer, a transparent resin layer, and a convex portion by thick printing are provided on the substrate, and the convex portion is Cosmetic materials that are synchronized with the pattern print layer have been proposed (see, for example, Patent Documents 2 and 3).

  When forming convex portions by thick printing, inorganic particles represented by silica, calcium carbonate, aluminum hydroxide, etc. are added to the ink that forms the convex portions, and thixotropic properties are imparted to the ink. In general, the transferability is improved, the denaturation of the ink after transfer is suppressed, and a convex portion having a delicate shape is formed with good reproducibility. However, in the case of the conventional decorative sheet, there is a problem that the convex portion is whitened due to the influence of the inorganic particles added to impart thixotropic properties, the transparency is lost, and the design feeling is impaired. In particular, in the case of a decorative material having a configuration in which the convex portions are in synchronization with the pattern pattern layer, there is a problem in that the design located under the white pattern appears cloudy due to the whitened convex portions, and the design inherent in the pattern pattern layer is greatly impaired.

Japanese Patent Laid-Open No. 9-17495 JP-A-10-86313 JP2013-123863A

  An object of the present invention is a decorative sheet having high design properties and excellent touch, a decorative plate formed by sticking the decorative sheet to an adherend, and a laminate of the decorative sheet on a molded resin layer. It is to provide a decorative resin molded product.

  As a result of intensive studies to develop a decorative sheet having high design properties and excellent touch, the present inventors laminated a low-gloss resin layer on a base sheet, and partially transparently formed thereon. It has been found that the above-mentioned problems can be solved by laminating a resin layer and forming a convex portion containing resin and organic particles on the transparent resin layer. The present invention has been completed based on such findings.

That is, the present invention relates to the following decorative sheet, decorative plate, and decorative resin molded product.
1. On the base sheet, a first resin layer containing a matting agent, a second resin layer partially provided on the first resin layer, and a resin and organic particles provided on the second resin layer The decorative sheet which has the convex part containing this order.
2. Item 2. The decorative sheet according to Item 1, wherein the content of the organic particles is 50% by mass or less of the solid content of the resin composition forming the convex portion.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the content of the organic particles is 2% by mass or more of the solid content of the resin composition forming the convex portion.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the organic particles have an average particle size of 15 to 50 µm.
5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein an area provided with the convex portion is 5 to 80% of an area of the second resin layer.
6). Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the second resin layer has a gloss higher than that of the first resin layer.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the second resin layer contains a matting agent. 8). The mass of the matting agent contained per unit mass of the solid content of the resin composition forming the second resin layer is the gloss contained per unit mass of the solid content of the resin composition forming the first resin layer. Item 8. The decorative sheet according to Item 7, which is smaller than the mass of the eraser.
9. Item 10. The decorative sheet according to any one of Items 1 to 8, which has a pattern layer between the base sheet and the first resin layer.
10. Item 10. The decorative sheet according to Item 9, wherein the second resin layer is provided in synchronization with the pattern of the pattern pattern layer.
11. Item 11. The decorative sheet according to Item 9 or 10, wherein the picture pattern layer is a wood grain pattern, and the second resin layer is provided on a portion of the wood grain pattern other than the winter eye pattern and / or the conduit pattern.
12 A decorative board comprising the decorative sheet according to any one of Items 1 to 11 on an adherend.
13. Item 12. A decorative resin molded article having the decorative sheet according to any one of Items 1 to 11 on a molded resin layer.

  In the decorative sheet of the present invention, a second resin layer having a gloss higher than that of the first resin layer is partially laminated on the first resin layer containing the matting agent, and the resin is formed on the second resin layer. And the convex part containing organic particle is set as the structure laminated | stacked, while having high designability, it can show the outstanding tactile sense.

It is a cross-sectional schematic diagram which shows an example of a layer structure of the decorative sheet of this invention.

  Hereinafter, the decorative sheet, the decorative plate, and the decorative resin molded product of the present invention will be described in detail.

1. The decorative sheet of the present invention includes a first resin layer containing a matting agent on a base sheet, a second resin layer partially provided on the first resin layer, and the second resin layer. It has the convex part containing resin and organic particle | grains provided on this order, It is characterized by the above-mentioned.

  In the decorative sheet of the present invention having the above characteristics, the second resin layer is partially laminated on the first resin layer containing the matting agent, and the second resin layer is laminated with the region where the second resin layer is laminated. There is a difference in gloss between the unexposed areas and high design properties (gross mat expression). Furthermore, the decorative sheet of the present invention having the above characteristics exhibits excellent tactile sensation without impairing the gloss mat expression described above, because the convex portions containing the resin and organic particles are laminated on the second resin layer. be able to.

  The decorative sheet of the present invention has a first resin layer, a second resin layer, and a convex portion in order on the base sheet, and the second resin layer and the second resin layer on the first resin layer. If the convex part is formed on the upper side, the specific configuration (layer configuration) is not limited. For example, a pattern layer can be provided between the base sheet and the first resin layer. Specifically, it is a decorative sheet in which a pattern layer is laminated on a base sheet, and a first resin layer, a second resin layer, and convex portions are formed in this order on the pattern layer. FIG. 1 shows the above example of the layer structure of the decorative sheet of the present invention. In FIG. 1, a decorative sheet 1 of the present invention has a pattern layer 3, a first resin layer 4, and a second resin layer 5 laminated in this order on a base sheet 2, and on the second resin layer 5. Further, a convex portion 6 is formed.

  Hereinafter, each layer which comprises a decorative sheet is demonstrated, referring FIG. In the present invention, the direction in which the convex portion is formed as viewed from the base material sheet is referred to as “upper” or “front surface”, and is opposite to the direction in which the convex portion is formed as viewed from the base material sheet. Is referred to as “bottom” or “back”. Moreover, in the following description, the lower limit of the numerical range represented by “to” means “more than or less” (for example, α to β is α to β).

The base sheet is not limited, and a fibrous sheet, a plastic base, a metal base, a wood base, and the like can be used.

  As the fibrous sheet, known fibrous sheets such as thin paper, inter-paper reinforcing paper, impregnated paper, titanium paper, coated paper, corrugated paper, linter paper, craft paper, and fine paper can be used. Specifically, wallpaper paper (pulp-based sheet sized with a known sizing agent); flame retardant paper (pulp-based sheet treated with flame retardants such as guanidine sulfamate and guanidine phosphate) ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper; synthetic fiber mixed paper (paper made by mixing pulp and synthetic fiber). In addition, what corresponds to a nonwoven fabric is included in the fibrous sheet used for this invention on classification.

  As the plastic substrate, various plastic sheets such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene (ABS), polyvinyl chloride, acrylic, polycarbonate, and the like can be used. As a metal base material, what made the undercoat of a coloring agent on a steel plate, aluminum, stainless steel etc. can be commercialized as a base material. Examples of the wood-based substrate include plywood, particle board, medium density fiber board, and the like.

The basis weight of the base sheet is not critical, preferably about 20 to 300 g / ^{m 2,} more preferably about 50 to 300 g / ^{m 2,} about 50~130g / ^{m 2} is more preferred.

  In addition, when using the decorative sheet of the present invention for injection molding or vacuum forming, it is preferable to use a plastic substrate as the substrate sheet in consideration of three-dimensional formability, such as ABS, acrylic, polycarbonate, etc. It is particularly preferable to use a film or the like. In consideration of three-dimensional formability, the thickness of the base sheet is preferably about 50 to 800 μm, and more preferably about 100 to 600 μm.

Pattern Pattern Layer The decorative sheet of the present invention may form a pattern pattern layer as necessary. The design pattern layer is usually provided on the front surface side of the base material sheet, but when a base material sheet having transparency is used, it may be provided on the back surface side of the base material sheet. In addition, in the decorative sheet of this invention, it becomes a decorative sheet excellent in the designability by setting it as the structure which the pattern pattern layer and the 2nd resin layer synchronize. Specifically, as shown in FIG. 1, the second resin layer may be synchronized with a portion where the pattern of the pattern layer is not formed, or conversely, the pattern of the pattern layer is formed. The structure which the 2nd resin layer tuned to the part which has may be sufficient.

  The design pattern layer imparts a design to the decorative sheet. Examples of the design pattern include wood grain pattern, leather pattern, stone pattern, sand pattern, tiled pattern, brickwork pattern, cloth pattern, geometric figure, character, symbol, abstract pattern, flower pattern, etc. It can be selected according to the purpose.

  The pattern pattern layer can be formed, for example, by printing a pattern pattern. Examples of printing methods include gravure printing, offset printing, silk screen printing, flexographic printing, electrostatic printing, and inkjet printing. As the printing ink, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin can be used.

  Examples of the colorant used in the ink include inorganic pigments such as carbon black, titanium white, zinc white, petal, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, and isoindolinones. Examples thereof include organic pigments such as pigments and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like. About 10-100 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of a coloring agent, about 15-50 mass parts is more preferable.

  The binder resin can be set according to the type of the base sheet. As binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, casein resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can be used. The binder resin can be used alone or in combination of two or more. “(Meth) acryl” means acryl or methacryl, and the same applies hereinafter.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as n-hexane, n-heptane, n-octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, and acetic acid-2- Ester-based organic solvents such as methoxyethyl and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl Ketone organic solvents such as isobutyl ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroether Chlorinated organic solvents Ren like; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in admixture of two or more.

  The thickness of the pattern layer is not particularly limited, and can be set as appropriate according to product characteristics. For example, the layer thickness at the time of coating is about 1 to 200 μm, and the layer thickness after drying is about 0.1 to 20 μm.

First Resin Layer The decorative sheet of the present invention has a first resin layer containing a matting agent on the base sheet or the pattern layer for the purpose of adjusting gloss. A 1st resin layer is formed as a whole surface solid printing layer on a base material sheet or a pattern pattern layer. Examples of the resin constituting the first resin layer include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate. , Silicon resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, polymethylpentene , Acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Alternatively, the first resin layer may be formed using an ionizing radiation curable resin. The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group that can be cross-linked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like. These resins can be used alone or in combination of two or more.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 1 to 15 Mrad, more preferably about 1 to 10 Mrad, and further preferably about 3 to 5 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resins.

  The first resin layer contains a matting agent. There is no limitation in particular as a matting agent, A well-known thing can be used widely. Examples of matting agents include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, aluminosilicate, and barium sulfate; resin (organic) particles such as acrylic beads, polyethylene, urethane resin, polycarbonate, and polyamide (nylon). Can be mentioned. The average particle diameter of the particles is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm. The addition amount of the matting agent is preferably 2 to 40% by mass, more preferably 5 to 30% by mass based on the resin composition (excluding the solvent) for forming the first resin layer. In addition, the shape of particle | grains is a polyhedron, a spherical form, scale shape, etc. Of the above inorganic particles and organic particles, silica is preferred.

  The thickness of the first resin layer is usually about 0.5 to 10 μm, but may exceed the above range depending on the use of the decorative sheet.

  In addition, when using the decorative sheet of the present invention for injection molding or vacuum forming, the ionizing radiation curable resin constituting the first resin layer from the viewpoint of improving the three-dimensional formability while enhancing the scratch resistance of the decorative sheet. It is preferable to use polycarbonate (meth) acrylate. The polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and two or more (meth) acrylates in the terminal or side chain. It may be a (meth) acrylate or the like. Moreover, it is preferable that the said polycarbonate (meth) acrylate has 2-6 functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable. Such polycarbonate (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more types. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate.

  In addition, when the decorative sheet of the present invention is used for injection molding or vacuum forming, the first resin layer is made of an ionizing radiation curable resin and a heat from the viewpoint of improving the three-dimensional formability while enhancing the scratch resistance of the decorative sheet. It is also preferable to comprise a mixture with a plastic resin. Examples of the thermoplastic resin include an acrylic resin, a urethane resin, and an olefin resin, and an acrylic resin is particularly preferable. The mixing ratio of the ionizing radiation curable resin and the thermoplastic resin is preferably about 10:90 to 75:25, more preferably about 25:75 to 50:50 in terms of mass ratio.

Second resin layer The decorative sheet of the present invention has a second resin layer for the purpose of adjusting gloss and the like. The second resin layer is partially provided on the first resin layer, and forms a region where the first resin layer containing the matting agent is exposed and a region where the first resin layer is not exposed. By giving a gloss difference, the decorative sheet of the present invention is given high designability. From the viewpoint of obtaining better design properties, the second resin layer preferably has a higher gloss than the first resin layer. The second resin layer is preferably a transparent resin layer. The second resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and translucent. Examples of the resin constituting the second resin layer include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensate. , Silicon resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, polymethylpentene , Acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Moreover, you may use the above-mentioned ionizing radiation curable resin. These resins can be used alone or in combination of two or more.

  The second resin layer can contain a matting agent for gloss adjustment. When the second resin layer contains a matting agent, the content of the matting agent in the second resin layer is preferably less than the content of the matting agent in the first resin layer. By making the content of the matting agent in the second resin layer less than the content of the matting agent in the first resin layer, the gloss of the second resin layer is made higher than the gloss of the first resin layer, and an excellent design It becomes easy to obtain sex. As a matting agent used for a 2nd resin layer, the thing similar to the thing quoted by the 1st resin layer can be used. The addition amount of the matting agent is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass on the basis of the resin composition for forming the second resin layer (excluding the solvent). Note that the content of the matting agent in the second resin layer is less than the content of the matting agent in the first resin layer is included per unit mass of the solid content of the resin composition forming the second resin layer. The mass of the matting agent is smaller than the mass of the matting agent contained per unit mass of the solid content of the resin composition forming the first resin layer.

  When the pattern pattern layer is present, it is preferable that the second resin layer is provided in synchronization with the pattern of the pattern pattern layer. By setting it as the structure which the design pattern layer and the 2nd resin layer synchronize, it can be set as the decorative sheet excellent in the designability. Specifically, as shown in FIG. 1, the second resin layer may be synchronized with a portion where the pattern of the pattern layer is not formed, or conversely, the pattern of the pattern layer is formed. The structure which the 2nd resin layer tuned to the part which has may be sufficient.

  In the decorative sheet of the present invention, the design pattern layer is a wood grain pattern, and a second resin layer having a gloss higher than that of the first resin layer is provided on a portion other than the wood grain winter pattern and / or the conduit pattern. It is preferable. Thereby, since the luster of the winter pattern and / or conduit pattern part of a grain becomes low, the outstanding design nature approximated to natural wood can be obtained. In order to form the second resin layer as described above, a known printing method is used by using a plate in which the winter pattern and / or the conduit pattern of the same grain as the pattern layer is reversed (that is, a negative state). It is preferable to print using. As the printing method, a gravure printing method, a screen printing method and the like are preferable.

  The second resin layer may be colored as long as it has transparency, but it is particularly desirable not to add a colorant.

  The thickness of the second resin layer is usually about 0.5 to 10 μm, but may exceed the above range depending on the use of the decorative sheet.

  When the decorative sheet of the present invention is used for injection molding or vacuum forming, the ionizing radiation curable resin constituting the second resin layer is used from the viewpoint of improving the three-dimensional formability while enhancing the scratch resistance of the decorative sheet. It is preferable to use polycarbonate (meth) acrylate. As the polycarbonate (meth) acrylate, the same one as described in the section of the first resin layer can be used.

  In addition, when the decorative sheet of the present invention is used for injection molding or vacuum forming, the second resin layer is made into an ionizing radiation curable resin and a heat from the viewpoint of improving the three-dimensional formability while enhancing the scratch resistance of the decorative sheet. It is also preferable to comprise a mixture with a plastic resin. Examples of the kind of the thermoplastic resin and the preferable mixing ratio of the ionizing radiation curable resin and the thermoplastic resin include the same as those described in the section of the first resin layer.

Convex part In the decorative sheet of this invention, the convex part containing resin and an organic particle is formed on the 2nd resin layer. It is preferable that the convex part in this invention is formed by raising printing as a so-called raising printing layer so that a desired design may be expressed. In addition, in this invention, a convex part is a form shown by convex shape in a cross-sectional schematic diagram as shown in FIG. 1, for example, only the form by which the cone-shaped or cylindrical protrusion is formed in the decorative sheet surface In addition, a form in which the protrusions are formed to extend linearly, such as a conduit pattern, is also included.

  The height of the convex portion of the decorative sheet of the present invention is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and particularly preferably 20 μm or more, from the viewpoint of developing excellent tactile sensation. Moreover, the upper limit with the preferable height of a convex part is 50 micrometers, and a more preferable upper limit is 40 micrometers. By making the upper limit of the height of a convex part into the said range, the decorative sheet of this invention shows the outstanding tactile sense, and can stabilize the tactile sense. In addition, in this specification, the height of a convex part is the value computed as an average value of the measured value of 10 points | pieces, observing the cross section of a decorative sheet with a scanning electron microscope (SEM).

  The resin forming the convex portion is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin) from the viewpoint of suppressing the deformation of the convex portion and obtaining a desired shape. . In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as the curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., and organic amine etc. can be added to epoxy resin. Peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutyl nitrile can be added to the unsaturated polyester resin.

  As a method for forming a convex portion with a thermosetting resin, for example, a solution of a thermosetting resin is applied by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, and is dried and cured. A method is mentioned.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group that can be cross-linked by irradiation with ionizing radiation in the molecule can be used. Examples of such ionizing radiation curable resins include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light and / or electron beams are desirable.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 1 to 15 Mrad, more preferably about 1 to 10 Mrad, and further preferably about 3 to 5 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  When the ionizing radiation curable resin is a resin having a radical polymerizable unsaturated group, examples of the photopolymerization initiator include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone , Diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. Further, when the ionizing radiation curable resin is a resin having a cationic polymerizable functional group, examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and freeloxy. At least one kind such as sulfoxonium diallyl iodosyl salt can be used.

  The addition amount of the photopolymerization initiator is not particularly limited, and is generally about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  As a method of forming a convex portion with an ionizing radiation curable resin, for example, an ionizing radiation curable resin solution is applied by a coating method such as a roll coating method, a gravure coating method, a gravure printing method, a silk screen printing method, or the like. The method of making it harden | cure by irradiation of ionizing radiation after making it dry is mentioned.

  The convex portion preferably contains organic particles having an average particle diameter of 15 to 50 μm in a proportion of 50% by mass or less, and in a proportion of 40% by mass or less in the solid content of the resin composition forming the convex part. More preferably. When the content of the organic particles is 50% by mass or less, the organic particles are uniformly distributed in the coating film (convex portion), so that the tactile sensation is stabilized. If the content of the organic particles exceeds 50% by mass, the organic particles may be aggregated, the height of the convex portion may not be stable, and the transparency of the convex portion may be impaired. . The content of the organic particles is preferably 2% by mass, and more preferably 10% by mass or more. When the content of the organic particles is less than 2% by mass, the tactile sensation becomes insufficient, and the thixotropic property of the resin composition forming the convex portion becomes insufficient, making it difficult to form the convex portion by thick printing. There is a risk.

  The organic particles are not particularly limited, and resin beads are usually used. Examples of the resin beads include acrylic beads, urethane beads, nylon beads, and styrene beads. Among these, it is preferable to use acrylic beads or urethane beads, and it is particularly preferable to use acrylic beads, from the viewpoint of enhancing the scratch resistance of the convex portions, in addition to suppressing the whitening of the convex portions and imparting excellent tactile sensation. Moreover, it is preferable to use a cross-linked resin bead from the viewpoint of imparting excellent tactile sensation and enhancing the scratch resistance of the convex portion. Specific examples of the crosslinked resin beads include crosslinked acrylic beads and crosslinked urethane beads.

  The organic particles contained in the protrusions preferably have an average particle diameter of 15 to 50 μm. As for the average particle diameter of the said organic particle, 20-35 micrometers is more preferable. If the average particle size of the organic particles is less than 15 μm, an excellent tactile sensation may not be obtained. On the other hand, if the average particle diameter of the organic particles exceeds 50 μm, the production stability is lowered, and it may be difficult to form convex portions having a desired shape with good reproducibility. In the present invention, since the organic resin is uniformly distributed, the height of the convex portion approximates the average particle diameter of the organic particles. In the case where the convex portion is formed by raised printing, the average particle diameter of the organic particles is preferably ½ or less of the plate depth from the viewpoint of ink transfer stability. In the present invention, the average particle diameter is a value measured by a laser diffraction / scattering method.

  In the decorative sheet of the present invention, the difference in gloss (60 ° gloss value) between the second resin layer and the convex portion is preferably 5 or less. By approximating the gloss of the second resin layer and the convex portion, the convex portion can be made inconspicuous, and thereby the tactile sensation by the convex portion can be obtained without impairing the gloss mat expression by the first resin layer and the second resin layer. It becomes possible to grant.

  The difference in gloss (60 ° gloss value) between the second resin layer and the convex portion may exceed 5. By slightly shifting the gloss difference between the second resin layer and the convex portion, it is possible to create a pseudo three-step gradation gloss mat expression.

  The area where the convex portions are provided is preferably 5 to 80% and more preferably 7 to 50% of the area of the second resin layer. By providing the convex portion within the above range, a decorative sheet having a better tactile feel can be obtained. Here, when the area of the convex part is different between the upper surface and the lower surface, such as a trapezoid (see FIG. 1), a conical shape, etc., the area where the convex part is provided is the convex part. Means the area of the surface in contact with the second resin layer.

  Although the convex portion is formed on the second resin layer, it is only necessary that at least a part of the convex portion is formed on the second resin layer. The part may exist directly on the first resin layer. That is, a part of the convex portion may be provided in a region where the second resin layer is not provided. Moreover, the convex part may be provided in synchronism with the pattern of the second resin layer, or may be provided regardless of the pattern of the second resin layer. From the viewpoint of further enhancing the three-dimensional effect by combining the visual design feeling and the tactile sensation, it is preferable that the convex portion is provided in synchronization with the pattern of the second resin layer.

  In addition, when using the decorative sheet of the present invention for injection molding or vacuum forming, the ionization constituting the convex portion from the viewpoint of improving the three-dimensional formability while suppressing the deformation of the convex portion and obtaining a desired shape. As the radiation curable resin, it is preferable to use polycarbonate (meth) acrylate. As the polycarbonate (meth) acrylate, the same one as described in the section of the first resin layer can be used.

  Further, when the decorative sheet of the present invention is used for injection molding or vacuum forming, the convex portions are ionized radiation curable resin and thermoplastic resin from the viewpoint of improving the three-dimensional formability while enhancing the scratch resistance of the decorative sheet. It is also preferable to comprise by a mixture with. Examples of the kind of the thermoplastic resin and the preferable mixing ratio of the ionizing radiation curable resin and the thermoplastic resin include the same as those described in the section of the first resin layer.

A colored concealment layer may be formed on the colored concealment layer base sheet as necessary. The colored concealing layer is formed as a whole surface solid printing layer on the base material sheet. The colored hiding layer can be, for example, a layer containing a pigment and a binder resin. This colored hiding layer can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, and offset printing using, for example, a printing ink containing a colorant, a binder resin, and a solvent. These inks may be known or commercially available.

  As the colorant, binder resin, and solvent, those used in the above-described pattern layer can be used. The thickness of the colored concealing layer is preferably about 1 to 10 μm.

A primer layer may be formed on the primer layer base sheet, the colored concealing layer, the design pattern layer, the first resin layer, or the second resin layer as necessary for the purpose of improving adhesion. Good.

  As the resin contained in the primer layer, for example, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like can be used. In particular, acrylic resin, chlorinated polypropylene and the like are preferable.

  Examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, and (meth) acrylate methyl- (meth) acryl. Such as butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer (meta ) Acrylic resin composed of a homopolymer of an acrylic ester or a copolymer containing the (meth) acrylic ester.

  Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).

  The polyol has two or more hydroxyl groups in the molecule. Examples of the polyol include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol.

  As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. Examples of isocyanates include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4′-diphenylmethane diisocyanate; aliphatics such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. (Or alicyclic) isocyanate or the like is used.

  The thickness of the primer layer is not limited and is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.

You may provide a back surface primer layer in the back surface (surface on the opposite side to the surface in which a convex part is formed) of a back surface primer layer base material sheet as needed. The back primer layer is effective when a decorative sheet is produced by laminating the decorative sheet of the present invention and the adherend.

  A back surface primer layer can be formed by apply | coating a well-known primer agent to a base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin) and the like, and a urethane-cellulose-based resin (for example, hexamethylene diisocyanate added to a mixture of urethane and nitrified cotton. Resin), a primer primer made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include a filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a light stabilizer. The blending amount of the additive can be appropriately set according to the product characteristics.

The application amount of the primer agent is not particularly limited, and is usually about 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² . Moreover, the thickness of a back surface primer layer is not specifically limited, Usually, it is about 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

2. Decorative plate By adhering the decorative sheet to an adherend, a decorative plate can be obtained. The adherend is not limited, and the same materials as those used for known decorative panels can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for a wood material. Specific examples of wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated. As the wood material, wood plywood, particle board, medium density fiber board (MDF) or the like is preferably used.

  The method of sticking the decorative sheet on the adherend is not limited, and a method of applying pressure after laminating the decorative sheet on the adherend via an adhesive is usually employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, and the like. These adhesives can be used alone or in combination of two or more.

  The decorative board manufactured in this way is, for example, an interior material of a building such as a wall, a ceiling, or a floor; an exterior material such as a balcony or a veranda; a surface decorative board or furniture of a fitting such as a window frame, a door, or a handrail; It can be used for a surface decorative plate of a cabinet such as a light electric or OA device.

3. Decorative resin molded product By integrating a molding resin with the decorative sheet of the present invention, a decorative resin molded product can be obtained. That is, the decorative resin molded product of the present invention has a configuration in which the decorative sheet of the present invention is laminated on a molded resin layer.

  The decorative resin molded product of the present invention is produced by various injection molding methods such as an insert molding method, an injection molding simultaneous decorating method, a blow molding method, and a gas injection molding method using the decorative sheet of the present invention. . Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferable. In addition, the decorative resin molded product of the present invention can also be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can be produced.

  In the decorative resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the application. The molding resin that forms the molding resin layer may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate (PC) resins, acrylic resins, vinyl chloride resins, and the like. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, as a thermosetting resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

4). Manufacturing method of decorative sheet As a manufacturing method of the decorative sheet, for example, a pattern layer, a first resin layer, and a second resin layer are formed in this order on a base sheet, and a resin is included on the second resin layer. The manufacturing method which forms a convex part is mentioned.

  For example, after printing a pattern by applying a resin composition for forming a pattern layer on a base sheet by a known printing method such as gravure printing, flexographic printing, silk screen printing, offset printing, The resin composition for forming the first resin layer is applied by a known printing method such as gravure printing, flexographic printing, silk screen printing, or offset printing to form the first resin layer. And a method of forming a second resin layer by pattern printing by a known printing method such as gravure printing or screen printing, and forming a convex portion on the second resin layer. Examples of the method of forming the convex portion with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, and is dried and cured. Moreover, as a method of forming a convex part with ionizing radiation curable resin, the method of apply | coating the solution of ionizing radiation curable resin by application | coating methods, such as a gravure coat method and a roll coat method, and irradiating ionizing radiation is mentioned, for example. .

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
A colored thin paper base paper for building materials (U-FLEX30 manufactured by Oji F-Tex Co., Ltd.) is prepared as a base sheet, and a thickness of 7 μm is obtained by gravure printing using an ink in which a colorant is blended with an acrylic resin on one side. A colored layer was applied, and a 4 μm thick pattern pattern layer was applied by gravure printing using an ink in which a colorant was mixed with an alkyd resin and a nitrocellulose resin. The wood grain pattern was formed so that the winter part was dark.

  Next, a two-part curable acrylic urethane resin composition comprising 71% by mass of an acrylic polyol resin and 29% by mass of silica particles (average particle size 2 μm) as a matting agent and hexamethylene diisocyanate as a curing agent (Showa) The first resin layer having a thickness of 5 μm was formed by gravure printing on the entire surface of the pattern layer using “TSU” manufactured by Ink Industry Co., Ltd. The first resin layer was set to have a gloss of 1.0 (60 ° gloss).

  Next, a two-component curable acrylic urethane resin composition comprising a main agent containing 6% by mass of silica particles (average particle size 2 μm) as a matting agent and 94% by mass of an acrylic polyol resin, and hexamethylene diisocyanate as a curing agent ( Showa Ink Industries Co., Ltd. “FW-NT”) and gravure printed to synchronize with the wood grain pattern in the pattern excluding the winter grain part of the wood pattern of the pattern layer, and the second resin layer with a thickness of 5 μm Formed. In addition, the 2nd resin layer was set so that gloss might be +3.1 (60 degree gloss) with respect to the gloss value of the convex part mentioned later.

  Next, 75% by mass of a two-component acrylic urethane resin mainly composed of an acrylic polyol resin and a curing agent hexamethylene diisocyanate, and 25 acrylic beads (average particle size 20 μm, particle size distribution 10 to 80 μm) as organic particles. Using ink containing% by mass, coating was formed by build-up printing using a pattern plate having a plate depth of 90 μm to form convex portions. The raised pattern was formed so that the area ratio was 25% with respect to the pattern coated with the second resin layer.

  Finally, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.

Examples 2 to 6 and Comparative Example 1
Except having formed the 2nd resin layer and the convex part as follows, it carried out similarly to Example 1, and obtained the decorative sheet of Examples 2-6 and the comparative example 1. FIG.

  The second resin layer is a two-part curable acrylic resin in which the amount of silica particles as a matting agent is the concentration shown in Table 1 below, the residual amount is a resin composed of an acrylic polyol, the main component is hexamethylene diisocyanate, and the curing agent. Using the urethane resin composition, gravure printing was performed so as to synchronize with the wood grain pattern in a pattern excluding the winter part of the wood grain pattern of the picture pattern layer to form a second resin layer having a thickness of 5 μm. In addition, the amount of the silica particles was adjusted so that the gloss of the second resin layer was about +5 or less with respect to the gloss value of the convex portion described later.

  The convex part uses a two-component acrylic urethane resin mainly composed of an acrylic polyol resin and hexamethylene diisocyanate as a curing agent, uses an ink containing particles listed in Table 1 below, and has a pattern depth of 90 μm. A convex portion was formed by coating by build-up printing using a slab. The raised pattern was formed so that the area ratio was 25% with respect to the pattern coated with the second resin layer.

Comparative Example 2
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the convex portions were not formed.

  The following evaluation was performed about the decorative sheet of the said Examples 1-6 and Comparative Examples 1-2.

In order to confirm that the convex portion height is excellent in touch, the cross section of the decorative sheet was observed with a scanning electron microscope (SEM), and the vertical height of the convex portion was measured. Ten points were measured and the average value was calculated. In addition, the standard of the perpendicular | vertical height of the convex part from which a tactile sensation is obtained is about 5 micrometers.

The surface of the particle transition state decorative sheet was observed with a scanning electron microscope (SEM), and the transition state of the particles contained in the convex portions was determined according to the following criteria.
○: A state in which the particles are transferred almost independently.
Δ: A state in which particles are densely transferred.
X: A state in which the particles are aggregated.

Under a light source of a white turbid fluorescent lamp (color rendering AA daylight color, D6500K, manufactured by Panasonic Corporation), the raised urethane coating part was visually confirmed and evaluated according to the following criteria.
◎: No cloudiness sensation ○: Slight cloudiness but no discomfort to the overall design △: White turbidity feeling a little discomfort to the overall design ×: Strong cloudiness What you feel

Ink for forming a gloss protrusions, or ink separately to form the second resin layer, in a similar manner the substrate sheet as in Example 1, a laminate picture pattern layer and the first resin layer are formed in this order The gloss value of each layer was measured using a portable gloss meter manufactured by Murakami Color Research Laboratory. In addition, the coating thickness was set similarly to the above-mentioned build-up layer and 2nd resin layer.

The entire sheet was visually confirmed under a light source of a design effect fluorescent lamp (color rendering AA daylight color, D6500K, manufactured by Panasonic Corporation), and evaluated according to the following criteria.
◎: The gloss mat effect of the conduit part is sufficiently confirmed, and the raised coating layer in the gloss part is not uncomfortable ○: The gloss mat effect of the conduit part is confirmed, and the raised coating layer in the gloss part is uncomfortable Less △: The gloss matte effect in the conduit part is confirmed, and a slightly uncomfortable feeling is felt in the raised coating layer in the gloss part ×: The gloss mat effect in the conduit part is weak and strong in the raised coating layer in the gloss part Something uncomfortable

Example 7
On the ABS resin film (thickness 400 μmm) as the base material layer, a woodgrain pattern layer (thickness 5 μm) was formed by gravure printing using an ink containing vinyl chloride-vinyl acetate-acrylic copolymer resin. . The wood grain pattern was formed so that the winter part was dark.

  Next, a first resin layer (thickness 3 μm) was formed on the entire surface by gravure printing on the pattern layer using a resin composition described later. Next, gravure printing is performed on the first resin layer using a resin composition to be described later so as to synchronize with the wood grain pattern in a pattern excluding the winter part of the wood grain pattern of the pattern layer. A layer (thickness 3 μm) was formed in a pattern. Next, on the second resin layer, a convex portion was formed by applying by a raised printing using a pattern plate having a plate depth of 90 μm using a resin composition described later.

  Finally, the electron beam was irradiated from the convex part side (acceleration voltage 165 kV, irradiation dose 50 kGy (5 Mrad)), the 1st resin layer, the 2nd resin layer, and the convex part were hardened, and the decorative sheet was obtained.

(Resin composition forming the first resin layer)
-Bifunctional polycarbonate urethane acrylate (weight average molecular weight 10,000) 73 mass%
・ Tetrafunctional urethane acrylate (weight average molecular weight 6,000) 4% by mass
・ Silica particles (average particle size 1.3 μm) 23% by mass

(Resin composition for forming the second resin layer)
-Bifunctional polycarbonate urethane acrylate (weight average molecular weight 10,000) 86% by mass
・ 4 functional urethane acrylate (weight average molecular weight 6,000) 5% by mass
・ Urethane beads (average particle size 3μm) 9% by mass

(Resin composition for forming convex portions)
-Bifunctional polycarbonate urethane acrylate (weight average molecular weight 10,000) 76% by mass
・ Tetrafunctional urethane acrylate (weight average molecular weight 6,000) 4% by mass
・ Urethane beads (average particle size 25 μm, particle size distribution 10 to 100 μm) 20% by mass

Examples 8-10
A decorative sheet was obtained in the same manner as in Example 7 except that the type, average particle size and particle size distribution, and particle concentration of the particles contained in the resin composition forming the convex portions were changed as shown in Table 2.

  The following evaluations were performed on the decorative sheets of Examples 7 to 10 described above or the decorative resin molded articles produced as described below.

Production decorative sheet of decorative resin molded product was heated to 180 ° C., and vacuum molding (preliminary molding) was performed using a vacuum molding die to obtain a molded sheet. Insert the resulting molded sheet into an injection mold, clamp the injection mold, inject the fluidized ABS resin into the mold from the base material layer side, and cool and solidify it as it is. A decorative resin molded product with an integrated sheet was obtained.

Using a contact-type surface roughness meter (Handy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.) It was measured. In addition, the standard of 10-point average roughness with which a tactile sensation is obtained is about 5 μm.

About each particle | grain transfer state and cloudiness feeling decorative sheet, it evaluated similarly to the case of Examples 1-6 and Comparative Examples 1-2.

Design effect Each decorative resin molded product was evaluated in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2.

1. Cosmetic sheet 2. 2. base material sheet Pattern layer 4. First resin layer 5. Second resin layer 6. Convex

Claims (13)

  On the base sheet, a first resin layer containing a matting agent, a second resin layer partially provided on the first resin layer, and a resin and organic particles provided on the second resin layer The decorative sheet which has the convex part containing this order.   The decorative sheet according to claim 1, wherein the content of the organic particles is 50% by mass or less of the solid content of the resin composition forming the convex portion.   The decorative sheet according to claim 1 or 2, wherein the content of the organic particles is 2% by mass or more of the solid content of the resin composition forming the convex portion.   The decorative sheet according to any one of claims 1 to 3, wherein an average particle diameter of the organic particles is 15 to 50 µm.   The decorative sheet according to any one of claims 1 to 4, wherein an area where the convex portions are provided is 5 to 80% of an area of the second resin layer.   The decorative sheet according to any one of claims 1 to 5, wherein the second resin layer has a gloss higher than that of the first resin layer.   The decorative sheet according to any one of claims 1 to 6, wherein the second resin layer contains a matting agent.   The mass of the matting agent contained per unit mass of the solid content of the resin composition forming the second resin layer is the gloss contained per unit mass of the solid content of the resin composition forming the first resin layer. The decorative sheet according to claim 7, wherein the decorative sheet is smaller than the mass of the eraser.   The decorative sheet according to any one of claims 1 to 8, further comprising a pattern layer between the base sheet and the first resin layer.   The decorative sheet according to claim 9, wherein a second resin layer is provided in synchronization with the pattern of the pattern pattern layer.   The decorative sheet according to claim 9 or 10, wherein the pattern pattern layer is a wood grain pattern, and the second resin layer is provided on a portion of the wood grain pattern other than the winter eye pattern and / or the conduit pattern.   A decorative board having the decorative sheet according to any one of claims 1 to 11 on an adherend.   A decorative resin molded product having the decorative sheet according to any one of claims 1 to 11 on a molded resin layer.