JP5747614B2 - Decorative sheet for vacuum forming and decorative material using the decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet used for vacuum forming, and a decorative material using the decorative sheet.

  Conventionally, when manufacturing decorative materials having a complicated three-dimensional solid shape, such as kitchen doors and schoolchildren's desk members, etc. A decorative sheet made of thermoplastic resin is spread on the surface of the base material for decorative material while being softened by heating, the space on the base material side of the decorative material of the decorative sheet is decompressed, and the space on the opposite side is added if necessary. A so-called vacuum forming method in which the decorative sheet is bonded and laminated while forming the decorative sheet along the three-dimensional solid shape of the surface of the decorative material substrate by pressing is widely used.

  As the above-mentioned vacuum forming method, heating of the decorative sheet and application of pressing force to the decorative material base material surface of the decorative sheet due to the pressure difference between the space on the decorative material base side of the decorative sheet and the space on the opposite side, The so-called membrane pressing method, which is performed through a flexible and elastic membrane rubber such as a silicone rubber film stretched on the side opposite to the base material for the decorative material of the decorative sheet, and without using the membrane rubber, There is a so-called membraneless press method in which the sheet is directly heated and the decorative sheet itself is used as a pressing force application medium. In Japan, membrane press vacuum forming machines have been mainly used.

  By the way, since the decorative sheet is located on the surface of a three-dimensional solid shape, surface physical properties such as scratch resistance and stain resistance are required. For this purpose, a surface protective layer is provided on the outermost surface of the decorative sheet. It is important. However, in the above-described vacuum forming method, since the decorative sheet is stretched by the vacuum pressure action, there is a problem that the surface protective layer of the curved surface portion of the molded product is cracked.

  With respect to such a problem, in Patent Document 1, a surface protection layer of a decorative sheet is obtained by crosslinking and curing a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a specific ratio. A decorative sheet for vacuum forming has been proposed which has both scratch resistance on the surface of a decorative sheet after vacuum forming and molding processability in vacuum forming.

By the way, in order to improve the design of the decorative sheet, in addition to providing a pattern on the decorative sheet, it is important to give a texture as well. It is required to give a feeling. An example of such a design is a gloss mat design.
A gloss mat design can be expressed by providing a low gloss layer with a surface protective layer on the decorative sheet, but the matte silica etc. contained in the low gloss layer can trigger cracks. Cheap. Therefore, it is more difficult to impart processability to a decorative sheet that represents a gloss matte design than to impart moldability to a mirror-type decorative sheet as described in Patent Document 1. Becomes higher.

JP 2009-234238 A

  The present invention has been made under such circumstances, has good molding processability, does not cause whitening or cracking during three-dimensional processing by vacuum forming, and has surface properties such as scratch resistance and contamination resistance. An object of the present invention is to provide an excellent gloss-matte decorative sheet for vacuum forming and a cosmetic material using the decorative sheet for vacuum forming.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
A base sheet, a decorative layer, and a transparent resin layer in this order, and further, a low gloss expression layer partially provided on the transparent resin layer, and covering the low gloss expression layer and the transparent resin A decorative sheet for vacuum forming having a surface protective layer that also covers a region where the low gloss expression layer is not provided on the layer, the resin constituting the surface protection layer, its thickness, and the low gloss expression layer It was found that the purpose can be achieved by specifying the particle size and the amount of silica added to the silica.
The present invention has been completed based on such findings.

That is, the present invention
<1>
A base sheet, a decorative layer, and a transparent resin layer in this order, and further, a low gloss expression layer partially provided on the transparent resin layer, and covering the low gloss expression layer and the transparent resin A decorative sheet for vacuum forming having a surface protective layer that also covers a region on the layer where the low gloss expression layer is not provided,
The surface protective layer is a crosslinked cured product of a resin composition containing an ionizing radiation curable resin, and the thickness thereof is 1 to 20 μm in a region where the low gloss expression layer is not provided.
The low-gloss expression layer contains silica particles having an average volume particle size of 0.5 to 25 μm in a proportion of 1 to 30 parts by mass with respect to 100 parts by mass of the resin component, and <2>
The present invention provides a cosmetic material having a decorative material base material and a decorative sheet layer formed by vacuum forming the vacuum forming decorative sheet of <1> along the surface of the decorative material base material.

  According to the present invention, by specifying the thickness of the surface protective layer and the particle size and amount of silica added to the low gloss layer, and further specifying the resin constituting the surface protective layer, A decorative sheet for vacuum forming that is excellent in processability as well as surface physical properties such as scratch resistance and contamination resistance can be obtained while being in a mat specification. By laminating the decorative sheet while vacuum forming along the surface shape of the base material for decorative materials, surface properties such as scratch resistance and contamination resistance and gloss matte design are imparted without causing whitening or cracking. Can do.

It is a schematic diagram which shows the cross section of an example of the decorative sheet for vacuum forming of this invention.

First, the decorative sheet for vacuum forming according to the present invention will be described.
[Decorative sheet for vacuum forming]
The decorative sheet for vacuum forming of the present invention (hereinafter sometimes simply referred to as “decorative sheet”) has a base sheet, a decorative layer, and a transparent resin layer in this order, and further a part on the transparent resin layer. And a surface protective layer that covers the low gloss development layer and also covers a region on the transparent resin layer where the low gloss development layer is not provided.
The surface protective layer is a crosslinked cured product of a resin composition containing an ionizing radiation curable resin, and has a thickness of 1 to 20 μm in a region where the low gloss expression layer is not provided. Moreover, the said low gloss expression layer contains a silica particle and resin with an average volume particle diameter of 0.5-25 micrometers, and content of this silica particle is 1-30 mass parts with respect to 100 mass parts of this resin.
The decorative sheet of the present invention may further have a layer other than the above-described layers as necessary.

Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing a cross section of an example of a decorative sheet for vacuum forming according to the present invention.
The decorative sheet 10 for vacuum forming of the present invention has a base sheet 11, a decorative layer 12 (121: colored hiding layer, 122: printed pattern layer), and a transparent resin layer 13 in this order, and further includes a transparent resin layer. A low gloss developing layer 14 partially provided on 13, and a surface protective layer 15 covering the low gloss developing layer 14 and also covering a region on the transparent resin layer 13 where the low gloss developing layer 14 is not provided. Have

(Base material sheet)
The substrate sheet 11 according to the present invention is selected in consideration of suitability for vacuum forming, and typically a resin sheet made of a thermoplastic resin is used. Examples of the thermoplastic resin include polyester resins, vinyl chloride resins, acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter referred to as “ABS resins”), and the like. In addition, the base material sheet 11 can also be used as a single layer sheet of the above-mentioned resin or a multilayer sheet of the same kind or different kind of resin.
Of the above resins, polyolefin resins and amorphous polyester resins are particularly preferable because moldability such as vacuum moldability, bending workability, and adhesion to an adherend are improved.

Examples of polyolefin resins include polyethylene (low density, medium density, or high density), polypropylene, polymethylpentene, polybutene, and ethylene-propylene random copolymer (for example, metallocene-catalyzed isotactic ethylene-propylene random copolymer). Highly crystalline non-elastomeric polyolefin-based resins such as propylene-butene copolymer or various olefin-based thermoplastic elastomers are used. As the olefin-based thermoplastic elastomer, for example, the following can be used.
(1) (A) Soft polypropylene comprising a mixture of 10 to 90% by mass of atactic polypropylene and (B) 90 to 10% by mass of isotactic polypropylene,
(2) a thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin,
(3) (A) Olefin polymer (crystalline polymer) such as polyethylene, polypropylene, polymethylpentene and (B) partially crosslinked ethylene-propylene copolymer rubber, unsaturated ethylene-propylene-nonconjugated diene ternary An olefin elastomer obtained by uniformly blending and mixing a monoolefin copolymer rubber such as a copolymer rubber;
(4) (B) Uncrosslinked monoolefin copolymer rubber (soft segment), (A) Olefin copolymer (crystalline, hard segment) and crosslinking agent are mixed, heated and subjected to shear stress. An olefin-based elastomer that is dynamically partially crosslinked,
(5) (A) peroxide-decomposable olefin polymer, (B) peroxide-crosslinked monoolefin copolymer rubber, (C) peroxide non-crosslinked hydrocarbon rubber, and (D) paraffinic, naphthenic, aromatic Olefin-based elastomers that are mixed with a mineral oil-based softener such as, and dynamically heat-treated in the presence of organic peroxides,
(6) An olefinic thermoplastic elastomer made of an ethylene-styrene-butylene copolymer.

  As an amorphous polyester resin, for example, a trademark “Eastar PETG 6763” (trade name) (extruded grade) manufactured by Eastman Chemical Co., Ltd. can be used. "Kanebo PET Sheet" (trade name) by Kanebo Co., Ltd., "Teijin Tetron Sheet" (trade name) by Teijin Ltd., "Denka A-PET Sheet" by Denki Kagaku Kogyo Co., Ltd. (trade name) ), "Toyobo PETMAX sheet" (trade name) by Toyobo Co., Ltd., "NAGASE A-PET sheet" (trade name) by Nagase Sangyo Co., Ltd., "Polytech A-PET sheet" (product) by Polytech Co., Ltd. Name), “SAEHAN APET SEET” (trade name) by SAEHAN, “NOVA CLEAR” by Mitsubishi Chemical Corporation "(Trade name)," sealer PT "(trade name), and the like can be used by DuPont-Mitsui poly Chemical Company. In addition, a resin or resin sheet called A-PET (sometimes referred to as APET) in the packaging material field is an amorphous polyester resin, and PET-G (sometimes referred to as PETG). The called resin or resin sheet is also an amorphous polyester resin.

  For example, in the case of “Eastar PETG 6763” manufactured by Eastman Chemical Co., Inc., terephthalic acid is used as the acid component, and ethylene glycol and 1,4-cyclohexanedi are used as the diol component. It is a copolymer resin combined with methanol. It is said that the crystallization rate can be reduced to about zero by adjusting the ratio of ethylene glycol and 1,4-cyclohexanedimethanol. Further, the physical properties can be adjusted by adjusting this ratio.

Examples of the acid component and diol component of the amorphous polyester resin include those shown in the above examples, but the amorphous polyester resin used in the present invention is not limited to these, and other acid components and Even a resin composed of a diol component can be used as long as it is an amorphous resin.
For example, as the acid component, in addition to terephthalic acid, aromatic dicarboxylic acids such as isophthalic acid and 2,6-naphthalenedicarboxylic acid; alicyclic dicarboxylic acids; fats such as adipic acid, azelaic acid, sebacic acid, and dimer acid Group dicarboxylic acid and the like.
Examples of the diol component include alicyclic diols other than the aforementioned 1,4-cyclohexanedimethanol; aliphatic diols such as propylene glycol, butylene glycol, polytetramethylene glycol, and neopentyl glycol; aromatic diols such as xylene glycol Etc.

  The amorphous polyester resin is usually a combination of one or more diol components and one or more acid components so that the total of the diol and acid components is three or more. Obtained as a polymer. Note that an amorphous resin may be a resin that does not cause crystallization at all, but may be a resin having a portion exhibiting crystallinity together with a portion exhibiting non-crystallinity. The amorphous polyester resin may be mixed with a crystalline polyester resin.

As described above, the base sheet 11 in the vacuum forming decorative sheet 10 of the present invention is preferably a sheet containing at least a polyolefin resin and / or an amorphous polyester resin.
The substrate sheet 11 according to the present invention may be colorless and transparent, but may be colored transparent or colored opaque (color concealing property). In order to color the base material sheet 11, a known colorant as described in the hiding layer 121 and the picture layer 122 described later may be added to the resin.
The base material sheet 11 according to the present invention is usually prepared as a resin sheet, and the thickness thereof is usually about 50 to 300 μm although it depends on the application. In addition to the single layer, the base sheet 11 may have a multilayer structure such as two or three layers, or may be a laminated sheet made of two or more kinds of resins.

(Decoration layer)
The decorative layer 12 according to the present invention is a layer provided to improve the designability of the decorative sheet 10 and is constituted by the concealing layer 121 and / or the pattern layer 122.
The concealing layer 121 is an entire solid layer that conceals the coloring of the base sheet 11. When the pattern layer 122 is laminated on the concealing layer 121, the coloring is selected according to the pattern layer 122. Moreover, when the base material sheet 11 functions as a concealment layer, the concealment layer 121 may not be provided, and the pattern layer 122 may be printed on the surface of the base material sheet 11.
The concealing layer 121 can be formed by printing using a known method such as gravure printing or printing method such as gravure coating or roll coating, usually with printing ink or paint. The thickness of the concealing layer 121 is about 1 to 10 μm, and usually about 5 μm.

In the present invention, the picture layer 122 laminated on the concealment layer 121 as desired is a layer that represents a pattern, a character, and the like. Although the pattern of the pattern layer 122 is arbitrary, it is a pattern composed of, for example, wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, and the like. The pattern layer 122 is usually formed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing with printing ink.
The thickness of the pattern layer 122 may be appropriately selected according to the pattern.

As a binder of ink or paint used for the concealing layer 121 and / or the pattern layer 122 constituting the decorative layer 12 according to the present invention, polyester resin, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer A combination, cellulose resin, or chlorinated polyolefin resin such as chlorinated polyethylene or chlorinated polypropylene is used alone or in combination. However, since the chlorinated polyolefin resin is a resin containing chlorine like the vinyl chloride resin, it is preferable to restrict its use when it is desired to use it as a non-vinyl chloride decorative sheet.
As the ink or paint, in addition to the above-mentioned binders made of various resins, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed. .

Colorants used in the ink or paint include inorganic pigments such as titanium white, zinc white, dial, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone yellow, Hansa Yellow A, and quinacridone. Red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, organic pigments (including dyes) such as aniline black, metal pigments made of metal powder such as aluminum, brass, titanium dioxide-coated mica, basic lead carbonate, etc. A pearlescent (pearl) pigment, a fluorescent pigment, or the like made of a foil powder is used.
The concealing layer 121 or the picture layer 122 may be a metal thin film layer or the like. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. Alternatively, a combination thereof may be used. The metal thin film layer may be provided on the entire surface or partially in a pattern.

(Transparent resin layer)
The transparent resin layer 13 is a resin layer that is transparent or translucent (uncolored or colored) so that the pattern layer 122 can be seen through, and a polyolefin-based resin, a polyester resin, or the like is preferably used.
Specific examples of the polyolefin resin used for the transparent resin layer 13 include various polyolefin resins used for the substrate sheet 11 described above.
The polyester resin used for the transparent resin layer 13 is preferably an amorphous polyester resin, and specific examples of the amorphous polyester resin include various amorphous polyester resins used for the base sheet 11 described above. By using a polyolefin resin or an amorphous polyester resin for the transparent resin layer 13, moldability such as vacuum moldability, bending workability, and adhesion to an adherend are particularly good.
The resin used for the transparent resin layer 13 may be the same as or different from the resin used for the base sheet 11. In addition to a single layer, it may have a multilayer structure such as two or three layers, or may be a laminated sheet made of two or more kinds of resins.

The transparent resin layer 13 was formed by laminating the concealment layer 121 and / or the pattern layer 122 on the base sheet 11 and forming a sheet (film) by a known film formation method such as a melt extrusion method or a calender method in advance. It can be formed by laminating resin sheets by dry lamination or heat fusion. Alternatively, the resin constituting the transparent resin layer 13 may be formed simultaneously with the film formation by the melt extrusion coating method (EC method) on the concealment layer 121 and / or the pattern layer 122 laminated.
The thickness of the transparent resin layer 13 (not a single layer but as a whole in the case of multiple layers) depends on the application, layer configuration (single layer, multilayer) and the like, but is usually about 10 to 400 μm.

Further, in the transparent resin layer 13, various additives such as a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer and the like are added within a range that does not impair the transparency or translucency. An agent may be added. When the transparent resin layer 13 is used as a semitransparent layer, for example, fine particle silica or the like may be appropriately added to the transparent resin layer 13 to make it semitransparent.
In addition, as the ultraviolet absorber, in addition to organic ultraviolet absorbers such as benzotriazole, benzophenone, and salicylic acid ester, particulate zinc oxide, cerium oxide, titanium oxide, etc. having a particle size of 0.2 μm or less An inorganic substance can be used.
Further, as the light stabilizer, radical scavengers such as hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and piperidine radical scavengers can be used. .

(Surface protective layer)
The surface protective layer 15 is a layer provided for the purpose of imparting surface physical properties such as scratch resistance and stain resistance to the decorative sheet 10 of the present invention, and is a low gloss layer partially provided on the transparent resin layer 13. While covering the expression layer 14, the area | region in which the low gloss expression layer 14 on the transparent resin layer 13 is not formed is also covered.
The surface protective layer 15 is a crosslinked cured product of a resin composition containing an ionizing radiation curable resin, and the resin composition may further contain a thermoplastic resin, silicone (meth) acrylate, an additive, and the like.
The thickness of the surface protective layer 15 is 1 to 20 μm, preferably 3 to 15 μm, more preferably 5 to 5 μm in a region where the low gloss expression layer 14 is not provided, from the viewpoint of gloss mat effect and molding processability. 10 μm.

<Ionizing radiation curable resin>
An ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ionizing radiation. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. As the ionizing radiation curable resin, a conventionally known compound may be appropriately used, and it can be appropriately selected from a polymerizable monomer, a polymerizable oligomer or a prepolymer conventionally used as an ionizing radiation curable resin. . Typical examples are described below.

  As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, the polymerizable oligomer is preferably an oligomer having a radically polymerizable unsaturated group in the molecule, particularly an acrylate oligomer having a radically polymerizable unsaturated group, such as an epoxy (meth) acrylate or urethane (meth) acrylate. Type, polyester (meth) acrylate type, polyether (meth) acrylate type, and the like. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.
In the present invention, among the ionizing radiation curable resins, a bifunctional urethane acrylate oligomer is preferable from the viewpoint of performance.

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.
In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

<Thermoplastic resin>
In the present invention, the resin composition used for the surface protective layer 15 may contain a thermoplastic resin. In the surface protective layer 15, the content of the thermoplastic resin is preferably in a range where the mass ratio of the thermoplastic resin / ionizing radiation curable resin is 0/100 to 70/30, and is 5/95 to 50/50. A range is more preferred. Within this range, the balance between molding processability and surface physical properties after cross-linking and curing to form the surface protective layer 15 becomes good.

The thermoplastic resin is not particularly limited, and various types of thermoplastic resins can be used.
Examples of the thermoplastic resin include (meth) acrylic resins such as (meth) acrylic acid esters, polyvinyl acetals (butyral resins) such as polyvinyl butyral, amorphous polyester resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate. , Polyolefin resins such as vinyl chloride resin, urethane resin, polyethylene and polypropylene, styrene resins such as polystyrene and α-methylstyrene, acetal resins such as polyamide, polycarbonate and polyoxymethylene, ethylene-4 fluoroethylene copolymer Fluorine resin such as polyimide, polylactic acid, polyvinyl acetal resin, liquid crystalline polyester resin, and the like. These may be used alone or in combination of two or more. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.

Among the above thermoplastic resins, those having a (meth) acrylic resin and / or a polyester resin as the main component are preferred in the present invention, and in particular, a monomer containing at least a (meth) acrylic acid ester as a monomer component. Those obtained by polymerization are preferred.
More specifically, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and other monomers Is preferred.

  Here, examples of the (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, and propyl methacrylate. Among these, methyl methacrylate is the most. preferable.

Next, examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above. Also in the polymer, those having methyl methacrylate as a main component are preferable. That is, a copolymer of methyl methacrylate and another (meth) acrylic acid ester monomer is preferable, and a copolymer of methyl methacrylate and methyl acrylate, a copolymer of methyl methacrylate and ethyl methacrylate, and the like are exemplified. . Of these, a copolymer of methyl methacrylate and methyl acrylate is most preferable from the viewpoint of effects. In addition, these copolymers may be random copolymers or block copolymers.
Moreover, in the copolymer of methyl methacrylate and other (meth) acrylic acid ester monomers, the structural unit derived from other (meth) acrylic acid ester monomers with respect to 100 moles of the structural unit derived from methyl methacrylate. Is preferably in the range of 0.1 to 200 mol. When the structural unit derived from another (meth) acrylic acid ester monomer is within the above range with respect to 100 moles of the structural unit derived from methyl methacrylate, the wear resistance, scratch resistance and solvent resistance are improved. .

Next, the copolymer of (meth) acrylate and other monomer is not particularly limited as long as the other monomer can be copolymerized with (meth) acrylate, but in the present invention, ( (Meth) acrylic acid, styrene, (anhydrous) maleic acid, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene , Cycloaliphatic olefin monomers such as 1-butene, 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, maleimides such as vinylcaprolactam, citraconic anhydride, N-phenylmaleimide , Vinyl ether And the like, particularly styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable.
In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

  In the copolymer of the (meth) acrylic acid ester and styrene and / or (anhydrous) maleic acid, styrene and / or (/) with respect to 100 mol of the structural unit derived from the (meth) acrylic acid ester. The structural unit derived from maleic anhydride) is preferably in the range of 0.1 to 200 mol. When the structural unit derived from styrene and / or (anhydrous) maleic acid is within the above range with respect to 100 moles of the structural unit derived from (meth) acrylic acid ester, the wear resistance, scratch resistance, solvent resistance Improves.

The thermoplastic resin preferably has a glass transition temperature Tg of 70 to 100 ° C. and a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio in the range of 1.2 to 2.5.
If the glass transition temperature Tg is 70 ° C. or higher, the polarity of the thermoplastic resin and the polarity of the silicone (meth) acrylate present in the surface protective layer are not repelled, and there is almost no occurrence of silicone unevenness. Becomes better. On the other hand, if Tg is 100 ° C. or less, sufficient elongation (flexibility) is exhibited at the time of vacuum forming, and the moldability is good.
When the Mw / Mn ratio is 1.2 or more, there is almost no occurrence of silicone unevenness, the appearance is good, and sufficient elongation (flexibility) is expressed during vacuum forming, and the moldability is good. On the other hand, if the Mw / Mn ratio is 2.5 or less, the resin composition has little thickening and the coating suitability is good.

<Silicone (meth) acrylate>
The resin composition used for the surface protective layer 15 may contain silicone (meth) acrylate. Silicone (meth) acrylate is added to the decorative sheet 10 mainly for the purpose of improving surface physical properties such as scratch resistance and stain resistance due to a synergistic effect with the ionizing radiation curable resin. Silicone (meth) acrylate is one of modified silicone oils in which a (meth) acryl group is introduced into one or both ends of a silicone oil composed of polysiloxane. Conventionally known silicone (meth) acrylates can be used, and are not particularly limited as long as the organic group is a (meth) acrylic group, and a modified silicone oil having 1 to 6 organic groups can be preferably used. . The structure of the modified silicone oil is roughly divided into a side chain type, a both-end type, a single-end type, and a side-chain both-end type depending on the bonding position of the organic group to be substituted. There is no particular limitation.
The content of the silicone (meth) acrylate may be appropriately adjusted so that the surface tension of the surface protective layer is in a desired range. However, from the viewpoint of sufficiently improving the contamination resistance and the effect of using the ionizing radiation. 0.5-4 mass parts is preferable with respect to 100 mass parts of curable resin, and 1.0-2.5 mass parts is more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 1000-20000 is mentioned, for example.

<Additives>
Moreover, various additives can be mix | blended with the resin composition used for the surface protective layer 15 according to the desired physical property of the surface protective layer 15 obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic. Examples of organic ultraviolet absorbers include benzotriazoles, specifically 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl). ) Benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

Examples of the wear resistance improver include α-alumina, silica, kaolinite, iron oxide, diamond, silicon carbide and the like for inorganic substances, and synthetic resin beads such as a crosslinked acrylic resin and a polycarbonate resin for organic substances. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable.
As the wear resistance improver, inorganic substances are preferable, and silica is most preferable among them. Silica improves friction resistance and does not hinder the transparency of the surface protective layer. As the silica, it is possible to appropriately select and use conventionally known silica, and for example, colloidal silica can be preferably mentioned. Colloidal silica is preferable because it hardly affects the transparency even when the addition amount is increased, and has little influence on printing because it does not impair the fluidity.
As the particle diameter of silica, those having a primary particle diameter of 5 to 1000 nm are preferably used, more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. When silica having a primary particle diameter of 1000 nm or less is used, transparency is secured. Moreover, the primary particle diameter of the silica used does not need to be one kind, and it is also possible to mix and use silica having different primary particle diameters.
The content of silica is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, silica, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

<Method for forming surface protective layer>
Regarding the formation of the surface protective layer 15, first, ionizing radiation curable resins such as polymerizable monomers and polymerizable oligomers, thermoplastic resins used as necessary, silicone (meth) acrylate, and various additives are respectively given in predetermined amounts. The resin composition is obtained by uniformly mixing at a ratio. The viscosity of the resin composition in this case is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the transparent resin layer 13 by a coating method to be described later. It may be added.
The resin composition thus prepared was subjected to gravure over the entire surface including the below-described low-gloss expression layer 14 partially provided on the transparent resin layer 13 and the region where the low-gloss expression layer 14 was not formed. It coats by well-known systems, such as a coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat, preferably a gravure coat, and forms an uncured resin layer.

Next, the uncured resin layer is cured by irradiating the uncured resin layer with ionizing radiation such as an electron beam or ultraviolet rays. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. Is preferred.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are By selecting the accelerating voltage so as to be substantially equal, it is possible to suppress the irradiation of the extra electron beam to the base material, and to minimize the deterioration of the base material due to the excess electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. Can be used.
When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

(Low gloss layer)
The decorative sheet of the present invention has the low gloss expression layer 14 together with the surface protective layer 15. This low gloss expression layer 14 is partially present on the transparent resin layer 13, and a low gloss region is formed in the surface protective layer immediately above and in the vicinity thereof. That is, the low gloss expression layer 14 has a function of developing low gloss on a part of the surface protective layer 15 (immediately above and near the low gloss expression layer 14). The expression of low gloss is the appropriate combination of materials and application conditions when an uncured product of ionizing radiation curable resin for forming the surface protective layer 15 on the surface of the low gloss expression layer 14 is applied. Depending on the selection, the resin component of the low gloss expression layer 14 and the surface protective layer 15 are considered to be due to interactions such as partial elution, dispersion, and mixing.

The gloss mat design of the decorative sheet 10 of the present invention produces a difference in glossiness between the low gloss region (due to the interaction with the low gloss expression layer 14) in the surface protective layer 15 and the surrounding non-low gloss region. This is due to that. Depending on the type of design expression, various glossiness differences are used to produce decorative sheets with good design properties. However, the glossiness (gross value) of the low gloss area is not limited as follows. , 20 or less is preferable from the viewpoint of increasing designability. Further, it is more preferable that the difference in glossiness between the low gloss region and the non-low gloss region is 10 or more in that the design property can be further increased.
When the decorative sheet 10 of the present invention is viewed from the surface protective layer 15 side, the low gloss region may be visually recognized as a concave portion, and as a whole, the low gloss region is visually recognized as an uneven pattern. There is also.

  Further, the upper part of the low gloss region on the outermost surface of the surface protective layer 15 may be raised with the formation of the low gloss expression layer 14 and have a convex shape. Since the surface of the surface protective layer 15 has such a convex shape, light is scattered at this portion, the surface area is increased, and the viewing angle for recognizing low gloss is widened. In addition to the effect, the visual unevenness is emphasized.

The low gloss expression layer 14 contains silica particles having an average volume particle size of 0.5 to 25 μm and a resin, and the content of the silica particles is 1 to 30 parts by mass with respect to 100 parts by mass of the resin.
The resin contained in the low gloss layer 14 has a property of causing interaction with the resin composition used for the surface protective layer 15 and is appropriately selected in relation to the resin composition (uncured product). Is. For example, a thermoplastic (non-crosslinked type) resin can be used. Specific examples thereof include polyvinyl acetals (butyral resins) such as acrylic resins, polyester resins, unsaturated polyester resins, vinyl chloride-vinyl acetate copolymers, urethane resins (for example, polyester urethane resins), and polyvinyl butyral. If necessary, one or more of these resins may be mixed in order to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and the surrounding non-low gloss region. It is not limited to.
Further, in order to improve the physical properties, an ionizing radiation curable resin, a thermosetting resin, or a curing agent thereof (isocyanate or the like) can be added as necessary to the extent that the moldability is not impaired.
Among the patterns to be expressed by the decorative layer 12, for example, a pattern having a visual concave portion due to a gloss difference can be obtained by erasing the gloss and synchronizing the portion where the concave portion is visually expressed with the low gloss expression layer 14 . When a wood grain pattern is to be expressed by the decorative layer 12, a pattern in which the conduit portion is visually concave due to the difference in gloss is obtained by synchronizing the low gloss developing layer 14 with the wood conduit portion.

  The low gloss expression layer 14 contains silica particles. By including silica particles in the composition for forming the low gloss expression layer 14, the composition can be provided with thixotropy. When the low gloss expression layer 14 is printed using a plate, The shape of the composition is maintained. As a result, the sharpness of the unevenness at the end portion that transitions from the convex portion to the concave portion can be emphasized, and a sharp design expression is possible.

The average volume particle diameter of the silica particles is 0.5 to 25 μm. If it is 25 μm or less, the stress at the time of processing diffuses due to an increase in the interfacial area, and voids generated at the interface absorb energy, or the inter-particle distance decreases, and plastic deformation between particles or voids occurs. It is possible to suppress whitening during expansion. From these viewpoints, it is preferably 15 μm or less, and more preferably 10 μm or less. Further, from the viewpoint of the matte effect, 1 μm or more is more preferable, and 3 μm or more is more preferable. The average volume particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method.
The content of the silica particles in the low gloss expression layer 14 is 1 to 30 parts by mass, preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of the balance between the gloss matte effect and the moldability. More preferably, it is 5-15 mass parts.

  In addition, it is preferable to surface-treat the above silica particles, because the adhesion between the resin binder and silica is improved and a tough coating film is formed when cured, and cracks and whitening during molding can be suppressed. Examples of the treatment method include silane coupling treatment and the like, and are not limited to organic and inorganic.

  In the present invention, the low-gloss expression layer 14 further contains extender pigments such as talc, clay, barium sulfate, barium carbonate, calcium carbonate, and magnesium carbonate in addition to the silica particles as long as the effects of the present invention are not impaired. Also good. In addition, an organic or inorganic coloring pigment may be added in order to achieve a higher design without impairing the effects of the present invention. A known pigment can be used as the pigment, and the color (pigment) to be used depending on the desired pattern and the amount of addition may be appropriately determined.

The thickness of the low gloss expression layer 14 is preferably 0.5 to 5 μm. The thickness of the surface protective layer 15 and the low gloss developing layer 14 is such that the thickness of the surface protective layer 15 (thickness in a region where the low gloss developing layer 14 is not formed) The thickness is preferably 1.5 times or more, more preferably 2 times or more. When the thickness of the surface protective layer 15 is 1.5 times or more the thickness of the low gloss developing layer 14, the low gloss developing layer 14 becomes relatively thin and cracks are not generated during molding.
Moreover, high designability can be exhibited when the thickness of the surface protective layer 15 is not more than 5 times the thickness of the low gloss developing layer 14.

Next, the decorative material of the present invention will be described.
[Cosmetic materials]
The decorative material of the present invention has a base material for decorative material, and a decorative sheet layer formed by vacuum forming the above-described decorative sheet for vacuum forming of the present invention along the surface of the base material for decorative material.
As a base material for decorative material, it is used for various adherends that can be laminated by vacuum forming. The adherend is a flat plate made of various materials, a plate material such as a curved plate, a three-dimensional article, a sheet (or film), or the like. For example, wood board materials such as wood veneer, such as wood veneer, wood plywood, particle board, MDF (medium density fiber board), etc., wood board materials used as 3D shaped articles, etc., board materials such as iron and aluminum, 3D shaped articles or Ceramic materials used as plate materials and three-dimensional articles such as metal materials used as sheets, ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates Material, acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber plate, three-dimensional shape Examples thereof include resin materials used as articles or sheets.

As a vacuum forming method for laminating the decorative sheet of the present invention on the adherend, the decorative sheet fixed to the fixed frame is heated with a heater through a silicone rubber sheet until the decorative sheet is softened to a predetermined temperature, and the heated and softened makeup is applied. A vacuum molding die is pressed against the sheet, and at the same time, air is sucked from the vacuum molding die with a vacuum pump or the like to firmly adhere the decorative sheet to the vacuum molding die. If necessary, compressed air pressing from the decorative sheet side may be used in combination.
After the decorative sheet comes into close contact with the vacuum forming mold, the decorative sheet is cooled, the vacuum forming mold is removed from the molded decorative sheet, and the decorative sheet formed from the fixed frame is removed. Vacuum forming is usually performed at about 80 to 130 ° C, preferably about 90 to 120 ° C.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
<Evaluation method>
(1) Designability (gross matte effect)
The design of the surface was visually evaluated. The evaluation criteria are as follows.
(Double-circle): The conduit part was recognized as a recessed part, and also the texture of the grain was obtained, and the design nature was very high.
○: The conduit part was recognized as a concave part, and the design was high.
○ △: Slightly inferior in design, but no problem in practical use.
(Triangle | delta): It was inferior to the designability.
X: The design was planar and the design was extremely inferior.

(2) Formability [crack (whitening)]
Molding was performed using a vacuum forming machine ("Surface Curved Vacuum Press" manufactured by STI), and visually evaluated for cracks / whitening on the curved surface. The evaluation criteria are as follows.
◎: No crack / whitening ○: Very slight crack / whitening is confirmed, but there is no problem in actual use.
○: Slight crack / whitening is confirmed, but there is no problem in actual use.
Δ: Crack / whitening is observed.
X: Many cracks / whitening are recognized.

(3) Scratch resistance Each decorative sheet was tested according to JIS L0849 [Abrasion tester type II (Gakushin type)] and evaluated according to the following criteria. The apparatus used for the test was a “Gakushin Abrasion Tester” manufactured by Tester Sangyo Co., Ltd., and evaluated using test pieces after 50 reciprocations at 500 g load using Kanakin No. 3 as a white cotton cloth for friction. The evaluation criteria are as follows.
◎: No scratches ○: No significant scratches on appearance ○ △: Slight scratches are observed, but there is no practical problem.
Δ: Scratched or gloss change occurs on the surface of 1/4 or more and 1/2 of the test surface ×: Scratch or gloss change occurs on 1/2 or more of the test surface

(4) Contamination resistance Contaminated with black quick-drying ink (M500-T1 black), and immediately after wiping with a dry cloth, the degree of contamination (remaining trace) on the surface was visually evaluated. The judgment criteria are as follows.
A: No trace is observed at all.
○: A trace of traces is recognized, but there is no problem in actual use.
○ △: A slight trace remains, but there is no problem in actual use.
X: Remaining trace is recognized.

(5) Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) of thermoplastic resin A high-speed GPC apparatus manufactured by Tosoh Corporation was used. The column used was “TSKgel αM” manufactured by Tosoh Corporation, the solvent was N-methyl-2-pyrrolidinone (NMP), and the measurement was performed at a column temperature of 40 ° C. and a flow rate of 0.5 cc / min. . The molecular weight and molecular weight distribution in the present invention were converted to polystyrene.

Example 1
Using a polyethylene resin sheet (manufactured by Mitsubishi Plastics Co., Ltd., “Art Ply (polyethylene)”, thickness of 100 μm) as a base sheet, a concealing layer that is a solid layer is gravure coated on one side of the polyethylene resin sheet, A woodgrain pattern layer was formed thereon by gravure printing to obtain a printed sheet. The hiding layer and the pattern layer use a mixed resin of vinyl chloride-vinyl acetate copolymer and acrylic resin in a 1 to 1 mass ratio as a binder resin, and a predetermined ratio of petrol and carbon black as a colorant. The colored ink used in 1 was used.

Next, an amorphous polyester resin (trademark “Easter PETG 6763” manufactured by Eastman Chemical Co., Ltd.) was extruded by a melt extrusion method from a T-die to form a non-colored transparent resin layer having a thickness of 200 μm.
Subsequently, this transparent resin layer was laminated | stacked on the wood grain pattern layer of the said printing sheet by the heat sealing | fusion method through the primer layer.
Next, untreated silica (silica A) having an average volume particle size of 5 μm is added to 100 parts by mass of the resin component in the polyester urethane printing ink having a number average molecular weight of 3,000 and a glass transition temperature (Tg) of 62.8 ° C. Using ink obtained by blending 15 parts by mass, it was applied on the transparent resin layer by gravure printing so as to synchronize with the conduit part of the above-mentioned pattern layer of wood grain, and a low gloss appearance with a thickness of 1.5 μm A layer was partially formed.
On the other hand, a transparent resin layer containing a resin composition in which 1% by mass of a bifunctional silicone methacrylate is blended with a bifunctional urethane acrylate oligomer (trade name “EB-1”, manufactured by Dainichi Seika Co., Ltd.), which is an electron beam curable resin. The entire surface including the region of the low gloss developing layer partially provided on the surface and the region where the low gloss developing layer was not formed was applied by a gravure reverse method so that the thickness after curing was 5 μm. After coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) was irradiated to crosslink and cure the resin composition to form a surface protective layer, and a gloss-mat type vacuum forming decorative sheet was produced. .
The performance evaluation results of this decorative sheet are shown in Table 1.

Examples 2-11 and Comparative Examples 1-8
As a resin composition in Example 1, an electron beam curable resin and a thermoplastic resin (polymethyl methacrylate, Tg: 75 ° C., Mw: 200,000, Mn: 125,000) are included in the proportions shown in Table 1. Except that the average volume particle diameter of silica, silica content, untreated or treated silica and the thickness of the low gloss expression layer are as shown in Table 1 In the same manner as in Example 1, decorative sheets for vacuum forming of each gloss mat specification were produced.
The performance evaluation results of each decorative sheet are shown in Table 1.

The gloss mat (difference in gloss) specification of the decorative sheet for vacuum forming of the present invention has good processability, does not cause whitening or cracks during three-dimensional processing by vacuum forming, and has a surface such as scratch resistance and stain resistance. Excellent physical properties. Therefore, it is suitably used for various vacuum-formed products as a decorative sheet used for surface decoration such as exterior, interior, joinery, furniture, and vehicle interior of buildings.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Decorative sheet for vacuum forming 11 Base sheet 12 Decoration layer 121 Colored concealment layer 122 Printed picture layer 13 Transparent resin layer 14 Low gloss expression layer 15 Surface protective layer

Claims (7)

A base sheet, a decorative layer, and a transparent resin layer in this order, and further, a low gloss expression layer partially provided on the transparent resin layer, and covering the low gloss expression layer and the transparent resin A decorative sheet for vacuum forming having a surface protective layer that also covers a region on the layer where the low gloss expression layer is not provided,
The transparent resin layer is a resin sheet having a thickness of 10 to 400 μm, in which the resin material forming the transparent resin layer is formed into a sheet by a melt extrusion method, a calender method, or a melt extrusion coating method,
The surface protective layer is a crosslinked cured product of a resin composition containing an ionizing radiation curable resin, and the thickness thereof is 1 to 20 μm in a region where the low gloss expression layer is not provided.
The low gloss appearance layer contains silica particles having an average volume particle size of 0.5 to 25 μm and a resin, and the content of the silica particles is 1 to 30 parts by mass with respect to 100 parts by mass of the resin. Cosmetic sheet.   The decorative sheet for vacuum forming according to claim 1, wherein the resin composition contains a thermoplastic resin in a range where a mass ratio of the thermoplastic resin / the ionizing radiation curable resin is 5/95 to 50/50.   The decorative sheet for vacuum forming according to claim 2, wherein the thermoplastic resin is a (meth) acrylic resin and / or a polyester resin.   The decorative sheet for vacuum forming according to any one of claims 1 to 3, wherein the silica particles are surface-treated.   The decorative sheet for vacuum forming according to any one of claims 1 to 4, wherein the ionizing radiation curable resin is an electron beam curable resin.   The decorative sheet for vacuum forming according to any one of claims 1 to 5, wherein the low gloss layer has a thickness of 0.5 to 5 µm.   A cosmetic material comprising: a decorative material base material; and a decorative sheet layer formed by vacuum forming the vacuum forming decorative sheet according to claim 1 along the surface of the decorative material base material.