JP2013075501A - Decorative sheet, and decorative resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a surface protection layer which combines scratch resistance, wear resistance and three-dimensional formability.SOLUTION: The decorative sheet has at least substrate film layer and a surface protection layer. The surface protection layer is composed of a cured product of ionizing radiation-curable resin composition including a synthetic resin particle, polycarbonate (meth)acrylate and/or acrylic silicone (meth)acrylate.

Description

  The present invention relates to a decorative sheet having a surface protective layer having both scratch resistance, wear resistance, and three-dimensional formability, and a decorative resin molded product having the above characteristics.

  A decorative resin molded product in which a decorative sheet is laminated on the surface of a molded product is used in various applications such as vehicle interior parts. As a molding method of such a decorative resin molded product, the decorative sheet is formed into a three-dimensional shape in advance by a vacuum mold, the decorative sheet is inserted into an injection mold, and the resin in a fluid state is placed in the mold. The insert molding method in which the resin and the decorative sheet are integrated by injection, or the decorative sheet inserted into the mold during the injection molding is integrated with the molten resin injected into the cavity, An injection molding simultaneous decorating method for decorating the surface of the resin molded body may be used.

Since the decorative resin molded product obtained by such a molding method is used in various applications such as vehicle interior parts as described above, the three-dimensional moldability that can sufficiently follow the three-dimensional molding, and the surface is scratch-resistant. In addition to surface properties such as chemical properties and chemical resistance, high-quality feeling has been demanded due to the recent trend toward consumer luxury products. For decorative resin molded products, the addition of texture such as matting, that is, design properties, in accordance with a specific portion of the pattern has also become an important issue.
In order to solve such a problem, the present applicant has previously applied for a decorative sheet having a texture such as matting by blending silica into the surface protective layer (see paragraph 0047 in Patent Document 1). ).

JP 2010-30277 A

In the decorative sheet described in Patent Document 1, since silica having a relatively high hardness is blended in the surface protective layer, physical properties such as scratch resistance, wear resistance, and three-dimensional formability may be reduced. there were.
Under such circumstances, the present invention provides a decorative sheet having a surface protective layer having both scratch resistance, abrasion resistance, and three-dimensional formability, and a decorative resin molded product having the above characteristics. Let it be an issue.

As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by the following invention. That is, the present invention
[1] An ionizing radiation curable resin composition having at least a base film layer and a surface protective layer, the surface protective layer comprising synthetic resin particles and polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. A decorative sheet characterized by comprising a cured product, and [2] at least an injection resin layer, a base film layer, a pattern ink layer, and a surface protective layer in order, the surface protective layer being a synthetic resin A decorative resin molded article comprising a cured product of an ionizing radiation curable resin composition containing particles and polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate,
I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative resin molded product provided with the decorating sheet | seat which has a surface protection layer which combines scratch resistance, abrasion resistance, and three-dimensional moldability, and the said characteristic can be provided.

It is a schematic diagram which shows the cross section of the one aspect | mode of the decorating sheet of this invention.

[Decorative sheet]
The decorative sheet of the present invention has at least a base film layer and a surface protective layer, and the surface protective layer includes ionizing resin particles and polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. It consists of hardened | cured material of a radiation curable resin composition, It is characterized by the above-mentioned.
According to the present invention, since the synthetic resin particles are blended as the matting agent with respect to the surface protective layer containing the specific ionizing radiation curable resin, the elasticity of the synthetic resin particles allows for scratch resistance and abrasion resistance. A decorative sheet having both properties and three-dimensional formability can be obtained.

Examples of the synthetic resin particles that can be used in the present invention include urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, polyester beads, melamine beads, and urethane acrylic beads. Beads, nylon beads and acrylic beads are preferred. These synthetic resin particles may be used alone or in combination of two or more.
The particle diameter of the synthetic resin particles used in the present invention is preferably 5 to 50 μm, more preferably 5 to 30 μm, and more preferably 8 to 12 μm, from the viewpoint of imparting a smooth texture to the surface of the decorative sheet and improving the design. Further preferred.
The particle diameter in the present invention is determined by using a Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1 and using compressed air to inject the powder to be measured from a nozzle and dispersing it in the air. This refers to the measurement by the jet type dry measurement method.
The specific gravity of the synthetic resin particles is preferably 0.7 to 1.5 g / cm ³ from the viewpoint of allowing the synthetic resin particles to be present on the surface layer of the surface protective layer and improving the scratch resistance and wear resistance. more preferably ^{8~1.2g / cm 3, 0.85~1.15g / cm} 3 is more preferred.

In the present invention, such synthetic resin particles are preferably added in an amount of 1 to 60 parts by mass, more preferably 5 to 50 parts by mass, and further preferably 10 to 40 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. To do. When the blending amount of the synthetic resin particles is within the above range, matting and touch can be effectively improved.
In the present invention, the surface protective layer is formed by blending the synthetic resin particles with the ionizing radiation curable resin composition. The coating amount of the resin composition at the time of formation is 5 to 50 g / m ^2. Preferably, 5-25 g / m < ² > is more preferable, and 8-12 g / m < ² > is still more preferable. When the coating amount is within the above range, it is possible to suppress the dropping of the synthetic resin particles from the surface protective layer while suppressing the cost.
In the present invention, the synthetic resin particles may partly protrude from the surface of the surface protective layer, or may be embedded in the surface protective layer. However, it is preferable that part of the particles protrude from the surface protective layer because scratch resistance and wear resistance are improved.

Hereinafter, the configuration of the decorative sheet of the present invention will be described in detail with reference to FIG.
Drawing 1 is a mimetic diagram showing one mode of a decoration sheet of the present invention. In FIG. 1, a picture layer, a primer layer, and a surface protective layer are sequentially laminated on a base film layer. The surface protective layer is formed by curing the ionizing radiation curable resin composition.

≪Base film layer≫
The base film layer is selected in consideration of the three-dimensional moldability, compatibility with the injection resin, and the like, and typically a resin film made of a thermoplastic resin is preferably used. As the thermoplastic resin, generally, acrylonitrile / butadiene / styrene resin (hereinafter referred to as “ABS resin”), acrylonitrile / styrene / acrylic ester resin (hereinafter referred to as “ASA resin”), acrylic resin, polypropylene, polyethylene Polyolefin resins such as polycarbonate resins, vinyl chloride resins and the like are preferably used. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. Further, the base film layer can be used as a single layer sheet of these resins or a multilayer sheet of the same kind or different kinds of resins.

  The base film layer preferably has a flexural modulus of 500 to 4,000 MPa at 25 ° C., more preferably 750 to 3,000 MPa. Here, the flexural modulus is a value measured according to JIS K7171. If the flexural modulus is 500 MPa or more, the decorative sheet has sufficient rigidity, and excellent surface characteristics and moldability can be obtained. In addition, when it is 3,000 MPa or less, sufficient tension can be applied in the case of producing by roll-to-roll, and it becomes difficult for sagging to occur. Good register.

  Although the thickness of a base film layer is suitably selected according to a use, it is about 50-1000 micrometers normally, 100-700 micrometers is more preferable, and 100-500 micrometers is still more preferable. When the thickness of the base film layer is within the above range, in addition to excellent surface properties, three-dimensional formability and design properties, printing workability (productivity) is also obtained, which is advantageous from the viewpoint of cost. .

The base film layer can be subjected to a physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides, if desired, in order to improve the adhesion with the layer provided thereon.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, the base film layer may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

  The base film layer may be colored with a coloring agent or may not be colored from the viewpoint of adjusting the above-mentioned color or design, etc., colorless and transparent, colored and transparent, and translucent Any aspect may be sufficient. Although it does not specifically limit as a coloring agent used for a base material, The coloring agent which does not discolor even under the high temperature of 150 degreeC or more is preferable, and what is necessary is just to use the existing dry color, paste color, a masterbatch resin composition.

≪Picture layer≫
The pattern layer gives decorativeness to the decorative resin molded product and is usually provided on the base film layer. The pattern layer is formed by various printing methods such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and ink jet printing. As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.

As the ink composition used for the pattern layer, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The binder is not particularly limited. For example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, Examples include butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin. These may be used singly or in combination of two or more.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used. Moreover, when a metal (plating) tone design is desired, a metal thin film layer may be provided as a pattern layer by vapor deposition, sputtering, or the like.

≪Primer layer≫
The decorative sheet according to the present invention can preferably have a primer layer between the pattern layer and the surface protective layer, if desired, in order to make fine cracks and whitening difficult to occur in the stretched portion of the surface protective layer.
The thickness of the primer layer is preferably 0.1 μm or more. When it is 0.1 μm or more, the surface protective layer has an effect of preventing cracking, breaking, whitening, and the like. On the other hand, if the thickness of the primer layer is 10 μm or less, it is preferable that the three-dimensional formability does not fluctuate since the drying and curing of the coating film is stable when the primer layer is applied. From this viewpoint, the thickness of the primer layer is preferably 1 to 10 μm.

Further, the primer layer preferably has a breaking elongation at 120 ° C. of 150% or more, more preferably 200% or more, measured under the following measurement conditions. When the elongation at break is 150% or more, fine cracks and whitening hardly occur at the stretched portion of the surface protective layer during vacuum forming.
(Measurement conditions for measuring elongation at break)
In accordance with JIS K7127: 1999, a sample having a width of 25 mm × length (distance between chucks) of 50 mm × thickness of 40 ± 10 μm was formed by curing (heating at 50 ° C. for 72 hours) the primer composition constituting the primer layer. After leaving the oven at 120 ° C. and leaving it for 120 seconds, the elongation at break is measured at a tensile rate of 50 mm / min.

  The primer composition constituting the primer layer includes urethane resin, (meth) acrylic resin, (meth) acrylic / urethane copolymer resin, vinyl chloride / vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, What uses chlorinated polyethylene etc. as binder resin is used preferably, These resin can be used 1 type or in mixture of 2 or more types. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic / urethane copolymer resin are preferable.

As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used. As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.
From the aspects of adhesion with the surface protective layer after crosslinking, difficulty in interaction after laminating the surface protective layer, physical properties, and moldability, acrylic polyol or polyester polyol as a polyol, and hexamethylene diisocyanate as a crosslinking material, It is preferable to combine with 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use acrylic polyol and hexamethylene diisocyanate in combination.

  (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers. Polymers, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate / (Meth) butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.

  As the (meth) acryl / urethane copolymer resin, for example, an acrylic / urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the above-mentioned various isocyanates are used. The acrylic / urethane (polyester urethane) block copolymer resin adjusts the acrylic / urethane ratio (mass ratio) in the range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.

<Inorganic particles>
The primer layer preferably contains inorganic particles from the viewpoint of preventing blocking. As the inorganic particles, inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin are preferable.
The average particle diameter of the inorganic particles is preferably from 0.1 to 5 μm, more preferably from 1 to 5 μm, still more preferably from 2 to 5 μm, from the viewpoint of improving the design properties. Moreover, 0.01-5 mass parts is preferable with respect to 100 mass parts of resin, and, as for content of an inorganic particle, 0.1-1 mass part is more preferable.

  The primer layer is composed of a gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, silk screen solid coat, wire bar coat, flow It is formed by a normal coating method such as a coat, comma coat, flow-through coat, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method in which a primer layer or an adhesive layer is formed on a thin sheet (film substrate) and then the surface of the target layer in the decorative sheet is coated.

≪Surface protective layer≫
The surface protective layer in the present invention is a layer containing the synthetic resin particles, and cures an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate as an ionizing radiation curable resin. It is a layer obtained by doing this.

<Ionizing radiation curable resin composition>
The ionizing radiation curable resin composition refers to a composition containing an ionizing radiation curable resin. An ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ionizing radiation. The 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.
In the present invention, polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate is used as the ionizing radiation curable resin composition. In the present invention, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning.

(Polycarbonate (meth) acrylate)
The polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and (meth) acrylate in the terminal or side chain. In addition, this (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing.

  This polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl groups of polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be mentioned.

The above polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing this polycarbonate polyol is a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.
The diol compound (A) used as a raw material is represented by the general formula HO—R ¹ —OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2 -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Furthermore, alcohols having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide are added to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or in combination of two or more.

  The compound (C) serving as the carbonyl component is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formate esters such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Etc. These may be used alone or in combination of two or more.

  The polycarbonate polyol is synthesized by subjecting the above-described diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound (A) and the polyhydric alcohol (B). The charged molar ratio of the compound (C) serving as the carbonyl component with respect to is preferably 0.2 to 2 equivalents relative to the hydroxyl group of the diol compound and the polyhydric alcohol.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charge ratio is 3 or more on average in one molecule, preferably 3 to 50, more preferably 3 to 20. Within this range, a necessary amount of (meth) acrylate groups are formed by the esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.
The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

The weight average molecular weight of the polycarbonate (meth) acrylate used in the present invention is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably more than 2,000 and not more than 50,000, and particularly preferably 5,000 to 20,000.
In addition, the weight average molecular weight of the polycarbonate (meth) acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

(Acrylic silicone (meth) acrylate)
The acrylic silicone (meth) acrylate used in the present invention is not particularly limited, and a part of the acrylic resin structure is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group. As long as it has two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the. As an example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned preferably, for example.

The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator.
Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These (meth) acrylate monomers are used alone or in combination of two.

  The silicone macromonomer is synthesized, for example, by living anionic polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator and capping with a radically polymerizable unsaturated group-containing silane. As a silicone macromonomer, following formula (1);

で表される化合物が好適に用いられる。ここで、式（１）中、Ｒ¹は、炭素数１〜４のアルキル基を示し、メチル基又はｎ−ブチル基が好ましい。Ｒ²は、１価の有機基を示し、−ＣＨ＝ＣＨ₂、−Ｃ₆Ｈ₄−ＣＨ＝ＣＨ₂、−（ＣＨ₂）₃Ｏ（ＣＯ）ＣＨ＝ＣＨ₂又は−（ＣＨ₂）₃Ｏ（ＣＯ）Ｃ（ＣＨ₃）＝ＣＨ₂が好ましい。Ｒ³は、それぞれ同一であっても異なっていてもよく、炭素数１〜６の炭化水素基を示し、炭素数１〜４のアルキル基又はフェニル基が好ましく、メチル基がより好ましい。また、ｎの数値は特に制限されず、例えばシリコーンマクロモノマーの数平均分子量は１，０００〜３０，０００が好ましく、１，０００〜２０，０００がより好ましい。

Is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a methyl group or an n- butyl group are preferable. R ² represents a monovalent organic group, —CH═CH ₂ , —C ₆ H ₄ —CH═CH ₂ , — (CH ₂ ) ₃ O (CO) CH═CH ₂ or — (CH ₂ ) _3. O (CO) C (CH ₃ ) ═CH ₂ is preferred. R ^{3 s} may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group. The numerical value of n is not particularly limited, and for example, the number average molecular weight of the silicone macromonomer is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

  The acrylic silicone (meth) acrylate obtained using the above-mentioned raw materials has structural units represented by the following formulas (2), (3) and (4), for example.

式（２）、（３）及び（４）中、Ｒ¹、Ｒ³は式（１）におけるものと同義であり、Ｒ⁴は水素原子又はメチル基を示し、Ｒ⁵は上記（メタ）アクリレートモノマー中のアルキル基又はグリシジル基あるいは上記（メタ）アクリレートモノマー中のアルキル基又はグリシジル基等の官能基を有していてもよいアルキル基を示し、Ｒ⁶は（メタ）アクリロイルオキシ基を有する有機基を示す。
上述のアクリルシリコーン（メタ）アクリレートは、１種を単独で又は２種を組み合わせて用いられる。

In formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the (meth) acrylate. An alkyl group or glycidyl group in the monomer, or an alkyl group which may have a functional group such as an alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ is an organic compound having a (meth) acryloyloxy group. Indicates a group.
The above-mentioned acrylic silicone (meth) acrylates are used alone or in combination of two.

  The acrylic silicone (meth) acrylate has a weight average molecular weight in terms of standard polystyrene as measured by GPC analysis of preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of improving the three-dimensional formability, chemical resistance and scratch resistance, it is particularly preferably 2,000 to 100,000.

  Moreover, it is preferable that the average molecular weight between crosslinking points of acrylic silicone (meth) acrylate is 100-2,500. If the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional formability, and if it is 2,500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, still more preferably 100 to 1,000.

  In the ionizing radiation curable resin composition, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate may be used alone or in combination of two or more.

(Multifunctional (meth) acrylate)
The ionizing radiation curable resin composition used in the present invention may contain a polyfunctional (meth) acrylate. In the present invention, the polyfunctional (meth) acrylate is not particularly limited as long as it is a bifunctional or higher (meth) acrylate. However, trifunctional or higher functional (meth) acrylates are preferred from the viewpoint of curability. Here, bifunctional means having two (meth) acryloyl groups which are ethylenically unsaturated bonds in a molecule | numerator.
The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.

Preferred examples of the polyfunctional (meth) acrylate oligomer include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates.
In addition, polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones that have polysiloxane bonds in the main chain (meta ) Acrylate oligomer, aminoplast resin (meth) acrylate oligomer obtained by modifying aminoplast resin having many reactive groups in a small molecule, and the like. Further, in combination with a polyfunctional (meth) acrylate oligomer, an oligomer having a cation polymerizable functional group in a molecule such as a novolac type epoxy resin, a bisphenol type epoxy resin, an aliphatic vinyl ether, or an aromatic vinyl ether may be used. .
The weight average molecular weight of these oligomers is preferably 1,000 to 20,000, and more preferably 1,000 to 10,000.

  Examples of the polyfunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and 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 dipentaeryth Ritoruhekisa (meth) acrylate. These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the present invention, the content of the polyfunctional (meth) acrylate is such that the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and the polyfunctional (meth) acrylate is 98: 2 to 60:40. It is preferable. When the mass ratio is smaller than 98: 2 (that is, when the amount of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate is 98% by mass or less), the scratch resistance is not lowered. On the other hand, when the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is greater than 60:40 (that is, the amount of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate) 3), the three-dimensional formability does not deteriorate. Preferably, the mass ratio of polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is 95: 5 to 65:35, more preferably 90:10 to 65:35.

In the present invention, together with the polyfunctional (meth) acrylate and the like, a monofunctional (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired for the purpose of reducing the viscosity. These monofunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.
Furthermore, in the present invention, for the purpose of improving moldability, a thermoplastic resin may be blended within a range that does not impair other performances. Specifically, an acrylic resin, an acrylic modified polyolefin resin, a chlorinated polyolefin resin, a polyamide resin, a rubber resin, or the like can be blended. These may be used alone or in combination of two or more.

  When using an ultraviolet curable resin composition as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator to 100 parts by mass of the ultraviolet curable 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 composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition 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.

Moreover, various additives can be mix | blended with the ionizing radiation curable resin composition which comprises a surface protective layer according to the desired physical property of the surface protective layer obtained. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, and leveling agents. , A thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and an anti-friction agent that can impart slipperiness such as wax. These additives can be appropriately selected from those commonly used.
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. Moreover, it can also be copolymerized and used to such an extent that the performance (a scratch resistance and three-dimensional moldability) as a surface protective layer is not impaired.

(Formation of surface protective layer)
Formation of the surface protective layer can be obtained by preparing a coating solution containing the above-mentioned ionizing radiation curable resin composition and synthetic resin particles, and applying and curing the coating solution. In addition, the viscosity of a coating liquid should just be a viscosity which can form a non-surface protective layer on the surface of a base material with the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the prepared coating liquid is coated on the base film layer, the pattern layer, or the primer layer so as to have the above coating amount, gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. Is applied by a known method, preferably gravure coating, to form an uncured resin layer.

In the present invention, the uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming a surface protective layer. 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. preferable.
In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a substrate that deteriorates due to an electron beam as the substrate film layer, the transmission depth of the electron beam and the thickness of the resin layer By selecting an accelerating voltage so as to be substantially equal, it is possible to suppress the irradiation of the extra electron beam to the base film layer, and to minimize the deterioration of the base material due to the excess electron beam. Can do.
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).
Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or 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.

  The surface protective layer thus formed has various functions by adding various additives, for example, a so-called hard coating function, anti-fogging coating function, and anti-fouling coating having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.

  In the present invention, the decorative sheet with a single-layer specification shown in FIG. 1 may be used, or a decorative sheet with a multi-layer specification may be used. Examples of the multi-layer decorative sheet include a base film layer provided with a concealing layer, a picture layer, a transparent resin film layer, a primer layer, and a surface protective layer in this order. Even when the decorative sheet has a multi-layer specification, each layer can be made of the same material as that of the single-layer specification. On the other hand, it is preferable to use the following materials for the concealment layer and the transparent resin film layer.

≪Hidden layer≫
The hiding layer is usually formed with an opaque color, and a so-called solid printing layer having a thickness of about 1 to 20 μm is preferably used. The ink composition for forming the concealing layer can be appropriately selected from those used for the above-described pattern layer and employed. By providing the concealing layer, it is possible to suppress the influence of color change and variation on the surface of the base film layer.
The concealing layer is a normal printing method such as gravure printing, offset printing, silk screen printing, printing from a transfer sheet, inkjet printing, gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating. It is formed by the usual coating method such as.

≪Transparent resin film layer≫
The resin film forming the transparent resin film layer is appropriately determined in consideration of transparency, three-dimensional formability, shape stability, chemical resistance, etc., but a thermoplastic resin film is preferable. As thermoplastic resins, generally acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylonitrile / butadiene / styrene resins (hereinafter referred to as “ABS resins”), polyethylene terephthalate (PET) and polyethylene naphthalate ( Polyester resin such as PEN), vinyl chloride resin or the like is used. Among these, from the viewpoint of scratch resistance and chemical resistance, acrylic resins, polyolefin resins, polycarbonate resins, and polyester resins are preferable, acrylic resins and polyester resins are more preferable, and polyester resins are more preferable.

The transparent resin film layer can be subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as desired in order to improve the adhesion with the layer provided on the transparent resin film layer. These physical or chemical surface treatments are similar to the treatments that can be performed on the base film layer.
The thickness of the transparent resin film layer is not particularly limited, but is preferably 10 to 200 μm and more preferably 15 to 150 μm in consideration of cost, three-dimensional formability, shape stability, and the like.

In addition, in this invention, in order to improve adhesiveness with injection resin, an adhesive layer can be provided in the back surface (surface on the opposite side to a surface protective layer) of a decorating sheet depending on necessity.
≪Adhesive layer≫
A thermoplastic resin or a curable resin is used for the adhesive layer depending on the injection resin. Examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride / vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. Can be used alone or in combination of two or more. Examples of the thermosetting resin include urethane resin and epoxy resin.

  The decorative sheet of the present invention can obtain a sufficiently high three-dimensional formability even when the thickness of the surface protective layer is larger than that of the conventional one. For example, it is also useful as a decorative sheet for vehicle exterior parts and the like.

[Decorative resin molded product]
The decorative resin molded product of the present invention has at least an injection resin layer, a base film layer, a pattern ink layer, and a surface protective layer in this order, and the surface protective layer comprises synthetic resin particles, polycarbonate (meth) acrylate, and / or Or it consists of hardened | cured material of an ionizing radiation-curable resin composition containing acrylic silicone (meth) acrylate. More specifically, the decorative resin molded product of the present invention uses the decorative sheet of the present invention, and various injections such as an insert molding method, an injection molding simultaneous decorating method, a blow molding method, and a gas injection molding method. It can be produced by a molding method, preferably an insert molding method and a simultaneous injection molding method.
In the decorative resin molded product of the present invention, for example, the above-described adhesive layer may be provided between the injection resin layer and the base film layer as necessary.

  In the insert molding method, in the vacuum forming process, the decorative sheet of the present invention is vacuum formed (offline pre-molding) into a molded product surface shape in advance using a vacuum forming die, and then the excess sheet is trimmed as necessary to form a molded sheet. Get. This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. To produce decorative resin molded products.

  As the injection resin layer, a resin corresponding to the application is used, and a thermoplastic resin such as a polyolefin resin such as polyethylene or polypropylene, an ABS resin, a styrene resin, a polycarbonate resin, an acrylic resin, or a vinyl chloride resin is representative. . Also, thermosetting resins such as urethane resins and epoxy resins can be used depending on the application.

Next, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) with this female mold ), The injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated with the outer surface of the resin molding simultaneously with the injection molding, Manufactures decorative resin molded products.
In the injection molding simultaneous decorating method, the decorative sheet receives the thermal pressure from the injection resin, so if the decorative sheet is close to the flat plate and the aperture of the decorative sheet is small, the decorative sheet may or may not be preheated. .
In addition, as injection resin used here, the thing similar to what was demonstrated by the insert molding method can be used.

  The decorative resin molded product produced as described above has good three-dimensional formability without cracks in the surface protective layer during the molding process, and the surface has high scratch resistance. In addition, the solvent resistance and chemical resistance are high.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
In addition, the material used by the Example and the comparative example is as follows.
(Ionizing radiation curable resin composition (EB1))
Bifunctional polycarbonate acrylate (weight average molecular weight = 10,000): 80 parts by mass Hexafunctional urethane acrylate oligomer (weight average molecular weight = 6,000): 20 parts by mass (ionizing radiation curable resin composition (EB2))
Acrylic silicone acrylate (weight average molecular weight = 20,000): 70 parts by mass
(Average molecular weight between crosslinking points after curing = 200)
Hexafunctional urethane acrylate oligomer (weight average molecular weight = 5,000): 30 parts by mass

Evaluation method (1) Three-dimensional formability (vacuum forming)
About the decorative sheet obtained by each Example and the comparative example, it vacuum-formed on the conditions shown below, and evaluated by the external appearance after shaping | molding. The evaluation criteria are as follows.
◎: No fine coating cracking or whitening occurs in a part of the three-dimensional shape portion or the maximum stretched portion, and there is no practical problem.
○: Fine coating cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, but there was no practical problem.
Δ: Slight coating cracking or whitening occurred in a part of the three-dimensional shape portion or the maximum stretched portion.
X: The coating film cracking and whitening were observed in the surface protective layer without following the shape of the mold.
<Conditions for vacuum forming>
The decorative sheet is heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming is performed using a vacuum forming die (maximum draw ratio: 100%) to form the internal shape of the die. After the sheet is cooled, the decorative sheet is released from the mold.

(2) Surface state The decorative sheet and the decorative molded product were observed visually, and the surface state was evaluated according to the following criteria.
O: The ionizing radiation curable resin can be uniformly applied without unevenness, unevenness, and matting agent aggregation.
Δ: The ionizing radiation curable resin was applied to some extent without aggregation of unevenness, unevenness, and matting agent.
X: The ionizing radiation curable resin has unevenness, irregularities, and aggregation of the matting agent, and it cannot be applied uniformly.
(3) Abrasion resistance The decorative sheet was subjected to an abrasion test with a Taber abrasion machine (abrasion wheel: CS-10, condition: 1 kg × 500 rotations) and evaluated according to the following criteria.
A: There is no exposure of the fabric.
O: There is a slight exposure of the fabric and the pattern is removed.
Δ: The dough is exposed more than half and the pattern is removed.
X: There is remarkable exposure of the fabric, and the pattern is completely removed.
(4) Scratch resistance About the decorative sheet obtained by each Example and the comparative example, the external appearance of the test piece after 10 reciprocations was evaluated using # 0000 steel wool with a load of 1.5 kgf. The evaluation criteria are as follows.
A: No scratches were observed on the surface, and the coating film was not scraped or whitened.
○: Although fine scratches were observed on the surface, the coating film was not scraped or whitened.
Δ: Minor scratches were observed on the surface, and the coating film was scraped or whitened.
X: The surface was markedly scratched, and the coating film was scraped or whitened.
(5) Tactile sensation Five evaluators touched the surface of the coating film of each sample lightly and evaluated the touch.
◎: When all 5 people feel soft touch and slime feeling 〇; When 3 or 4 people feel soft touch feeling and slime feeling ×: Less than 2 people feel soft touch feeling and slime feeling If

(6) Measurement of molecular weight 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. . In addition, the weight average molecular weight in this invention performed polystyrene conversion.

Example 1
An ABS resin film (flexural modulus: 1,800 MPa, thickness: 400 μm, hereinafter referred to as “ABS”) is used as the base film layer, and a vinyl chloride / vinyl acetate copolymer resin composition is formed on the surface of the film. A woodgrain pattern layer was formed by gravure printing using a printing ink comprising:
A primer composition containing acrylic polyol and hexamethylene diisocyanate (hexamethylene diisocyanate was blended so as to have the same NCO equivalent as the OH equivalent of acrylic polyol) on the pattern layer was gravure so as to have a thickness of 2 μm. The primer layer was provided by applying by reverse. Next, the ionizing radiation curable resin composition (EB1) having the above composition containing urethane beads is applied on the primer layer so that the application amount is 10 g / m ^2, and an accelerating voltage is applied to the uncured resin composition layer. The surface protection layer was formed by irradiating an electron beam of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin composition, thereby obtaining a decorative sheet. About the obtained decorating sheet, it evaluated by the said method. The evaluation results are shown in Table 1.

Example 2
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that EB2 was used as the resin composition constituting the surface protective layer. The results are shown in Table 1.

Example 3
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that the blending amount of the synthetic resin particles was changed as shown in Table 1. The results are shown in Table 1.

Example 4
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that the particle diameter of the synthetic resin particles was changed as shown in Table 1. The results are shown in Table 1.

Example 5
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that the synthetic resin particles were changed to nylon beads. The results are shown in Table 1.

Example 6
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that a molded PET film having a thickness of 50 μm was provided as a transparent resin film layer between the pattern layer and the primer layer. The results are shown in Table 1.

Example 7
A decorative sheet was used in the same manner as in Example 6 except that an acrylic film having a thickness of 125 μm was used as the transparent resin film layer, and an ABS resin film having a thickness of 350 μm was used as the base film layer. Produced and evaluated. The results are shown in Table 1.

Comparative Example 1
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that silica was used in place of the urethane beads. The results are shown in Table 1.

Comparative Example 2
A decorative sheet was produced and evaluated in the same manner as in Example 1 except that the synthetic resin particles were not used. The results are shown in Table 1.

The decorative sheet of the present invention has a rapid temperature drop, a rapid stretching speed, and a high degree of stretching from a heating temperature of about 160 ° C. to a temperature at the time of contact with the mold in a normal insert molding method and injection molding simultaneous decoration method. Even under these conditions, cracks and cracks do not occur, and the three-dimensional formability is good.
Moreover, it was confirmed that the surface of the manufactured decorative resin molded product has excellent scratch resistance.

  The decorative sheet of the present invention is used in various decorative resin molded products, for example, interior materials or exterior materials of vehicles such as automobiles, construction members such as baseboards, and fringes, joinery such as window frames and door frames, and walls. It is suitably used for decorative resin molded products for uses such as interior materials for buildings such as floors and ceilings, housings of household electrical appliances such as television receivers and air conditioners, and containers.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base film layer 3 Picture layer 4 Primer layer 5 Surface protective layer 6 Synthetic resin particles

Claims (7)

  Curing of an ionizing radiation curable resin composition having at least a base film layer and a surface protective layer, the surface protective layer comprising synthetic resin particles and polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate A decorative sheet characterized by comprising a thing.   The decorative sheet according to claim 1, wherein the synthetic resin particles are at least one selected from urethane beads, nylon beads, and acrylic beads.   The decorative sheet according to claim 1 or 2, wherein the particle diameter of the synthetic resin particles is 5 to 50 µm.   The decoration sheet according to any one of claims 1 to 3, wherein the addition amount of the synthetic resin particles is 1 to 60 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.   The decorative sheet according to any one of claims 1 to 4, wherein the acrylic silicone (meth) acrylate has a weight average molecular weight of 1,000 to 150,000.   The decorative sheet according to any one of claims 1 to 5, wherein an average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is 100 to 2,500.   At least an injection resin layer, a base film layer, a pattern ink layer, and a surface protective layer are provided in this order, and the surface protective layer contains synthetic resin particles and polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. A decorative resin molded product comprising a cured product of an ionizing radiation curable resin composition.

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