JP2008105420A - Decorative sheet for three-dimensional processing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet for three-dimensional processing, having a good molding property and mold releasability, and improved in scratch resistance and solvent resistance, free from cracks, damages or the like on the surface caused by molding. <P>SOLUTION: In the decorative sheet for three-dimensional processing having at least surface protective layers laminated on a support body, the decorative sheet has a breaking elongation (following JIS K 7127) more than 300% in a temperature higher than the heat distortion temperature by 40°C measured by the ASTM D648 method of the support body, and the surface protective layer is formed by cross-linking and curing an ionizing radiation curable resin composition and has a film as thick as 0.2 to 6.0 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to interior materials or exterior materials for vehicles such as automobiles, construction members such as skirting boards and circular edges, furniture such as window frames and door frames, interior materials for buildings such as walls, floors, and ceilings, and television receivers. The present invention relates to a decorative sheet for three-dimensional processing used in a decorative molded body for uses such as housings and containers of home appliances such as air conditioners.

DESCRIPTION OF RELATED ART Conventionally, the decorative molded body manufactured by shape | molding the sheet | seat which decorated the surface of adherends, such as a resin molding, is used for various uses. A decorative molded body whose surface is decorated by this decorative sheet molding method is obtained. Therefore, since the decorative sheet used in this manufacturing method is decorated by extending the sheet, molding performance that does not cause cracks on the surface by molding is required, and at the same time, from the viewpoint of use of the molded product, scratch resistance Also, good solvent resistance and the like are required.
For example, in Patent Document 1, a laminated sheet for covering the surface of an injection molded article obtained by laminating a clear cured layer of a crosslinkable composition having a specific glass transition temperature and crosslink density on a sheet-like base material of a thermoplastic resin. A laminated sheet having a breaking elongation of 30 to 300% has been proposed.
However, in three-dimensional processing, in order to prevent the decorative sheet from cracking, it is not satisfactory at a breaking elongation of 30 to 300%, and a sheet that can be stretched by 300% or more has poor mold separation, scratch resistance, The fact is that the solvent resistance is also poor.
Therefore, further improvements in formability during three-dimensional processing, mold separation, scratch resistance, solvent resistance, and the like are required.

JP 2000-202975 A

  Under such circumstances, the present invention is a three-dimensional that has good moldability, good mold separation, no cracks, scratches, etc. on the surface due to molding, and improved scratch resistance and solvent resistance. It is an object to provide a decorative sheet for processing.

As a result of intensive studies in order to achieve the above object, the present inventor has found that the above object can be solved by improving the surface protective layer. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.
1. A decorative sheet for three-dimensional processing formed by laminating at least a surface protective layer on a support, wherein the decorative sheet for three-dimensional processing is at a temperature 40 ° C higher than the thermal deformation temperature of the support according to ASTM D648 method. Has a breaking elongation exceeding 300% (based on JIS K 7127), and the surface protective layer is obtained by crosslinking and curing the ionizing radiation curable resin composition, and has a film thickness of 0.2 to 6.0 μm. A decorative sheet for three-dimensional processing, comprising:
2. The three-dimensional processing according to 1 above, wherein the storage elastic modulus of the surface protective layer at 140 ° C. measured under the following measurement conditions is in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa. Decorative sheet.
Storage elastic modulus measurement conditions: In accordance with JIS K7244-1 and 7244-4, a sheet of 10 mm width and 15 μm thickness formed by crosslinking and curing the ionizing radiation curable resin composition was 10 mm in distance between clamps. The measurement is performed at a temperature of 30 ° C., an end temperature of 180 ° C., a temperature increase rate of 5 ° C./min, and a measurement frequency of 1 Hz.
3. 3. The three-dimensional processing according to 1 or 2 above, wherein the ionizing radiation curable resin composition is a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a ratio (mass ratio) of 75:25 to 20:80. Decorative sheet.
4). The decorative sheet for three-dimensional processing according to any one of 1 to 3, wherein a transparent thermoplastic resin layer is further provided between the support and the surface protective layer.
5. 5. The decorative sheet for three-dimensional processing as described in 4 above, wherein a second thermoplastic resin layer is further provided between the support and the transparent thermoplastic resin layer.
6). The decorative sheet for three-dimensional processing according to any one of 3 to 5, wherein the ionizing radiation curable resin is an electron beam curable resin.
7). The decorative sheet for three-dimensional processing according to any one of the above 1 to 6, wherein the three-dimensional processing is insert molding.

  The decorative sheet for three-dimensional processing of the present invention has good moldability and good mold separation, does not cause cracks or scratches on the surface by molding, and has high scratch resistance and solvent resistance.

Hereinafter, the present invention will be described with reference to the drawings. Drawing 1 is a mimetic diagram showing the section of the 1st embodiment of the decoration sheet for three-dimensional processing of the present invention.
The decorative sheet 10 for three-dimensional processing of the present invention is formed by laminating at least a surface protective layer 12 on a support 11.
The stretchability of the decorative sheet 10 of the present invention is greatly affected by the stretchability of the support 11. Therefore, it is required that the decorative sheet 10 has a breaking elongation exceeding 300% at a temperature 40 ° C. higher than the thermal deformation temperature of the support 11 by the ASTM D648 method. This is for preventing surface cracks or cracks of the decorative sheet 10 in the three-dimensional processing of a complicated shape. From this viewpoint, a breaking elongation of 380% or more is preferable. Moreover, if it is 500% or less, since a required film thickness can be ensured after extending | stretching and shape retention property becomes favorable, it is preferable. In addition, the support body 11 used for the decorative sheet 10 of the present invention may be either a single layer or a plurality of layers.
Moreover, it is required that the surface protective layer 12 provided in the decorative sheet 10 of the present invention has a film thickness of 0.2 to 6.0 μm. This is because if the film thickness is less than 0.2 μm, the scratch resistance and solvent resistance decrease, and if it exceeds 6.0 μm, the moldability, elongation at break and scratch resistance decrease. From this viewpoint, a film thickness of 0.7 to 6.0 μm is preferable.

2 to 5 are schematic views showing cross sections of other embodiments of the decorative sheet for three-dimensional processing of the present invention. However, the decorative sheet for three-dimensional processing of the present invention is not limited to these embodiments.
In the second embodiment of the decorative sheet 10 of the present invention shown in FIG. 2, a transparent thermoplastic resin layer 13 is further provided between the support 11 and the surface protective layer 12.
In the third embodiment of the decorative sheet 10 of the present invention illustrated in FIG. 3, a second thermoplastic resin layer 14 is further provided between the support 11 and the transparent thermoplastic resin layer 13.
In the fourth embodiment of the decorative sheet 10 of the present invention shown in FIG. 4, an adhesive layer 16, a printing layer 15, a transparent thermoplastic resin layer 13, a primer layer 17, and a surface protective layer are formed on a support 11. 12 are laminated. Here, the printing layer 15 may be laminated on either the front side or the back side of the transparent thermoplastic resin layer 13, or may be laminated on the surface of the support 11.
Moreover, the 5th embodiment of the decorating sheet 10 of this invention described in FIG. 5 is adhesive layer 16b on the support body 11, the 2nd thermoplastic resin layer 14, the printing layer 15, and adhesive layer 16a. The transparent thermoplastic resin layer 13, the primer layer 17, and the surface protective layer 12 are laminated. Here, the printing layer 15 may be laminated on either the front side or the back side of the transparent thermoplastic resin layer 13. In addition, when the second thermoplastic resin layer 14 is transparent or translucent, the printing layer 15 may be laminated on the surface of the support 11 or the back side of the second thermoplastic resin layer 14. The same material may be used for the adhesive layers 16a and 16b, or they may be different.

  The surface protective layer 12 according to the present invention needs to be formed by crosslinking and curing an ionizing radiation curable resin composition in order to achieve a scratch- and solvent-resistant surface protective function. Here, the ionizing radiation curable resin is a resin having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.

The surface protective layer 12 according to the present invention preferably has a storage elastic modulus in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa. When the storage elastic modulus is 1.2 × 10 ⁸ Pa or less, the surface protective layer can be molded without cracking during vacuum molding. In the case of a cross-linked resin, the higher the storage elastic modulus in the rubber state, the lower the average molecular weight between cross-linking points, that is, the higher the cross-linking density, so that the surface scratch resistance, solvent resistance, etc. are improved. Therefore, if the storage elastic modulus is within this range, a well-decorated decorative sheet can be obtained that satisfies a high level of moldability and surface scratch resistance after the surface protective layer is formed.

  As the polymerizable monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate having two or more functions is preferable. . Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. 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, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, propionic acid modified dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaery Ritoruhekisa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  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, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule (a bifunctional, trifunctional, tetrafunctional or higher polyfunctional oligomer), such as an epoxy (meth) acrylate, urethane ( Examples include meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates. 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, with (meth) acrylic acid, a polyurethane oligomer obtained by a reaction between polyether polyol or polyester polyol and polyisocyanate. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acids and polyhydric alcohols 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.

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. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  As the ionizing radiation curable resin composition according to the present invention, an electron beam curable resin composition is preferably used. 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.

  In the present invention, the ionizing radiation curable resin composition is preferably a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a ratio (mass ratio) of 75:25 to 20:80. Within this range, the balance of formability, scratch resistance and solvent resistance after cross-linking and curing to form the surface protective layer is good. In this respect, the mass ratio of the ionizing radiation curable resin and the thermoplastic resin is more preferably in the range of 60:40 to 20:80, and particularly preferably in the range of 60:40 to 25:75.

  Examples of the thermoplastic resin used in the ionizing radiation curable resin composition according to the present invention include (meth) acrylic resins such as poly (meth) acrylic acid esters, polyvinyl acetals (butyral resin) such as polyvinyl butyral, polyethylene terephthalate, Polyester resins such as polybutylene terephthalate, vinyl chloride resins, urethane resins, polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene and α-methylstyrene, acetal resins such as polyamide, polycarbonate, and polyoxymethylene, ethylene-4 fluorine Fluorine resins such as fluorinated ethylene copolymer, polyimide, polylactic acid, polyvinyl acetal resin, liquid crystalline polyester resin, and the like, and these may be used alone or in combination of two or more. Good. 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 as a main component are preferred in the present invention, and in particular, those obtained by polymerizing a monomer containing at least a (meth) acrylic acid ester as a monomer component. preferable.
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. 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 scratch resistance and the 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.
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 mol of the structural unit derived from (meth) acrylic acid ester, the scratch resistance and the solvent resistance are also improved. .

The (meth) acrylic resin preferably has a weight average molecular weight in the range of 60,000 to 150,000. When the weight average molecular weight is within this range, the moldability after crosslinking and curing to form the surface protective layer, and the surface scratch resistance and solvent resistance can all be obtained at a high level.
Here, the weight average molecular weight was measured by gel permeation chromatography (GPC). For the measurement, a high-speed GPC apparatus manufactured by Tosoh Corporation was used. The column used was TSKgel αM (trade name) 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.

Moreover, various additives can be mix | blended with the ionizing radiation-curable resin composition which concerns on this invention according to the desired physical property of the cured resin layer obtained. Examples of the additive include a weather resistance improver, a scratch 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. As the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle size of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-) is specifically mentioned. 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. Further, 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 scratch resistance improver include spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide as inorganic 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. Examples of organic substances include waxes such as polyethylene wax, and synthetic resin beads such as crosslinked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving scratch resistance, and it is relatively easy to obtain spherical particles.
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, 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.

  In addition, depending on the desired physical properties of the surface protective layer 12 obtained by curing the ionizing radiation curable resin composition according to the present invention, various additives may be added for various functions such as high hardness and scratch resistance. A so-called hard coat function, anti-fogging coat function, anti-fouling coating function, anti-glare coating function, anti-reflection coating function, ultraviolet shielding coating function, infrared shielding coating function and the like can be imparted.

The transparent thermoplastic resin layer 13 laminated on demand for the purpose of expanding the design effect or the like on the decorative sheet 10 of the present invention is selected in consideration of transparency and suitability for vacuum forming. The resin film made of a plastic resin is preferably formed of a single layer sheet or a multilayer sheet single layer or multilayer of the same or different resins.
Examples of the thermoplastic resin used for the transparent thermoplastic resin layer 13 include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter referred to as “ABS resins”), polyethylene terephthalate resins, poly Polyester resins such as butylene terephthalate resin, vinyl chloride resin, cycloolefin resin, polyimide resin and the like are used. Among these, acrylic resin, polypropylene resin, polyethylene resin, polycarbonate resin, ABS resin or polyester resin are preferable in terms of transparency and moldability.
As an acrylic resin, for example, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer An acrylic resin such as (meth) acrylate refers to acrylate or methacrylate.
The thickness of the transparent thermoplastic resin layer 13 is selected according to the application, but is usually about 20 to 1,000 μm, and about 50 to 500 μm is preferable in consideration of cost and the like.

The transparent thermoplastic resin layer 13 according to the present invention has a physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides as desired in order to improve the adhesion with the layer provided thereon. Can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and 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.
Further, the transparent thermoplastic resin layer 13 may be subjected to a treatment such as forming a primer layer 17 if desired, and a coating for adjusting the color or a pattern from a design viewpoint is formed in advance as the printing layer 15. May be.

The second thermoplastic resin layer 14 laminated on the decorative sheet 10 of the present invention as desired is typically a single layer sheet of a resin film made of a thermoplastic resin or a multilayer sheet single layer of the same or different resin. Or it is preferable to form with a multilayer. The second thermoplastic resin layer 14 may be provided as a colored thermoplastic resin layer for the purpose of imparting concealment or aiming at a design effect, or a transparent or translucent thermoplastic resin aiming at another design effect. It may be provided as a layer.
Examples of the thermoplastic resin used for the second thermoplastic resin layer 14 include the same ones as the transparent thermoplastic resin layer 13. As a coloring agent used for a colored thermoplastic resin layer, what is used for the printing layer 15 mentioned later is mentioned.
Although the thickness of the 2nd thermoplastic resin layer 14 is selected according to a use, it is about 20-1,000 micrometers normally, and when considering the cost etc., about 50-500 micrometers is preferable.

As the support 11 used in the decorative sheet 10 of the present invention, an ABS resin, a polyolefin resin, a styrene resin, an acrylic resin, a vinyl chloride resin, a polycarbonate resin, or the like is preferable. As the polyolefin resin, a polypropylene resin is preferable. Among these resins, an ABS resin and a polypropylene resin are more preferable, and an ABS resin is particularly preferable in order to prevent cracks, scratches and the like on the surface of the molded body. Since the support 11 is used to reinforce the decorative sheet 10 and maintain the form of an integrated product, the support 11 preferably has a thickness of 100 to 500 μm.
As described above, the support 11 may be either a single layer or a plurality of layers, but as a case of a plurality of layers, for example, the surface of the support 11 is subjected to blocking prevention treatment, primer treatment or acid treatment, and blocking on the surface. The case where a prevention layer, a primer layer, or an acid modification layer is formed is mentioned.
In addition, a resin layer containing a pigment, a matting agent, or the like, for example, a mat resin layer, may be formed between the support 11 and the surface protective layer 12 in order to produce a design that cannot be expressed only by the printing layer 15.

The printing layer 15 that is optionally laminated as shown in FIG. 4 or 5 is preferably composed of a picture layer and / or a concealing layer.
The pattern layer gives decorativeness to the resin molded body, and is formed by printing various patterns using ink and a printing machine. 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 or 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 pattern ink 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, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Arbitrary resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins and the like may be used alone 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.

The hiding layer is generally a layer provided as desired, and is often provided for the purpose of preventing the pattern color of the decorative sheet from being affected by changes and variations in the color of the surface of the support 11. Usually, an opaque color is often used, and a so-called solid print layer having a thickness of about 1 to 20 μm is preferably used. The concealing layer is formed by known printing or coating means such as gravure printing or roll coating.
When the second thermoplastic resin layer 14 is laminated as a colored thermoplastic resin and exhibits concealing properties, the concealing layer as the printing layer 15 may not be provided.

In this invention, in order to improve the adhesiveness of each layer, you may provide the adhesive bond layer 16 between each layer depending on necessity. For example, as shown in FIGS. 4 and 5, adhesive layers 16 and 16 b can be provided between the support 11 and the printing layer 15 in order to improve the adhesion between the support 11 and the printing layer 15. Further, as shown in FIG. 5, in order to improve the adhesion between the transparent thermoplastic resin layer 13 and the printing layer 15, an adhesive layer 16 a is optionally provided between the transparent thermoplastic resin layer 13 and the printing layer 15. Can be provided.
As the adhesive layer, a thermoplastic resin or a curable resin is used depending on the injection resin. Examples of the thermoplastic resin 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 resins (for example, a two-component curable type composed of an isocyanate curing agent and various polyols), epoxy resins, and the like.
The thickness of the adhesive layer may be appropriately determined according to the required physical properties and the like, but is usually about 1 to 100 μm. The method for forming the adhesive layer is not particularly limited, but usually, known printing or coating means such as gravure printing, roll coating, etc. as an ink or coating liquid comprising a resin liquid obtained by diluting the above resin with a diluent solvent. To form. Further, in the adhesive layer, in order to adjust and improve various physical properties such as printing (or coating) suitability of the ink (or coating liquid), other auxiliary materials such as constitution Various additives such as pigments may be added.

  In the present invention, the primer layer 17 can be appropriately provided in order to improve the adhesion between the surface protective layer 12 and the transparent thermoplastic resin layer 13. Examples of the material of the primer layer 17 provided as desired include, for example, an acrylic resin, a urethane resin (for example, a two-component curing type composed of an isocyanate curing agent and various polyols), an acrylic urethane resin, a vinyl chloride-vinyl acetate copolymer, And ethylene-vinyl acetate copolymer. A two-component curable urethane resin is preferable from the viewpoint that the adhesion between the surface protective layer 12 and the transparent thermoplastic resin layer 13 is enhanced and the weather resistance is enhanced, and the adhesiveness hardly deteriorates with time.

The surface protective layer 12 is formed by preparing a coating solution containing the ionizing radiation curable resin composition according to the present invention described above, and applying this to the surface of the support 11 or the transparent thermoplastic resin layer 13 or the primer layer 17. It can obtain by apply | coating through and carrying out cross-linking hardening. In addition, the viscosity of a coating liquid should just be a viscosity which can form a non-hardened resin layer on the surface of a base material by the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the prepared coating liquid is applied to the surface of the transparent thermoplastic resin layer 13 so that the thickness after curing is as described above, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, 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 an electron beam and ultraviolet rays to cure the uncured resin 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 a resin deteriorated by an electron beam is used as the transparent thermoplastic resin layer 13, the transmission depth of the electron beam and the resin layer By selecting an accelerating voltage so that the thicknesses are substantially equal, it is possible to suppress the irradiation of an extra electron beam to the transparent thermoplastic resin layer 13, and minimize the deterioration of the resin due to the excess electron beam. You can stay.
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, and a high frequency type. 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.

In the case of FIG. 1, the method for producing the decorative sheet 10 for three-dimensional processing of the present invention may be printed or coated with the surface protective layer 12 on the surface of the support 11. In the case of FIG. 3, for example, the surface protective layer 12 may be laminated on the surface of the transparent thermoplastic resin layer 13, and the second thermoplastic resin layer 14 and the support 11 may be laminated sequentially on the back surface.
In the case of FIG. 4, for example, the primer layer 17 is laminated on the surface side of the transparent thermoplastic resin layer 13, and the surface protective layer 12 is further laminated on the surface, and the printing layer is formed on the back surface side of the transparent thermoplastic resin layer 13. 15, ie, a picture layer and / or a concealing layer are sequentially laminated. Then, after laminating the adhesive layer 16 on the printing layer 15, the support 11 is laminated.
An example of the manufacturing method in the case where the second thermoplastic resin layer 14 is provided as shown in FIG. As shown in FIG. 4, the primer layer 17 is laminated on the surface side of the transparent thermoplastic resin layer 13, and the surface protective layer 12 is further laminated on the surface. Moreover, the printing layer 15 is laminated | stacked on the surface side of the 2nd thermoplastic resin layer 14, and the adhesive bond layer 16a is further laminated | stacked on the surface. Thereafter, the back surface side of the transparent thermoplastic resin layer 13 and the adhesive layer 16a on the front surface side of the second thermoplastic resin layer 14 are bonded together by lamination or the like. Thereafter, the adhesive layer 16 b is laminated on the back side of the second thermoplastic resin layer 14 by coating or the like, and is bonded to the support 11.
Usually, in FIG. 2, 3 or 5, for example, when the transparent thermoplastic resin layer 13 or the second thermoplastic resin layer 14 and the support 11 are the same resin material, the adhesive layer 16 may not be necessary. For example, in FIG. 3, when the transparent thermoplastic resin layer 13 and the second thermoplastic resin layer 14 are the same resin material, the adhesive layer 16 may not be necessary.
The order of application described above may be changed as appropriate for the convenience of manufacturing.
The above lamination is performed by known printing or coating means such as gravure printing or roll coating.

  In an insert molding method suitable as a three-dimensional processing method using the decorative sheet 10 of the present invention, in the vacuum forming step, the decorative sheet 10 of the present invention is previously vacuum-formed into a molded body surface shape by a vacuum forming die, and then Trim the excess part as necessary to obtain a molded sheet. This molded sheet is inserted into an injection mold, the injection mold is clamped, a resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated with the outer surface of the resin molded product. A decorative resin molding is manufactured.

  As the injection resin, 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. In addition, thermosetting resins such as urethane resins and epoxy resins can be used depending on applications.

  The decorative resin molded body produced as described above has no cracks or cracks in its surface protective layer during the molding process, and its surface has high scratch resistance and solvent resistance. Furthermore, in the production method of the present invention, the surface protective layer is completely cured at the production stage of the decorative sheet, and therefore a step of crosslinking and curing the surface protective layer after producing the decorative resin molded body is unnecessary.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the moldability of the decorative sheet, the elongation at break, the storage elastic modulus E ′ of the surface protective layer at 140 ° C., scratch resistance, solvent resistance, and mold releasability were measured according to the following methods.
(1) Formability About the decorative sheet obtained by each Example and the comparative example, insert molding was performed by the method shown below, and it evaluated by the external appearance after shaping | molding. The evaluation criteria are as follows.
○: No abnormality in appearance Δ: Minor gloss change or crack generation in most of the three-dimensional shape part or 300% stretched part ×: Significant gloss change or crack generation in the entire stretched part <insert molding>
The decorative sheet is heated to 140-160 ° C. with an infrared heater and softened. Next, vacuum molding is performed using a mold having the same shape as the female mold for injection molding, and the inner mold is molded. The decorative sheet was released from the mold, and unnecessary parts were trimmed to obtain a molded sheet. The molded sheet was inserted into an injection mold, the injection mold was clamped, and the fluidized heat-resistant ABS resin was injected into the mold at an injection resin temperature of 230 ° C. and solidified to produce a decorative resin molded body. .
(2) Elongation at break Since the stretchability of the decorative sheet 10 of the present invention is greatly affected by the stretchability of the support 11, at a temperature 40 ° C. higher than the thermal deformation temperature of the support by the ASTM D648 method, JIS K When the tensile test based on 7127 was performed, the initial length L ₀ of the sample piece of the decorative sheet, and when a visible crack occurred in the sample piece of the decorative sheet or at the time of breakage (the sample piece without cracking) There was determined according to the following equation from the length L ₁ of the sample piece in the case of rupture).
Elongation at break (%) = {(L ₁ −L ₀ ) × 100} / L ₀
The measurement conditions were a test piece having a width of 25 mm and a length of 120 mm, a tensile speed of 50 mm / min, a distance between chucks of 80 mm, and a distance between marked lines of 50 mm.
When the support has a plurality of layers, the measurement temperature condition is set considering the thickest layer as the support.
(3) Storage elastic modulus E '
The resin composition produced in each Example and Comparative Example was applied on a polyethylene terephthalate (hereinafter referred to as “PET”) film that had not been surface-treated so that the film thickness after crosslinking and curing was about 15 μm. The uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin composition. The cured film was peeled off from the PET film, and a test piece having a width of 10 mm and a length of 20 mm was cut out. Using this test piece, in accordance with JIS K7244-1 and 7244-4, using a dynamic viscoelasticity measuring device (“RSA II” manufactured by Rheometric Science F.E.), storage at 140 ° C. The elastic modulus E ′ was measured. The measurement was performed at a distance between clamps of 10 mm, a start temperature of 30 ° C., an end temperature of 180 ° C., a temperature increase rate of 5 ° C./min, and a measurement frequency of 1 Hz.
(4) Scratch resistance The decorative sheet produced in each example and comparative example was tested (500 g load, 100 times) in accordance with JIS L0849 (Abrasion tester type II (Gakushin type)). Evaluation based on the criteria. The apparatus used for the test is “Gakushin Abrasion Tester” manufactured by Tester Sangyo Co., Ltd. The evaluation criteria are as follows.
○: No damage.
X: Scratch or gloss change occurred.
(5) Solvent resistance After dropping a 50% aqueous ethanol solution onto the decorative sheet surface, it was wiped off after 1 minute, and the presence or absence of a change in the coating film of the surface protective layer was visually determined and evaluated according to the following criteria.
○: No change at all.
X: Change is recognized.
(6) Mold releasability The mold releasability of the molded body after vacuum molding and the mold releasability of the molded body after injection molding were evaluated. When the molded product is removed from the mold, if the surface protective layer does not cause wrinkles, blisters, peeling, etc., and there is no problem with the appearance, it is judged as good (○), and the mold is not easily separated from the surface. If wrinkles, blisters, peelings, etc. occurred and there was a problem with the appearance, it was judged as defective (x). The mold releasability of the vacuum molded body was evaluated by molding so that the mold and the surface protective layer face each other.

Examples 1 and 2 and Comparative Examples 1-4
A copolymer having a molar ratio of methyl methacrylate (MMA) and methyl acrylate (MA) of 100: 5 was added to 33 parts by mass of tetrafunctional urethane acrylate which is an electron beam curable resin (hereinafter referred to as “EB”) 67 parts by mass of a weight average molecular weight (Mw): 1.0 × 10 ⁵ and a number average molecular weight (Mn): 0.60 × 10 ⁵ ) called “PMMA-1” is mixed to obtain an electron beam curable resin composition. It was. The mass ratio of EB: PMMA-1 is 33:67.
Next, an acrylic urethane primer 1 μm is formed by gravure coating on the surface of a support made of a colored ABS resin sheet having a thickness of 400 μm with a heat deformation temperature of 80 ° C. according to ASTM D648 method, and the above-mentioned electronic The linear curable resin composition was applied by gravure coating so as to have the values described in Table 1. This uncured resin layer is irradiated with an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin composition to form a surface protective layer to obtain a decorative sheet for three-dimensional processing. It was.
The moldability, elongation at break, storage elastic modulus E ′ of the surface protective layer at 140 ° C., scratch resistance, solvent resistance and mold releasability of the six types of decorative sheets obtained as described above are as described above. The method was evaluated. The results are shown in Table 1.

Examples 3-8
A printing layer was formed on the transparent thermoplastic resin layer shown in Table 1. In Examples 3, 4, 7, and 8, the same acrylic urethane primer as in Examples 1 and 2 was gravure coated on the transparent thermoplastic resin layer on the side opposite to the printed layer to form a primer layer. On the layer, the electron beam curable resin composition shown in Table 1 was applied by gravure coating. In Examples 5 and 6, the electron beam curable resin composition shown in Table 1 was applied by gravure coating on the transparent thermoplastic resin layer opposite to the printed layer without forming a primer layer. . These uncured resin layers were irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin composition to form a surface protective layer.
Next, a two-component curable urethane resin adhesive was applied onto the printed layer to form an adhesive layer, which was adhered to a support made of the same colored ABS resin sheet as in Examples 1 and 2. The obtained sheet was cured at 40 ° C. for 3 days to accelerate the curing of the adhesive layer 16b, and the decorative sheet 10 was obtained.
The moldability, elongation at break, storage elastic modulus E ′ of the surface protective layer at 140 ° C., scratch resistance, solvent resistance and mold releasability of the six types of decorative sheets obtained as described above are as described above. The method was evaluated. The results are shown in Table 1.

Example 9
A printing layer is formed on the surface of the second thermoplastic resin layer 14 which is a colored polypropylene film having a thickness of 60 μm, and a two-component curable urethane resin is bonded to the surface of the transparent thermoplastic resin layer 13 which is a transparent polypropylene film having a thickness of 60 μm. The agent was formed with a gravure coat to a thickness of about 5 μm to form an adhesive layer 16a.
Next, the printing layer side on the second thermoplastic resin layer 14 and the adhesive layer 16a side on the transparent thermoplastic resin layer 13 were bonded. On the surface of the transparent thermoplastic resin layer 13 of the obtained laminate, the same acrylic urethane primer as in Examples 1 and 2 is gravure coated to form a primer layer, and the electron beam curable resin shown in Table 1 is formed on the primer layer. The composition was applied by gravure coating. This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin composition to form a surface protective layer.
The two-component curable urethane resin adhesive is gravure coated on the second thermoplastic resin layer 14 side of the obtained laminate to form an adhesive layer 16b having a thickness of 10 μm. The same colored ABS resin sheet as in Examples 1 and 2 Adhered to a support consisting of The obtained sheet was cured at 40 ° C. for 3 days to accelerate the curing of the adhesive layer 16b, and the decorative sheet 10 was obtained.
The decorative sheet of Example 9 obtained as described above has the moldability, elongation at break, storage elastic modulus E ′ of the surface protective layer at 140 ° C., scratch resistance, solvent resistance and mold releasability described above. The method was evaluated. The results are shown in Table 1.

注） 破断伸度（％)において、「３８７＜」とあるのは、破断伸度が３８７％を超えることを確認して試験を打ち切ったことを示す。
表面保護層の材料Ａ〜Ｃ及び透明熱可塑性樹脂層の材料Ｄ〜Ｅの組成内容
表面保護層の材料Ａ：（ＥＢ／ＰＭＭＡ−１）＝（３３／６７）（質量部）
表面保護層の材料Ｂ：（ＥＢ／ＰＭＭＡ−２）＝（３３／６７）（質量部）
表面保護層の材料Ｃ：（ＥＢ／ポリエステル−１）＝（２５／７５）（質量部）
透明熱可塑性樹脂層の材料Ｄ：ポリプロピレン樹脂 無延伸ポリプロピレン(プロピレン−エチレンランダムコポリマー)、軟化点：１２５℃、ヘイズ(曇価)：７.０
透明熱可塑性樹脂層の材料Ｅ：アクリル樹脂 メタクリル酸メチル樹脂(ＰＭＭＡ)、軟化点：１０５℃、ヘイズ(曇価)：０.５
ここで、ＥＢは４官能ウレタンアクリレートであり、ＰＭＭＡ−１は上記の通りであり、ＰＭＭＡ−２はメタクリル酸メチル（ＭＭＡ）単独重合体｛重量平均分子量（Ｍｗ）：１．１×１０⁵、数平均分子量（Ｍｎ）：０．６４×１０⁵、多分散度（Ｍｗ／Ｍｎ）：１．７２｝であり、ポリエステル−１はポリエステル樹脂｛重量平均分子量（Ｍｗ）：０．８６×１０⁵、数平均分子量（Ｍｎ）：０．４１×１０⁵、多分散度（Ｍｗ／Ｍｎ）：２．１｝である。

Note) In the breaking elongation (%), “387 <” indicates that the test was terminated after confirming that the breaking elongation exceeded 387%.
Composition of surface protective layer materials A to C and transparent thermoplastic resin layer materials D to E Surface protective layer material A: (EB / PMMA-1) = (33/67) (parts by mass)
Surface protective layer material B: (EB / PMMA-2) = (33/67) (parts by mass)
Surface protective layer material C: (EB / polyester-1) = (25/75) (parts by mass)
Material D of transparent thermoplastic resin layer: Polypropylene resin Unstretched polypropylene (propylene-ethylene random copolymer), softening point: 125 ° C., haze (cloudiness value): 7.0
Material of transparent thermoplastic resin layer E: Acrylic resin Methyl methacrylate resin (PMMA), softening point: 105 ° C., haze (cloudiness value): 0.5
Here, EB is a tetrafunctional urethane acrylate, PMMA-1 is as described above, PMMA-2 is a methyl methacrylate (MMA) homopolymer {weight average molecular weight (Mw): 1.1 × 10 ⁵ , Number average molecular weight (Mn): 0.64 × 10 ⁵ , polydispersity (Mw / Mn): 1.72}, polyester-1 is a polyester resin {weight average molecular weight (Mw): 0.86 × 10 ⁵ , Number average molecular weight (Mn): 0.41 × 10 ⁵ , polydispersity (Mw / Mn): 2.1}.

As can be seen from Table 1, the decorative sheets of Examples 1 to 9 have good moldability, breaking elongation, scratch resistance, and solvent resistance, and the storage elastic modulus of the surface protective layer at 140 ° C. E ′ was in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa.
On the other hand, in the decorative sheet of Comparative Example 1, the storage elastic modulus E ′ at 140 ° C. of the surface protective layer is in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa, and the elongation at break However, since the thickness of the surface protective layer was too thin, both scratch resistance and solvent resistance were poor.
Further, in the decorative sheets of Comparative Examples 2 to 4, the storage elastic modulus E ′ at 140 ° C. of the surface protective layer is in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa, and the solvent resistance. However, the elongation at break was low and the scratch resistance was poor.
Furthermore, as a result of evaluating the mold releasability of the molded body after vacuum molding and the mold releasability of the molded body after injection molding, each of Examples 1 to 9 and Comparative Examples 1 to 4 was both after vacuum molding and injection. Both mold releasability after molding was good.

  The decorative sheet for three-dimensional processing of the present invention includes, for example, interior materials or exterior materials of vehicles such as automobiles, construction members such as baseboards and rims, joinery such as window frames and door frames, walls, floors, ceilings, and the like. It is suitably used as a decorative molded body for uses such as interior materials of buildings, television receivers, casings of household electrical appliances such as air conditioners, and containers.

It is a schematic diagram which shows the cross section of one embodiment of the decoration sheet for three-dimensional processing of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the decorating sheet for three-dimensional processing of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the decorating sheet for three-dimensional processing of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the decorating sheet for three-dimensional processing of this invention. It is a schematic diagram which shows the cross section of the other embodiment of the decorating sheet for three-dimensional processing of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Decorating sheet 11 Support body 12 Surface protective layer 13 Transparent thermoplastic resin layer 14 2nd thermoplastic resin layer 15 Print layer 16 Adhesive layer 17 Primer layer

Claims (7)

  A decorative sheet for three-dimensional processing formed by laminating at least a surface protective layer on a support, wherein the decorative sheet for three-dimensional processing is at a temperature 40 ° C higher than the thermal deformation temperature of the support according to ASTM D648 method. Has a breaking elongation exceeding 300% (based on JIS K 7127), and the surface protective layer is obtained by crosslinking and curing the ionizing radiation curable resin composition, and has a film thickness of 0.2 to 6.0 μm. A decorative sheet for three-dimensional processing, comprising: 3. The three-dimensional image according to claim 1, wherein the storage elastic modulus of the surface protective layer at 140 ° C. measured under the following measurement conditions is in the range of 7.7 × 10 ^{5 to} 1.2 × 10 ⁸ Pa. Decorative sheet for processing.
Storage elastic modulus measurement conditions: In accordance with JIS K7244-1 and 7244-4, a sheet of 10 mm width and 15 μm thickness formed by crosslinking and curing the ionizing radiation curable resin composition was 10 mm in distance between clamps. The measurement is performed at a temperature of 30 ° C., an end temperature of 180 ° C., a temperature increase rate of 5 ° C./min, and a measurement frequency of 1 Hz.   The three-dimensional processing according to claim 1 or 2, wherein the ionizing radiation curable resin composition is a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a ratio (mass ratio) of 75:25 to 20:80. Decorative sheet.   The decorative sheet for three-dimensional processing according to any one of claims 1 to 3, wherein a transparent thermoplastic resin layer is further provided between the support and the surface protective layer.   The decorative sheet for three-dimensional processing according to claim 4, wherein a second thermoplastic resin layer is further provided between the support and the transparent thermoplastic resin layer.   The decorative sheet for three-dimensional processing according to any one of claims 3 to 5, wherein the ionizing radiation curable resin is an electron beam curable resin.   The decorative sheet for three-dimensional processing according to any one of claims 1 to 6, wherein the three-dimensional processing is insert molding.

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