JP2018052094A - Decorative sheet for three-dimensional molding, decorative resin molded article, and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet for three-dimensional molding, excellent in three-dimensional molding properties and chemical resistance.SOLUTION: A decorative sheet (1) for three-dimensional molding includes a base material sheet (2) and a surface protective layer (3) disposed on the base material sheet (2). In the decorative sheet (1), the surface protective layer (3) includes a cured product of an ionization radiation curable resin composition including a thermoplastic resin whose weight-average molecular weight converted by a standard polystyrene is 100,000-250,000 and whose glass-transition temperature is 95°C or higher and a (meth)acryloyl morpholine.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet for three-dimensional molding, a decorative resin molded product, and a method for producing them.

  Decorative resin molded products that have been decorated by laminating decorative sheets on the surface of the molded resin are used in various applications such as vehicle interior parts. As a molding method for such a decorative resin molded product, a decorative sheet that has been previously molded into a three-dimensional (three-dimensional) shape (off-line pre-molding) using a vacuum mold, a pressure mold, etc. is inserted into an injection mold and melted. An insert molding method (for example, refer to Patent Document 1) in which resin is injected into a mold and the molded decorative sheet and the resin are integrated, and the decorative sheet is inserted into the injection mold, and then applied in the mold. An injection molding simultaneous decorating method in which a decorative sheet is molded (online pre-molding), a molten resin is injected into a mold, and the molded decorative sheet and the resin are integrated (see, for example, Patent Documents 2 and 3) Etc. are known.

  In the insert molding method, in the process of preforming a decorative sheet with a vacuum forming mold, the decorative sheet is brought into close contact with the inner peripheral surface of the mold, and the decorative sheet is stretched by a vacuum action or a pneumatic action. In addition, in the simultaneous injection molding decoration method, pressure or shear stress is applied to the decorative sheet when the molten resin is injected, in addition to stretching of the decorative sheet in the process of preforming with an injection mold. Therefore, the decorative sheet is required to have three-dimensional formability (particularly, mold elongation). In addition, in order to improve the chemical resistance of the surface of the decorative resin molded product, the decorative sheet is required to have chemical resistance.

  As a decorative sheet, a decorative sheet having a surface protective layer as an outermost layer is known (for example, see Patent Documents 4 to 7).

  Patent Document 4 discloses a cured product of an ionizing radiation curable resin composition containing a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene and a polyfunctional (meth) acrylate monomer. A decorative sheet having a surface protective layer is described.

  Patent Document 5 describes a decorative sheet having a surface protective layer made of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and monofunctional (meth) acrylate.

  Patent Document 6 describes a decorative sheet having a surface protective layer made of a cured product of a curable resin composition containing a polyol and a polyisocyanate.

  Patent Document 7 describes a decorative sheet having a surface protective layer made of a cured product of a resin composition containing a blocked isocyanate.

JP 2004-322501 A Japanese Patent Publication No. 50-19132 Japanese Examined Patent Publication No. 61-17255 JP 2012-91497 A JP 2012-218277 A JP 2012-97248 A Japanese Patent Laying-Open No. 2015-19311

  However, since the surface protective layer of the decorative sheet described in Patent Document 4 has a three-dimensional crosslink formed by a polyfunctional (meth) acrylate monomer, the molding elongation of the decorative sheet is reduced. In addition, the surface protective layer of the decorative sheet described in Patent Document 5 is inferior in chemical resistance as compared to a surface protective layer containing a thermoplastic resin having a high molecular weight and a high glass transition temperature. Moreover, since the surface protective layer of the decorative sheet described in Patent Documents 6 and 7 has a three-dimensional urethane bond, it reduces the moldability of the decorative sheet. In addition, since the surface protective layer of the decorative sheet described in Patent Documents 6 and 7 is formed using a two-component curable resin composition, it is not suitable for continuous production of sheets with Roll To Roll.

  Therefore, an object of the present invention is to provide a decorative sheet excellent in three-dimensional formability and chemical resistance, a decorative resin molded product including the decorative sheet, and a manufacturing method thereof.

In order to solve the above problems, the present invention provides the following inventions.
[1] A three-dimensional decorative sheet comprising a base sheet and a surface protective layer provided on the base sheet,
The surface protective layer contains a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene, and a glass transition temperature of 95 ° C. or more, and (meth) acryloylmorpholine. The decorative sheet formed of a cured product of an ionizing radiation curable resin composition.
[2] The decorative sheet according to [1], wherein the cured product of the ionizing radiation curable resin composition contains a (meth) acrylic resin containing the (meth) acryloylmorpholine as a structural unit.
[3] The mass ratio of the thermoplastic resin and the (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition is 40:60 to 90:10, described in [1] or [2]. Decorative sheet.
[4] The decorative sheet according to any one of [1] to [3], wherein the thermoplastic resin is a (meth) acrylic resin containing a (meth) acrylic acid ester as a structural unit.
[5] A decorative resin molded product comprising the decorative sheet according to any one of [1] to [4] and a resin molded body integrated with the decorative sheet.
[6] A method for producing a decorative sheet according to any one of [1] to [4],
Preparing a base sheet,
A thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted into standard polystyrene, directly or via an intermediate layer, and a glass transition temperature of 95 ° C. or more on the substrate sheet; A step of forming an ionizing radiation curable resin composition layer containing (meth) acryloylmorpholine, and curing the ionizing radiation curable resin composition layer by irradiating the ionizing radiation curable resin composition layer with ionizing radiation. The process of
The manufacturing method of a decorating sheet containing this.
[7] The decoration according to [6], wherein a mass ratio of the thermoplastic resin and the (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition layer is 40:60 to 90:10. Sheet manufacturing method.
[8] The method for producing a decorative sheet according to [6] or [7], wherein the thermoplastic resin is a (meth) acrylic resin containing a (meth) acrylic acid ester as a structural unit.
[9] A method for producing a decorated resin molded product according to [5],
The step of heating and softening the decorative sheet according to any one of [1] to [4],
A step of preforming the decorative sheet softened by vacuum suction and adhering it along the molding surface of the injection mold; and a resin in a fluid state in a cavity formed by clamping the injection mold A process for producing a decorative resin molded product, comprising the step of injecting the resin and integrating the resin on the base sheet side of the decorative sheet.
[10] A method for producing a decorated resin molded product according to [5],
After heating and softening the decorative sheet according to any one of [1] to [4], vacuum forming into a three-dimensional shape with a vacuum forming die to form a molded body of the decorative sheet, and The molded body is inserted into an injection mold, the resin in a fluid state is injected into a cavity formed by clamping the injection mold, and the resin is integrated on the base sheet side of the molded body. The manufacturing method of a decorative resin molded product including a process.
[11] A method for producing a decorated resin molded product according to [5],
[1] to [4] is a sealed space in which the decorative sheet and the resin molded body are arranged, and the sealed space is partitioned into an upper space and a lower space with the decorative sheet as a boundary, The base sheet side of the decorative sheet is located on the lower space side, and the resin molded body forms the sealed space located in the lower space;
A step of evacuating the upper space and the lower space;
Heating and softening the decorative sheet,
The step of raising the resin molded body and pressing it against the surface of the decorative sheet on the base sheet side; and the upper space in an atmospheric pressure state or a pressurized state; The manufacturing method of a decorative resin molded product including the process of closely_contact | adhering the said resin molding and the said decorating sheet.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in three-dimensional moldability and chemical resistance, the decorative resin molded product provided with this decorative sheet, and those manufacturing methods are provided.

FIG. 1 is a cross-sectional view schematically showing a configuration of a decorative sheet for three-dimensional molding according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a configuration of a decorative resin molded product according to one embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

<Decoration sheet for three-dimensional molding>
As shown in FIG. 1, the decorative sheet for three-dimensional molding 1 according to an embodiment of the present invention includes a base sheet 2 and a surface protective layer 3 provided on the base sheet 2.

  For "three-dimensional molding", in addition to the use of producing a three-dimensional molded body of a decorative sheet (a molded body having a three-dimensional shape), a two-dimensional molded body of a decorative sheet (a molded body having a sheet shape) The use for producing is also encompassed.

<Base material sheet>
As shown in FIG. 1, the base sheet 2 has a first main surface S1 and a second main surface S2 located on the opposite side of the first main surface S1, and is provided on the first main surface S1. Support layer.

  As the base sheet 2, a resin sheet made of a thermoplastic resin is usually used from the viewpoint of suitability for vacuum forming and pressure forming. The resin sheet may be a single layer sheet or a multi-layer sheet. When the resin sheet is a multilayer sheet, the multilayer sheet constituting the resin sheet may be composed of the same resin or may be composed of different resins. Examples of the thermoplastic resin constituting the resin sheet include acrylonitrile-butadiene-styrene resin (ABS resin), acrylic resin, polyester resin, polyolefin resin, polycarbonate resin, and vinyl chloride resin. A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  Examples of polyester resins include esters of aromatic dicarboxylic acids (acid components) such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aliphatic diols (alcohol components) such as ethylene glycol, diethylene glycol, butanediol, and hexanediol. Examples of the copolymer obtained by bonding include polyethylene terephthalate, polybutylene terephthalate, and ethylene-terephthalate-isophthalate copolymer.

  Examples of the polyolefin resin include polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and the like.

  The base sheet 2 may contain a colorant. With the colorant, the base sheet 2 can be colored, transparent, colored, opaque, or the like. Examples of the colorant include carbon 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 Organic pigments or dyes composed of particles such as phthalocyanine blue; Metal pigments composed of scaly foils such as aluminum and brass; Pearlescent pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate Etc. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The base sheet 2 may contain additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers.

  Although the thickness of the base material sheet 2 can be suitably adjusted according to the use of the decorating sheet 1, it is about 0.05-1.0 mm normally, and from viewpoints of manufacturing cost etc., Preferably it is 0.05- It is about 0.7 mm.

  One or both of the first main surface S1 and the second main surface S2 of the base sheet 2 is oxidized or roughened in order to improve adhesion with a layer or member provided in contact with the base sheet 2 A physical or chemical surface treatment such as law may be applied. Examples of the surface treatment by the oxidation method include corona discharge treatment, plasma treatment, chrome oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, etc., and examples of the surface treatment by the concavo-convex method include a sand blast method, Examples include solvent processing methods. These surface treatments are appropriately selected according to the type of the base sheet 2, but in general, a corona discharge treatment method is preferably used in terms of effects and operability.

<Surface protective layer>
The surface protective layer 3 imparts surface properties such as chemical resistance, scratch resistance, and wear resistance to the decorative sheet 1 to protect the surface of the decorative sheet 1. As shown in FIG. 1, the surface protective layer 3 is located on the outermost side of the decorative sheet 1. “Chemical resistance” also includes solvent resistance properties.

  As shown in FIG. 1, the surface protective layer 3 is provided on the base sheet 2. In “provided on the base sheet 2”, in addition to the case where the surface protective layer 3 is directly provided on the first main surface S <b> 1 of the base sheet 2, the surface protective layer 3 is formed of the base sheet 2. The case where it is provided via the intermediate layer 4 on the first main surface S1 is also included. In the present embodiment, the surface protective layer 3 is provided on the first main surface S <b> 1 of the base sheet 2 via the intermediate layer 4.

  The thickness of the surface protective layer 3 is not particularly limited, but is usually about 1 to 1000 μm, preferably 1 to 50 μm, more preferably from the viewpoint of achieving both excellent three-dimensional formability and chemical resistance. Is 1-30 μm.

  The surface protective layer 3 contains a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene and a glass transition temperature of 95 ° C. or more, and (meth) acryloylmorpholine. It is formed of a cured product of an ionizing radiation curable resin composition.

<Ionizing radiation curable resin composition>
The ionizing radiation curable resin composition comprises a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene and a glass transition temperature of 95 ° C. or more, (meth) acryloylmorpholine, Containing. A glass transition temperature (Tg) can be calculated | required with the measuring method based on JISK7121, for example using a suggestion calorimeter (DSC, Shimadzu Corporation make, model number: DSC-60).

  The ionizing radiation curable resin composition is a composition containing an ionizing radiation curable resin. In the present embodiment, the ionizing radiation curable resin composition contains at least (meth) acryloylmorpholine as an ionizing radiation curable resin. The ionizing radiation curable resin is a resin that is cured by causing a polymerization reaction upon irradiation with ionizing radiation and changing to a polymer structure. Ionizing radiation has energy quanta that can polymerize or crosslink molecules among electromagnetic waves or charged particle beams. As the ionizing radiation, ultraviolet rays (UV) or electron beams (EB) are usually used. However, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays can also be used. .

<(Meth) acryloylmorpholine>
(Meth) acryloylmorpholine is a monofunctional (meth) acrylate monomer. “(Meth) acryloylmorpholine” means acryloylmorpholine or methacryloylmorpholine. Monofunctional means having one ethylenically unsaturated bond ((meth) acryloyl group) in the molecule. (Meth) acryloylmorpholine is polymerized by irradiating ionizing radiation curable resin composition containing (meth) acryloylmorpholine with ionizing radiation, and (meth) acryloylmorpholine is included as a structural unit. Is formed. When using (meth) acryloylmorpholine, which is a monofunctional (meth) acrylate monomer, compared with using polyfunctional (meth) acrylate monomer, three-dimensional crosslinking in the cured product of ionizing radiation curable resin composition This can suppress the decrease in the three-dimensional formability (particularly, the mold elongation) of the decorative sheet 1 due to the three-dimensional crosslinking. In addition, (meth) acryloylmorpholine has a high glass transition temperature (145 ° C.) when polymerized and polymerized, so in addition to excellent three-dimensional formability, it has chemical resistance not only at room temperature but also at high temperature. It can be applied to the surface protective layer 3. “(Meth) acrylate monomer” means an acrylate monomer or a methacrylate monomer, and “(meth) acryloylmorpholine” means acryloylmorpholine or methacryloylmorpholine.

  The content of (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition is preferably 50% by mass or more based on the entire ionizing radiation curable resin contained in the ionizing radiation curable resin composition. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is substantially 100 mass%.

<Thermoplastic resin>
The thermoplastic resin contained in the ionizing radiation curable resin composition is not particularly limited as long as the weight average molecular weight converted to standard polystyrene is 100,000 or more and 250,000 or less, and is a known thermoplastic. Resin can be used. Here, the weight average molecular weight of the thermoplastic resin is a value measured by a gel permeation chromatography (GPC) method, and is a value measured under conditions using polystyrene as a standard sample.

  The weight average molecular weight of the thermoplastic resin can be appropriately adjusted in the range of 100,000 to 250,000, preferably 100,000 to 200,000, more preferably 100,000 to 170,000. is there. When the weight average molecular weight of the thermoplastic resin is within the above range, the decorative sheet 1 can be provided with excellent three-dimensional formability and chemical resistance.

  Examples of the thermoplastic resin include (meth) acrylic resin, polyvinyl acetal (butyral resin) such as polyvinyl butyral, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyolefin such as vinyl chloride resin, urethane resin, polyethylene, and polypropylene, Styrene resins such as polystyrene and α-methylstyrene, acetal resins such as polyamide, polycarbonate and polyoxymethylene, fluororesins such as ethylene-4 fluoroethylene copolymer, polyimide, polylactic acid, polyvinyl acetal resin, liquid crystalline polyester resin Etc. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type. When using in combination of 2 or more types, you may use as a copolymer of the monomer which comprises these thermoplastic resins, and may mix and use each thermoplastic resin. “(Meth) acrylic resin” means acrylic resin or methacrylic resin.

  Among the above thermoplastic resins, (meth) acrylic resins are preferable, and (meth) acrylic resins containing at least a (meth) acrylic acid ester monomer as a structural unit are more preferable. Specifically, a homopolymer of (meth) acrylate monomer, a copolymer of two or more different (meth) acrylate monomers, or a copolymer of (meth) acrylate monomers and other monomers Coalescence is preferred. The “(meth) acrylic acid ester monomer” means an acrylic acid ester monomer or a methacrylic acid monomer.

  Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, (meth ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) ) Acrylate and the like are mentioned as preferred examples, and methyl (meth) acrylate is more preferred. Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid ester selected from these (meth) acrylic acid ester monomers. These copolymers may be random copolymers or block copolymers.

  The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it is copolymerizable with the (meth) acrylic acid ester. For example, (meth) acrylic acid , Styrene, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, (meth) acrylonitrile, (meth) acrylamide, butadiene, isoprene , Cyclobutane olefin monomers such as isobutene, 1-butene, 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinyl caprolactam, citraconic anhydride, N-phenylmaleimide, etc. Maleimides, bi Ethers and the like as examples Shi preferred, even more preferably styrene and (anhydrous) maleic acid. 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 the (meth) acrylic acid ester monomer and another monomer may be a random copolymer or a block copolymer.

  The thermoplastic resin contained in the ionizing radiation curable resin composition may be dissolved or dispersed in a solvent as necessary, and diluted to a viscosity that can be applied to the substrate sheet 2. Examples of the solvent or dispersion medium used for dissolving or dispersing the thermoplastic resin include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, and acetic acid. Ester organic solvents such as 2-methoxyethyl and 2-ethoxyethyl acetate; alcohol organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone Ketone organic solvents such as methyl isobutyl ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloro Inorganic solvents and the like such as water, ethylene, chlorinated organic solvents tetrachlorethylene or the like. A solvent or a dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, it is preferable to use methyl ethyl ketone.

  When the thermoplastic resin contained in the ionizing radiation curable resin composition contains a (meth) acrylic resin, the content of the (meth) acrylic resin is preferably 30% by mass or more with respect to the entire thermoplastic resin. More preferably, it is 50% by mass or more, and still more preferably 70% by mass or more.

<Mass ratio of thermoplastic resin to (meth) acryloylmorpholine>
The mass ratio of the thermoplastic resin and (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition (the content of the thermoplastic resin: the content of (meth) acryloylmorpholine) is not particularly limited. However, it is preferably 40:60 to 90:10, more preferably 50:50 to 80:20, and still more preferably 70:30. When the mass ratio of the thermoplastic resin contained in the ionizing radiation curable resin composition to the (meth) acryloylmorpholine is within the above range, the decorative sheet 1 is provided with excellent three-dimensional formability and chemical resistance. Can do.

<Other resin components>
The ionizing radiation curable resin composition can contain other components in addition to the thermoplastic resin and (meth) acryloylmorpholine as long as the object of the present invention is not impaired. Examples of other components include ionizing radiation curable resins other than (meth) acryloylmorpholine. As ionizing radiation curable resins other than (meth) acryloylmorpholine, one or more resins such as monomers, oligomers, prepolymers, etc., having polymerizable unsaturated bonds, epoxy groups and the like that can be cross-linked by irradiation with ionizing radiation. Can be used. Examples of the ionizing radiation curable resin include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, silicon resins such as siloxane, polyesters, epoxies, and the like. Among these, the formation of three-dimensional crosslinks in the cured product of the ionizing radiation curable resin composition is suppressed, whereby the three-dimensional formability of the decorative sheet 1 resulting from the three-dimensional crosslinks (particularly, mold elongation). From the viewpoint of suppressing the decrease in the viscosity and the viewpoint of decreasing the viscosity of the ionizing radiation curable resin composition, it is preferable to use a monofunctional (meth) acrylate.

  Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and other monomers, oligomers, prepolymers and the like. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Monofunctional (meth) acrylates can be used in the form of monomers, oligomers, prepolymers, etc., but are preferably used in the form of oligomers from the viewpoint of improving three-dimensional moldability. Examples of the monofunctional (meth) acrylate oligomer include urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polybutadiene (meth) acrylate oligomer, silicone ( A meth) acrylate oligomer, an aminoplast (meth) acrylate oligomer, etc. are mentioned.

  The ionizing radiation curable resin composition includes a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, and a cup. Various additives commonly used in resin compositions such as ring agents, plasticizers, antifoaming agents, fillers, solvents, and coloring agents are added to the surface protective layer 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 ionizing radiation curable resin composition may contain a component involved in the curing reaction of the ionizing radiation curable resin, for example, a photopolymerization initiator (sensitizer), if necessary. For example, when the ionizing radiation curable resin composition is cured by irradiation with ultraviolet rays, the ionizing radiation curable resin composition preferably contains a photopolymerization initiator (sensitizer). In addition, since the ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, when the ionizing radiation curable resin composition is cured by irradiation with an electron beam, the ionizing radiation curable resin composition is a photopolymerization initiator ( (Sensitizer) may not be included.

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

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

<Hardened product of ionizing radiation curable resin composition>
The cured product of the ionizing radiation curable resin composition contains a (meth) acrylic resin containing (meth) acryloylmorpholine as a structural unit. The “(meth) acrylic resin containing (meth) acryloylmorpholine as a structural unit” means that all or part of the monomer constituting the (meth) acrylic resin is (meth) acryloylmorpholine. In the (meth) acrylic resin containing (meth) acryloylmorpholine as a structural unit, all the monomers constituting the (meth) acrylic resin are (meth) acryloylmorpholine (that is, the content ratio of (meth) acryloylmorpholine is 100% by mass) is preferable. Thereby, excellent three-dimensional moldability and chemical resistance can be imparted to the surface protective layer 3.

  The (meth) acrylic resin containing (meth) acryloylmorpholine as a structural unit is formed by polymerization of (meth) acryloylmorpholine. A (meth) acrylic resin containing (meth) acryloylmorpholine as a structural unit is a random polymerization or block polymerization of (meth) acryloylmorpholine and one or more other monofunctional (meth) acrylate monomers, oligomers, prepolymers, etc. Copolymers such as

  The content of (meth) acryloylmorpholine in the (meth) acrylic resin containing (meth) acryloylmorpholine as a constituent unit is preferably 50% by mass with respect to the entire (meth) acrylic resin containing (meth) acryloylmorpholine as a constituent unit. Or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably substantially 100% by mass.

<Intermediate layer>
As shown in FIG. 1, the decorative sheet 1 includes an intermediate layer 4 between the base sheet 2 and the surface protective layer 3. However, the intermediate layer 4 can be omitted. Therefore, the embodiment in which the surface protective layer 3 is directly provided on the base sheet 2 is also included in the present invention.

  In this embodiment, the intermediate | middle layer 4 has the decoration layer 41 and the primer layer 42 in order from the base material sheet 2 side. However, the number of layers constituting the intermediate layer 4 is not particularly limited, and may be 1 or 2 or more. The intermediate layer 4 is not limited to the decorative layer, the primer layer, or a combination thereof. The intermediate layer 4 may have, for example, an adhesive layer.

<Decoration layer>
The decorative layer 41 imparts decorative properties to the decorative sheet 1. As shown in FIG. 1, the decoration layer 41 is provided on the first main surface S <b> 1 of the base sheet 2. However, the decoration layer 41 may be provided on the second main surface S2, or may be provided on both the first main surface S1 and the second main surface S2. The decoration layer 41 may be formed on the entire first main surface S1 and / or the second main surface S2 of the base sheet 2, or the first main surface S1 and / or the second main surface of the base sheet 2. You may form in a part of surface.

  Examples of the decoration layer 41 include a colored layer, a pattern layer, and combinations thereof.

  The colored layer imparts a desired color to the decorative sheet 1. The colored layer is, for example, a solid layer formed on the entire first main surface S1 of the base sheet 2. The colored layer can function as a concealing layer that prevents changes and variations in the color of the base sheet 2 from affecting the color of the design of the decorative sheet 1. Examples of the method for forming the solid layer include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, roll coating, knife coating, air knife coating, and die coating. , Lip coat method, comma coat method, kiss coat method, flow coat method, dip coat method and the like. The color of the colored layer is usually an opaque color, but may be a transparent color in the case where a base color or pattern such as the substrate sheet 2 is utilized. Moreover, when utilizing the color or pattern of foundation | substrates, such as the base material sheet 2, it is not necessary to form a colored layer.

  The pattern layer is a layer that imparts a desired pattern to the decorative sheet 1. The pattern layer is, for example, a printed layer formed on a part or the whole of the first main surface S1 of the base sheet 2 or a part or the whole of the surface of the colored layer. Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. Examples of patterns that make up the pattern layer include spring and fall wood areas with cross-sections of rings, wood grain patterns composed of conduits, leather (leather) patterns, marbles, granite, sandstone, and other stone surfaces. Examples include eye patterns, grain patterns, tiled patterns, brickwork patterns, cloth patterns, geometric figures, characters, symbols, abstract patterns, etc., and patterns such as marquetry and patchwork that combine these patterns. These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by special color multicolor printing performed by preparing individual color plates constituting the pattern. Can also be formed.

  The ink used for forming the decorative layer 41 is, for example, a mixture of a solvent or a dispersion medium and components such as a colorant and a binder resin. The ink may contain a colorant, extender pigment, stabilizer, plasticizer, catalyst, curing agent, and the like as other components. The ink may be an aqueous composition from the viewpoint of reducing the VOC (volatile organic compound) of the sheet.

  Examples of colorants contained in the ink include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue; quinacridone red, isoindolinone Organic pigments or dyes such as yellow and phthalocyanine blue; metal pigments composed of scaly foils such as aluminum and brass; pearlescent pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate Can be mentioned. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the binder resin contained in the ink include urethane resin, (meth) acryl urethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate- (meth) acryl copolymer resin, and chlorinated polypropylene resin. (Meth) acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin (nitrified cotton), cellulose acetate resin and the like. Binder resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the solvent or dispersion medium contained in the ink include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid -2-Ethoxyethyl and other ester organic solvents; methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol and other alcohol organic solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based organic solvents; diethyl ether, dioxane, tetrahydrofuran and other ether-based organic solvents; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloro Chlorinated organic solvents such as ethylene; inorganic solvents such as water. A solvent or a dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

  The decoration layer 41 may be formed by a method such as a hand-drawn method, an ink sink method, a photographic method, a transfer method, a laser beam drawing method, or an electron beam drawing method. When the decoration layer 41 is a metal layer (metal thin film) such as aluminum, chromium, gold, silver, or copper, the decoration layer 41 can be formed by a method such as a vapor deposition method, a sputtering method, or an etching method.

  The thickness of the decoration layer 41 can be appropriately adjusted according to product characteristics, but the thickness at the time of ink coating is, for example, about 1 to 200 μm, and the thickness after drying is, for example, about 0.1 to 20 μm. And a solid printing layer of about 1 to 20 μm is preferable.

<Primer layer>
As shown in FIG. 1, the primer layer 42 is provided between the decoration layer 41 and the surface protective layer 3, and improves the adhesiveness of these layers. The decorative sheet 1 may include a primer layer between the other two adjacent layers in order to improve the adhesion between the other two adjacent layers (for example, the base sheet 2 and the decorative layer 41). .

  The primer layer can be formed of a resin. Examples of the resin constituting the primer layer 42 include (meth) acrylic resin, urethane resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, butyral resin, and chlorination. Examples include polypropylene resin and chlorinated polyethylene resin. Of these resins, urethane resins, (meth) acrylic resins, and (meth) acrylic-urethane copolymer resins are preferred. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  Further, from the viewpoint of improving the adhesion between the decorative layer 41 and the surface protective layer 3, the primer composition constituting the primer layer 42 is preferably formed using a crosslinking agent (curing agent). Examples of such a primer composition include a two-component curable resin having a polyol as a main component and an isocyanate as a cross-linking agent (curing agent). In particular, from the viewpoint of improving the physical properties such as three-dimensional formability of the decorative sheet 1, polyols such as (meth) acryl polyol, polycarbonate polyol and polyester polyol, and crosslinking agents such as hexamethylene diisocyanate and 4,4-diphenylmethane diisocyanate. Are preferably used in appropriate combination. Among these, it is more preferable to use a combination of (meth) acrylic polyol and hexamethylene diisocyanate.

  Examples of the (meth) acrylic resin constituting the primer layer 42 include, for example, a homopolymer of (meth) acrylate ester, a copolymer of two or more different (meth) acrylate esters, and a (meth) acrylate ester And copolymers with other monomers. Preferably, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate-butyl (meth) acrylate (Meth) acrylic acid esters such as coalescence, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate copolymer The (meth) acrylic resin which consists of a homopolymer or a copolymer containing is used.

  Examples of the urethane resin constituting the primer layer 42 include polyurethane polymerized using a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent). The polyol used as the main agent is an alcohol (polyhydric alcohol) having two or more hydroxyl groups in the molecule. Examples of the polyol include polyester polyol, polyethylene glycol, polypropylene glycol, (meth) acryl polyol, and polyether. A polyol, a polycarbonate polyol, etc. are mentioned. As the isocyanate used as a crosslinking agent (curing agent), polyisocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogen Aliphatic (or alicyclic) isocyanates such as added tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate can be mentioned. Moreover, it is also possible to comprise a primer layer with what mixed urethane resin and butyral resin.

  As (meth) acryl-urethane copolymer resin, (meth) acryl-urethane (polyester urethane) block copolymer resin is mentioned, for example. Examples of the crosslinking agent (curing agent) include the above-mentioned various isocyanates. The (meth) acryl-urethane (polyester urethane) block copolymer resin has a (meth) acryl / urethane ratio (mass ratio), preferably (9/1) to (1/9), more preferably, as desired. Since it can adjust in the range of (8/2)-(2/8) and can be used for various decorating sheets, it is especially preferable as resin used for a primer composition.

  Further, the primer layer 42 may be provided with a weather resistance improver, an adhesion improver, a leveling agent, a thixotropic agent, an antiblocking agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and the like as necessary. Various additives may be added.

<Adhesive layer>
The decorative sheet 1 has two adjacent layers in order to improve the adhesion between the two adjacent layers (for example, the base sheet 1 and the decorative layer 41) and the adhesion between the decorative sheet 1 and the resin molded body. An adhesive layer may be provided between or on the second main surface S2 of the decorative sheet. The adhesive constituting the adhesive layer can be appropriately selected according to the layer and the resin molded body, and for example, a thermoplastic resin or a thermosetting resin is used. Thermoplastic resins include (meth) acrylic resins, (meth) acrylic modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins In addition, examples of the thermosetting resin include a urethane resin and an epoxy resin. These resin may be used individually by 1 type, and may be used in combination of 2 or more type. The adhesive layer can be formed by a known layer forming method such as a coating method using an adhesive composition comprising these resins. The thickness of the adhesive layer is usually about 0.1 to 50 μm, and preferably 1 to 30 μm from the viewpoint of obtaining sufficient adhesiveness.

<Method for producing decorative sheet for three-dimensional molding>
The decorative sheet 1 is, for example,
Forming a decorative layer 41 on the base sheet 2;
It can be manufactured by a method including a step of forming the primer layer 42 on the decoration layer 41 and a step of forming the surface protective layer 3 on the primer layer 42.

  In the manufacturing method, first, the decoration layer 41 is formed on the first main surface S1 of the base sheet 2. Before the decoration layer 31 is formed, the first main surface S1 of the base sheet 2 may be subjected to treatment such as corona discharge treatment, plasma treatment, and ozone treatment. In addition, a primer layer or an adhesive layer may be formed on the first main surface S1 of the base sheet 2 before the decoration layer 41 is formed.

  In the manufacturing method, the primer layer 42 is then formed on the decorative layer 41.

  In the manufacturing method, the surface protective layer 3 is then formed on the primer layer 42. The surface protective layer 3 includes a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene and a glass transition temperature of 95 ° C. or more on the primer layer 42; An ionizing radiation curable resin composition containing acryloylmorpholine can be applied and cured. The uncured ionizing radiation curable resin composition layer formed by application of the ionizing radiation curable resin composition becomes a surface protective layer 3 by irradiating with an ionizing radiation such as an electron beam or an ultraviolet ray to obtain a cured product. . When an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately adjusted according to the resin used, the thickness of the layer, and the like. For example, uncured ionizing radiation curing at an acceleration voltage of about 70 to 300 kV. The functional resin composition layer can be cured. In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a material that deteriorates due to an electron beam is used as the base sheet 2, the penetration depth of the electron beam and the ionizing radiation curable resin composition are used. By selecting an accelerating voltage so that the thicknesses of the layers are substantially equal, it is possible to suppress irradiation of an extra electron beam to the base sheet 2, and the deterioration of the base sheet 2 due to the excess electron beam. Can be kept to a minimum. The irradiation dose is preferably an amount at which the crosslinking density of the ionizing radiation curable resin is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), and preferably 10 to 50 kGy (1 to 5 Mrad). As the electron beam source, for example, various electron beam accelerators such as a Cockloft 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 addition, since (meth) acryloylmorpholine is polymerized and hardly soluble in an organic solvent generally used for dissolving the resin composition, the ionizing radiation curable resin composition using (meth) acryloylmorpholine as a monomer. After being coated on the primer layer 42, it is polymerized (cured) by irradiation with ionizing radiation. A thermoplastic resin contained in the ionizing radiation curable resin composition and having a weight average molecular weight converted to standard polystyrene of 100,000 to 250,000 and a glass transition temperature of 95 ° C. or higher is a normal temperature. Since it is a solid, it must be dissolved and diluted in a solvent. However, since the thermoplastic resin has low solubility in a solvent, it is necessary to dissolve and dilute it using an organic solvent having high solubility such as methyl ethyl ketone. On the other hand, when dissolving and diluting using only an organic solvent such as methyl ethyl ketone, problems in production such as deterioration of the base sheet 2, moisture absorption at the time of volatilization of the organic solvent, and residual organic solvent on the decorative sheet 1 obtained, etc. There is. Since the monomer of (meth) acryloylmorpholine has a low viscosity, when used in combination with such a thermoplastic resin, it plays the role of diluting the thermoplastic resin. In addition, monofunctional (meth) acrylate monomers generally have an irritating odor and are harmful to living organisms, but (meth) acryloylmorpholine monomers are compared to other monofunctional (meth) acrylate monomers. Since the boiling point is high, it is difficult to evaporate, and since it is almost odorless, a safer and odorless decorative sheet 1 can be produced.

<Decorative resin molded product>
As shown in FIG. 2, a decorative resin molded product 10 according to an embodiment of the present invention includes a decorative sheet 1 and a resin molded body 5 integrated with the decorative sheet 1. As shown in FIG. 2, the resin molded body 5 integrated with the decorative sheet 1 is located on the second main surface S2 side of the base sheet 2 of the decorative sheet 1. The decorative resin molded product 10 is formed by forming the decorative sheet 1 as necessary and then integrating it with the resin molded body 5.

<Resin molding>
The resin molded body 5 in the decorative resin molded product 10 of the present invention may be any that can be integrated with the decorative sheet 1 during injection molding. Examples of the material of the resin molded body 5 include a thermoplastic resin and a thermosetting resin.

  Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the thermosetting resin include a urethane resin and an epoxy resin. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The decorative resin molded product 10 includes, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; television receivers, air conditioners, and the like. It can be used for various purposes such as housings for home appliances; containers and the like.

<Method for producing decorative resin molded product>
The decorative resin molded product 10 can be manufactured using, for example, the decorative sheet 1 by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method. . Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferable. Moreover, the decorative resin molded product 10 is manufactured also by a decoration method such as a vacuum pressure bonding method in which the decorative sheet 1 or the molded body is pasted on a three-dimensional resin molded body 5 prepared in advance. Can do. Examples of such a vacuum pressure bonding method include a TOM method (Three Dimension Overlay Method).

As an insert molding method, for example,
After the decorative sheet 1 is heated and softened, the decorative sheet 1 is vacuum-formed into a three-dimensional shape by a vacuum forming die, and an extra portion of the vacuum-formed decorative sheet 1 is trimmed as necessary. The step of forming a molded body, and the molded body of the decorative sheet 1 are inserted into an injection mold, and the resin in a fluid state is injected into a cavity formed by clamping the injection mold. The method of including the process of integrating resin to the base material sheet 2 side of a molded object is mentioned.

  In an example of the insert molding method, the decorative sheet 1 is heated and softened by a hot platen, and then in the vacuum forming step, the softened decorative sheet 1 is vacuum-formed into a molded product surface shape in advance by a vacuum forming die (offline). (Preliminary molding), and trimming excess portions as necessary to obtain a molded body of the decorative sheet 1. Next, the molded body is inserted into an injection mold (for example, an injection mold), the injection mold is clamped, and the resin in a fluid state is added in a cavity formed by clamping the injection mold. By injecting the molded body of the decorative sheet 1 toward the base sheet 2 side, solidifying the filled resin and integrating the decorative sheet 1 on the outer surface of the resin molded body 5, a decorative resin molded product 10 can be manufactured.

  In the vacuum forming step, the heating temperature when the decorative sheet 1 is heated and softened is not particularly limited, and is appropriately adjusted according to the type of resin constituting the decorative sheet 1, the thickness of the decorative sheet 1, and the like. For example, it is about 120-200 degreeC. In the integration step, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

As an injection molding simultaneous decoration method, for example,
Heating and softening the decorative sheet 1,
Formed by vacuum-sucking the softened decorative sheet 1 and bringing it into close contact with the molding surface of an injection mold (for example, an injection mold), and clamping the injection mold There is a method including a step of injecting a resin in a fluid state into the cavity and integrating the resin on the base sheet side of the decorative sheet 1.

  In an example of the simultaneous injection molding decorating method, the decorative sheet 1 is used as a female mold that is also used as a vacuum mold having a suction hole for injection molding, and the surface protective layer 3 side of the decorative sheet 1 is directed to the female mold side. The decorative sheet 1 is heated and softened from the base sheet 2 side by a hot platen, and the softened decorative sheet 1 is vacuum-sucked from the female mold side so as to adhere to the molding surface of the female mold. To perform preforming (online preforming). Next, the female mold and the male mold are clamped, and in a cavity formed by clamping the female mold and the male mold, the resin in a fluid state is directed toward the base sheet 2 side of the pre-decorated decorative sheet 1 The decorative resin molded product 10 can be manufactured by solidifying the filled resin and integrating the decorative sheet 1 on the outer surface of the resin molded body 5.

  In the preforming step of the simultaneous injection molding decoration method, the heating temperature of the decoration sheet 1 is not particularly limited, and is appropriately adjusted according to the type of resin constituting the decoration sheet 1, the thickness of the decoration sheet 1, and the like. For example, it is about 70-130 degreeC. Moreover, in the injection molding process, the temperature of the resin in the fluidized state is not particularly limited, but can be, for example, about 180 to 320 ° C.

As a vacuum pressure bonding method, for example,
It is a sealed space in which the decorative sheet 1 and the resin molded body 5 are arranged, and the sealed space is divided into an upper space and a lower space with the decorative sheet 1 as a boundary, and the base sheet 2 side of the decorative sheet 1 is a lower space. A step of forming a sealed space located on the side and in which the resin molded body 5 is located in the lower space;
A step of evacuating the upper space and the lower space;
Heating and softening the decorative sheet 1,
The resin molded body 5 is raised and pressed against the surface of the decorative sheet 1 on the base sheet 2 side, and the upper space is brought into an atmospheric pressure state or a pressurized state, and the resin molded body is caused by a pressure difference between the upper space and the lower space. The method of including the process of closely_contact | adhering 5 and the decorating sheet 1 is mentioned.

  In the vacuum pressure bonding method, for example, a vacuum forming machine including a lower chamber box in which a space opening upward is formed and an upper chamber box in which a space opening downward is formed can be used. The lower chamber box is installed below the upper chamber box, and the opening of the upper chamber box and the opening of the lower chamber box are opposed to each other. When the lower part of the upper chamber box and the upper part of the lower chamber box are joined by the downward movement of the upper chamber box and / or the upward movement of the lower chamber box, the space in the upper chamber box and the lower side A sealed space is formed by the space in the chamber box. The sealed space is inserted between the upper chamber box and the lower chamber box, and is partitioned into an upper space and a lower space with the decorative sheet 1 held in the sealed space as a boundary. If the lower part of the upper chamber box and the upper part of the lower chamber box are separated by the upward movement of the upper chamber box and / or the downward movement of the lower chamber box, the sealed state of the sealed space is released. .

  The vacuum forming machine further includes a movable table provided in the space of the lower chamber box and movable up and down. The resin molded body 5 is placed on this movable table.

  The vacuum forming machine is decorated in the sealed space so that the sealed space formed by the space in the upper chamber box and the space in the lower chamber box is partitioned into the upper space and the lower space with the decorative sheet 1 as a boundary. A holding unit that holds the sheet 1, a heating unit that heats the decorative sheet 1 held by the holding unit, and a pressure adjustment unit that adjusts the pressure in the upper space and the lower space in the sealed space are further provided. The heating unit includes a heating plate such as a near infrared heater or an infrared heater. For example, the pressure adjusting unit is connected to the upper chamber box to bring the upper space into a vacuum state, an atmospheric pressure state, or a pressurized state, and connected to the lower chamber box to bring the lower space into a vacuum state. Has a pump and the like.

  In an example of the vacuum pressure bonding method using the above-described vacuum forming machine, first, the resin molded body 5 is placed on a movable table. Next, the decorative sheet 1 is inserted between the upper chamber box and the lower chamber box and held by the holding unit. Under the present circumstances, the decorating sheet 1 is hold | maintained so that the base material sheet 2 side of the decorating sheet 1 may be located in the lower space side. Next, the lower part of the upper chamber box and the upper part of the lower chamber box are joined by moving the upper chamber box downward and / or moving the lower chamber box upward, and the space in the upper chamber box and the lower side A sealed space is formed by the space in the chamber box. The sealed space thus formed is partitioned into an upper space and a lower space with the decorative sheet 1 as a boundary. Next, the upper space and the lower space are brought into a vacuum state by the pressure adjusting unit, and the decorative sheet 1 is heated and softened by the heating unit. Next, by raising the movable table, the resin molded body 5 placed on the movable table is raised and softened from below the decorated sheet 1, and the resin molded body 5 is the base sheet of the decorated sheet 1. Press against the 2 side surface. Next, the upper space is brought into an atmospheric pressure state or a pressurized state by the pressure adjusting unit (that is, the pressure in the upper space is adjusted to a pressure higher than that of the lower space in a vacuum state), and the pressure difference between the upper space and the lower space Thus, the resin molded body 5 and the decorative sheet 1 are brought into close contact with each other and integrated to form the decorative resin molded product 10. At this time, the decorative sheet 1 is stuck to the surface of the resin molded body 5 while being stretched. Thereafter, the sealed state of the sealed space is released and the decorative resin molded product 10 is taken out. An excess portion of the decorative resin molded product 10 taken out may be trimmed as necessary.

  Although the heating temperature of the decorating sheet 1 by a heating part is not specifically limited, Although it can adjust suitably according to the kind of resin which comprises the decorating sheet 1, the thickness of the decorating sheet 1, etc., it is 60-200, for example. It is about ℃.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is limited to the content of a following example, and is not interpreted.

(1) Production of decorative sheet for three-dimensional molding Using an ABS resin film (bending elastic modulus: 2000 MPa, thickness: 400 μm) as a base sheet, gravure printing using an acrylic resin composition on the surface of the film A decorative layer was formed. Subsequently, a composition containing acrylic polyol and hexamethylene diisocyanate (hexamethylene diisocyanate was blended so that the NCO equivalent was the same as the OH equivalent of the acrylic polyol) was applied to the surface of the decorative layer by gravure coating as a primer layer. did. The thickness of the primer layer was 3 μm.
Next, the surface of the primer layer is coated with an ionizing radiation curable resin composition containing a thermoplastic resin having the composition shown in Table 1 below and acryloylmorpholine or pentaerythritol triacrylate, and irradiated with an electron beam to protect the surface. A layer was formed.
The thermoplastic resins A to C included in the ionizing radiation curable resin composition used the resins shown below.
Thermoplastic resin A: weight average molecular weight: 120,000, glass transition temperature Tg: 105 ° C., homopolymer of methyl methacrylate Thermoplastic resin B: weight average molecular weight: 90,000, glass transition temperature Tg: 105 ° C., methyl methacrylate Homopolymer of thermoplastic resin C: weight average molecular weight: 120,000, glass transition temperature Tg: 90 ° C., copolymer of methyl methacrylate and methacrylic acid, and the ionizing radiation curable resin composition is irradiated with an electron beam It was applied by gravure coating so that the thickness after curing by 10 was 10 μm. Further, the ionizing radiation curable resin composition was cured by irradiating an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) as ionizing radiation.

(2) Evaluation of three-dimensional formability (molding elongation) Each of the decorative sheets produced in (1) is heated to 160 ° C. with an infrared heater to be softened, and then vacuum formed using a vacuum forming die. After forming into each internal shape of type | mold AD of the following shape, after cooling the decorating sheet, it mold-released and the molded object of the decorating sheet was obtained. The three-dimensional formability (molding elongation) of each decorative sheet was evaluated based on the appearance of the obtained decorative sheet.
Shape A: Mold having a portion with a maximum draw ratio of 70% Shape B: Mold having a portion with a maximum draw ratio of 150% Shape C: Mold having a portion with a maximum draw ratio of 200% Shape D: Part having a maximum draw ratio of 300% Note that the “maximum draw ratio” in each die represents the percentage of the area increase when the area of the decorative sheet before drawing is 100%. That is, for example, when a decorative sheet is stretched using “a mold having a portion with a maximum draw ratio of 70%”, the area of the decorative sheet before stretching is 100%, and the area is 170% at the maximum. It means to stretch.

The evaluation criteria for three-dimensional formability (mold elongation) are as follows.
A: The surface protective layer was free from cracks and whitening, and had a good appearance.
B: Slight whitening was observed at the maximum stretched part, but the appearance was satisfactory in practical use.
C: Cracks and whitening were observed in the maximum stretched portion, and the appearance was problematic in practice.
D: Cracks and whitening were observed in portions other than the maximum stretched portion and the maximum stretched portion, and the appearance was problematic in practice.
The evaluation results are shown in Table 1 below.

(3-1) Evaluation of chemical resistance (alcohol resistance) A sheet piece (50 mm × 50 mm) of a decorative sheet obtained in Examples and Comparative Examples was prepared, and a gauze soaked with 10% ethanol aqueous solution was used. The surface protective layer of each sheet piece was rubbed 100 times with a load of 500 gf. The alcohol resistance of each decorative sheet was evaluated based on the appearance of the sheet piece after rubbing.

The evaluation criteria for alcohol resistance are as follows.
A: There was no change in the state of the surface protective layer, and the appearance was good.
B: Although slight whitening and gloss reduction were observed on the surface protective layer, the appearance was satisfactory in practical use.
The evaluation results are shown in Table 1 below.

(3-2) Evaluation of chemical resistance (anti-sun cream resistance) Prepared sheet pieces (50 mm × 50 mm) of decorative sheets obtained in Examples and Comparative Examples, and commercially available sunscreen cosmetics (cream) 0 .5 g was uniformly applied to the surface protective layer of each sheet piece. After each sheet piece coated with sunscreen cosmetics is left in an oven at 80 ° C. for 1 hour, the surface of each sheet piece is washed with a neutral detergent, and the appearance (test surface) where sunscreen cosmetics are applied Based on the above, the sunscreen resistance of each decorative sheet was evaluated. In addition, sunscreen cosmetics are those of commercially available SPF50, and include the following components.
1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) -1,3-propanedione 3%
Salicylic acid 3,3,5-trimethylcyclohexyl 10%
2-ethylhexyl salicylate 5%
2-ethylhexyl 2-cyano-3,3-diphenylacrylate 10%

The evaluation criteria of sunscreen cream resistance are as follows.
A: No abnormalities such as whitening, swelling, gloss reduction, cracking, and peeling of the coating film were observed on the test surface, and the appearance was good.
B: Although slight whitening of the coating film was confirmed on a part of the test surface, the appearance was not a problem in practical use.
C: Although slight whitening, swelling, and gloss reduction of the coating film were confirmed on a part of the test surface, the appearance was not a problem in practical use.
D: Abnormalities such as whitening, swelling, gloss reduction, cracking, peeling, etc. of the coating film were confirmed over the entire test surface, and the appearance was poor and there were practical problems.
The evaluation results are shown in Table 1 below.

  As shown in Table 1, containing a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene and having a glass transition temperature of 95 ° C. or more, and (meth) acryloylmorpholine The decorative sheet for three-dimensional molding of Examples 1 to 5 provided with a surface protective layer formed of a cured product of an ionizing radiation curable resin composition is from a temperature of about 160 ° C. to a temperature when contacting the mold. Even under the conditions of a rapid temperature drop, a rapid stretching speed, and a high degree of stretching, cracks and cracks did not occur, and the three-dimensional formability was good. Furthermore, it was confirmed that the surface of the decorative sheet for three-dimensional molding of Examples 1 to 5 has excellent chemical resistance. That is, the three-dimensional formable decorative sheet of the present invention exhibits excellent three-dimensional formability and chemical resistance.

1: decorative sheet 2: base material sheet 3: surface protective layer 4: intermediate layer 41: decorative layer 42: primer layer 5: resin molding S1: first main surface of the base material sheet S2: second of the base material sheet Main face

Claims (11)

A three-dimensional decorative sheet comprising a base sheet and a surface protective layer provided on the base sheet,
The surface protective layer contains a thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted to standard polystyrene, and a glass transition temperature of 95 ° C. or more, and (meth) acryloylmorpholine. The decorative sheet formed of a cured product of an ionizing radiation curable resin composition.   The decorative sheet according to claim 1, wherein the cured product of the ionizing radiation curable resin composition contains a (meth) acrylic resin containing the (meth) acryloylmorpholine as a structural unit.   The decorative sheet according to claim 1 or 2, wherein a mass ratio of the thermoplastic resin and the (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition is 40:60 to 90:10.   The decorative sheet according to any one of claims 1 to 3, wherein the thermoplastic resin is a (meth) acrylic resin containing a (meth) acrylic acid ester as a structural unit.   A decorative resin molded product comprising the decorative sheet according to any one of claims 1 to 4 and a resin molded body integrated with the decorative sheet. It is a manufacturing method of the decorating sheet according to any one of claims 1 to 4,
Preparing a base sheet,
A thermoplastic resin having a weight average molecular weight of 100,000 or more and 250,000 or less converted into standard polystyrene, directly or via an intermediate layer, and a glass transition temperature of 95 ° C. or more on the substrate sheet; A step of forming an ionizing radiation curable resin composition layer containing (meth) acryloylmorpholine, and curing the ionizing radiation curable resin composition layer by irradiating the ionizing radiation curable resin composition layer with ionizing radiation. The process of
The manufacturing method of a decorating sheet containing this.   The production of a decorative sheet according to claim 6, wherein a mass ratio of the thermoplastic resin and the (meth) acryloylmorpholine contained in the ionizing radiation curable resin composition layer is 40:60 to 90:10. Method.   The method for producing a decorative sheet according to claim 6 or 7, wherein the thermoplastic resin is a (meth) acrylic resin containing a (meth) acrylic acid ester as a structural unit. It is a manufacturing method of the decorative resin molded product according to claim 5,
Heating and softening the decorative sheet according to any one of claims 1 to 4,
A step of preforming the decorative sheet softened by vacuum suction and adhering it along the molding surface of the injection mold; and a resin in a fluid state in a cavity formed by clamping the injection mold A process for producing a decorative resin molded product, comprising the step of injecting the resin and integrating the resin on the base sheet side of the decorative sheet. It is a manufacturing method of the decorative resin molded product according to claim 5,
After heating and softening the decorative sheet according to any one of claims 1 to 4, vacuum forming into a three-dimensional shape with a vacuum forming mold, and forming a molded body of the decorative sheet; and The molded body is inserted into an injection mold, the resin in a fluid state is injected into a cavity formed by clamping the injection mold, and the resin is integrated on the base sheet side of the molded body. The manufacturing method of a decorative resin molded product including a process. It is a manufacturing method of the decorative resin molded product according to claim 5,
A sealed space in which the decorative sheet and the resin molded body according to any one of claims 1 to 4 are arranged, wherein the sealed space is partitioned into an upper space and a lower space with the decorative sheet as a boundary, The base sheet side of the decorative sheet is located on the lower space side, and the resin molded body forms the sealed space located in the lower space;
A step of evacuating the upper space and the lower space;
Heating and softening the decorative sheet,
The step of raising the resin molded body and pressing it against the surface of the decorative sheet on the base sheet side; and the upper space in an atmospheric pressure state or a pressurized state, by a pressure difference between the upper space and the lower space The manufacturing method of a decorative resin molded product including the process of closely_contact | adhering the said resin molding and the said decorating sheet.

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