JPH07171927A - Patterned three-dimensional molded product and production thereof - Google Patents

Abstract

PURPOSE:To produce a patterned three-dimensional molded product not generating the thermal deformation of a base material and having good dimensional accuracy with enhanced workability even in a case using a thermoplastic resin low in heat resistance as the base material in a vacuum laminating molding method and a vacuum press laminating molding method. CONSTITUTION:An ionizing radiation curable adhesive cured within a short time without applying heating is used as the adhesive of a decorative sheet 1 and a base material 2 in place of a thermal adhesive. The adhesive is cured by incorporating an ionizing radiation irradiation device in a laminating mold in the same process as a laminating mold or by the irradiation with ionizing radiation by a separate device after molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional molded article and a method for producing the same, and more particularly, to an improved vacuum lamination molding method and vacuum press lamination molding method suitable for a molded article made of a thermoplastic resin which is weak against high heat. TECHNICAL FIELD The present invention relates to a surface decoration product and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, in response to the demand for higher design of plastic molded products, products in which the outer surface of the molded product is painted by various methods have been used in many fields. For example, various products such as home electric appliances, furniture, kitchen utensils, etc. are provided with design characteristics to enhance the commercial value of the products. Among them, as a decoration method for a molded product having a three-dimensional outer surface, after the molded product is molded, a decorative sheet having a decorative layer provided with a pattern or the like by printing in advance on a substrate sheet of a thermoplastic resin is used. Decorative layer using a transfer type decorative sheet that is attached along the outer surface of the molded product in a state of being softened by heat, or a releasable base material sheet of thermoplastic resin provided with a decorative layer such as a pattern Have been used.

Specific examples of the conventional painting method include a vacuum lamination molding method and a vacuum press lamination molding method. The vacuum lamination molding method is to make the decorative sheet conform to the shape of the base material by applying pressure to the outer surface of the base material that is the adherend by softening the decorative sheet with heat and then using air pressure. It is a method of laminating and attaching while deforming. Usually, in this method, as disclosed in, for example, Japanese Patent Publication No. 56-45768 and Japanese Patent Laid-Open No. 4-288214, an upper chamber located above and a lower chamber located below the upper chamber and facing each other. An apparatus consisting of a chamber and a substrate stand inside the lower chamber is used. In the manufacturing, the base material is placed on the base material stand and the decorative sheet is placed on the upper part of the lower chamber. Next, the upper chamber and the lower chamber are brought into contact with each other, so that the upper and lower chambers are separated into two chambers by a decorative sheet and are made airtight, and then the both chambers are decompressed. Next, the decorative sheet is heated by the heater disposed in the upper chamber so that the decorative sheet can be formed, and the base table moves upward to start contact between the base and the decorative sheet. After that, the decompression of the upper chamber is released, the decorative sheet is pressed against the outer surface of the base material by utilizing the pressure difference between the upper chamber and the lower chamber, and the heat-sensitive coating applied to the back surface of the decorative sheet and / or the outer surface of the base material. The function of the adhesive is to bond and fix the decorative sheet to the base material.

On the other hand, the vacuum press lamination molding method is similar to the vacuum lamination molding method, except that the contraction pressure of the rubber-like elastic film is used in addition to the air pressure for the pressure contact of the decorative sheet with the base material. It is slightly different in that it is performed through a rubber-like elastic film heated by a heater, and is characterized by uniform heating of a decorative sheet and stronger pressure contact force. Usually, in this method, as disclosed in, for example, Japanese Patent Laid-Open No. 5-131545, a rubber-like elastic film is arranged on the lower opening surface of the upper chamber,
On the other hand, the lower chamber is an apparatus in which a base material stand having an air through hole on the upper opening surface is arranged. In the manufacturing, the base material is placed on the base material stand, and the decorative sheet is placed on the base material. Next, the upper chamber and the lower chamber are brought into contact with each other, and the decorative sheet is pressed against the outer surface of the base material by utilizing the pressure difference generated between the upper chamber and the lower chamber, and is heated by a heater arranged in the upper chamber. The decorative sheet can be heated and molded by contacting the rubber-like elastic film, and the decorative sheet is adhered and fixed to the base material by the function of the heat-sensitive adhesive applied to the back surface of the decorative sheet and / or the outer surface of the base material. It is a thing.

In both of the above methods, there are adhesive type and transfer type decorative sheets. In the sticking type, a sticking sheet provided with a decorative layer made of a base material sheet or the like and, if necessary, a heat-sensitive adhesive layer is laminated on a base material via the heat-sensitive adhesive layer. The transfer type means that after a transfer sheet provided with a decorative layer to be transferred on a releasable substrate sheet and, if necessary, a heat-sensitive adhesive layer is attached, the release sheet is peeled off and only the decorative layer is formed. Is attached and transferred to the substrate via the heat-sensitive adhesive layer. When the heat-sensitive adhesive is applied to the outer surface of the base material, or when the heat-sensitive adhesive is applied to the decorative sheet immediately before, the heat-sensitive adhesive layer may not be provided on the decorative sheet side. Further, as the heat-sensitive adhesive layer used in these conventional techniques, a thermoplastic resin such as polyvinyl acetate or a thermosetting resin such as an isocyanate-curable polyurethane has been used.

[0006]

In both the vacuum lamination molding method and the vacuum press lamination molding method, a decorative layer is attached or transferred onto the outer surface of a molded article via an adhesive. As such an adhesive, a heat-sensitive adhesive is used, but in order for the decorative layer to be sufficiently adhered and fixed to the base material, it must satisfy the desired heat resistance under the usage environment of the molded product. Therefore, at the time of attaching or transferring the decorative sheet, the temperature at which the heat-sensitive adhesive is softened to develop the initial adhesive force and the decorative sheet is initially fixed to the base material is usually higher than or equal to the heat resistant temperature of the obtained three-dimensional molded article with painting. Required. Therefore, in the step of laminating the decorative sheet to the base material,
The adhesive is heated, but the base material is also heated at that time. However, in the case of a plastic molded product, a thermoplastic resin is very often used as a base resin, and a resin having low heat resistance or a molded product having a shape that is easily deformed by pressure during lamination molding is deformed and is not applicable. It can be difficult. In particular, when a molded product is combined with another molded product to assemble one product, even a slight dimensional defect is likely to result in defective assembly. Moreover, inexpensive thermoplastic resins often have low heat resistance, and when a low-cost three-dimensional molded article is produced, deformation tends to occur, which is a very troublesome problem. In addition, in the conventional manufacturing by the lamination molding method, the heating time for developing the initial adhesive strength of the heat-sensitive adhesive, and the temperature of the adhesive decreases after the initial adhesion is started, and the decorative layer is fixed to the base material. It took a cooling time to complete. Although these are performed partially in parallel with the pressure adjustment time of the upper chamber and the lower chamber, even if the pressure can be adjusted quickly, the heating time and the cooling time are in terms of the heat capacity of the decorative sheet and the molded product. This causes a long molding time, and higher productivity has been earnestly desired.

[0007]

In order to solve the above-mentioned problems and to achieve the object, the three-dimensional molded article with a picture of the present invention,
The three-dimensional molded article is characterized in that a decorative layer is laminated on the outer surface of the base material via an ionizing radiation curable adhesive.

As a manufacturing method thereof, a vacuum lamination in which a decorative sheet including at least a decorative layer is made to face a substrate and the decorative sheet is laminated and adhered along the outer surface of the substrate to be adhered by heat and air pressure. In the molding method, or in the vacuum press lamination molding method in which the decorative sheet is laminated and adhered along the outer surface of the substrate to be adhered by heat, air pressure and a rubber-like elastic film, the adhered surface side of the decorative sheet or / and The outer surface of the base material has an ionizing radiation-curable adhesive layer formed thereon, and after the decorative sheet is laminated and adhered along the outer surface of the base material, the ionization layer interposed between the decorative layer and the base material is applied. A method for producing a painted three-dimensional molded article, characterized in that the radiation-curable adhesive layer is irradiated with ionizing radiation from the front surface side of the decorative sheet and / or the back surface side of the base material to be cured.

As another manufacturing method, a decorative sheet comprising at least a releasable substrate sheet and a decorative layer is made to face the substrate, and the decorative sheet is adhered to the outer surface of the substrate by heat and air pressure. In a vacuum lamination molding method in which the releasable base material sheet is peeled off after transferring and the decorative layer is transferred to the outer surface of the base material, or the decorative sheet is adhered by heat, air pressure and a rubber-like elastic film. In a vacuum press lamination molding method in which a releasable base material sheet is peeled off after being laminated and attached along the outer surface of a barrel base material, and the decorative layer is transferred to the outer surface of the base material, a surface to which the decorative layer of the decorative sheet is attached The ionizing radiation-curable adhesive layer is formed on the side and / or the outer surface of the base material, and after the decorative sheet is laminated and attached along the outer surface of the base material, Before or after peeling the material sheet, there is an electric current between the decorative layer and the substrate. The radiation curable adhesive layer, it is an decorating method for producing a three-dimensional molded article characterized by curing the ionizing radiation from the back side of the front side or / and the base of the decorative sheet was irradiated. Furthermore, in the above-mentioned manufacturing method, in a state where the decorative sheet is laminated and adhered along the outer surface of the base material, and at least the vicinity of the adhesive is in a vacuum or a reduced pressure state than atmospheric pressure, A method for producing a three-dimensional molded article with a painting characterized by irradiating ionizing radiation to cure an adhesive. Furthermore, in the above-mentioned manufacturing method, the method of manufacturing a three-dimensional molded article with a feature is characterized in that irradiation in a vacuum or reduced pressure state is performed with ultraviolet rays, and then the adhesive is further cured with an electron beam. . In addition, the above-mentioned three-dimensional molded article and the manufacturing method thereof are characterized in that the base material is mainly a thermoplastic resin, and the three-dimensional molded article and a manufacturing method thereof.

First, the decorative sheet used in the present invention will be described. Decorative sheets are roughly classified into a sticking type and a transfer type. The adhesive type decorative sheet is composed of at least a decorative layer. The simplest structure is that the base sheet itself has a design property by mixing color pigments, pearl pigments, etc., the base sheet itself constitutes a decorative layer, and the base sheet is provided with an adhesive. It is a configuration that does not have. In this case, the adhesive is applied to the outer surface of the substrate to be adhered and used, or is applied to the adhered surface of the decorative sheet immediately before use. However, usually, a decorative layer is formed on the base sheet by printing a pattern layer, vapor deposition of a metal thin film or the like to form a decorative layer composed of the pattern layer and the base sheet, and if necessary, an adhesive layer on the adherend side. The sheet formed with is used as a decorative sheet. The pattern layer may be provided on the surface of the base material sheet, which is the front surface side after the decorative sheet is attached, and if the base material sheet is transparent, the decorative layer may be provided on the back surface side of the base material sheet. Further, a protective layer may be provided by coating a resin paint or the like on the layer on the surface side after sticking in order to improve the physical properties of the surface.

On the other hand, the transfer type decorative sheet is composed of at least a releasable base sheet and a decorative layer. The simplest structure is, for example, a structure in which a pattern layer formed by printing or the like on a releasable substrate sheet is used as a decorative layer. In this case, as in the case of the pasting type, the adhesive is applied on the side of the base material as the adherend, or is applied on the back surface of the decorative sheet immediately before.
If necessary, a decorative sheet having a structure in which an adhesive layer is further formed on the picture layer on the surface of the decorative sheet to be adhered can be used as the decorative sheet. The releasable substrate sheet can be used as it is if the substrate sheet itself has an appropriate releasability, otherwise, a releasable substrate is one having a release layer formed on the substrate sheet. Used as a sheet. Further, when the pattern layer is directly formed on the base sheet, the pattern layer becomes the outermost layer after transfer, so that the surface property is improved and the releasability from the releasable base sheet is adjusted. For the purpose of stabilization, a decorative sheet having a structure in which a release layer is interposed between the releasable base sheet and the pattern layer to form a decorative layer including at least the release layer and the pattern layer is also used.

In the above-mentioned sticking-type and transfer-type decorative sheets, the protective layer for the purpose of surface protection is not limited to the method of preparing at the stage of the decorative sheet, but it may be, for example, after the sticking or transferring to the base material. It may be formed by plate coating or the like.

Here, a part of the decorative sheets having various configurations used will be specifically described with reference to FIG. The decorative sheet 1 shown in (a) of FIG. 8 is of a sticking type and includes a base sheet 40, a decorative layer 5 including a pattern layer 51 and a protective layer 53, and an ionizing radiation curable adhesive layer 6. It is an example of a constituted makeup sheet. The decorative sheet 1 shown in (b) of FIG. 8 is a decorative sheet having a configuration in which the ionizing radiation-curable adhesive layer 6 is not provided in the decorative sheet of (a). The decorative sheet 1 shown in (c) of FIG. 8 is of a transfer type, and a release layer 42 is formed on the base material sheet 40 to form a release base material sheet 41, on which a release layer 52 and a pattern layer are provided. Decorative layer 5 consisting of 51
And a further ionizing radiation curable adhesive layer 6 is formed. Further, the decorative sheet 1 shown in (d) is a decorative sheet having a constitution in which the ionizing radiation-curable adhesive layer 6 is not provided in the decorative sheet of (c).

Each component of the decorative sheet used next will be described more specifically. The base sheet is not particularly limited as long as it has good moldability, and is used as it is when used as a sticking type and as a layer formed on the base sheet when used as a transfer type. If the releasability is relevant, the substrate sheet itself is used as the releasable substrate sheet, and if there is no releasability, the substrate sheet on which the release layer is formed is used as the releasable substrate sheet. What is used as such a substrate sheet, for example, polyvinyl chloride, polyvinylidene chloride, vinyl acetate-vinyl chloride copolymer, polyvinyl fluoride, polyvinyl butyral, vinyl resin such as polyvinylidene fluoride, polystyrene,
Methyl methacrylate-styrene copolymer, acrylonitrile-styrene copolymer (AS), acrylonitrile-
Styrene resins such as butadiene-styrene copolymer (ABS), acrylic resins such as polyethylmethacrylate and polymethylmethacrylate, olefin resins such as polyacrylonitrile, polyethylene, polypropylene and polymethylpentene, nylon 6, nylon 66 Polyamide resin such as polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, low crystallinity polyester resin such as polyarylate, rubber-based resin such as butadiene rubber, chloroprene rubber, silicone rubber, vinylon, polyvinyl alcohol Such as vinyl alcohol resin, cellulose resin such as athicel cellulose, nitrocellulose, thermoplastic resin film having moldability such as polycarbonate, or a laminate thereof. And the like. As the base sheet, one having a breaking elongation of 100% or more at room temperature is desirable from the viewpoint of moldability, and the thickness of the base sheet is usually 20 to
It is about 200 μm, but especially 50 from the viewpoint of moldability.
The range of ˜100 μm is preferred.

As the release layer formed on the base sheet to form the release base sheet, for example, a release agent such as fluororesin, various waxes and silicones is used as a known vehicle such as acrylic resin or cellulose. Resin, formed by coating a composition added to a vinyl resin or the like, or a releasable resin, for example, fluororesin, silicone, melamine resin,
An olefin resin, a urethane resin, an aminoalkyd resin, an epoxy resin, an ionizing radiation-curable acrylic resin or the like is coated or a thermoplastic resin is formed by melt extrusion lamination.

In the case of a sticking type decorative sheet, the decorative layer may be a single base sheet having a design feeling. The base sheet having a design feeling is, for example, a sheet in which the base sheet itself contains a colorant such as a pigment, a dye, or a pearl pigment, a matting agent, or a sheet having an uneven surface formed by embossing or the like. Is. The pattern layer constituting the decorative layer is, for example, a vinyl chloride-vinyl acetate copolymer, a printed pattern formed by dispersing a pigment, a dye or the like in a binder such as an acrylic resin, a known printing ink, the entire surface or partial vapor deposition of aluminum or the like. A pattern or the like, or a combination thereof.
Further, the protective layer constituting the decorative layer improves surface physical properties such as scratch resistance, chemical resistance and stain resistance of the decorative layer after being attached or transferred. In the case of the transfer type, the peeling layer serves as a protective layer, and the same known thermoplastic resin used for forming the pattern layer is used. For excellent scratch resistance, etc., a thermosetting resin, ionizing radiation is used. A curable resin or the like is used. When an ionizing radiation-curable adhesive is applied to the outer surface of the base material that is the adherend, the ionizing radiation-curable adhesive layer can be omitted on the decorative sheet side. Corona discharge treatment on the back surface, that is, the surface of the decorative layer,
A surface easy adhesion treatment such as a primer treatment may be performed.

The ionizing radiation-curable adhesive is a feature of the present invention, and is an adhesive that is cured by ionizing radiation. Ionizing radiation is radiation having an energy quantum sufficient to crosslink and polymerize molecules such as ultraviolet rays, electron beams, and γ rays. Further, the term "curing" as used herein means that the constituent molecules of the adhesive are cross-linked or chain-extended into a high molecular weight by radical polymerization, ionic polymerization, addition polymerization, polycondensation or the like due to the action of ionizing radiation, and are softened before irradiation. A phenomenon in which temperature, elastic modulus, breaking stress, etc. increase. The ionizing radiation-curable adhesive used in the present invention may be a liquid or a solid at room temperature. In the case of a solid, the ionizing radiation-curable adhesive layer is preliminarily prepared as a decorative sheet having a structure in which the ionizing radiation-curable adhesive layer is formed beforehand. The sheet may be stored in a rolled-up form, or may be applied to a substrate as an adherend in advance and stored. Alternatively, in the process of sticking or transferring, after deforming and pressing the decorative sheet onto the outer surface of the base material, the air between the decorative sheet and the base material is sufficiently degassed, and then the ionizing radiation curable adhesive is heated and softened to make it heat-sensitive. It is also possible to adopt a two-step process in which the adhesive strength as an adhesive is developed and then the adhesive strength is further enhanced by curing with ionizing radiation. In the case of a liquid, it is used by a method of coating on the back surface of the decorative sheet or the outer surface of the base material before sticking or transferring.

Examples of the ionizing radiation-curable resin used as the ionizing radiation-curable adhesive include polymerizable unsaturated bonds such as a plurality of acryloyl groups, methacryloyl groups, acryloyloxy groups and methacryloyloxy groups in the molecule,
A composition in which a prepolymer, an oligomer and / or a monomer having a thiol group or an epoxy group are appropriately mixed can be used. When the composition is in a liquid state, it may be semi-cured by irradiation with ionizing radiation to adjust the viscosity or be solidified before or after the coating is formed on the decorative sheet side and / or the base material side. .

The above-mentioned prepolymers and oligomers include
For example, unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, epoxy resins, polyester methacrylates, polyether methacrylates, polyol methacrylates, acrylic resin methacrylates,
Methamines such as melamine methacrylate and silicon methacrylate, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylic resin acrylates, melamine acrylates, acrylates such as silicon acrylates and the like can be mentioned.

Examples of the above-mentioned monomer include styrene-based monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate and acryl. Acrylic esters such as butyl acrylate, methoxybutyl acrylate, phenyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, etc. Acid esters, acrylic acid-2- (N, N-
Diethylamino) ethyl, methacrylic acid-2- (N, N
-Dimethylamino) ethyl, acrylic acid-2- (N, N
-Dibenzylamino) ethyl, methacrylic acid-2-
(N, N-dimethylamino) methyl, acrylic acid-2-
Substituted amino alcohol esters of unsaturated acids such as (N, N-diethylamino) propyl, monofunctional monomers such as unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, Bifunctional monofunctional compounds such as neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and propylene glycol dimethacrylate. A quantity,
Polyfunctional compounds such as trifunctional or higher monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate, or Polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate,
Examples thereof include pentaerythritol tetrathioglycol.

Although the above-mentioned substances can be sufficiently cured by electron beams, when they are cured by irradiation with ultraviolet rays, they are used as photopolymerization initiators such as acetophenones, benzophenones, Michler benzoyl benzoate, benzyl methyl ketal and α-. Amyloxime ester, tetramethylmeuram monosulfide, thioxanthone, and / or n-butylamine, triethylamine, tri-n-butylphosphine or the like as a photosensitizer are mixed and used.

In the case of UV curing, a photopolymerization initiator and / or a photosensitizer is added to one or more of the above ionizing radiation curable resins, and a polymerizable monomer is further added if necessary. A mixture of a non-ionizing radiation curable thermoplastic resin, a solvent and the like can be used as an ionizing radiation curable adhesive.
The solvent is also used so that the composition of solid ionizing radiation curable resin can be applied as a coating liquid.

Non-ionizing radiation curable thermoplastic resins include, for example, ethyl cellulose, nitrocellulose, acetyl cellulose, ethyl hydroxyethyl cellulose,
Cellulose derivatives such as cellulose acetate propionate, polystyrene, poly α-methylstyrene, styrene resins such as acrylonitrile-styrene copolymer, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, Acrylic resin such as acrylate-styrene copolymer, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, vinyl polymer such as polyvinyl butyral, rosin, rosin modified Maleic acid resin, rosin-modified phenol resin, polymerized rosin, rosin-based resin such as rosin ester, urethane resin,
Examples thereof include polyester resins and ionomers.

The ionizing radiation-curable adhesive layer may be formed by applying a coating liquid containing the above composition by a known coating method. For example, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, comma coating, brush coating, spray coating and the like are used. In the case of forming on a base material, among these, methods such as curtain flow coating, brush coating, and spray coating are used. Further, the ionizing radiation-curable adhesive layer is preferably one having a breaking elongation of 100% or more at room temperature from the viewpoint of moldability, from the viewpoint of low temperature molding. The thickness of the ionizing radiation curable adhesive layer is usually about 5 to 50 μm, preferably 5 to 20 μm.
The range of μm is preferable. Depending on the shape of the base material, if the thickness is less than 5 μm, the thickness extended in the stretched portion will be thin and the adhesion performance will be impaired. Conversely, if it is greater than 20 μm, coating will be difficult with the coating method, and a large amount of energy will be required during curing. Therefore, it also causes a time extension, and the amount of resin increases, which is uneconomical. As the irradiation time of the ionizing radiation, in the vacuum lamination molding or vacuum press lamination molding step, the decorative sheet is vacuum sucked onto the base material, and at least the vicinity of the adhesive is less than the vacuum or atmospheric pressure and the oxygen concentration decreases. It is preferable to perform it in the state where The reason for this is that oxygen is unnecessarily consumed as active species in the high molecular weight reaction by the ionizing radiation curable resin, and the curing reaction (crosslinking or the like) is hindered.
In this case, a particularly preferable oxygen concentration is 5000 PPM or less.

Next, regarding the base material to be painted with the above decorative sheet, the most effective one in the molded article and the manufacturing method according to the present invention is the base material mainly containing a thermoplastic resin. For example, polystyrene, acrylonitrile-styrene copolymer (AS), styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS), acrylic resin such as polymethylmethacrylate (MMA), polycarbonate, polyethylene, polypropylene, poly Examples include olefin resins such as methylpentene and polyamide resins such as nylon 6 and nylon 66. Among these, it is particularly effective for a resin that is easily deformed by heat. The base material is not limited to the thermoplastic resin in the three-dimensional molded article with a paint and the method for producing the same, which uses the ionizing radiation curable resin disclosed in the present invention as an adhesive. The base material is not particularly limited as long as at least one of the decorative sheet and the base material is transparent to ionizing radiation. For example, various thermosetting resins, ceramics such as glass, wood, metal and the like may be used. The use of ionizing radiation-curable adhesives for these base materials also improves the environmental temperature resistance of the resulting three-dimensional molded article, and in the manufacturing method, the heating time of the adhesive is omitted and the solidification time is shortened. The effect of improving productivity and the like can be obtained.

Next, the method for producing a three-dimensional molded product with a picture according to the present invention will be described in more detail. The vacuum lamination molding method and the vacuum press lamination molding method which are the objects of the present invention,
A conventionally known device can be used as it is. In this case, the ionizing radiation-curable adhesive may be cured by taking out the processed product, which has been temporarily adhered by transferring and transferring, from the laminate molding apparatus and then performing the curing with another known ionizing radiation irradiation apparatus. Good. However, by incorporating an ionizing radiation irradiation device in the lamination molding device, temporary adhesion for attachment / transfer and main adhesion by curing can be performed in one step. Moreover, for the reasons described above, the decorative sheet is attached to the base material by vacuum suction,
By irradiating with the oxygen concentration near the adhesive low, it is possible to prevent curing inhibition due to the oxygen concentration of the adhesive, and to eliminate the need for a separate process and device for filling an inert gas and creating a vacuum atmosphere. There are advantages.

FIG. 1 is a schematic configuration diagram of a vacuum lamination molding apparatus 10 incorporating an ionizing radiation irradiation apparatus. There is an upper chamber 11 which can be moved up and down by a vertical movement means 13 such as a hydraulic cylinder, and a lower chamber 21 which faces the upper chamber 11 and is downward. A heater 12 is arranged inside the upper chamber 11. Inside the lower chamber 21, there is a base material table 22 which can be moved up and down by a vertical movement means 23 such as a hydraulic cylinder. The base material table 22 has an opening at the central portion on which the base material 2 is placed, and the lower part thereof. The ionizing radiation irradiation device 25 is arranged at a position where the base material 2 can be irradiated from below. The upper chamber 11 and the lower chamber 21 have supply / exhaust ports 14 and 24, respectively, and their internal pressures can be adjusted independently.

The manufacturing method using such a vacuum lamination molding apparatus is as follows.
First, with the upper chamber 11 moving upward and separated from the lower chamber 21 and the upper chamber and the lower chamber being opened, the substrate 2 as an adherend is placed on the substrate stand 22 and the decorative sheet 1 is lowered. It is placed on the upper surface of the chamber 21. When the ionizing radiation curable adhesive is separately formed on the outer surface of the decorative sheet or the base material, it is applied and formed at this stage. When the ionizing radiation-curable adhesive contains a solvent, the solvent is also dried by this stage. Otherwise, the solvent may foam during the depressurizing operation of the lower chamber 21 in the subsequent step, which is not convenient. Then, the upper chamber 11 is moved downward and pressed against the lower chamber 21 to seal the upper chamber 11 and the lower chamber 21. FIG. 1 shows this sealed state.
Next, the pressure inside the upper chamber 11 and the lower chamber 21 is reduced. If necessary, the heater 12 is used to heat and soften the decorative sheet 1 so that it can be molded. The base material table 22 is moved upward to a position where the base material 2 can come into contact with the decorative sheet 1.
FIG. 2 shows this state. Next, the decompression of the upper chamber 11 is released, and the decorative sheet 1 is deformed and pressed along the outer surface of the base material 2 due to the pressure difference between the upper chamber 11 and the lower chamber 21.
In addition to returning the pressure of the upper chamber 11 to the atmospheric pressure, the pressure in the upper chamber 11 and the lower chamber 21 is increased to increase the pressure difference between the upper chamber 11 and the lower chamber 21 as necessary, and the decorative sheet 1 is transformed into the base material 2. The pressing force may be enhanced.

Further, in this case, when an ionizing radiation-curable adhesive which is solid at room temperature is used, it is disclosed in JP-A-5-13.
As disclosed in Japanese Patent No. 1545, as such an ionizing radiation curable adhesive, the temperature at which the initial adhesive force is developed by softening and melting by heating is higher than the temperature of the decorative sheet at the time of the above deformation pressure contact. By using the one set to be high, the deformation pressure contact is performed, and after that, the decorative sheet 1 is brought into close contact with the base material 2 by the initial adhesive force.
It is possible to effectively prevent bubbles remaining near the ionizing radiation curable adhesive layer. When a liquid ionizing radiation curable adhesive is used, initial adhesion is obtained when the decorative sheet 1 comes into contact with the ionizing radiation curable adhesive, so that at least the lower chamber 21 is sufficiently decompressed, and It is preferable that the adhesion phenomenon of the decorative sheet 1 to the base material 2 occurs in sequence on the outer surface of the base material. However, the heating temperature for obtaining the initial adhesion of the adhesive is limited to such a level that the base material is not softened or deformed.

In this way, a state is obtained in which the decorative sheet 1 is initially fixed to the outer surface of the substrate 2 by the initial adhesion of the ionizing radiation curable adhesive. Next, the ionizing radiation irradiation device 25 irradiates ionizing radiation from the back side of the base material 2 to cure the ionizing radiation curable adhesive, and the decorative sheet 1
Is firmly fixed to the base material 2. FIG. 3 shows this state. Finally, when the lower chamber 21 is depressurized and the upper chamber 11 is pressurized, the pressure is also released to bring both chambers to atmospheric pressure, and the upper chamber 11 is moved upward to move the upper chamber 11 and the lower chamber 21.
Is opened and the base material 2 to which the decorative sheet 1 is attached is taken out. In this way, a three-dimensional molded article with a picture according to the present invention is obtained. When the decorative sheet is a transfer type, the releasable substrate sheet is peeled off at this point to obtain a desired three-dimensional molded article with a picture. The above-mentioned ionizing radiation curable adhesive may be completely cured in the apparatus. However, the fixing of the decorative sheet 1 and the base material 2 may be performed without irradiation to a degree sufficient for the process work or with some irradiation. If obtained, the product may be taken out from the apparatus and then completely irradiated with ionizing radiation to be completely cured in consideration of efficiency. In this case, in a good mode, the irradiation inside the device is generally small and convenient, but an ultraviolet irradiation device that is inferior in transparency and reactivity is used, and irradiation outside the device is transmitted instead of the large device and bulky. It is preferable to use an electron beam irradiation device which is excellent in both reactivity and reactivity. or,
Although the reason is unknown, it is better to cure with ultraviolet light first and then with electron beam than with ultraviolet light or electron beam only, to obtain a higher crosslink density and better adhesive strength and heat resistance. There is also an effect of improving. Also, FIG.
In the example of the apparatus described above, the ionizing radiation was irradiated from the side of the base material 2. However, if the base material 2 is impermeable to ionizing radiation, of course, an irradiation device is provided outside the decorative sheet 1 and the surface of the decorative sheet 1 is exposed. Irradiate.

On the other hand, in the case of a device which does not have a built-in ionizing radiation irradiation device, after the decorative sheet 1 is brought into close contact with the outer surface of the base material 2 by the initial adhesive force of the ionizing radiation curing type adhesive, After setting the pressure of the chamber 11 and the lower chamber 21 to atmospheric pressure, the upper chamber 11 is moved upward to open the upper chamber 11 and the lower chamber 21, the molded product is taken out, and the ionizing radiation curing type adhesion is performed using another irradiation device. Allow the agent to cure.

Also in the case of the vacuum press lamination molding method, the method of curing the ionizing radiation curable adhesive is basically the same as the vacuum lamination molding method. However, there is a slight difference in that a rubber-like elastic film is used. FIG. 4 is a schematic configuration diagram of a vacuum press lamination molding apparatus 30 incorporating an ionizing radiation irradiation apparatus. There is an upper chamber 11 which can be moved up and down by an up-and-down moving means 13 above, and a lower chamber 21 which faces the upper chamber 11 and below. A heater 12 is arranged inside the upper chamber 11. The lower opening surface of the upper chamber 11 is entirely covered with a rubber-like elastic film 15. Silicon rubber or the like is usually used for the rubber-like elastic film 15. The upper surface of the lower chamber 21 serves as a base material table 22 having a plurality of exhaust holes 26. The base material table 22 has an opening at the central portion on which the base material 2 is placed, and an ionizing radiation irradiation device 25 is provided at the lower portion thereof.
Is arranged at a position where it can be illuminated from below. Upper chamber 11
The lower chamber 21 and the lower chamber 21 have supply / exhaust ports 14 and 24, respectively, and the internal pressures of the respective ports can be adjusted independently.

In the manufacturing method using the vacuum press laminating apparatus, first, the base material 2 to be adhered is placed on the base material mount 22 in a state where the upper chamber 11 moves upward and is separated from the lower chamber 21. Further, the decorative sheet 1 is arranged from above the base material 2. When the ionizing radiation curable adhesive is separately formed on the outer surface of the decorative sheet or the base material, it is applied and formed at this stage. When the ionizing radiation-curable adhesive contains a solvent, the solvent is also dried by this stage. Otherwise, the solvent may foam during the depressurizing operation of the lower chamber 21 in the subsequent step, which is not convenient. FIG. 4 shows the separated state of the upper chamber 11 and the lower chamber 21. Then, the upper chamber 11 is moved downward and brought into pressure contact with the lower chamber 21, and the upper chamber 11 and the lower chamber 21
Seal. FIG. 5 shows this state. Next, the inside of the lower chamber 21 is decompressed and the inside of the upper chamber 11 is pressurized. Further, if necessary, the heater 12 is used to heat and soften the decorative sheet 1 through the rubber-like elastic film 15 so that the decorative sheet 1 can be molded. As a result, the decorative sheet 1 is arranged along the outer surface of the base material 2 in the upper chamber 1
The pressure difference between the lower chamber 21 and the lower chamber 21 and the contraction pressure of the rubber-like elastic film cause deformation and pressure contact.

At this time, when the ionizing radiation-curable adhesive is solid at room temperature, the ionizing radiation-curable adhesive is heated by heating, as disclosed in JP-A-5-131545. When the temperature at which the initial adhesive force is expressed by softening or melting is set to be higher than the temperature of the decorative sheet at the time of the deformation pressure welding, the makeup by the initial adhesive force after the deformation pressure welding is used. By allowing the sheet 1 to adhere to the base material 2, it is possible to effectively prevent air bubbles from remaining near the ionizing radiation-curable adhesive layer. When a liquid ionizing radiation-curable adhesive is used, initial adhesion is obtained when the decorative sheet 1 contacts the ionizing radiation-curable adhesive, so the base material 2 of the decorative sheet 1 is used.
It is advisable to select the outer surface shape of the molded product and adjust the operating pressure to the rubber-like elastic film so that the adhesion phenomenon to the outer surface of the base material occurs in sequence.

In this way, a state is obtained in which the decorative sheet 1 is initially fixed to the outer surface of the base material 2 by the initial adhesion of the ionizing radiation curable adhesive. Next, the ionizing radiation irradiation device 25 irradiates ionizing radiation from the back side of the base material 2 to cure the ionizing radiation curable adhesive, and the decorative sheet 1
Is firmly fixed to the base material 2. FIG. 6 shows this state. Finally, the decompression of the lower chamber 21 is released, and the pressure of the upper chamber 11 is released to bring both chambers to the atmospheric pressure, and the upper chamber 11 is moved upward to separate the upper chamber 11 and the lower chamber 21 from each other. The base material 2 to which the sheet 1 is attached is taken out. In this way, a three-dimensional molded article with a picture according to the present invention is obtained. When the decorative sheet is a transfer type, the releasable substrate sheet is peeled off at this point to obtain a desired three-dimensional molded article with a picture. Incidentally, the curing of the ionizing radiation curable adhesive as in the vacuum lamination molding method,
An irradiation device may be provided in the apparatus and completely cured in the apparatus. However, as long as the fixation of the decorative sheet 1 and the base material 2 is obtained without irradiation to a sufficient degree in the process work or by a certain amount of irradiation. In consideration of efficiency, the product may be taken out of the apparatus and then separately irradiated with ionizing radiation to be completely cured.
In this case, as a preferred embodiment, as in the vacuum lamination molding method, there is an embodiment in which UV irradiation is performed inside the apparatus and then electron beam irradiation is performed outside the apparatus.

On the other hand, in the case of a device which does not have a built-in ionizing radiation irradiation device, after the decorative sheet 1 is brought into close contact with the outer surface of the base material 2 by the initial adhesive force of the ionizing radiation curing type adhesive, After the upper chamber 11 is moved upward by separating the upper chamber 11 and the lower chamber 21 by setting the pressure of the chamber 11 and the lower chamber 21 to the atmospheric pressure, the molded product is taken out, and the ionizing radiation curing type adhesive is applied by using another irradiation device. Allow the agent to cure.

The vacuum press lamination molding method is disclosed in
As disclosed in Japanese Patent No. 131545, for example, before the upper chamber 11 and the lower chamber 21 are assembled and sealed, the upper chamber 11 is pressurized to make the rubber-like elastic film 15 convex downward, and the makeup is applied. There are various operating pressure adjustments for the upper chamber 11 and the lower chamber 21, such as contacting with the seat 1, but the method for producing a three-dimensional molded article with a paint according to the present invention is not particularly limited.

FIG. 7 is a schematic configuration diagram of another embodiment in which the ionizing radiation irradiation device is installed above the inside of the upper chamber 11 in the vacuum lamination molding device. When the ionizing radiation irradiation device is built in, it may be in the upper chamber 11 and / or the lower chamber 21. In the vacuum press lamination molding apparatus, if the rubber-like elastic film 15 installed on the lower opening surface of the upper chamber 11 does not have good permeability to ionizing radiation, only the lower part is installed.

[0039]

According to the three-dimensional molded article and the method for producing the same according to the present invention, the bonding between the decorative sheet for painting the outer surface of the base material and the base material is performed by an ionizing radiation curable adhesive which does not require heating for the curing reaction. A conventional heat-sensitive adhesive is not necessary for bonding. When the ionizing radiation-curable adhesive is a liquid, the adhesive already has an initial adhesive force at room temperature, and thus the adhesive is heated to develop the initial adhesive force like a conventional heat-sensitive adhesive. No need. Even when the ionizing radiation-curable adhesive is solid, unlike conventional heat-sensitive adhesives, it is possible to impart sufficient heat resistance to the adhesive in the subsequent curing reaction, so soften or melt the adhesive. The heating temperature for expressing the initial adhesive strength can be set as an independent temperature, which is separate from the heat resistant temperature of the obtained three-dimensional molded article, and as a result, it is lower than the conventional heat-sensitive adhesive. Can be set. The heating temperature for forming the decorative sheet does not need to be high or low to express the initial adhesive strength of the adhesive, and in the case of a transfer type decorative sheet, the releasable base sheet is the final three-dimensional molding with painting. Since it does not remain in the product and is not related to the heat resistance of the final product, it can be set independently for the decorative sheet, and it can be set at a lower temperature than in the past depending on the formability of the decorative sheet. If the physical properties of the decorative sheet have moldability even at room temperature, room temperature molding is possible.
Also, when curing the ionizing radiation while the decorative sheet is attached to the base material by vacuum suction, the adhesive does not cause curing inhibition by oxygen in the air, and additionally vacuum suction, inert gas filling process Is also unnecessary. In addition, UV cure the adhesive with at least a vacuum around the adhesive, and then
When adopting the method of electron beam curing outside the equipment, in addition to reducing the inhibition of curing of the adhesive by oxygen remaining between the base material and the adhesive, the reason for this is unknown, but the crosslinking of the adhesive The density is also improved, resulting in better adhesion. As a result, the temperature rise that the base material undergoes when the decorative sheet and the adhesive are heated can be basically and effectively suppressed. Therefore, even a base material made of a thermoplastic resin having low heat resistance is prevented from being deformed due to a temperature rise.

[0040]

EXAMPLES Examples and comparative examples of the present invention will be shown below to compare the effects of the present invention.

Example 1 As a transfer type decorative sheet, a releasable substrate sheet was used as a transparent polyvinyl chloride film (W-500 manufactured by Riken Vinyl Industry Co., Ltd., thickness 100 μm).
m), a 2 μm-thick release layer of nitrocellulose-based release ink and a multicolored pattern layer of mixed ink of acrylic resin and vinyl chloride-vinyl acetate copolymer are formed by gravure printing, and adhered to this. An adhesive solution (three bond 30 manufactured by Three Bond Co., Ltd.) prepared by adding a benzophenone photopolymerization initiator to a polyfunctional acrylic prepolymer and diluting an ionizing radiation curable adhesive layer having a thickness of 5 μm
56) was applied by the gravure coating method and the solvent was dried to form a decorative sheet. On the other hand, a front panel of an air conditioner made of a clear ABS resin having a large number of slit-shaped openings was prepared as a base material for a thermoplastic resin molded article. The decorative sheet and the base material are 250 to 4
With a vacuum lamination molding device that has an ultraviolet irradiation device consisting of a high-pressure mercury lamp (output per lamp: 80 W / cm) having a main wavelength distribution of 00 nm on the substrate stand and the inner ceiling of the upper chamber,
After placing the decorative sheet and the base material, decompress the upper chamber and the lower chamber,
Next, pressurize the upper chamber to 0.3 MPa to deform and press the decorative sheet against the outer surface of the base material, and heat the decorative sheet to a sheet temperature of 50 ° C with the heater in the upper chamber to bond the adhesive. A force was exerted to cause initial adhesion, and then ultraviolet rays of a high pressure mercury lamp were irradiated from below the base material for 5 seconds while the pressure in the lower chamber was 1 kPa (oxygen concentration 2000 PPM) to cure the adhesive. Then, the upper chamber and the lower chamber were returned to atmospheric pressure, the molded product was taken out from the apparatus, and the releasable base material sheet of the decorative sheet was peeled off to obtain a three-dimensional molded product with a picture according to the present invention. The obtained molded product was good without thermal deformation of the substrate.

Example 2 The three-dimensional molded article with a picture prepared in Example 1 was taken out of the apparatus, and then an electron beam with an accelerating voltage of 150 keV was irradiated from the side of 3 Mrad decorative layer by an electron beam irradiation apparatus to obtain an adhesive. Was further cured. The surface of the makeup layer is # 000
When the steel wool of 0 was rubbed 10 times back and forth, no scratch was observed on the surface and, of course, the surface was not whitened and the pattern was not peeled off.

Example 3 As a sticking type decorative sheet, a transparent polyvinyl chloride film (W-500 manufactured by Riken Vinyl Industry Co., Ltd., W-500, thickness 100 μm) was formed on one surface of a substrate sheet.
m) was used to form a transparent pattern consisting of an uneven line pattern having an uneven height of 10 μm by curing an ultraviolet curable resin with a silk screen and curing it with a high pressure mercury lamp of 80 W / cm. An ionizing radiation curable adhesive layer was formed on the other surface of the substrate sheet in the same manner as in Example 1. On the other hand, as the base material of the molded product, the same one as in Example 1 was used except that a colored resin containing a filler was used. In the vacuum lamination molding apparatus, the same procedure as in Example 1 was carried out except that the ultraviolet irradiation was performed from above the decorative sheet. The obtained molded product was good without thermal deformation of the substrate.

Comparative Example A decorative sheet was prepared in the same manner as in Example 1 except that a heat-sensitive adhesive composed mainly of a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer was used as the adhesive for the decorative sheet. Created. Next, using the same vacuum lamination molding apparatus as that used in Example 1, after arranging the decorative sheet and the base material, the decorative sheet is heated by the heater provided in the upper chamber while depressurizing the upper chamber and the lower chamber. Heat the sheet for 120 seconds to bring the temperature of the sheet to 120 ° C. to bring the adhesive layer into the state of exhibiting the initial adhesive strength, and keep the temperature at that temperature, then 0.3 M in the upper chamber.
The pressure was applied to Pa to deform and adhere the decorative sheet to the outer surface of the base material. After 30 seconds as the cooling time of the adhesive, the upper chamber and the lower chamber were returned to atmospheric pressure, the molded product was taken out of the apparatus, and the releasable base material sheet of the decorative sheet was peeled off to obtain a three-dimensional molded product with painting. . The obtained molded product was defective because the substrate was thermally deformed. When the surface of the decorative layer was rubbed with # 0000 steel wool, the surface was innumerable scratches and whitened, and part of the pattern wear disappeared in the pattern portion where the pattern ink was thin (light density). It was

[0045]

Since the present invention is constructed as described above, it has the following effects. Since the amount of heat received by the base material during molding can be reduced, the base material will not be thermally deformed even if a resin having low heat resistance is used as the base material. For this reason, the dimensional accuracy of the obtained three-dimensional molded product with a picture is improved, and a dimensional defect which becomes a problem when the molded product is assembled is eliminated. Also,
An inexpensive resin can be used, and a three-dimensional molded product with a picture can be provided at a lower cost. Furthermore, since the curing of the adhesive is completed in a short time without heating by ionizing radiation, the lamination molding time is shortened and the productivity is improved. Further, in the case of a solventless ionizing radiation curable adhesive, the occurrence of blistering on the outer surface of the painted three-dimensional molded product caused by the generation of bubbles due to the residual solvent, which occurs when the adhesive is not sufficiently dried, is eliminated. .

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a vacuum lamination molding apparatus used in the present invention and a diagram showing one step of a manufacturing method.

FIG. 2 is a diagram showing another step of the manufacturing method by the vacuum laminating apparatus.

FIG. 3 is a diagram showing another step of the manufacturing method by the vacuum laminating apparatus.

FIG. 4 is a schematic configuration diagram of a vacuum press lamination molding apparatus used in the present invention and a diagram showing one step of a manufacturing method.

FIG. 5 is a diagram showing another step of the manufacturing method by the vacuum press laminating apparatus.

FIG. 6 is a diagram showing another step of the manufacturing method by the vacuum press laminating apparatus.

FIG. 7 is a schematic configuration diagram of another embodiment of the vacuum lamination molding apparatus used in the present invention.

FIG. 8 is a longitudinal sectional view showing an example of various decorative sheets used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Base material 10 Vacuum lamination molding apparatus 11 Upper chamber 12 Heater 13,23 Vertical movement means 14,24 Air supply / exhaust port 15,25 Ionizing radiation irradiation device 16 Rubber-like elastic film 21 Lower chamber 22 Base material stand 26 Exhaust hole 30 Vacuum Press Laminating Machine 40 Base Material Sheet 41 Releasable Base Material Sheet 42 Release Layer 5 Decorative Layer 51 Picture Layer 52 Release Layer 53 Protective Layer 6 Ionizing Radiation Curable Adhesive Layer

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Claims (7)

[Claims] 1. A three-dimensional molded article with a paint, characterized in that a decorative layer is laminated on the outer surface of a base material with an ionizing radiation-curable adhesive layer interposed therebetween. 2. A vacuum lamination molding method, wherein a decorative sheet comprising at least a decorative layer is made to face a base material, and the decorative sheet is laminated and adhered along the outer surface of a base material as an adherend by heat and air pressure, or In a vacuum press laminating method for laminating and attaching a decorative sheet along the outer surface of a base material as an adherend by heat, air pressure and a rubber-like elastic film, the adhered surface side of the decorative sheet and / or the outer surface of the base material Is an ionizing radiation curable adhesive layer formed by laminating a decorative sheet along the outer surface of a base material, and then interposing the adhesive layer between the decorative layer and the base material. A method for producing a painted three-dimensional molded article, comprising irradiating the layer with ionizing radiation from the front surface side of the decorative sheet and / or the back surface side of the base material to cure the layer. 3. A decorative sheet comprising at least a releasable substrate sheet and a decorative layer is faced to the substrate, and the decorative sheet is laminated and attached along the outer surface of the substrate to which the decorative sheet is adhered by heat and air pressure. In a vacuum lamination molding method in which the releasable base material sheet is subsequently peeled off and the decorative layer is transferred to the outer surface of the base material, or by heat,
Laminate a decorative sheet along the outer surface of a substrate as an adherend by air pressure and a rubber-like elastic film, and then peel off the releasable substrate sheet to transfer the decorative layer to the outer surface of the substrate. In the molding method, the surface of the decorative sheet to which the decorative layer is adhered and / or the outer surface of the base material has an ionizing radiation curable adhesive layer formed thereon, and the decorative sheet is formed along the outer surface of the base material. The ionizing radiation-curable adhesive layer interposed between the decorative layer and the base material after being laminated and before or after the release of the releasable base material sheet is provided on the surface side of the decorative sheet or / and the base material. A method for producing a three-dimensional molded article with a coating, which comprises irradiating with ionizing radiation from the back side of the resin to cure. 4. The method for manufacturing a three-dimensional molded article with a paint according to claim 2 or 3, wherein the decorative sheet is laminated and adhered along the outer surface of the base material, and at least in the vicinity of the adhesive. A method for producing a painted three-dimensional molded article, which comprises irradiating with ionizing radiation to cure the adhesive in a state of being in a vacuum or a pressure lower than atmospheric pressure. 5. The method for producing a three-dimensional molded article with a paint according to claim 4, wherein irradiation in a vacuum or reduced pressure is performed with ultraviolet rays, and then the adhesive is further cured with an electron beam. A method of manufacturing a three-dimensional molded product with a picture. 6. The three-dimensional molded article with a paint according to claim 1, wherein the base material is mainly composed of a thermoplastic resin. 7. The method for producing a painted three-dimensional molded article according to claim 2, 3, 4 or 5, wherein the base material is mainly composed of a thermoplastic resin. Method.