JP5593751B2 - Three-dimensional molded decorative film, method for producing the same, decorative molded product using the same, and method for producing the same - Google Patents

Description

  The present invention relates to a three-dimensional molded decorative film for simultaneous injection molding transfer used in a decorative molded product by injection molding.

Conventionally, an injection molding simultaneous decorating method is used for decorating a resin molded body having a complicated surface shape such as a three-dimensional curved surface. The injection molding simultaneous decorating method is to integrate the decorative film inserted in the mold during injection molding with the molten injection resin injected into the cavity and decorate the surface of the resin molded body Generally, it is roughly classified into an injection molding simultaneous laminate decoration method and an injection molding simultaneous transfer decoration method depending on the difference in the configuration of the decorative film integrated with the resin molded body.
In the injection molding simultaneous transfer decorating method, the decorative film for injection molding simultaneous transfer decorating is directed to the mold with the transfer layer side heated from the transfer layer side with a hot platen, and the decorative film is placed in the mold. Molded to conform to the shape, closely attached to the inner surface of the mold and clamped, then injected the molding resin melted into the cavity to integrate the decorative film and the molding resin, and then decorated molded product Is cooled and taken out from the mold, and a decorative molded product to which the transfer layer is transferred is obtained by peeling the base material of the decorative film.

  As a transfer sheet used for the injection molding simultaneous transfer decoration method, for example, on the releasable surface of the releasable sheet, it is solid at room temperature in an uncured state and is an ultraviolet curable or electronic material that is a thermoplastic resin. A transfer sheet characterized by having an uncured resin of a linear curable resin has been proposed (see Patent Document 1). Since the uncured resin has thermoplasticity and solvent solubility, the transfer sheet is non-flowable and non-adhesive when apparently painted or dried or touched by hand. A pattern layer can be formed on the uncured resin layer. However, when cured in the form of a sheet, sufficient moldability cannot be obtained. Therefore, after being transferred to a transfer medium by an injection simultaneous molding method, the film is cured by irradiation with ultraviolet rays or electron beams. However, in this method, since the uncured resin layer flows during the simultaneous injection molding, the sheet may not be transferred well to the molded body, and it is very difficult to cure uniformly. There was a problem.

In addition, a transfer sheet provided with a protective layer made of an ionizing radiation curable resin, which is a thermoplastic solid in an uncured state, on a substrate with good moldability is placed in an injection mold and transferred. After vacuum forming or vacuum / pressure forming the sheet, the resin is cured by irradiating with ionizing radiation to form a protective layer, and the mold is closed and the molten resin is injected to perform injection molding. A method for producing a molded product characterized in that a protective layer having high hardness is formed therein (see Patent Document 2).
Also in this method, after vacuum forming or vacuum / pressure forming, the protective layer is formed by irradiating with ionizing radiation to form a protective layer, so the same problem as the decorative film disclosed in Patent Document 1 There is a point. That is, when cured in the state of a sheet, sufficient moldability can not be obtained, and after vacuum forming or vacuum / pressure forming, curing is performed by irradiating ultraviolet rays or electron beams. Since the uncured resin layer flows during the pressure forming, there are cases where the transfer to the molded body is not performed well.

In order to solve such a problem, Patent Document 3 discloses that a surface protective layer made of a cured product of an acrylate ionizing radiation curable resin is laminated on the surface side of a transparent substrate sheet, and the back surface of the substrate sheet. A decorative sheet is disclosed in which a decorative layer and an adhesive layer mainly composed of a vinyl chloride-vinyl acetate copolymer are laminated in this order, and the decorative sheet is bonded to the decorative sheet. After inserting the agent layer in the direction in contact with the injection resin between both male and female molds, both molds were clamped, and the resin in a fluid state was injected into the cavity formed by both molds to solidify the resin. Subsequently, a method of simultaneous decorating injection molding is disclosed in which the mold is opened to obtain a decorated molded product in which the decorative sheet is laminated and integrated with a resin molded product.
In this case, a decorative molded product is produced by the injection molding simultaneous decorating method using a decorative sheet laminated with a surface protective layer made of a cured product of an ionizing radiation curable resin. The problem which arises when producing a decorative molded product using the transfer sheet which has uncured resin of ionizing radiation curable resin as described in 1 and patent document 2 does not generate | occur | produce.

  On the other hand, in Patent Document 4, in a transfer sheet in which a release layer, a primer layer, a pattern layer, and an adhesive layer are laminated in this order on one surface of a base sheet, the release layer is an ionizing radiation curable type. A transfer sheet comprising a resin and a primer layer comprising a urethane two-component curable resin is disclosed, and the primer layer is provided to improve adhesion between the pattern layer and the release layer. ing.

JP-A-63-132095 JP-A-6-155518 Japanese Patent Laid-Open No. 2002-2225070 JP-A-4-189600

  The technique described in Patent Document 3 is a decorative resin even when the protective layer transferred as the outermost layer of the decorative resin molded product contains an ionizing radiation curable resin and the protective layer is crosslinked and cured. Although it is a technique superior to the techniques described in Patent Documents 1 and 2 such as being well transferred to a molded article, the base sheet used for the transfer sheet is taken into the decorative resin molded article, There was a problem that the type of the base sheet was unavoidable.

Therefore, the present inventors performed simultaneous injection molding transfer using a three-dimensional decorative film, and after removing the decorative molded product from the mold, in order to peel and remove the base material of the decorative film As a three-dimensional decorative film, for example, focusing on a decorative film with a structure in which a release layer, a protective layer, a decorative layer and, if necessary, an adhesive layer are laminated in this order on a substrate, earnest research Has been repeated.
And in the decorative molded product which requires weather resistance, in order to raise the interface adhesive force of the protective layer which consists of hardened | cured material of the ionizing radiation-curable resin composition after a weather resistance test, and a decoration layer, it is 2 between layers. Although it is advantageous to provide a primer layer composed of a liquid curable resin layer, it has been found that the provision of the primer layer has a problem that the transition of the decorative layer deteriorates.
In order to cope with this problem, as a result of further research, it has been found that the glass transition temperature Tg of the primer layer may be increased to a certain temperature or higher. Patent Document 4 does not mention Tg of the primer layer at all.

  Under such circumstances, the present invention is a decorative film used in an injection molding simultaneous transfer decorative method for imparting design properties to a decorative resin molded product, and is the outermost surface of the decorative resin molded product. The protective layer transferred as a layer contains an ionizing radiation curable resin, and even if the protective layer is cross-linked and cured, it is well transferred to the decorative resin molded product and does not deteriorate the transferability of the decorative layer. It is another object of the present invention to provide a decorative film and a method for producing the same, and a decorative molded product using the same and a method for producing the decorative film, which have good weather resistance adhesion between the decorative layer and the protective layer.

  As a result of intensive research to achieve the above-mentioned problems, the present inventors have provided a primer layer having a glass transition temperature of 65 ° C. or more, which is a two-component curing type, between the protective layer and the decorative layer. The inventors have found that the above problems can be solved. The present invention has been completed based on such findings.

That is, the present invention
[1] A three-dimensional molded decorative film for simultaneous injection molding, wherein a release layer, a protective layer, a primer layer, and a decorative layer are laminated in this order on a substrate, wherein the protective layer is And a cured product of an ionizing radiation curable resin composition containing a polymerizable (meth) acrylate oligomer, the primer layer is a two-component curable type, and its glass transition temperature Tg is 65 ° C. or higher. Three-dimensional decorative film,
[2] The three-dimensional decorative film according to [1], wherein the primer layer is a polyurethane two-component curable resin layer using an acrylic polymer polyol.
[3] The three-dimensional molded decorative film according to [1] or [2], further including an adhesive layer on the decorative layer,
[4] A method for producing a three-dimensional molded decorative film for simultaneous injection molding, comprising a step of laminating a release layer on a substrate, and an ionization containing a polymerizable (meth) acrylate oligomer on the release layer A step of laminating a radiation curable resin composition layer, a step of irradiating the ionizing radiation curable resin composition layer with ionizing radiation to crosslink and cure the ionizing radiation curable resin composition layer to form a protective layer, the protection A three-dimensional decorative film comprising a step of laminating a primer layer with a glass transition temperature Tg of 65 ° C. or higher and a step of laminating a decorative layer on the primer layer. Production method,
[5] A step of crosslinking and curing the ionizing radiation curable resin composition layer to form a protective layer, and a step of laminating a primer layer having a glass transition temperature Tg of 65 ° C. or more on the protective layer. The method for producing a three-dimensional decorative film according to the above [4], which comprises a step of subjecting the surface of the protective layer formed to corona discharge treatment or plasma treatment.
[6] The method for producing a three-dimensional decorative film according to [4] or [5], further including a step of laminating an adhesive layer on the decorative layer,
[7] Three-dimensional decorative decoration obtained by the three-dimensional decorative film according to any one of [1] to [3] or the manufacturing method according to any of [4] to [6] A decorative molded product using a film, and [8] the three-dimensional decorative film according to any one of [1] to [3], or any one of [4] to [6] above. The step of heating the three-dimensional molded decorative film from the base material side by a heating plate with the base material side of the three-dimensional molded decorative film obtained by the manufacturing method directed into the mold, the heated three-dimensional molded additive A process of preforming a decorative film along the inner shape of the mold and closely contacting the inner surface of the mold to clamp the mold, a process of injecting an injection resin into the mold, and a decoration from the mold after the injection resin cools A step of taking out the molded product and a step of peeling the substrate and the release layer from the decorative molded product. The method of manufacturing decorative moldings,
Is to provide.

  According to the present invention, it is a decorative film used in an injection molding simultaneous transfer decorative method for imparting design properties to a decorative resin molded product, and is transferred as the outermost layer of the decorative resin molded product. The protective layer contains an ionizing radiation curable resin, and even if the protective layer is cross-linked and cured, the protective layer is transferred to the decorative resin molded article well, and the decorative layer and the decorative layer are not deteriorated. It is possible to provide a decorative film and a method for producing the decorative film that have good weather resistance adhesion to the protective layer, a decorative molded product using the film, and a method for producing the decorative film.

It is a schematic diagram which shows the cross section of an example of the three-dimensional shaping | molding decoration film of this invention. It is a schematic diagram which shows the cross section of an example of the decorative molded product of this invention.

Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing a cross section of an example of the three-dimensional molded decorative film of the present invention.
The three-dimensional decorative film 10 of the present invention shown in FIG. 1 is formed by laminating a release layer 12, a protective layer 13, a primer layer 14, a decoration layer 15 and an adhesive layer 16 in this order on a substrate 11. It is a three-dimensional molded decorative film for simultaneous injection molding transfer.

[Base material]
The substrate 11 according to the present invention is selected in consideration of suitability for vacuum forming, and a resin film made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylonitrile-butadiene-styrene resin (ABS resin); vinyl chloride resin.
The thickness of the resin film used for this invention is 10-150 micrometers normally, 10-125 micrometers is preferable and 10-80 micrometers is more preferable.
Moreover, the base material 11 can use the single layer film of these resin, or the multilayer film by the same kind or different resin.

In the present invention, it is preferable to use a polyester film as the substrate 11 in terms of heat resistance, dimensional stability, moldability, and versatility.
The polyester resin which comprises a polyester film means the polymer containing the ester group obtained by polycondensation from polyhydric carboxylic acid and polyhydric alcohol. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid. Polyhydric alcohols include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, and bisphenol. A etc. are mentioned. Further, the polyester resin used in the present invention may be a copolymer of three or more kinds of polyvalent carboxylic acids and polyhydric alcohols, and is a copolymer with monomers and polymers such as diethylene glycol, triethylene glycol, and polyethylene glycol. There may be.

Preferred examples of the polyester resin used for the polyester film include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Polyethylene terephthalate (PET) has heat resistance and dimensional stability. This is particularly preferable.
The polyester resin may be a homopolymer, a copolymer, or a copolymer obtained by copolymerizing a third component. For example, a polyester resin having polyethylene terephthalate, which is generally excellent in heat resistance and dimensional stability as a main component (usually 90 mol% or more, preferably 95 mol% or more), and polybutylene terephthalate, which is generally excellent in moldability, as a main component (usually 90 mol%). Mol% or more, preferably 95 mol% or more). The blending ratio may be appropriately selected depending on the dynamic elastic modulus of the film to be obtained, and is usually 70/30 to 95/5 in mass ratio, and preferably in the range of 75/25 to 85/15. Since the polyester film blended in this way is excellent in heat resistance, dimensional stability, and moldability, it can be suitably used as the base material of the present invention.

  The polyester film preferably contains fine particles for the purpose of improving workability. Fine particles include inorganic particles such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide and kaolin, organic particles made of acrylic resin, and internal precipitation particles. And so on. The average particle size of the fine particles is preferably 0.01 to 5.0 μm, more preferably 0.05 to 3.0 μm. Moreover, 0.01-5.0 mass% is preferable and, as for content of the microparticles | fine-particles in a polyester-type resin, 0.1-1.0 mass% is more preferable. Moreover, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents, and the like can be blended as necessary.

  The polyester film used for this invention is manufactured as follows, for example. First, the above polyester-based resin and other raw materials are supplied to a known melt extrusion apparatus such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester-based resin to be melted. Next, while extruding the molten polymer, it is rapidly cooled and solidified in the form of a rotating cooling drum to a temperature not higher than the glass transition temperature to obtain a substantially amorphous unoriented sheet. This sheet is obtained by stretching in a biaxial direction to form a film and heat-setting. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Moreover, you may extend | stretch longitudinally and / or a horizontal direction again before or after performing heat setting as needed. In the present invention, in order to obtain sufficient dimensional stability, the draw ratio is preferably 7 times or less, more preferably 5 times or less, and further preferably 3 times or less, as an area ratio. If it is within this range, when the obtained polyester film is used for a three-dimensional molded decorative film, the three-dimensional molded decorative film does not shrink again in the temperature range when the injection resin is injected. Necessary film strength can be obtained. In addition, a polyester film may be manufactured as described above, or a commercially available one may be used.

In addition, the polyester film can be subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as desired for the purpose of improving the adhesion with a release layer described later.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
The base material may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing interlayer adhesion between the base material and the layer provided thereon. In addition, when using a commercially available thing as a polyester film, what was surface-treated as mentioned above previously and the thing in which the easily adhesive layer was provided can also be used for this commercial item.

[Release layer]
The release layer 12 is provided in order to easily peel the transfer layer 17 composed of the protective layer 13, the primer layer 14, the decoration layer 15, and the adhesive layer 16 from the base material sheet 11. As shown in FIG. 1, the release layer 12 may be a solid release layer covering the entire surface (entirely solid), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability.

The release layer is made of fluorine resin, acrylic resin (for example, acrylic-melamine resin), polyester resin, polyolefin resin, polystyrene resin, polyurethane resin, cellulose resin, vinyl chloride-acetic acid. Vinyl-based copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers that form the thermoplastic resins, or those modified with (meth) acrylic acid or urethane, alone or in plural It can form using the resin composition which mixed. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer 12 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.
The thickness of the release layer 12 is usually about 0.01 to 5 μm, and preferably 0.05 to 3 μm.

[Protective layer]
The protective layer 13 is made of a cured product of an ionizing radiation curable resin composition containing a polymerizable (meth) acrylate oligomer. The polymerizable (meth) acrylate oligomer preferably has a weight average molecular weight Mw of 1000 to 40000. If the weight average molecular weight Mw of the polymerizable (meth) acrylate oligomer is 1000 or more, the peel strength after transfer is not too high, and if the weight average molecular weight Mw is 40000 or less, the peel strength is not too low. . From these viewpoints, the weight average molecular weight Mw is more preferably 1500 to 25000, and particularly preferably 2000 to 20000.

In the present invention, the polymerizable (meth) acrylate oligomer used as the ionizing radiation curable resin in the ionizing radiation curable resin composition constituting the protective layer 13 includes a plurality of radically polymerizable unsaturated groups in the molecule. Functional (meth) acrylate oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate are examples.
Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, as the polymerizable (meth) acrylate oligomer, there are other polybutadiene (meth) acrylate oligomers having a high hydrophobicity having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and silicone having a polysiloxane bond in the main chain (methamethacrylate). ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules.
One of the above polymerizable (meth) acrylate oligomers may be used alone, or two or more thereof may be used in combination.
Of the above polymerizable (meth) acrylate oligomers, polyfunctional urethane (meth) acrylate oligomers are preferable, and bifunctional urethane (meth) acrylate oligomers are particularly preferable from the viewpoint of moldability.

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

Furthermore, in the present invention, for the purpose of imparting more scratch resistance and the like to the protective layer, a polyfunctional (meth) acrylate monomer is not impaired along with the polymerizable (meth) acrylate oligomer. It can be used together as appropriate within the range.
Examples of the polyfunctional (meth) acrylate monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, and di Examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. The initiator for photopolymerization can be appropriately selected from conventionally used initiators and is not particularly limited. For example, for a polymerizable (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 ON, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, etc. Can be mentioned.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

Further, the protective layer 13 may contain a filler as desired. By including a filler, tackiness can be further improved and printability can be imparted.
As the type of filler, for example, particles made of inorganic substances such as silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, organic polymers such as acrylic resin, polyethylene, urethane resin, polycarbonate, polyamide (nylon), etc. are used. . Of these, silica is preferable because it has an effect of reducing tackiness, is easy to handle, and is inexpensive.
The average particle diameter of the filler is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and the addition amount is 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin forming the protective layer. The range is preferable, and the range of 0.5 to 5 parts by mass is more preferable. The shape of the particles is a polyhedron, a sphere, a scale shape, or the like.

  The thickness of the protective layer 13 is usually about 1 to 50 μm, and preferably in the range of 5 to 15 μm.

The protective layer 13 has various functions by adding various additives, for example, a so-called hard coating function, anti-fogging coating function, anti-fouling coating function, anti-glare coating function, reflection, having high hardness and scratch resistance. It is also possible to impart a prevention coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like.
In addition, the protective layer 13 can be subjected to corona discharge treatment or plasma treatment as necessary for the purpose of improving adhesion with the primer layer 14 provided on the protective layer 13.

[Primer layer]
In the three-dimensional decorative film of the present invention, in order to further improve the weather resistance adhesion between the decorative layer 15 and the protective layer 13 without deteriorating the transferability of the decorative layer 15 described later, A primer layer 14 is provided between 15 and the protective layer 13.
The primer layer is a two-component curable resin layer and needs to have a glass transition temperature Tg of 65 ° C. or higher in order to fully exhibit the above effects. Although there is no restriction | limiting in particular in the upper limit of the said glass transition temperature Tg, Usually, it is about 110 degreeC, and preferable Tg is the range of 70-100 degreeC. The primer layer 14 is preferably a transparent or translucent layer. The two-component curable resin layer is particularly preferably a layer made of a polyurethane two-component curable resin.

As the polyurethane-based two-component curable resin, for example, a curing agent is added immediately before use to a polymer polyol such as vinyl chloride-vinyl acetate copolymer, polyester, urethane, acrylic, or a mixture thereof. Used. As the curing agent, polyisocyanate is preferable, for example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like, or adducts of the above-mentioned various isocyanates. Alternatively, a multimer, for example, an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer, or the like can be used.
The polymer polyol is preferably a polyester polyol, such as poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), poly (butylene seba). Kate), polycaprolactone, etc. are used. Acrylic polymer polyols can also be preferably used.
A coating solution obtained by dissolving the resin in a solvent is applied and dried by a known method to form a primer layer. About the thickness of a primer layer, it is about 0.5-20 micrometers normally, Preferably, it is the range of 1-5 micrometers.

[Decoration layer]
The decorative layer 15 according to the present invention is usually composed of a picture layer and / or a concealing layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is generally a solid layer and is provided for concealing coloring such as injection resin. Is a layer. In the concealing layer, a decorative layer may be formed alone in addition to the case of being provided inside the pattern layer in order to enhance the pattern of the pattern layer. Further, the decorative layer may be a transparent transfer foil or a colored transfer foil.
The pattern layer according to the present invention is a layer provided to express a pattern, a character, and a pattern-like pattern. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and the like can be mentioned.
The decorative layer 15 is formed on the primer layer 14 by using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing. 1 is formed between the primer layer 14 and the adhesive layer 16. The thickness of the decorative layer 15 is preferably 3 to 40 μm and more preferably 10 to 30 μm from the viewpoint of design.

  As the binder resin of the printing ink used for forming the decorative layer 15, polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, and the like are preferable. The main component is preferably an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. Among these, when an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin or another acrylic resin is mixed, the printability and moldability are improved, which is preferable. Here, the acrylic resin includes polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer. Examples include acrylic resins such as polymers (where (meth) acrylate refers to acrylate or methacrylate), modified acrylic resins such as fluorine, and these can be used as one or a mixture of two or more. In addition, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl ( Acrylic polyol obtained by copolymerizing (meth) acrylate ester having a hydroxyl group in the molecule such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Can also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin / vinyl chloride-vinyl acetate copolymer resin = 1/9 to 9/1 (mass ratio). In addition, as a subcomponent resin, if necessary, other resins, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polypropylene, and other chlorinated polyolefin resins. May be mixed.

  Examples of the colorant used in the decorative layer 15 according to the present invention include aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass and other metals, alloys, or scale-like foil powders of metal compounds. It consists of foil powder such as metallic pigment, mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, and basic lead carbonate. Pearlescent pigments, fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, zinc white, petal, Inorganic pigments such as vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone Be low, Hansa Yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, be mixed Indanthrene Blue RS, (including dyes) organic pigments such as aniline black one or more.

Although such a decoration layer 15 is a layer provided in order to provide the designability to the three-dimensional molded decorative film of the present invention, a metal thin film layer or the like may be further formed for the purpose of improving the designability. good. The metal thin film layer can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. This metal thin film layer may be provided on the entire surface or may be partially provided in a pattern.
In addition to the above components, the printing ink used for forming the decorative layer 15 is appropriately added with an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like. be able to. The printing ink is provided in a form in which the above components are usually dissolved or dispersed in a solvent. Any solvent can be used as long as it dissolves or disperses the binder resin, and an organic solvent and / or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve acetate, and alcohols.

[Adhesive layer]
The adhesive layer 16 according to the present invention is formed to transfer the protective layer 13, the primer layer 14, and the decorative layer 15 to the decorative molded product with good adhesiveness, and is provided as necessary. Is a layer. As the adhesive layer 16, in the injection molding simultaneous transfer decorating method, the injection molding resin and the three-dimensional molded decorating film can be bonded with good adhesion and without peeling off at the end. It is desirable.

Examples of the adhesive layer 16 include those composed of a heat-sensitive adhesive, a pressure adhesive, and the like. In the present invention, the adhesive layer 16 can be adhered to a decorative molded product by heating and pressing as necessary. A heat seal layer that develops is preferable. Examples of the resin used for the adhesive constituting the adhesive layer 16 include an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a styrene-acryl copolymer resin, Examples thereof include at least one resin selected from polyester resins and polyamide resins. One or two or more resins selected from the above resins are made into a form that can be applied such as a solution or an emulsion by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. It can be formed by coating and drying.
The thickness of the adhesive layer 16 is preferably about 0.1 to 6 μm from the viewpoint that the three-dimensional decorative film can be efficiently transferred to the decorative molded product.

  The adhesive layer 16 includes organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, cyanoacrylate compounds, salicylate compounds, zinc, titanium, cerium, tin, iron, etc. It is possible to contain an additive of fine particles having an inorganic ultraviolet absorbing ability such as an oxide of the above. Further, as an additive, a coloring pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent brightening agent, and the like can be appropriately contained as necessary.

[Method for producing three-dimensional decorative film]
The method for producing a three-dimensional decorative film of the present invention is a method for producing a three-dimensional decorative film 10 for simultaneous injection molding transfer, and includes the following steps [1] to [7].
[1] A step of laminating the release layer 12 on the substrate 11;
[2] A step of laminating an ionizing radiation curable resin composition layer containing a polymerizable (meth) acrylate oligomer on the release layer 12;
[3] A step of irradiating the ionizing radiation curable resin composition layer with ionizing radiation to crosslink and cure the ionizing radiation curable resin composition layer to form the protective layer 13;
[4] Step of performing corona discharge treatment or plasma treatment on the surface of the protective layer 13 provided as desired [5] A primer layer having a two-component curing type and a glass transition temperature Tg of 65 ° C. or higher on the protective layer 13 14 is laminated,
[6] A step of laminating the decorative layer 15 on the primer layer 14, and [7] A step of laminating the adhesive layer 16 on the decorative layer 15 provided as desired.
The layering method of the release layer 12, the protective layer 13, the primer layer 14, the decoration layer 15, and the adhesive layer 16 to be laminated on the substrate 11 is a known printing or coating means such as gravure printing or roll coating. Used.
When the decorative layer 15 is a combination of a pattern layer and a concealing layer as described above, for example, the first layer may be stacked and then dried, and then the next layer may be stacked.

In the step of forming the protective layer 13 in the present invention, the ionizing radiation curable resin composition is formed by irradiating the ionizing radiation curable resin composition layer laminated on the release layer 12 with ionizing radiation such as an electron beam or ultraviolet rays. The material layer is crosslinked and cured. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but the ionizing radiation curable resin composition layer is usually used at an accelerating voltage of about 70 to 300 kV. It is preferable to cure.
In addition, in electron beam irradiation, since the transmission capability increases as the acceleration voltage is higher, when a base material that deteriorates due to an electron beam is used as the base material 11, the transmission depth of the electron beam and the thickness of the resin layer are By selecting the accelerating voltage so as to be substantially equal, it is possible to suppress irradiation of the extra electron beam to the base material 11 and to minimize the deterioration of the base material due to the excess electron beam. .
The irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 60 kGy (1 to 6 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

[Method of manufacturing decorative molded product]
The above-described three-dimensional molded decorative film of the present invention or the three-dimensional molded decorative film manufactured as described above is suitably used for injection molding simultaneous transfer decorative.
The manufacturing method of the decorative molded product of the present invention by injection molding simultaneous transfer decoration includes the following steps (1) to (5).
(1) First, the step of directing the base material side of the three-dimensional molded decorative film into the mold and heating the three-dimensional molded decorative film from the base material side with a hot platen,
(2) A step of pre-molding the heated three-dimensional decorative film so as to conform to the shape in the mold and closely contacting the inner surface of the mold to clamp the mold,
(3) A step of injecting the injection resin into the mold,
(4) A step of taking out the decorative molded product from the mold after the injection resin has cooled, and (5) a step of peeling the substrate and the release layer from the decorative molded product.

In the said process (1) and (2), it is preferable that the temperature which heats a three-dimensional shaping decorative film is the range below glass melting temperature of a base material, and less than melting temperature (or melting | fusing point). Usually, it is more preferable to carry out at a temperature near the glass transition temperature.
In addition, said glass transition temperature vicinity refers to the range of about glass transition temperature +/- 5 degreeC, and when using a suitable polyester film as a base material, it is generally about 70-130 degreeC.

In the step (3), an injection resin to be described later is melted and injected into the cavity to integrate the three-dimensional decorative decorative film and the injection resin. When the injection resin is a thermoplastic resin, it is made into a fluid state by heating and melting, and when the injection resin is a thermosetting resin, the uncured liquid composition is injected in a fluid state at room temperature or appropriately heated. Cool and solidify. As a result, the three-dimensional decorative film is integrated with the formed resin molded body and attached to form a decorative molded product. The heating temperature of the injection resin depends on the injection resin, but is generally about 180 to 320 ° C.
After the decorative molded product thus obtained is cooled and taken out from the mold, the protective layer 13, the primer layer 14, the decorative layer 15 and the adhesive are peeled off by peeling off the substrate 11 and the release layer 12. The decorative molded product to which the transfer layer 17 composed of the layer 16 is transferred is obtained.

[Production method: Injection resin]
The injection resin used for the decorative molded product is not particularly limited as long as it is a thermoplastic resin that can be injection molded or a thermosetting resin (including a two-component curable resin), and various resins are used. Can do. Examples of such thermoplastic resin materials include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; polystyrene, acrylonitrile-styrene copolymers, ABS resins (acrylonitrile-butadiene-styrene copolymer resins), and the like. Styrene resins; acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyacrylonitrile; polyolefin resins such as polyethylene, polypropylene, polybutene, polyethylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, Examples thereof include polyester resins such as polybutylene terephthalate; polycarbonate resins. Examples of the thermosetting resin include a two-component reaction curable polyurethane resin and an epoxy resin. These resins may be used alone or in combination of two or more.
These resins include various additives as required, such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, calcium carbonate, aluminum hydroxide, etc. Inorganic powders, wood powders, fillers such as glass fibers, lubricants, mold release agents, antistatic agents, colorants and the like can be added. Note that as the injection resin, a resin colored by adding a colorant may be used as appropriate according to the application. As the colorant, a known colorant similar to that which can be used for the aforementioned base material can be used.
There is no restriction | limiting in particular about the thickness of the injection resin molding which comprises a decorative molded product, Although it selects according to the use of the said decorative molded product, Usually, 1-5 mm, Preferably it is 2-3 mm.

FIG. 2 is a schematic view showing a cross section of an example of the decorative molded product of the present invention.
The decorative molded product 20 is formed by laminating a transfer layer 17 including a protective layer 13, a primer layer 14, a decoration layer 15, and an adhesive layer 16 on an injection resin molded body 18 via the adhesive layer 16. It has an integrated structure.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Manufacture of three-dimensional decorative film)
On the biaxially stretched PET film (thickness: 75 μm) subjected to easy adhesion treatment as a substrate, an acrylic-melamine resin was applied by a gravure method to form a release layer (thickness: 3 μm).
Next, an electron beam curable resin, which is a bifunctional urethane acrylate oligomer having a weight average molecular weight Mw 15000, is applied onto the release layer by the gravure reverse method, and an electron having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad). The electron beam curable resin was cross-linked and cured by irradiating a line to form a protective layer (thickness: 12 μm).
Next, after the corona discharge treatment is applied to the surface of the protective layer, a solution of a polyurethane two-component curable resin having various glass transition temperatures is applied thereon, and a primer layer (thickness: 1.5 μm) is applied. Formed.
Next, a black printing ink (acrylic resin: 50% by mass, vinyl chloride-vinyl acetate copolymer) using an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin on the primer layer. Resin: 50% by mass) was subjected to gravure printing at a coating amount of 3 g / m ² to form a full-color decorative layer. Furthermore, an acrylic resin [softening temperature: 125 ° C.] was subjected to gravure printing at a coating amount of 4 g / m ² to form an adhesive layer, and a three-dimensional molded decorative film having the configuration shown in FIG. 1 was produced. .

<Evaluation method>
(1) Weight average molecular weight of electron beam curable resin The value measured by GPC analysis and converted with standard polystyrene was used.
(2) Glass transition temperature Tg of two-component curable resin used for primer layer
By the differential calorimetry (DSC) method, the temperature at which the peak shoulder is reached was defined as the glass transition temperature Tg.
(3) Weather resistance adhesion between decorative layer and protective layer About laminated film composed of base material, protective layer, various primer layers and decorative layer before laminating adhesive layer, weather resistance between decorative layer and protective layer Adhesion was determined and evaluated by the following method.
Using an Atlas Xenon weatherometer (program: SAE J1885), the adhesion between the decorative layer and the protective layer when the integrated illuminance reached 100 MJ was evaluated by a cross-cut adhesion test (2 mm interval).
(4) Transferability of the decorative layer to the primer layer The laminated film composed of the base material, the protective layer, various primer layers and the decorative layer before the adhesive layer was laminated, and the primer layer and the adhesive layer were not provided. Except for this, CIE (International Commission on Illumination) L defined in JIS Z 8729-1994 is used for each of the laminated films composed of the base material, the protective layer and the decorative layer obtained by the same operation as described above. ^* a ^* b ^* L in the color system ^*, a ^* and b ^* a, color analyzer in the field conditions of the D65 light source and 10 degrees [manufactured by Konica Minolta Holdings, Inc., model name "spectrophotometer (CM-3700d)"] It measured using.
From the L ^* , a ^*, and b ^* values of the two, the color difference ΔE ^* ab was determined from the following equation from the brightness difference ΔL ^* and the hue differences Δa ^* , Δb ^* .
Color difference ΔE ^* ab = √ (ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ²
The color difference Delta] E ^* ab is well metastatic for the primer of smaller decorative layer, Delta] E ^* ab is acceptable as long as 11 or less.

Examples 1 and 2 and Comparative Examples 1-8
The polyurethane two-component curable resin used for the primer layer includes an acrylic polymer polyol (hereinafter abbreviated as “acrylic polyol”) and / or a urethane polymer polyol (hereinafter abbreviated as “urethane polyol”), and a curing agent. It is a reaction product with a polyisocyanate compound, and Table 1 shows Tg of a polymer polyol raw material and a two-component curable resin.
Table 1 also shows the types of primers provided between the protective layer and the decorative layer, the weather resistance adhesion between the decorative layer and the protective layer evaluated by the method described above, and the transferability of the decorative layer to the primer. The relationship is shown.

As is apparent from Table 1, the three-dimensional molded decorative films of Examples 1 and 2 using a two-component curable resin having a Tg of 65 ° C. or higher as a primer layer have a very small color difference ΔE ^* ab, It can be seen that the transferability of the layer to the primer is good. On the other hand, the three-dimensional decorative film of Comparative Examples 1 to 7 using a two-component curable resin having a Tg of less than 65 ° C. for the primer layer has a color difference ΔE ^* ab of more than 11, and is difficult to transfer. I know that there is.
In addition, as shown in Comparative Example 8, it can be seen that the weather resistance adhesion between the decorative layer and the protective layer is low in the case of a film using a one-component curable resin for the primer layer even when Tg is 65 ° C. or higher. .

(Production of decorative molded products)
The decorative film obtained above was heated at a hot platen temperature of 150 ° C. and molded so as to conform to the shape in the mold of injection molding, and was brought into close contact with the inner surface of the mold. The mold used was a 80 mm square size, 10 mm rising and 2R tray shape with a high deep drawing degree. On the other hand, an ABS resin [manufactured by Nippon A & L Co., Ltd., trade name “Crustic MTH-2”] was used as an injection resin, which was melted at 230 ° C. and then injected into the cavity. After removing from the mold at a temperature of 80 ° C., the substrate is peeled off, and a transfer layer comprising a protective layer, a primer layer, a decoration layer, and an adhesive layer is transferred and formed on the surface. A decorative molded product was obtained. In the present invention, deep drawing refers to a shape in which the area ratio before and after the decorative film is formed is 130% or more, and high deep drawing means that the area ratio is large. Say.

  The three-dimensional molded decorative film of the present invention is a decorative film used in an injection molding simultaneous transfer decorative method for imparting designability to a decorative resin molded product, and is the outermost surface of the decorative resin molded product. The protective layer transferred as a layer contains an ionizing radiation curable resin, and even if the protective layer is cross-linked and cured, it is well transferred to the decorative resin molded product and does not deteriorate the transferability of the decorative layer. Moreover, the weather resistance adhesion between the decorative layer and the protective layer can be improved.

DESCRIPTION OF SYMBOLS 10 Three-dimensional molded decorative film 11 Base material 12 Release layer 13 Protective layer 14 Primer layer 15 Decorative layer 16 Adhesive layer 17 Transfer layer 18 Injection-molded resin molded body 20 Decorative molded product

Claims (10)

A three-dimensional decorative film for simultaneous injection molding, wherein a release layer, a protective layer, a primer layer, and a decorative layer formed by printing ink are laminated in this order on a base material, The protective layer is made of a cured product of an ionizing radiation curable resin composition containing a polymerizable (meth) acrylate oligomer, the primer layer is a polyurethane two-component curable resin layer , and its glass transition temperature Tg is 65 ° C. A three-dimensional decorative film characterized by the above.   The three-dimensional molded decorative film according to claim 1, wherein the primer layer is a polyurethane two-component curable resin layer using an acrylic polymer polyol.   The three-dimensional molded decorative film according to claim 1, further comprising an adhesive layer on the decorative layer. The printing ink is at least one selected from the group consisting of polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins as a binder resin. The three-dimensional molded decorative film according to any one of claims 1 to 3. A method for producing a three-dimensional decorative decorative film for simultaneous injection molding, comprising a step of laminating a release layer on a substrate, and an ionizing radiation curable composition containing a polymerizable (meth) acrylate oligomer on the release layer A step of laminating a resin composition layer; a step of irradiating the ionizing radiation curable resin composition layer with ionizing radiation to crosslink and cure the ionizing radiation curable resin composition layer to form a protective layer; on the protective layer; A three-dimensional process comprising a step of laminating a primer layer having a glass transition temperature Tg of 65 ° C. or higher with a polyurethane-based two-component curable resin, and a step of laminating a decorative layer using a printing ink on the primer layer. Manufacturing method of molded decorative film. Between the step of forming a protective layer by crosslinking and curing the ionizing radiation curable resin composition layer, and the step of laminating a primer layer having a glass transition temperature Tg of 65 ° C. or more on the protective layer. The method for producing a three-dimensional molded decorative film according to claim 5 , further comprising a step of subjecting the surface of the formed protective layer to corona discharge treatment or plasma treatment. Furthermore, the manufacturing method of the three-dimensional molded decoration film of Claim 5 or 6 which has the process of laminating | stacking an adhesive bond layer on the said decoration layer. The printing ink is at least one selected from the group consisting of polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins as a binder resin. The manufacturing method of the three-dimensional shaping decoration film in any one of Claims 5-7 containing these. A decorative molded article using the three-dimensional molded decorative film according to any one of claims 1 to 4 or the three-dimensional molded decorative film obtained by the production method according to any one of claims 5 to 8. . The three-dimensional molded decorative film according to any one of claims 1 to 4 or the substrate side of the three-dimensional molded decorative film obtained by the production method according to any one of claims 5 to 8 is placed in a mold. The step of heating the three-dimensional molded decorative film from the base material side with a hot platen, and preliminarily molding the heated three-dimensional molded decorative film along the inner shape of the mold and closely contacting the inner surface of the mold A mold clamping step, an injection resin injection into the mold, a step of taking out the decorative molded product from the mold after the injection resin cools, and a peeling of the base material and the release layer from the decorative molded product The manufacturing method of the decorative molded product including the process to do.

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