JP5764866B2 - 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 along the shape, tightly attached to the inner surface of the mold and clamped, then injected the molten injection resin into the cavity to integrate the decorative film and the injection resin, and then cooled the decorative molded product Then, the decorative molded product to which the transfer layer is transferred is obtained by removing the substrate from the mold and peeling the substrate.

  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 material by an injection simultaneous molding method, the film is cured by irradiation with ultraviolet rays or electron beams. However, with this method, the uncured resin layer may flow during simultaneous injection molding, so the sheet may not be transferred well to the molded body, especially in deep-drawn molded products. There was a problem that it was very difficult to cure.

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.

JP-A-63-132095 JP-A-6-155518

  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 an 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 can be transferred well to a deep-drawn decorative resin molded product, for wear resistance and printability It is an object to provide an excellent decorative film, a manufacturing method thereof, a decorative molded product using the same, and a manufacturing method thereof.

As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be solved by using a specific ionizing radiation curable resin as a protective layer. 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, which is formed by laminating a release layer, a protective layer, a colored layer, and an adhesive layer in this order on a substrate, and the protective layer has a weight. A three-dimensional molded decorative film comprising a cured product of an ionizing radiation curable resin composition containing a polymerizable (meth) acrylate oligomer having an average molecular weight Mw of 3000 to 40000,
[2] 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 a polymerizability with a weight average molecular weight Mw of 3000 to 40000 on the release layer ( A step of laminating an ionizing radiation curable resin composition layer containing a (meth) acrylate oligomer, and 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 A method for producing a three-dimensional decorative film, comprising a step of forming a layer, a step of laminating a colored layer on the protective layer, and a step of laminating an adhesive layer on the colored layer,
[3] A decorative molded product using the three-dimensional decorative film described in [1] above, and [4] a three-dimensional decorative film base obtained by the manufacturing method described in [2] above. A step of heating the three-dimensional decorative film from the base material side with a heating plate with the material side facing the mold, and preliminarily molding the heated three-dimensional decorative film along the shape of the mold A process in which the mold is brought into close contact with the inner surface of the mold, a process of injecting the injection resin into the mold, a process of taking out the decorative molded product from the mold after the injection resin cools, and a base material from the decorative molded product And the manufacturing method of the decorative molded product including the process of peeling a peeling layer is provided.

  According to the present invention, even when the protective layer is crosslinked and cured, the three-dimensional molded decorative film excellent in wear resistance and printability, which can be satisfactorily transferred to a decorative resin molded product, a method for producing the same, and a method for using the same. It is possible to provide a decorative molded product and a manufacturing method thereof.

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 the sample for evaluation of the protective layer used for the three-dimensional molded decoration film of this invention. It is a top view which shows the shape of the sample for evaluation of the protective layer used for the three-dimensional shaping decoration film 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 a preferred 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 has a release layer 12, a protective layer 13, a primer layer 14, a colored layer 15, and an adhesive layer 16 provided on a substrate 11. It is a three-dimensional molded decorative film for simultaneous injection molding that is laminated in order.

[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 be used as a single layer film of these resins, or a multilayer film made of the same or different resins.

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, dodecadicarboxylic 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, preferably 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 sheet 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.
In addition, 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 each layer. 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 to easily peel the transfer layer composed of the protective layer 13, the primer layer 14, the coloring layer 15, and the adhesive layer 16, which are optionally laminated, from the base material sheet 11. It is. 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 weight 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 having a weight average molecular weight Mw of 3000 to 40000. If the weight average molecular weight Mw of the polymerizable (meth) acrylate oligomer is less than 3000, three-dimensional molding is lowered and deep drawing becomes difficult. On the other hand, when the weight average molecular weight Mw exceeds 40000, the printability is lowered. That is, when the weight average molecular weight Mw of the polymerizable (meth) acrylate oligomer is increased, the viscosity is increased, so that the solid content of the resin composition when the printable viscosity is obtained is reduced, and the desired thickness of the protective layer 13 is reduced. There is a risk that it cannot be obtained by recoating.
From the viewpoint of achieving both moldability and printability, the weight average molecular weight Mw of the polymerizable (meth) acrylate oligomer is preferably 5,000 to 20,000, and particularly preferably 7,000 to 17,000.

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.

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.
From this viewpoint, it is preferable that the ionizing radiation curable resin in the ionizing radiation curable resin composition according to the present invention consists only of a polymerizable (meth) acrylate oligomer having a weight average molecular weight Mw of 3000 to 40000.

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 beads, 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.

[Primer layer]
In the three-dimensional decorative film of the present invention, a primer layer 14 is preferably further laminated between the protective layer 13 and a colored layer 15 described later. This is because the adhesion between the protective layer 13 and the colored layer 15 can be further improved by laminating the primer layer 14. The primer layer 14 is preferably a transparent or translucent layer, such as polyurethane resin, polyester resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, chlorinated resin. One kind of resin such as polyethylene and chlorinated polypropylene, or a mixture of two or more kinds is used, and those using a polyurethane two-component curable resin are particularly preferable.
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.

[Colored layer]
The colored layer 15 according to the present invention includes a pattern 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.
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 colored layer 15 is usually known printing such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, ink jet printing, etc., on the protective layer 13 or the primer layer 14 described above. By forming by the method, it is formed between the protective layer 13 and the adhesive layer 16 as shown in FIG. The thickness of the colored 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 colored 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 for the colored 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 colored layer 15 is a layer provided in order to provide designability to the three-dimensional decorative film of the present invention, a metal thin film layer or the like may be further formed for the purpose of improving 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 colored 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 preferably formed in order to transfer the protective layer 13, the primer layer 14, which is optionally laminated, and the colored layer 15 to the decorative molded product with good adhesiveness. 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 exhibits adhesion to a decorative molded product by heating and pressurizing as necessary. It is preferable that it is a heat seal layer. Examples of the resin used for the adhesive layer 16 include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamides. Examples thereof include resins such as resin. Applying or drying one or more of these resins in a form that can be applied, such as a solution or emulsion, by selecting a suitable method from the application methods listed in the release layer. Can be formed.
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 an organic UV absorber such as a benzophenone compound, a benzotriazole compound, an oxalic acid anilide compound, a cyanoacrylate compound, and a salicylate compound, as well as zinc, titanium, cerium, tin, and iron. An additive of fine particles having an inorganic ultraviolet absorbing ability such as an oxide can be used. 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 used as necessary.

[Method for producing three-dimensional decorative film]
The manufacturing method of the three-dimensional decorative film of the present invention is a manufacturing method of the three-dimensional decorative film 10 for simultaneous injection molding transfer, and includes the following steps [1] to [5].
[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 having a weight average molecular weight Mw of 3000 to 40000 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 a protective layer 13;
[4] A step of laminating the colored layer 15 on the protective layer 13 and [5] a step of laminating the adhesive layer 16 on the colored layer 15.
And it is preferable to include the process of laminating | stacking the primer layer 14 on the protective layer 13 between the process of forming the protective layer 13, and the process of laminating | stacking the colored layer 15 further.
The layering method of the release layer 12, the protective layer 13, the primer layer 14, the colored layer 15, and the adhesive layer 16 that are laminated on the base material 11 is known printing such as gravure printing, roll coating, or the like. A coating means is used.
When the colored layer 15 is a combination of a pattern layer and a concealing layer as described above, for example, one 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. 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 three-dimensional decorative film of the present invention obtained as described above is suitably used for injection molding simultaneous transfer decoration.
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 heating the three-dimensional shaped decorative film from the base material side by a hot plate with the base side of the three-dimensional shaped decorative film obtained by the production method of the present invention directed into the mold,
(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 removing 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 steps (1) and (2), the temperature for heating the three-dimensional decorative film is preferably in the range of near the glass transition temperature of the base sheet and less than the melting temperature (or melting 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 base material 11 and the release layer 12 are peeled off to peel off the protective layer 13, the primer layer 14 provided as desired, and the colored layer 15 And the decorative molded product to which the transfer layer composed of the adhesive layer 16 is transferred.

[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 above-mentioned substrate 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.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Evaluation method)
1. Weight average molecular weight A value measured by GPC analysis and converted to standard polystyrene was used.
2. Formability Using the protective layer evaluation sample 10a composed of the base material 11, the release layer 12 and the protective layer 13 shown in FIG. 2, vacuum forming is performed in a mold, and the appearance after three-dimensional forming is as follows. It was evaluated by.
○: No abnormal appearance.
(Triangle | delta): The crack generate | occur | produced in the 200% extending | stretching part.
X: Cracks occurred in the entire stretched part.

3. Elongation at break at 120 ° C (%)
The test piece 10a having the layer configuration shown in FIG. 2 and the planar shape shown in FIG. 3 was held in a constant temperature layer at 120 ° C. for 30 seconds, and then a tensile test was performed at a pulling rate of 200 mm / min to measure the elongation at break (%). In FIG. 3, a represents the total length of the test piece, b represents the width of the test piece (25 mm), and L represents the initial distance between the chucks (50 mm). “134 <” means that the elongation at break is larger than 134%. Further, MD refers to the stretching direction (flow direction) of the biaxially stretched PET film that is the base material, and TD refers to the direction (vertical direction) perpendicular to the stretching direction of the biaxially stretched PET film that is the base material. Say.

4). Abrasion resistance The three-dimensional decorative film obtained in each Example and Comparative Example was evaluated by a taper abrasion test (conditions: wear wheel: CS-10, load: 250 gf, 1000 reciprocations). The evaluation was performed based on whether or not the molded resin was exposed by the taper wear test.
○: Not exposed.
×: Exposed.
5. Printability Regarding printability, the appearance of the coated surface was evaluated according to the following criteria.
◯: Appearance of the coated surface is smooth. Δ: Although the plate surface is visible on the coated surface, there is no problem with printability.
×: The appearance of the coated surface is very rough

Examples 1-4 and Comparative Examples 1-4
An acrylic-melamine resin was applied by a gravure method on a biaxially stretched PET film (thickness: 75 μm) subjected to easy adhesion treatment to form a release layer (thickness: 3 μm).
Next, any one of the electron beam curable resins EB-1 to EB-7 having the weight average molecular weight shown in Table 1 is used as the electron beam curable resin composition as shown in Table 1 to form the release layer. It was applied by gravure reverse method and irradiated with an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to crosslink and cure the electron beam curable resin composition to form a protective layer (thickness: 12 μm). .
In addition, EB-1 thru | or EB-6 were bifunctional urethane acrylate oligomers, and EB-7 was a tetrafunctional urethane acrylate oligomer.
In Comparative Example 3, 20 parts by mass of electron beam curable resin EB-5, thermoplastic resin (molar ratio of methyl methacrylate to methyl acrylate 100: 5, weight average molecular weight (Mw): about 80 parts by mass of 40 to 60,000, a copolymer having an average number molecular weight (Mn) of about 60,000 and a polydispersity (Mw / Mn) of 1.67) was mixed to obtain an electron beam curable resin composition.
Next, a polyurethane two-component curable primer solution was applied onto the protective layer to form a primer layer (thickness: 1.5 μm).
Next, a printing ink (acrylic resin: 50 mass%, vinyl chloride-vinyl acetate copolymer resin: acrylic resin and vinyl chloride-vinyl acetate copolymer resin: binder resin on the primer layer) (50% by mass) is subjected to gravure printing at a coating amount of 3 g / m ² to form a woodgrain pattern layer, and a resin composition (acrylic) comprising an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin Resin: 50% by mass, vinyl chloride-vinyl acetate copolymer resin: 50% by mass) is applied with gravure printing at a coating amount of 4 g / m ² to form an adhesive layer, and eight types of three-dimensional molding decoration A film was obtained. Table 8 shows the results of evaluating these eight types of three-dimensional decorative decorative films by the above method.

［注］
第１表中、「１３４＜」とは、「１３４より大きいことをいう。」

[note]
In Table 1, “134 <” means “greater than 134”.

  As is clear from Table 1, the three-dimensional decorative film of Examples 1 to 4 has formability, wear resistance, and printability as compared with the three-dimensional decorative film of Comparative Examples 1 to 4. Established properly.

  The three-dimensional molded decorative film of the present invention is suitably used for various decorative molded products by the injection molding simultaneous transfer decorative method.

DESCRIPTION OF SYMBOLS 10 Three-dimensional shaping decorative film 11 Base material 12 Release layer 13 Protective layer 14 Primer layer 15 Colored layer 16 Adhesive layer

Claims (9)

  A three-dimensional decorative film for injection molding simultaneous transfer, which is formed by laminating a release layer, a protective layer, a colored layer and an adhesive layer in this order on a substrate, and the protective layer has a weight average molecular weight Mw11000. A three-dimensional decorative film comprising a cured product of an ionizing radiation curable resin composition containing ˜40000 polymerizable (meth) acrylate oligomer.   The three-dimensional decorative film according to claim 1, wherein a primer layer is further laminated between the protective layer and the colored layer.   The three-dimensional molded decorative film according to claim 1 or 2, wherein the substrate is a polyester film.   The three-dimensional decorative film according to any one of claims 1 to 3, wherein the polymerizable (meth) acrylate oligomer is a bifunctional oligomer.   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, a polymerizable (meth) acrylate having a weight average molecular weight Mw of 11000 to 40000 on the release layer A step of laminating an ionizing radiation curable resin composition layer containing an oligomer, and 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. A method for producing a three-dimensional decorative film, comprising: a step, a step of laminating a colored layer on the protective layer, and a step of laminating an adhesive layer on the colored layer.   The method for producing a three-dimensional molded decorative film according to claim 5, further comprising a step of laminating a primer layer on the protective layer between the step of forming the protective layer and the step of laminating the colored layer. .   The method for producing a three-dimensional decorative film according to claim 5 or 6, wherein the substrate is a polyester film. The method for producing a three-dimensional molded decorative film according to any one of claims 5 to 7, wherein the polymerizable (meth) acrylate oligomer is a bifunctional oligomer.   The base material side of the three-dimensional decorative film obtained by the manufacturing method according to claim 5 is directed into the mold, and the three-dimensional decorative film is heated from the base material side by a hot platen. A step of preliminarily molding the heated three-dimensional decorative film so as to conform to the shape in the mold and clamping the mold in close contact with the inner surface of the mold, a step of injecting an injection resin into the mold, A process for producing a decorative molded product, comprising a step of taking out a decorative molded product from a mold after the injection resin has cooled, and a step of peeling the substrate and the release layer from the decorative molded product.

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