Laminated film for decorating 3D molded products and method for decorating 3D molded products

Abstract

To provide a laminated film for three-dimensional molding decoration which can stably maintain a good three-dimensional design property for a long period of time because of having a hologram layer in a layer.SOLUTION: A laminated film for three-dimensional molding decoration has a base material layer (A), a clear coating layer (B) composed of an energy ray-curable coated film, a protective layer (C) for laminating a metal vapor-deposited surface, a metal vapor-deposited layer (D) composed of indium or tin, and an adhesive layer (E), wherein the protective layer (C) contains a reactive resin and a curing agent, and the metal vapor-deposited layer (D) has an uneven pattern of a hologram pattern on at least the clear coating layer (B) side.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate film for decorating three-dimensional molded products and a method for decorating three-dimensional molded products. [Background technology]

[0002] BACKGROUND ART Molded products made from plastics, metals, and various other materials are generally decorated on their surfaces for the purposes of imparting design features to the surface or protecting the surface.

[0003] One known method of decoration is film decoration using laminated films. This involves creating a film layer for decorating a molded product and then adhering it to the molded product. It has been investigated to create a new three-dimensional design by forming a fine concave-convex pattern called a hologram pattern on such decorative sheets.

[0004] Patent Documents 1 and 2 disclose a film for three-dimensional decoration having a concave-convex pattern on the surface layer. However, these three-dimensional decorative films do not have a holographic appearance because they do not have a metal layer, and furthermore, because they have a textured pattern on the surface, the textured pattern is likely to disappear during decorative molding.

[0005] Patent document 3 discloses a synthetic resin decorative film comprising an adhesive layer protective sheet having an uneven surface, an adhesive layer provided on the uneven surface of the adhesive layer protective sheet, a decorative layer containing a colorant and a synthetic resin, and a skin layer containing a synthetic resin and having unevenness formed on the surface opposite to the decorative layer (Claim 1). However, the presence of the metal decorative layer does not give the appearance of a hologram.

[0006] Patent Documents 4 and 5 disclose decorative films having an uneven layer within the film, rather than on the surface, but do not achieve both sufficient hardness and stretchability.

[0007] Patent Document 6 discloses a laminated film for decorating three-dimensional molded products, which has a metal vapor deposition layer. However, it does not have a textured shape to give it a holographic appearance. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2019-202448 [Patent Document 2] Japanese Patent Application Laid-Open No. 2018-12279 [Patent Document 3] Japanese Patent Application Publication No. 2018-149725 [Patent Document 4] Japanese Patent Publication No. 2020-28981 [Patent Document 5] Japanese Patent Application Publication No. 2020-104467 [Patent Document 6] International Publication No. 2016 / 080423 Summary of the Invention [Problem to be solved by the invention]

[0009] In view of the above, the present invention provides a laminate film for decorating three-dimensional molded products, which has a hologram layer therein and can stably maintain good three-dimensional design for a long period of time. [Means for solving the problem]

[0010] The present invention provides a laminated film having a substrate film layer (A), a clear coating layer (B) made of an energy ray-curable coating film, a protective layer (C) for laminating a metal vapor-deposited surface, a metal vapor-deposited layer (D) made of indium or tin, and an adhesive layer (E), the protective layer (C) contains a reactive resin and a curing agent, the metal vapor deposition layer (D) has a holographic pattern on at least the clear coating layer (B) side; The clear coating layer (B) is formed from an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3); the reactive resin contained in the protective layer (C) is an epoxy resin or polyurethane resin having a hydroxyl group, the amount of the reactive resin blended in the protective layer (C) is 10 to 70% by weight, and the curing agent contained in the protective layer (C) is at least one curing agent having only a primary isocyanate group; The present invention relates to a laminated film for decorating three-dimensional molded products, characterized in that the temperature range in which it exhibits a breaking elongation of 30 to 500% is within a range of 40 to 130°C.

[0011] above The laminated film for decorating three-dimensional molded products preferably has a breaking elongation of 30 to 500% at 80°C.

[0012] The present invention also relates to a method for decorating a three-dimensional molded product, characterized in that the adhesive layer of the above-mentioned laminated film for decorating a three-dimensional molded product is adhered to the three-dimensional molded product under heating conditions. The present invention provides a decorated molded product obtained by adhering the above-mentioned laminated film for decorating three-dimensional molded products onto a three-dimensional molded product, The three-dimensional molded product is also a decorative molded product that is at least one of an automobile interior part, an automobile exterior part, a housing for a home appliance, and a bathroom vanity. [Effects of the Invention]

[0013] The laminated film for decorating three-dimensional molded products of the present invention makes it possible to obtain three-dimensional molded products that have a holographic design for a long period of time. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a schematic diagram showing an example of the laminate structure of a laminate film for decorating three-dimensional molded products of the present invention. [Figure 2] 1 is a schematic diagram showing an example of the laminate structure of a laminate film for decorating three-dimensional molded products of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below. (Laminated film for decorating 3D molded products) The laminate film for decorating three-dimensional molded products of the present invention is a film used in the decorative molding of three-dimensional molded products. That is, the decorative film is adhered to various molded products to impart design features and surface protection functions to the molded products. At this time, it is deformed to fit the surface of the three-dimensional shape and adheres tightly.

[0016] The laminate film for decorating three-dimensional molded products of the present invention comprises a substrate film layer (A), a clear coating layer (B) made of an energy ray-curable coating film, a protective layer (C) for laminating the metal vapor deposition surface, a metal vapor deposition layer (D) made of indium or tin, and an adhesive layer (E) for adhering the laminate film to the molded product. If necessary, the laminate film may also comprise a release layer (F), a design layer (G), an ultraviolet absorbing layer (H), etc. These layers can be arranged in various laminate configurations as needed.

[0017] In the present invention, the metal vapor deposition layer (D) is characterized in that it has a fine uneven shape of a hologram pattern at least on the surface on the side of the clear coating film layer (B). In other words, because the fine unevenness is formed inside the laminate film for decorating 3D molded products, it has the advantage of being less likely to warp or crack when it is attached to the molded product. Also, since a hologram pattern with smaller unevenness than usual is formed inside, it can be given a unique design by the hologram. Furthermore, since the uneven pattern is not on the outermost surface, dirt does not adhere to the recesses, the protrusions do not wear, and there is an advantage that the uneven shape is less likely to deteriorate.

[0018] The laminated film for decorating three-dimensional molded products having the above-mentioned layer structure has a metal vapor deposition layer (D) sandwiched therebetween, with a protective layer (C) and an adhesive layer (E) on the top and bottom of the metal vapor deposition layer (D), and the protective layer (C) contains a reactive resin and further contains a curing agent.

[0019] Conventional laminate films for decorating 3D molded products often lack hardness after decorative molding, have reduced water resistance, and suffer from poor adhesion at the metal deposition interface, resulting in insufficient performance. These issues can be resolved by adding a curing agent to the protective layer or adhesive layer and curing each layer, but adding a sufficient amount of curing agent makes it impossible to ensure stretchability (over 300%) during the vacuum molding process, resulting in film breakage or poor appearance due to stretching distortion of the film.

[0020] Therefore, by blending a reactive resin into the protective layer (C) and further using a specific curing agent, it is possible to ensure stretchability during decorative molding, while making it less likely that problems such as hardness and water resistance will occur after decorative molding.

[0021] Furthermore, the laminate film for decorating three-dimensional molded products of the present invention can be suitably applied to vacuum forming. When a laminate film for decorating three-dimensional molded products is bonded to a molded product by injection molding, the high temperature treatment can cause distortion or cracks in the textured pattern. On the other hand, vacuum forming does not require high temperature treatment and does not have such problems, but sufficient stretchability is required. The laminate film for decorating three-dimensional molded products of the present invention has a breaking elongation of 30 to 500% at 40 to 130°C before curing, and therefore exhibits stretchability that is suitable for vacuum forming.

[0022] Specific embodiments of the laminated structure will be described below with reference to the drawings. The first laminated structure shown in Figure 1 is a laminated film in which a release layer (F), a clear coating layer (B), a protective layer (C), a metal vapor deposition layer (D), and an adhesive layer (E) are laminated in this order on a base film (A). In this first laminated structure, when used, the base film (A) is peeled off together with the release layer (F), and the resulting laminated film consisting of four layers, the clear coating layer (B), the protective layer (C), the metal vapor deposition layer (D), and the adhesive layer (E), is adhered to a molded product and cured for use.

[0023] The second laminate structure shown in Fig. 2 is a laminate film in which a clear coating layer (B) is laminated on a base film (A), and a protective layer (C), a metal vapor deposition layer (D), and an adhesive layer (E) are laminated in this order on the opposite surface. As shown in Fig. 2, in an embodiment in which the base film layer (A) is adjacent to the metal vapor deposition layer (D) and the base film layer (A) is used without being peeled off, the protective layer (C) may be present between the base film layer (A) and the metal vapor deposition layer (D).

[0024] (Base film layer (A)) The base film layer (A) also functions as a carrier film when producing the laminate film of the present invention, i.e., it is used as a base for forming each layer when producing the laminate film for decorating three-dimensional molded products of the present invention.

[0025] The film forming the base film layer (A) is not particularly limited, and examples thereof include conventionally known films such as soft polyvinyl chloride films, unstretched polypropylene films, unstretched polyester films, polycarbonate films, acrylic resin films, and fluorine films. Among these, films formed from polyester and / or polyolefin are preferred, and unstretched polyester films are more preferred, particularly from the standpoint of energy-saving and low-temperature processability. The thickness of the base film layer (A) is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm. Thicknesses outside this range are undesirable in terms of function as a carrier film and economic efficiency during electromagnetic radiation curing.

[0026] (Clear coating layer (B)) The clear coating film layer (B) used in the present invention is an energy ray-curable coating film, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film, and it can be any known energy ray-curable coating film. The energy ray-curable coating film can be deformed into the shape of the object to be decorated while still in the form of a laminate film for decorating three-dimensional molded products, and then the resin can be cured by irradiating it with energy rays. Therefore, it can be easily deformed into the shape of the object to be decorated, and the coating layer after decoration exhibits excellent performance in terms of strength, appearance, chemical resistance, etc.

[0027] Among these, it is preferable to use an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). By using such a composition, the coating can be easily stretched during use and can easily be deep-drawn, resulting in good conformability to three-dimensional shapes. Another advantage is that it is less likely to cause blocking.

[0028] In the active energy ray-curable coating composition, the total amount of the polyurethane acrylate (B1), the monomer / oligomer having an unsaturated double bond (B2), and the polymerization initiator (B3) is preferably 40 to 98% by weight based on the total solid content of the composition. This specific blending ratio is preferred because it allows the desired effects to be achieved.

[0029] Furthermore, the active energy ray-curable coating composition preferably contains 50 to 99 parts by weight of (B1) and 1 to 50 parts by weight of (B2) per 100 parts by weight of the total ((B1) + (B2)) of the solid contents of (B1) and (B2), and contains 0.5 to 20 parts by weight of (B3) per 100 parts by weight of the total ((B1) + (B2)) of the solid contents of (B1) and (B2). This allows the coating composition to have good blocking resistance and deep drawability (stretchability) before curing. Furthermore, the coating composition can have high scratch resistance, surface hardness, chemical resistance, and impact resistance after curing. Below, (B1) to (B3) will be explained in detail.

[0030] (Polyurethane acrylate (B1)) Polyurethane acrylate (B1) is a compound that has a urethane bond and a (meth)acrylate group in the molecule. Its use improves stretchability during decorative molding and allows for easy deep drawing, resulting in good conformability to three-dimensional shapes.

[0031] The polyurethane acrylate (B1) is not particularly limited, and any known polyurethane acrylate can be used. For example, i) A compound obtained by reacting an equivalent amount of a compound having two or more isocyanate groups in the molecule with an equivalent amount of a compound having one or more hydroxyl groups and one or more double bond groups in the molecule; ii) a compound obtained by reacting a condensate of a polyol with a monobasic acid and / or a polybasic acid and / or an acid anhydride thereof with a compound having two or more isocyanate groups in the molecule, and then further reacting the resulting compound with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule; iii) A compound obtained by reacting a polyol with a compound having two or more isocyanate groups in the molecule, and then reacting the compound with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule; etc.

[0032] In the above i) to iii), examples of compounds having one or more hydroxyl groups and one or more double bond groups in the molecule include 2-hydroxy(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc., and commercially available products such as the Placcel C(M)A series (trade name, Daicel Chemical Industries, Ltd.). In the above ii) to iii), examples of polyhydric alcohols include polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane, etc., and commercially available products such as the Placcel Diol series (trade name, Daicel Chemical Industries, Ltd.) and the Placcel Triol series (trade name, Daicel Chemical Industries, Ltd.).

[0033] The polyol is not particularly limited, and known acrylic polyols, polyester polyols, polycarbonate polyols, etc. Also, various low molecular weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, neopentyl glycol, etc. can be used as needed.

[0034] The polyol preferably has a polycarbonate diol skeleton in a proportion that results in a polycarbonate concentration of 0.5 to 75 wt% (the proportion of polycarbonate relative to the total amount of polyurethane acrylate (B1), calculated based on the proportions of the components blended as raw materials). Use of a polycarbonate diol skeleton provides the advantage of exhibiting toughness, preventing blistering during decorative molding, and preserving the design appearance (preventing cracks). The polycarbonate diol is more preferably contained in an amount of 2 to 70% by weight.

[0035] The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and examples thereof include aromatic compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate; aliphatic compounds such as hexamethylene diisocyanate; alicyclic compounds such as isophorone diisocyanate; and monomers thereof and polymers such as biuret types, isocyanurate types, and adduct types thereof.

[0036] Commercially available polyisocyanates include Duranate 24A-90PX (NCO: 23.6%, trade name, manufactured by Asahi Kasei Corporation), Sumidur N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethanes Co., Ltd.), Takenate D165N-90X (trade name, manufactured by Mitsui Chemicals, Inc.), Sumidur N-3300, Sumidur N-3500 (all trade names, manufactured by Sumitomo Bayer Urethanes Co., Ltd.), Duranate THA-100 (trade name, manufactured by Asahi Kasei Corporation), etc. Blocked isocyanates obtained by blocking these polyisocyanates can also be used as needed.

[0037] The polyurethane acrylate (B1) may partially contain urea bonds. In order to make the polyurethane acrylate have a urea bond, a polyamine compound may be used in part of the synthesis of the polyurethane acrylate. The polyamine compound that can be used is not particularly limited, and examples thereof include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, and piperazine. alicyclic polyamines such as 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4'- and / or 4,4'-diamine, and norbornanediamine; aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane; and dimer diamines in which the carboxyl groups of dimer acids have been converted to amino groups, and dendrimers having primary or secondary amino groups at the terminals.

[0038] The polyurethane acrylate (B1) preferably has a double bond equivalent of 130 to 600 g / eq, more preferably 150 to 300 g / eq. If the double bond equivalent is less than 130 g / eq, the cured film may have poor crack resistance and impact resistance. If the double bond equivalent is more than 600 g / eq, the cured film may have poor scratch resistance, surface hardness, and chemical resistance. The double bond equivalent is a value calculated based on the blending ratio of the raw materials used in the production of the resin.

[0039] The polyurethane acrylate (B1) preferably has a weight-average molecular weight of 3,000 to 200,000. A weight-average molecular weight of less than 3,000 may result in poor blocking resistance. A weight-average molecular weight of more than 200,000 may result in poor compatibility between the resulting polyurethane acrylate (B1) and the unsaturated double bond-containing monomer / oligomer (B2) contained in the clear coating composition. Additionally, a weight-average molecular weight of more than 200,000 tends to increase the viscosity of the clear coating composition. Furthermore, diluting the clear coating composition with an organic solvent to alleviate this increased viscosity may significantly reduce the solids content of the clear coating composition, potentially resulting in poor processability. In this specification, the weight-average molecular weight was measured by the method described below.

[0040] The polyurethane acrylate (B1) preferably has a urethane concentration of 300 to 2000 g / eq. If the urethane concentration is less than 300 g / eq, the compatibility of the resulting polyurethane acrylate (B1) with the unsaturated double bond-containing monomer / oligomer (B2) contained in the clear coating composition decreases. In addition, if the urethane concentration is less than 300 g / eq, the viscosity of the clear coating composition tends to increase. Furthermore, if the clear coating composition is diluted with an organic solvent to alleviate this increased viscosity, the solids content in the clear coating composition may decrease significantly, potentially resulting in poor processability. If the urethane concentration exceeds 2000 g / eq, problems such as poor blocking resistance and impact resistance may occur. The urethane concentration is calculated by dividing the weight-average molecular weight of the resin by the number of urethane bonds, based on the blending ratio of the raw materials used in the production of the resin.

[0041] The polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1,000 g / eq. If the urea concentration is less than 500 g / eq, the compatibility of the resulting polyurethane acrylate (B1) with the unsaturated double bond-containing monomer / oligomer (B2) contained in the clear coating composition decreases. In addition, if the urea concentration is less than 500 g / eq, the viscosity of the clear coating composition tends to increase. Furthermore, if the clear coating composition is diluted with an organic solvent to alleviate this increased viscosity, the solids content in the clear coating composition may decrease significantly, potentially resulting in poor processability. If the urea concentration exceeds 1,000 g / eq, the blocking resistance may be impaired. The urea concentration is calculated by dividing the weight-average molecular weight of the resin by the number of urea bonds, based on the blending ratio of the raw materials used in the production of the resin.

[0042] The polyurethane acrylate (B1) may be modified with fluorine and / or silicone, i.e., the polyurethane acrylate (B1) may be synthesized by the above-mentioned method using a monomer containing fluorine or a silicone unit, or the polyurethane acrylate (B1) obtained by the above-mentioned method may have a functional group that is reacted with a compound containing fluorine and / or silicone.

[0043] (Monomers and oligomers with unsaturated double bonds (B2)) Any known monomer / oligomer (B2) having an unsaturated double bond can be used, for example, the following compounds can be used. The monomer / oligomer (B2) having an unsaturated double bond preferably has a weight-average molecular weight of 3,000 or less. That is, to complement the performance of the polyurethane acrylate (B1), a relatively low-molecular-weight monomer / oligomer having an unsaturated double bond is used. Those that fall under the category of polyurethane acrylate (B1) do not fall under the category of monomer / oligomer (B2) having an unsaturated double bond.

[0044] By blending a predetermined amount of the above-mentioned monomer / oligomer (B2) having an unsaturated double bond, a coating film with a high crosslinking density can be formed, which is preferable in that the physical properties of the clear coating film layer can be improved.

[0045] Examples of the (meth)acrylate having a functionality of 2 include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, and the like. Of these, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. can be preferably used.

[0046] Examples of (meth)acrylates having three functional groups include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, etc. Among these, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc. are preferably used.

[0047] Examples of (meth)acrylates having four functional groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, pentaerythritol propylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc. Among these, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. can be preferably used.

[0048] Examples of (meth)acrylates having 4 or more functional groups include polyfunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. These monomers may be used alone or in combination of two or more.

[0049] Examples of (meth)acrylic oligomers include epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate. Here, polyester acrylate prepolymers can be obtained by, for example, esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by condensation of a polycarboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid. Epoxy acrylate prepolymers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low-molecular-weight bisphenol epoxy resin or novolac epoxy resin to esterify it. Urethane acrylates can generally be obtained by reacting a polyester polyol, polyether polyol, or polycarbonate polyol with an isocyanate monomer or prepolymer, and then reacting the resulting product with an acrylate monomer having a hydroxyl group. These (meth)acrylic oligomers may be used alone or in combination of two or more kinds, and may also be used in combination with the above-mentioned polyfunctional (meth)acrylate monomers.

[0050] As the monomer / oligomer (B2) having an unsaturated double bond, commercially available products such as UV 1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can also be used.

[0051] (Polymerization initiator (B3)) As the polymerization initiator (B3), an energy ray polymerization initiator can be used, which initiates polymerization by electromagnetic rays such as ultraviolet (UV) rays and electron beams. These energy ray polymerization initiators are not particularly limited, and any known initiators can be used.

[0052] Specifically, examples of the energy ray polymerization initiator include benzoin-based compounds such as benzoin methyl ether; anthraquinone-based compounds such as 2-ethylanthraquinone; benzophenone-based compounds such as benzophenone; sulfide-based compounds such as diphenyl sulfide; thioxanthone-based compounds such as 2,4-dimethylthioxanthone; acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone; phosphinoxide-based compounds such as 2,4,6-trimethylbenzoin diphenylphosphinoxide; and ultraviolet (UV) curing polymerization initiators such as Irgacure (registered trademark)-184 and Irgacure-819 (both manufactured by BASC). One or more of these compounds can be used as the polymerization initiator.

[0053] (B1) to (B3) blending amounts) It is preferable that (B1) is contained in an amount within the range of 50 to 99 parts by weight and (B2) is contained in an amount within the range of 1 to 50 parts by weight, with the total weight of the solid contents of (B1) and (B2) ((B1) + (B2)) being 100 parts by weight, and that (B3) is contained in an amount within the range of 0.5 to 20 parts by weight, with respect to 100 parts by weight of the total weight of the solid contents of (B1) and (B2) ((B1) + (B2)).

[0054] If the content of the polyurethane acrylate (B1) is less than 50 parts by weight, blocking resistance will decrease, which is undesirable. If the content of the polyurethane acrylate (B1) is more than 99 parts by weight, scratch resistance and surface hardness will be insufficient, which is undesirable. The lower limit is more preferably 55 parts by weight or more, and even more preferably 65 parts by weight or more. The upper limit is more preferably 98 parts by weight or less, and even more preferably 95 parts by weight or less.

[0055] If the content of the monomer / oligomer (B2) having an unsaturated double bond is less than 1 part by weight, the scratch resistance and surface hardness will be insufficient, which is undesirable. If the content of the monomer / oligomer (B2) having an unsaturated double bond is more than 50 parts by weight, the blocking resistance will decrease, which is undesirable. The lower limit is more preferably 2 parts by weight or more, and even more preferably 5 parts by weight or more. The upper limit is more preferably 45 parts by weight or less, and even more preferably 35 parts by weight or less.

[0056] If the content of the polymerization initiator (B3) is less than 0.5 parts by weight, the clear layer cannot be sufficiently cured, and the resulting clear layer may not have the physical properties of scratch resistance, surface hardness, chemical resistance, and impact resistance. If the content of the polymerization initiator (B3) is more than 20 parts by weight, unreacted polymerization initiator (B3) may remain in the clear coating film, which may deteriorate the clear coating film due to sunlight outdoors, etc., and may result in poor weather resistance.

[0057] The above clear coating composition preferably contains 0.5 to 20 parts by weight of a thiol compound and / or an amine compound. The thiol compound and / or amine compound is not particularly limited, and examples thereof include commonly used thiol compounds and amine compounds.

[0058] Examples of the amine compound include, but are not limited to, aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, and diethylenetriamine; alicyclic polyamines such as 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3-, and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4'- and / or 4,4'-diamine, and norbornanediamine; aromatic amines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, and 4,4-bis-(sec-butyl)diphenylmethane; and diamine dimer acids in which the carboxy groups of dimer acids are converted to amino groups, dendrimers having amino groups at the terminals, and polyamines having amines as a repeating structure.

[0059] Examples of the thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, 4-t-butyl-1,2-benzenedithiol, bis-(2-mercaptoethyl)sulfide, 4,4'-thiodibenzenethiol, benzenedithiol, glycol dimercaptoacetate, glycol dimercaptopropionate, ethylene bis(3-mercaptopropionate), polyethylene glycol dimercaptoacetate, polyethylene glycol di-(3-mercaptopropionate) ), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenofluorene bis(ethoxy-3-mercaptopropionate), 4,8-bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3-propanedithiol, 1,8-dimercapto-3,6-dioxaoctane, thioglycerol bismercaptoacetate, and other bifunctional thiols: trimethylolpropane (tris-mercaptopropionate) (TMPTMP), trimethylolpropane Trifunctional thiols such as tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptoacetate), tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,2,3-trimercaptopropane, and tris(3-mercaptopropionate)triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; poly(mercaptopropylmethyl)siloxane (PMPMS), 4-mercaptomethyl-3,6-dithia-1,Polyfunctional thiols include, but are not limited to, 8-octanedithiol, pentaerythritol tetrakis(3-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptobutyrate).

[0060] The clear coating film layer (B) used in the laminated film for decorating three-dimensional molded products of the present invention is as described above, but more preferably, the polyurethane acrylate (B1) is Double bond equivalent: 130~600g / eq Molecular weight Mw:3000~200000 Urethane concentration: 300~2000g / eq, It is preferable that the clear coating layer (B) is formed from a coating composition that satisfies these properties. It is preferable to use a composition that satisfies these properties. Forming the clear coating layer (B) from such a clear coating composition is preferable in that it provides blocking resistance, high scratch resistance, surface hardness, chemical resistance, and good impact resistance. Furthermore, the polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g / eq.

[0061] The weight average molecular weight in this specification was measured using HLC-82220GPC manufactured by Tosoh Corporation under the following measurement conditions. Column: TSKgel Super Multipore HZ-M (3 columns) Developing solvent: tetrahydrofuran Column inlet oven 40℃ Flow rate: 0.35 ml / min. Detector: RI Standard polystyrene: Tosoh Corporation PS oligomer kit

[0062] (Other ingredients) The clear coating composition may contain compounds that are usually added as coating materials as other components. In this case, the amount of other components is preferably 60% by weight or less, more preferably 40% by weight or less, and most preferably 20% by weight or less, based on the total solid content of the coating. Examples of other components include ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins and crosslinking agents, pigments, surface conditioners, antifoaming agents, conductive fillers, solvents, etc.

[0063] Furthermore, a solvent may be used to mix the components contained in the clear coating composition or to adjust the viscosity. Examples of the solvent include esters, ethers, alcohols, amides, ketones, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. These solvents may be used alone or in combination of two or more of the conventionally known organic solvents used in coatings. When using the above solvents, if volatile substances remain in the laminated film, they may volatilize during decoration of the substrate, causing pinholes and blisters. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminated film.

[0064] Furthermore, the clear coating composition preferably further contains 0.5 to 60 parts by weight (solid content ratio in the coating) of an inorganic or organic filler with an average primary particle diameter of 100 nm or less. This improves blocking resistance, high scratch resistance, and surface hardness. The lower limit of the blending amount is more preferably 1 wt. %, and the upper limit is more preferably 50 wt. %.

[0065] Examples of the inorganic filler include silica, finely powdered glass, alumina, calcium carbonate, kaolin, clay, sepiolite (magnesium silicate), talc (magnesium silicate), mica (aluminum silicate), xonotlite (calcium silicate), aluminum borate, hydrotalcite, wollastonite (calcium silicate), potassium titanate, titanium oxide, barium sulfate, magnesium sulfate, magnesium hydroxide, yttria, ceria, silicon carbide, boron carbide, zirconia, aluminum nitride, silicon nitride, eutectic mixtures thereof, and non-metallic inorganic materials obtained by molding, firing, etc., known as ceramic fillers. Among these, silica, alumina, zirconia, and eutectic mixtures thereof are preferred in terms of cost and effectiveness.

[0066] Examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins. Commercially available organosilica sols such as MIBK-ST, MEK-ST-UP, MEK-ST-L, and MEK-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.), SIRMIBK15ET%-H24, SIRMIBK15ET%-H83, and ALMIBK30WT%-H06 (CIK Nanotech) can also be used.

[0067] The clear coating composition may contain 0.5 to 20% by weight (solid content ratio in the coating) of a polyisocyanate compound having an isocyanate group. The incorporation of a polyisocyanate compound is preferred in that it can impart moldability (stretchability) and scratch resistance. The lower limit of the amount incorporated is more preferably 2% by weight, and the upper limit is more preferably 18% by weight.

[0068] The clear coating composition may be a colored, transparent coating containing a coloring pigment. That is, by combining a metal vapor deposition layer with such a colored, transparent clear layer, decoration with colored metal vapor deposition can be achieved. The coloring pigment that can be used in the clear coating composition is not particularly limited, and any known coloring pigment can be used.

[0069] The thickness of the clear coating layer is not particularly limited, but is preferably 3 to 60 μm. To maintain properties such as surface hardness and scratch resistance, it is preferable to ensure a specified film thickness. Depending on the method used to form the coating, a viscosity of 50 mPa·s to 5000 mPa·s is preferred, with 100 mPa·s to 3000 mPa·s being more preferred. If the viscosity is lower than this, it becomes difficult to ensure a film thickness and workability deteriorates. If the viscosity is higher than this, coating becomes difficult and the appearance may be poor. Furthermore, air tends to become trapped, causing problems such as swelling during molding.

[0070] (Protective layer (C)) The laminate film for decorating three-dimensional molded products according to the present invention forms a protective layer (C) between the clear coating layer (B) and the metal vapor deposition layer (D). That is, if the metal vapor deposition layer (D) is provided in a position in contact with the clear coating layer (B), when the uncured clear coating layer (D) moves due to stretching in an uncured state, the metal vapor deposition layer (D) may also move, which may result in a deterioration in appearance. Therefore, by providing the protective layer (C), the appearance of the metal vapor deposition layer (D) is less likely to be disturbed.

[0071] Furthermore, when a metal vapor deposition layer (B) is formed on an uncured clear coating layer (B), it may be difficult to form the metal vapor deposition layer (D). Therefore, from the viewpoint of alleviating such problems, providing a protective layer (C) that has good vapor deposition properties can improve such problems.

[0072] In addition, the metal vapor deposition layer (D) may have poor adhesion to other layers. For this reason, it is preferable to form a protective layer (C) made of a material that has excellent adhesion to other materials and provide the protective layer (C) on the metal vapor deposition layer (D) to improve adhesion to other layers. This can improve adhesion to, for example, the clear coating layer (B) and the design layer (G) described below.

[0073] Examples of resins that can be used in the protective layer (C) include acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, urethane resins, epoxy resins, and styrene resins. Among these, urethane resins are preferred, and urea bond-containing urethane resins are more preferred. The resins can be used alone or in combination of two or more.

[0074] In the present invention, the protective layer (C) is characterized by containing a reactive resin and a curing agent.

[0075] The reactive resin is a resin that reacts with a curing agent to form a crosslinked structure and harden. For example, resins having hydroxyl groups, such as epoxy resins, polyurethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, and styrene resins, can be used. Among these, it is preferable to use epoxy resins or polyurethane resins having hydroxyl groups. The use of epoxy resin or polyurethane resin having a hydroxyl group has the advantage that it can satisfy various performance requirements such as adhesion to a metal vapor deposition layer, chemical resistance, water resistance, and stretchability during molding.

[0076] (Epoxy resin with hydroxyl groups) Examples of the epoxy resin having a hydroxyl group include a resin obtained by condensing epichlorohydrin and bisphenol to a high molecular weight in the presence of a catalyst such as an alkali catalyst as needed; bisphenol-type epoxy resins such as bisphenol A type and bisphenol F type; and novolac-type epoxy resins.

[0077] Examples of the bisphenol include bis(4-hydroxyphenyl)methane (bisphenol F), 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butyl-phenyl)-2,2-propane, p-(4-hydroxyphenyl)phenol, oxybis(4-hydroxyphenyl), sulfonylbis(4-hydroxyphenyl), 4,4'-dihydroxybenzophenone, and bis(2-hydroxynaphthyl)methane. Of these, bisphenol A and bisphenol F are preferred. The bisphenols can be used alone or in a mixture of two or more.

[0078] Furthermore, examples of the novolac epoxy resin, which is an epoxy resin suitable as a reactive resin having a hydroxyl group, include various novolac epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and phenol glyoxal epoxy resin having multiple epoxy groups in the molecule.

[0079] The hydroxyl group-containing epoxy resin may be a modified epoxy resin. Examples of modified epoxy resins include acrylic-modified epoxy resins, urethane-modified epoxy resins, and amine-modified epoxy resins. For example, an acrylic-modified epoxy resin can be prepared by reacting the bisphenol-type epoxy resin or the novolac-type epoxy resin with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid. For example, a urethane-modified epoxy resin can be prepared by reacting the bisphenol-type epoxy resin or the novolac-type epoxy resin with a polyisocyanate compound.

[0080] Examples of epoxy resins having a hydroxyl group include Arakid 9201N, 9203N, 9205, 9208, KA-1439, and Mobitex 401 manufactured by Arakawa Chemical Industries, Ltd.; jER1004, jER1007, 1255HX30 (bisphenol A skeleton), and YX8100BH30 manufactured by Mitsubishi Chemical Corporation; and Epiclon H-301-35PX, Epiclon H-303-45M, Epiclon H-353, and Epiclon H-360 manufactured by DIC Corporation.

[0081] The number average molecular weight (Mn) of the hydroxyl group-containing epoxy resin is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 80,000 or less, and particularly preferably 2,000 or more and 50,000 or less. In the present invention, the number average molecular weight (Mn) is a value calculated in terms of polystyrene by gel permeation chromatography (GPC). Specifically, the analysis was performed on a TOSOH HLC-8200 using a TSKgel SuperMultiporeHZ-M column, with the column temperature set to 40°C, THF used as the eluent, a flow rate of 0.35 ml / min, detection by RI, a sample concentration of 0.02%, and polystyrene as the standard sample.

[0082] By ensuring that the number average molecular weight (Mn) of the epoxy resin having hydroxyl groups is within the above range, it is possible to maintain the water-blocking properties and heat resistance required for the coating film of the decorative molded product, and it is also possible to ensure the stretchability during decorative molding.

[0083] The glass transition temperature (Tg) of the epoxy resin having hydroxyl groups is preferably 120°C or lower, and more preferably 115°C or lower. The glass transition temperature (Tg) of the epoxy resin having hydroxyl groups is preferably 50°C or higher, and more preferably 55°C or higher. For example, the glass transition temperature (Tg) of the epoxy resin having hydroxyl groups can be in the range of 50°C or higher and 120°C or lower. In the present invention, the glass transition temperature (Tg) can be measured using, for example, Reogel-E4000 (manufactured by UBC Corporation) or the like.

[0084] By ensuring that the glass transition temperature (Tg) of the epoxy resin having hydroxyl groups is within the above range, the water barrier properties and heat resistance required for the coating film of the decorated molded product can be maintained, and excellent stretchability can be ensured in sync with the softening of the molded film when heated during decorative molding.

[0085] (Polyurethane resin with hydroxyl groups) The polyurethane resin having hydroxyl groups can be obtained by a conventional method, such as by reacting a polyester polyol (a1) with a polyisocyanate compound (a2) under conditions of an excess of hydroxyl groups.

[0086] The polyester polyol (a1) can be obtained by a conventional method, for example, by charging a polyhydric alcohol and a polybasic acid into a reaction vessel and reacting them at 180 to 250° C. while heating and stirring.

[0087] <Polyhydric alcohol> Examples of the polyhydric alcohol include saturated and unsaturated low-molecular-weight glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, cyclohexanediol, cyclohexanedimethanol, 1,4-butynediol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylolpropane, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A; alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether; and monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester. Furthermore, a polyester polyol can also be obtained by ring-opening polymerization of a cyclic ester compound.

[0088] <Polybasic acid> Examples of the polybasic acid include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimer acid, and anhydrides thereof.

[0089] <Polyisocyanate compound (a2)> As the polyisocyanate compound (a2), various known aromatic, aliphatic, or alicyclic diisocyanates, as well as trifunctional isocyanates, can be used as needed. For example, aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and tolylene diisocyanate. Aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and the like. Examples of diisocyanates include 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acid are converted to isocyanate groups. Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, and norbornane diisocyanate. Examples of trifunctional isocyanates include adducts, isocyanurates, and biuret compounds in which the above diisocyanates are trifunctionalized with trimethylolpropane or the like.

[0090] <Chain extender> The chain extender used to obtain a polyurethane resin having hydroxyl groups can be any of various known polyhydric alcohols, including various known saturated and unsaturated low-molecular-weight glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butyldiol, and dipropylene glycol, as well as dimer diols in which the carboxyl groups of dimer acids have been converted to hydroxyl groups.

[0091] The number average molecular weight (Mn) of the polyurethane resin having a hydroxyl group is preferably from 1,000 to 150,000, more preferably from 3,000 to 100,000, and even more preferably from 5,000 to 50,000. When the number average molecular weight (Mn) of the polyurethane resin having hydroxyl groups is within the above range, it has the advantage of maintaining the water-blocking properties and heat resistance required for the coating film of the decorated molded product and ensuring stretchability during decorative molding.

[0092] The number average molecular weight (Mn) is a value calculated as polystyrene by gel permeation chromatography (GPC) of the resin, and can be obtained in the same manner as above.

[0093] The glass transition temperature (Tg) of the polyurethane resin having a hydroxyl group is preferably from -30°C to 80°C, more preferably from -30°C to 60°C, and even more preferably from -30°C to 50°C. By ensuring that the glass transition temperature (Tg) of the hydroxyl group-containing polyurethane resin is within the above range, the water-blocking properties and heat resistance required for the coating film of the decorated molded product can be maintained, and excellent stretchability can be ensured in sync with the softening of the molded film when heated during decorative molding.

[0094] The acid value of the reactive resin used in the present invention is preferably 0.5 to 300 mgKOH / g. By ensuring that the acid value of the reactive resin is within the above range, it is possible to obtain an advantageous crosslinking density that maintains the water-blocking properties and heat resistance required for the coating film of the decorated molded product and ensures stretchability during decorative molding. The lower limit of the acid value of the reactive resin is more preferably 2.0 mgKOH / g, and the upper limit of the acid value of the reactive resin is more preferably 250 mgKOH / g. In this specification, the acid value was evaluated in accordance with JIS K 0070-1992 (potentiometric titration method). Specifically, a phenolphthalein solution was added as an indicator to a solvent consisting of a 4:1 volumetric mixture of diethyl ether and ethanol, and the mixture was neutralized with a 0.1 mol / L potassium hydroxide ethanol solution. Approximately 5 g of sample was precisely weighed into a beaker, 50 mL of solvent was added, and the mixture was completely stirred and dissolved on a panel heater (80°C). The acid value was determined by potentiometric titration with a 0.1 mol / L potassium hydroxide ethanol solution.

[0095] In the protective layer (C), the amount of reactive resin blended is preferably 10 to 70% by weight in the protective layer (C). Within this range, the water-blocking properties and heat resistance required for the coating film of the decorated molded product can be maintained, and a crosslinking density can be obtained that ensures stretchability during decorative molding. In addition, durability such as weather resistance, and other required properties other than water and heat resistance, as well as coating performance, can be achieved at the same time. The lower limit of the reactive resin content is more preferably 20% by weight, and the upper limit of the reactive resin content is more preferably 50% by weight.

[0096] (hardening agent) Furthermore, in the present invention, it is necessary to use a hardener in the protective layer. By using a curing agent, the fluidity of the metal vapor deposition layer during vacuum molding of the laminated film for decorating three-dimensional molded products can be suppressed, and stretchability can be ensured while preventing appearance defects such as distortion of the hologram pattern.Furthermore, hardness after molding can be ensured, making it less likely to cause problems such as water-resistant peeling.

[0097] In the present invention, examples of the curing agent include isocyanate monomers, polyisocyanates, and blocked isocyanates. Among these, it is preferable to use polyisocyanates. By using polyisocyanates as curing agents, the desired reactivity can be obtained, the fluidity of the metal vapor deposition layer during molding can be suppressed, and the required physical properties can be obtained after molding. In addition, there is an advantage that it is preferable from the viewpoint of safety during paint production and application.

[0098] The curing agent used in the present invention is preferably at least one curing agent having only a primary isocyanate group.

[0099] A primary isocyanate group is defined as a monovalent functional group (-CH2NCO) in which two hydrogen atoms (H) are bonded to the carbon atom (C) to which the isocyanate group (-NCO) is bonded.

[0100] In the present invention, the curing agent (IA) having only a primary isocyanate group does not include one in which the primary isocyanate group is blocked with a blocking agent.

[0101] Examples of the curing agent (IA) having only a primary isocyanate group include isocyanates having only a primary isocyanate group, such as aliphatic isocyanates having a primary isocyanate group, alicyclic isocyanates having a primary isocyanate group, and araliphatic isocyanates having a primary isocyanate group.

[0102] The aliphatic isocyanate having only a primary isocyanate group is a chain (straight-chain or branched-chain: acyclic) aliphatic isocyanate having a primary isocyanate group, and examples thereof include aliphatic diisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and dodecamethylene diisocyanate.

[0103] Examples of alicyclic isocyanates having only primary isocyanate groups include alicyclic diisocyanates such as 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (hydrogenated XDIs).

[0104] Examples of araliphatic isocyanates having only primary isocyanate groups include araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI).

[0105] These isocyanates having only primary isocyanate groups may be used alone or in combination of two or more kinds.

[0106] As the isocyanate having only a primary isocyanate group, from the viewpoints of light resistance and handleability, preferably, an aliphatic isocyanate having a primary isocyanate group or an alicyclic isocyanate having a primary isocyanate group is used, and from the viewpoint of chemical resistance, more preferably, an aliphatic polyisocyanate having a primary isocyanate group is used.

[0107] As the aliphatic isocyanate having a primary isocyanate group, from the viewpoints of availability and stretchability during molding, preferably, 1,5-pentamethylene diisocyanate (PDI) and 1,6-hexamethylene diisocyanate (HDI) are used, and more preferably, 1,6-hexamethylene diisocyanate (HDI) is used.

[0108] Commercially available isocyanates having only the primary isocyanate group include Desmodur N3800 (trade name, manufactured by Sumika Covestro Urethane Co., Ltd.), Takenate D-178NL, Stabio D-370N, D-376N (Mitsui Chemicals, Inc.), Desmodur H, N75MPA / X, N3200, N3300, N3390EA, N3400, N3600, N3790BA, N3800, N3900, XP2580, XP2840, Sumidur HT (Sumika Covestro Urethane Co., Ltd.), Duranate 24A-100, 22A-75P, TPA-100, TKA-100, P301-75E, D101, D201 (Asahi Kasei Corporation), and the like.

[0109] The amount of isocyanate to be added is preferably determined depending on the OH equivalent of the reactive resin in the protective layer (C) and the NCO equivalent of the isocyanate. The isocyanate (IA) is preferably mixed in a ratio (OH:NCO) of 1:0.8 to 1:2.0. The amount of isocyanate (IA) is preferably 0.5 to 10 parts by weight relative to the total amount of the protective layer (C).

[0110] The number of types of isocyanates is not limited to two, and two or more types may be used as appropriate within the scope that achieves the purpose.

[0111] (curing catalyst) When the reactive resin having a hydroxyl group and the curing agent are reacted and cured, a curing catalyst may be added. Examples of the curing catalyst include tin catalysts, amine catalysts, and lead catalysts, among which organotin compounds are preferably used, such as dibutyltin dilaurate (DBTL), dibutyltin oxide, and tetra-n-butyl-1,3-diacetoxystannoxane.

[0112] The amount of curing catalyst is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total solid content of the reactive resin and isocyanate compound. If the amount of curing catalyst is less than 0.1 part by weight, curing of (IA) becomes difficult, and the fluidity of the metal vapor deposition layer during decorative molding cannot be suppressed, resulting in a poor appearance. If the amount of curing catalyst is more than 10 parts by weight, the paint tends to gel before coating, or the paint tends to cure too much during decorative molding, resulting in insufficient stretchability and cracking of the coating film.

[0113] The thickness of the protective layer (C) is not particularly limited, but is preferably, for example, 10 to 50 μm. The lower limit is more preferably 15 μm. The upper limit is more preferably 30 μm. If it is less than 10 μm, it may be difficult to ensure sufficient water-blocking properties in the stretched portion, and if it is more than 50 μm, coating and drying become difficult and there is a tendency for it to be disadvantageous in terms of cost.

[0114] Furthermore, since it is necessary for the coating material for the protective layer (C) to sufficiently penetrate into the irregularities on the surface of the metal vapor deposition layer, it is preferable that the viscosity of the coating material for the protective layer (C) is low.

[0115] (Adhesive layer (E)) The adhesive layer (E) is used to adhere and bond the laminate film to the surface of the three-dimensional molded product when decorating the three-dimensional molded product with the laminate film.

[0116] The adhesive resin contained in the adhesive layer (E) is preferably selected from the group consisting of urethane resin, acrylic resin, olefin resin, vinyl chloride / vinyl acetate resin, epoxy resin and butyral resin, and contains at least one adhesive resin having a softening temperature of 20 to 100°C. Examples include Byron UR-3200 (manufactured by Toyobo Co., Ltd.), Diferamine MAU-2600 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), UR-1361ET (manufactured by Toagosei Co., Ltd.), and Xp012N35 (manufactured by Mitsui Chemicals Co., Ltd.).

[0117] The adhesive layer (E) preferably has a total light transmittance of 20% or less. In particular, it is preferable to reduce the transmittance in the visible light region (wavelength 380 to 810 nm). The total light transmittance is preferably 15% or less, and more preferably 10% or less.

[0118] In this way, by making the adhesive layer (E) have a low total light transmittance, reflection on the substrate surface is reduced, and Rayleigh scattering and Mie scattering in the metal vapor deposition layer are reduced, thereby improving the design. Rayleigh scattering and Mie scattering occur when reflected light hits the metal vapor deposition layer when it whitens. Therefore, if the amount of reflected light from the metal surface can be reduced, the deterioration of the design due to Rayleigh scattering and Mie scattering can be suppressed. Furthermore, by making the adhesive layer (E) have the above total light transmittance, light transmittance is reduced, which is also preferable in that the light resistance of the substrate is improved.

[0119] The total light transmittance in this specification was measured using a spectrophotometer U-4100 (Hitachi High-Technologies) in the wavelength range of 380.0 nm to 810.0 nm using an integrating sphere. The light source was a halogen lamp. The total light transmittance is the transmittance of the adhesive layer (E) alone. Therefore, when measuring the adhesive layer (E) of a laminated film for decorating three-dimensional molded products, a method of peeling it off and measuring the total light transmittance of only the adhesive layer (E) may be used, or the composition of the adhesive layer (E) may be determined, a single film having the same composition and thickness may be produced, and the total light transmittance of that single film may be measured.

[0120] In order to reduce the light transmittance of the adhesive layer (E), various color pigments are blended in. The color pigments are not particularly limited, and examples thereof include glitter pigments such as interference mica pigments, white mica pigments, and graphite pigments; inorganic color pigments such as yellow lead, yellow iron oxide, red iron oxide, carbon black, and titanium dioxide; and extender pigments such as kaolin, clay, silica, zinc oxide, calcium carbonate, and precipitated barium sulfate.

[0121] The color pigment is most preferably carbon black. Carbon black is particularly preferred in terms of its light blocking and concealing properties for the lower coating film. When carbon is added, it is preferably added in an amount of 0.4 to 20% by weight based on the total solid content of the adhesive layer (E). Examples of the carbon black include Carbon Black MA100 and #2650 (manufactured by Mitsubishi Chemical Corporation), CORAX N660 (manufactured by Orion Engineered Carbons Co., Ltd.), Color Black CW200P (manufactured by Evonik Degussa Japan Co., Ltd.), Monarch 1300 (manufactured by Cabot), Raven 1255P, and Raven 5000ULTRA3 (manufactured by Columbian). These commercially available known adhesives can be used by blending various colorants such as carbon so that the total light transmittance is 20% or less.

[0122] From the above viewpoint, the present invention is particularly preferably used to impart design properties to metal substrates. Furthermore, the above-mentioned effects are even more pronounced in fields such as automobile wheels, which have complex shapes and are prone to problems due to deformation.

[0123] The adhesive used in the adhesive layer (E) can be prepared by adding and mixing a pigment dispersion resin, a coloring pigment, a solvent, and optional components in any order. Additives may also be included as needed. Examples of additives include resin components other than the pigment dispersion resin, thickeners, antifoaming agents, film-forming aids, antifreeze agents, anti-sagging agents, anti-settling agents, crosslinking accelerators, curing agents, leveling agents, surface conditioners, plasticizers, preservatives, anti-mold agents, UV stabilizers, and UV absorbers.

[0124] Dispersing machines for preparing the adhesive include an SG mill, ball mill, bead mill, spike mill, pearl mill, dyno mill, two- or three-roll mill, extruder, paint shaker, ultrasonic treatment, homogenizer, kneader, flushing treatment, etc. Dispersing media include zircon beads, zirconia beads, soda-lime glass beads, alkali-free beads, alumina beads, silicon beads, etc. The adhesive layer (E) may be formed by applying and drying the above adhesive, or by laminating an adhesive sheet.

[0125] The thickness of the adhesive layer (E) is not particularly limited, but is preferably, for example, 10 to 50 μm. The upper limit is more preferably 30 μm, and most preferably 25 μm. If it is less than 10 μm, there is a possibility that sufficient adhesion cannot be ensured in the stretched portion, and if it is more than 50 μm, coating and drying become difficult and there is a disadvantage in terms of cost.

[0126] (Metal vapor deposition layer (D) made of indium or tin) Vapor deposition is a method of forming a thin film by heating and vaporizing a vapor deposition material in a vacuum chamber and attaching it to the surface of a substrate placed at a distance. In the present invention, the metals used for vapor deposition are tin and indium. -3 ~10 -4Since a vacuum of about Pa is required, the container must first be evacuated. Therefore, deposition is a completely batch process, and continuous processing is not possible.

[0127] In addition, the deposition method for film is generally as follows: (1) Place a film roll and a target metal in a chamber, (2) Evacuate the chamber (10 -3 ~10 -4 (2) The target is heated and vapor is generated, which vaporizes the film surface, and (3) the chamber is opened to the atmosphere when vapor deposition is complete. Compared to direct vapor deposition on components, this process is more economically efficient because, despite being a batch process, one roll of film is processed continuously. Another advantage is that the thickness and quality of the vapor-deposited film can be easily controlled. However, the film itself cannot be used to create three-dimensional objects.

[0128] The metal vapor deposition layer (D) made of indium or tin in the present invention can be formed by a conventional vapor deposition method using these metals. By using indium or tin, a metal layer with good elongation can be obtained, so that when forming into a three-dimensional shape, cracking or whitening does not occur, and there is no adverse effect on the appearance. Among these, indium is particularly preferred.

[0129] In the present invention, the use of indium or tin as the metal vapor deposition layer (D) has the advantage that cracking and whitening are less likely to occur due to the discontinuous vapor deposition effect. Furthermore, partial cross-linking can be achieved between the protective layer (C) and adhesive layer (E) present above and below the metal vapor deposition layer (D), improving interlayer adhesion between the protective layer (C) and adhesive layer (E) and maintaining the hardness of the laminated film after decorative molding.

[0130] The metal vapor deposition layer (D) preferably has an optical density of 0.6 to 1.4. If the optical density of the metal vapor-deposited layer is less than 0.6, the amount of vapor-deposited metal is insufficient, and sufficient metallic luster cannot be obtained in the stretched portion.Furthermore, if the optical density exceeds 1.4, whitening due to microcracks becomes significant in the stretched portion, and good metallic luster cannot be obtained, which is undesirable.

[0131] In the present invention, the optical density of the metal vapor deposition layer (D) was measured using a color transmission densitometer (DM-500, manufactured by Dainippon Screen Mfg. Co., Ltd.). The thickness of the metal vapor deposition layer (D) was measured by observing the cross section of the film using an FE-SEM S4800 (acceleration voltage 5 kV) manufactured by Hitachi.

[0132] When such a metal vapor deposition layer (D) is formed, its thickness is preferably 0.02 to 5 μm. By setting the thickness to such a value, the above-mentioned object can be satisfactorily achieved. The thickness and optical density of the metal vapor deposition layer (D) are closely related, and the greater the thickness, the higher the optical density of the metal vapor deposition layer. Although it depends on the material of the layer to be vapor deposited, the thickness of the metal vapor deposition layer is generally 0.02 μm to 0.08 μm when the optical density is 0.6 to 1.4.

[0133] The lower limit of the thickness is more preferably 0.03 μm, and the upper limit of the thickness is more preferably 0.1 μm, and even more preferably 0.05 μm.

[0134] In the present invention, the metal vapor deposition layer has a holographic pattern of projections and recesses. The holographic pattern is a nano-order projection and recess pattern, and the holographic design is expressed by interference between light incident on the surface of the metal vapor deposition layer having such a projection and recess pattern and light reflected from the surface of the metal vapor deposition layer.

[0135] In the present invention, the metal vapor deposition layer (D) has the above-mentioned uneven pattern at least on the side of the clear coating layer (B). That is, since the clear coating layer (B) side is the outer side, by forming a surface having a holographic design on this side, a good appearance can be obtained. The uneven pattern that expresses the holographic design may be provided on the entire surface, or may be formed only on a part of the surface.

[0136] As described above, the laminate film for decorating three-dimensional molded products of the present invention has the above-mentioned textured pattern at least on the clear coating layer (B) side of the metal vapor deposition layer. When the above-mentioned laminate film is used to decorate a three-dimensional molded product, the clear coating layer is located near the surface, and the metal vapor deposition surface is located below the textured pattern. Since reflected light intensity is required to express a hologram design, a metal vapor deposition layer is required below the textured pattern.

[0137] The uneven pattern will be described in detail below. The metal vapor deposition layer preferably has a concave-convex structure on its surface, with multiple convex portions (protrusions) arranged at a pitch (the distance between the apexes of adjacent convex portions) equal to or less than the wavelength of visible light (780 nm). This allows for a good holographic design.

[0138] Examples of the shape of the convex portions include a shape consisting of a columnar lower portion and a hemispherical upper portion (a bell shape), a cone shape (a conical shape), or a tapered shape that narrows toward the tip (a conical shape). The base of the gap between the convex portions may be horizontal or inclined.

[0139] The average pitch of the plurality of convex portions is preferably 100 to 5000 nm, more preferably 200 to 2000 nm, from the viewpoint of sufficiently preventing the occurrence of optical phenomena such as moire and rainbow unevenness. Such a configuration prevents the occurrence of problems in appearance. Specifically, the average pitch of the plurality of convex portions refers to the average value of the pitches of all adjacent convex portions within a 1 μm square area in a planar photograph taken with a scanning electron microscope.

[0140] The average height of the plurality of convex portions is preferably 10 to 2000 nm, more preferably 50 to 1000 nm, from the viewpoint of achieving a preferable average aspect ratio of the plurality of convex portions described below. This configuration prevents insufficient hologram design. Specifically, the average height of the plurality of convex portions refers to the average height of 10 convex portions lined up in a row in a cross-sectional photograph taken with a scanning electron microscope. However, when selecting the 10 convex portions, convex portions with missing or deformed portions (such as portions deformed when preparing the measurement sample) are excluded.

[0141] The average aspect ratio of the plurality of convex portions is preferably 0.1 or more and 1.5 or less, more preferably 0.2 or more and 1.0 or less. If the average aspect ratio of the plurality of convex portions is less than 0.1, excellent hologram design may not be obtained. If the average aspect ratio of the plurality of convex portions is greater than 1.5, the processability of the concave-convex structure may decrease, causing sticking or poor transfer when forming the concave-convex structure. The average aspect ratio of the plurality of convex portions refers to the ratio of the average height to the average pitch (height / pitch) of the plurality of convex portions described above.

[0142] The method for forming such surface irregularities is not particularly limited, and examples thereof include a method in which a holographic irregularity pattern processed on the surface of a metal roll, a flat plate, or a UV-curable resin film is transferred to a deposition surface. As such a method, any commonly known method can be applied. The substrate having the holographic irregularity pattern on its surface can be obtained by a known method.

[0143] The laminate film for decorating three-dimensional molded products of the present invention may further include, in addition to the above layers, a release layer (F) and a design layer (G) formed by printing, as needed. Providing a design layer (G) formed by printing is preferred in that a unique design appearance can be obtained that combines the design of the printing with the design of the metal vapor deposition layer.

[0144] Furthermore, when the design layer (G) formed by printing is printed using energy ray-curable ink, it is preferable to provide an ultraviolet absorbing layer (H). That is, the energy ray-curable ink needs to be cured when the film is produced, and it is preferable to prevent the clear coating layer (B) from curing at the same time as the ink is cured. Since the ultraviolet absorbing layer (H) is provided for the above-mentioned purpose, it is preferable to provide it between the design layer (G) formed by printing and the clear coating layer (B).

[0145] (Release layer (F)) In the present invention, when the release layer (F) is provided, any known material can be used, and for example, it can be formed using a silicone-based release agent or the like. The peel strength between the release layer (F) and the clear coating layer (B) is preferably 0.05 to 8.0 N / 25 mm, more preferably 0.1 to 5.0 N / 25 mm. If it is less than 0.05 N / 25 mm, workability will be poor, as the base film layer (A) may peel off during film production and decorative molding, while if it exceeds 8.0 N / 25 mm, peeling of the film after molding may be difficult.

[0146] (Design layer (G) formed by printing) The laminate film for decorating three-dimensional molded products of the present invention may have a design layer (G) formed by printing. The provision of such a layer is preferred in that a unique appearance can be obtained by combining the printed layer with the metal vapor deposition layer. The printing method is not particularly limited, and the layer can be formed by known methods such as inkjet printing, screen printing, offset printing, or flexographic printing. In particular, inkjet printing is preferred in that it allows various printed layers to be formed inexpensively. Furthermore, printing may be performed using energy beam curable ink.

[0147] (Ultraviolet absorbing layer (H)) When a UV absorbing layer (H) is provided, the strength is 3 to 1000 N / cm at 40 to 130°C.2 It is preferable that the surface tension is 20 to 60 mN / m and the transmittance of ultraviolet light at 290 nm to 430 nm is 20% or less. If the strength is low, swelling occurs during molding, and if it is high, moldability is insufficient. In addition, if the surface tension is low, the ink will bleed, and if it is high, the ink will repel, either of which will result in poor printed images. In addition, if the UV transmittance is high, sufficient UV blocking effect will not be obtained. That is, it has sufficient surface tension for inkjet printing, sufficient UV blocking ability to prevent hardening of the clear coating layer, and sufficient strength to prevent problems during molding.

[0148] The strength of the ultraviolet absorbing layer (H) was measured by measuring the film strength of the ultraviolet absorbing layer alone at a temperature of 60°C, a tension speed of 50 mm / min, and an elongation of 200% using an autograph AG-IS manufactured by Shimadzu Corporation.

[0149] The surface tension of the ultraviolet absorbing layer (H) was calculated by measuring the contact angles of water and methylene iodide using an automatic contact angle meter DSA20 (manufactured by Kurtz).

[0150] The ultraviolet transmittance of the ultraviolet absorbing layer (H) was measured in the wavelength range of 290.0 nm to 430.0 nm using a UV-visible spectrophotometer U-4100 (Hitachi High-Technologies).

[0151] Furthermore, it is preferable that the ultraviolet absorbing layer (H) absorbs ultraviolet rays but easily transmits visible light, because if visible light is not transmitted, the design layer will be difficult to see from the outside.

[0152] The ultraviolet absorbing layer (H) is preferably formed from a coating composition containing a binder resin (H1) and an ultraviolet absorber (H2). By adjusting the formulation and combination of these components, a layer satisfying the above-mentioned parameters can be formed.

[0153] The binder resin (H1) is not particularly limited, and resins such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, and styrene resin can be used, with urethane resin being preferred and urea bond-containing urethane resin being more preferred. They can be blended alone or in combination of two or more. It is preferably in the range of 85 to 99% by weight based on the total amount of the ultraviolet absorbing layer (H).

[0154] The ultraviolet absorber (H2) is not particularly limited, and examples thereof include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and hydroxybenzoate-based ultraviolet absorbers.

[0155] Examples of the triazine-based ultraviolet absorbers include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-hydroxymethylphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-hydroxymethylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, and 2-[2-hydroxy-4-(2-hydroxyethyl)phenyl]-4,6-diphenyl-s-triazine.

[0156] Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2'-dihydroxy-4,4'-diethoxybenzophenone. hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2'-dihydroxy-4,4'-di(hydroxymethyl)benzophenone, 2,2'-dihydroxy-4,4'-di(2-hydroxyethyl)benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di(hydroxymethyl)benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di(2-hydroxyethyl)benzophenone, and the like.

[0157] Examples of the benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-t-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(hydroxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-hydroxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(3-hydroxypropyl)phenyl]-2H-benzotriazole, and 2-[2'-hydroxy-3'-methyl-5'-(hydroxymethyl)phenyl]-2H-benzotriazole.

[0158] Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate.

[0159] Examples of the hydroxybenzoate ultraviolet absorbers include phenyl salicylate, resorcinol monobenzoate, 4-t-butylphenyl salicylate, 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3',5-di-t-butyl-4'-hydroxybenzoate, 2,4-di-t-amylphenyl-3',5-di-t-butyl-4'-hydroxybenzoate, and hexadecyl-3',5-di-t-butyl-4'-hydroxybenzoate.

[0160] As the ultraviolet absorber (H2), triazine-based, benzophenone-based, and benzotriazole-based ultraviolet absorbers are preferred because they have high ultraviolet absorption properties over a wide wavelength range (approximately 280 to 360 nm) from short wavelengths to long wavelengths. The ultraviolet absorber may be one of the above compounds, or two or more of them may be used in combination. Specifically, Tinuvin 400, 900, 447, and 1130 (manufactured by BASF) can be used. The amount of ultraviolet absorber (H2) to be added varies depending on the ultraviolet absorber used, and is not particularly limited as long as it satisfies the above-mentioned ultraviolet transmittance, but is preferably in the range of 1 to 15 wt % and more preferably in the range of 3 to 10 wt % relative to the total amount of the ultraviolet absorbing layer (H). If it is less than 1 wt %, the ultraviolet blocking effect may be insufficient. If it exceeds 15 wt %, the strength of the ultraviolet absorbing layer may decrease, resulting in insufficient moldability, and it is also disadvantageous in terms of cost.

[0161] The ultraviolet absorbing layer (H) may contain a surface conditioner (H3). That is, depending on the type of resin used in the ultraviolet absorbing layer (H), it may be difficult to maintain the surface tension within the above-mentioned range. In this case, the surface conditioner (H3) can be added to maintain the surface tension within the above-mentioned range.

[0162] The surface conditioner (H3) is not particularly limited, and examples thereof include polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, etc. Specific examples thereof include BYK-300, BYK-342, and BYK-349 (manufactured by BYK-Chemie Japan). The amount of the surface conditioner (H3) to be added is not particularly limited, but is preferably within the range of 0.01 to 5% by weight based on the total amount of the ultraviolet absorbing layer (H).

[0163] The thickness of the ultraviolet absorbing layer (H) is not particularly limited, but is preferably, for example, 3 to 30 μm, and more preferably 5 to 25 μm. If the layer is too thin, it becomes difficult to obtain sufficient ultraviolet shielding performance and strength, while if the layer is too thick, there is no particular improvement in performance, and it is disadvantageous in terms of cost, and coating and drying become difficult.

[0164] (Easy adhesive layer (J)) In the case of an embodiment in which the base film layer (A) is adjacent to the metal-deposited layer (D) and is used without peeling off, as shown in Figure 2, it is preferable to subject one or both sides of the base film layer (A) to a corona treatment or to provide an easy-adhesion layer (J), which improves adhesion between the base film layer (A) and the clear coating layer (B) or between the base film layer (A) and the metal-deposited adhesive layer or protective layer (C).

[0165] Specifically, the easy-adhesion layer (J) is preferably a layer made of polyester resin-based easy-adhesion coat PET134 Anchor for PET manufactured by Toyo Ink Co., Ltd., or the like.

[0166] (breaking elongation) The laminate film for decorating three-dimensional molded products of the present invention has a breaking elongation of 30 to 500% at 40 to 130°C before curing. In other words, by having such a breaking elongation in the above temperature range, the film can be easily adapted to vacuum forming, and the effects of the present invention can be suitably obtained. Achieving a value within such a numerical range is possible by adjusting the components of each layer that forms the film. In the present invention, "having a breaking elongation of 30 to 500% at 40 to 130°C" means that the temperature range in which the breaking elongation is 30 to 500% is within 40 to 130°C, and sufficient extensibility can be obtained by molding at that temperature.

[0167] The breaking elongation is a value obtained by measuring the elongation at the time when any layer breaks, in a state including the base film layer (A), using an autograph AG-IS manufactured by Shimadzu Corporation, at a temperature range of 40 to 130°C and a pulling rate of 50 mm / min. Depending on the properties of the film, it is sufficient that the breaking elongation is within the above-mentioned range at any temperature within the range of 40 to 130°C.

[0168] (Laminated film manufacturing method) Each layer other than the base film layer (A) and the metal vapor deposition layer (D) constituting the laminate film for decorating three-dimensional molded products of the present invention can be formed by preparing a coating composition in which the components constituting each layer are dissolved in a solvent, and then applying and drying this onto the base film layer (A) or the release layer (F). A specific example of the method is presented below.

[0169] For example, a step (1-1) of sequentially forming a clear coating layer (B) and a protective layer (C) made of an energy ray-curable coating film on a substrate film layer (A); Separately, a step (1-2) of sequentially forming an adhesive layer (E) and a metal vapor deposition layer (D) made of indium or tin on the cover film; and It is preferable to obtain the film by a manufacturing method characterized by including a step (1-3) of laminating the film obtained in the above step (1-1) and the film obtained in the above step (1-2) by a lamination method so that the protective layer (C) and the metal vapor deposition layer (D) are in contact with each other.

[0170] The coating method for forming each of the above layers is not particularly limited, and may be, for example, spray coating using a sprayer, or coating using an applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. After the coating solution is applied by the above coating method, the coating solution can be formed by heating and drying to remove the solvent in the coating solution.

[0171] The adhesive layer (E) may be formed by lamination instead of coating and drying. A metal vapor deposition layer (D) may then be formed on the adhesive layer (E) thus formed, and this may then be laminated to a multilayer film having necessary layers formed on a base film layer (A).

[0172] The method for forming the metal vapor deposition layer (D) made of indium or tin is not particularly limited, and can be carried out by a commonly known method. As described above, the process of forming a metal vapor deposition layer (D) on the adhesive layer (E) formed on the cover film and laminating it with the protective layer (C) by a lamination method has the advantage that the use of a heat-resistant cover film improves drying during coating, suppresses outgassing during vacuum deposition, and results in a good metallic appearance.

[0173] The method for forming the uneven pattern on the metal vapor deposition layer (D) is not particularly limited, and it can be formed by a known transfer method. For example, first, a metal vapor deposition layer (D) is formed on the adhesive layer (E). A flat plate or film having a holographic pattern formed thereon can be pressed onto the surface of the metal vapor deposition layer (D) of the resulting laminated film to transfer the pattern. Alternatively, the resulting laminated film can be wound up and rolled up while being pressed against a metal roll having a pattern, thereby transferring the pattern.

[0174] Furthermore, a release layer (E), a clear coating layer (B), and a protective layer (C) are sequentially formed on the base film layer (A), and the protective layer (C) surface of the resulting laminated film is pressed against the metal vapor deposition layer (D) surface having a textured pattern formed on the adhesive layer (E), thereby obtaining the decorative laminated film of the present invention.

[0175] Furthermore, when carrying out the step (1-1), a step of forming a design layer (G) by printing may also be included.

[0176] (Manufacturing method for decorative molded products) The present invention also includes a method for decorating a three-dimensional molded product, in which the adhesive layer (E) of the laminate film for decorating a three-dimensional molded product is bonded to the three-dimensional molded product under heating conditions. When decorating a molded product using the laminate film for decorating three-dimensional molded products of the present invention, a method of adhering the adhesive layer (E) onto the three-dimensional molded product by vacuum forming is preferred. Since the laminate film for decorating three-dimensional molded products of the present invention has the above-mentioned configuration, it is preferable to carry out decoration in accordance with a predetermined heating method during vacuum molding.

[0177] When decorating a molded product using a laminated film for decorating three-dimensional molded products, it is preferable to use a vacuum / compressed air molding machine. The vacuum / compressed air molding machine may be a commonly used one, but is preferably one that includes an upper box and a lower box that are driven vertically and have openings facing each other, a sheet clamp frame that is installed above the lower box and supports the laminated film for decorating three-dimensional molded products, a near-infrared heater that is disposed in the upper box, and a table that is driven vertically within the lower box.

[0178] That is, if necessary, the base film layer (A) is peeled off from the laminate film, and the laminate film is pressure-bonded to the substrate surface so that the adhesive layer faces the substrate surface and the laminate film is adhered to the substrate surface for decoration. Thereafter, each layer is cured by electromagnetic wave irradiation or heating to obtain a coating film. Alternatively, the base film layer (A) may be peeled off after pressure bonding and curing.

[0179] After completion of vacuum forming, the clear coating layer (B) of the resulting decorated molded product is cured by irradiating it with energy rays such as ultraviolet rays, thereby obtaining a decorated molded product in which the clear coating layer (B) is energy-cured.

[0180] In producing the above decorated molded product, the cover film is peeled off, and the laminated film is pressed against the surface of the molded product so that the adhesive layer (E) faces the surface of the molded product and the laminated film is adhered to the surface of the molded product to decorate it. The base film layer (A) may be peeled off either before or after curing.

[0181] The three-dimensional molded products that can be suitably decorated with the laminate film of the present invention are not particularly limited, but examples thereof include automobile exterior parts such as wheels, bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors; automobile interior parts such as instrument panels, center consoles, and door switch panels; housings of home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures; and bathroom vanities.

[0182] Among the uses mentioned above, the laminate film of the present invention can be particularly suitably used in the decoration of metal wheels. Automotive exterior parts such as aluminum wheels require performance requirements such as heat resistance and water resistance, and the laminate film of the present invention has high hardness after decorative molding and does not whiten due to heat or moisture. In addition, since the surface of a metal wheel reflects light, it is prone to deterioration of appearance due to Rayleigh scattering and Mie scattering. Furthermore, since the shape is complex, there are many areas that are highly stretched, and deterioration of appearance is likely to occur in these areas. Furthermore, since it is an article that requires good appearance, it is particularly preferable to suppress deterioration of appearance due to Rayleigh scattering and Mie scattering. Applying the laminate film for decorating three-dimensional molded products of the present invention to a metal wheel solves these problems. [Example]

[0183] The present invention will be explained below with reference to examples. In the examples, % in the blending ratio means % by weight unless otherwise specified. The present invention is not limited to the examples described below. The compounds used are as shown in Table 1.

[0184] <Synthesis Example 1: Preparation of polyurethane acrylate (B1)> A reaction vessel equipped with a stirrer, reflux condenser, thermometer, air inlet, and manhole was prepared. While the inside of the reaction vessel was purged with air, 200.0 g of polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight determined by terminal functional group quantification = 1,000), 80.0 g of 1,4-butanediol, and 120.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) were charged. Next, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became homogeneous, 314.2 g of 4,4'-methylenebis-cyclohexyl diisocyanate was charged at 50°C, and the mixture was reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by diluting with solvent, and the reaction was allowed to proceed until the absorption at 2,270 cm-1 due to free isocyanate groups, as measured by infrared absorption spectroscopy, disappeared. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone reached 1:1, yielding a resin solution containing polyurethane. The viscosity of the resulting resin solution was 200 dPa·s / 20°C, the solids content was 45%, and the double bond equivalent was 600 g / eq. Furthermore, the weight-average molecular weight of the polyurethane measured by GPC was 44,000.

[0185] <Adjusting the clear coating solution> The polyurethane acrylate (B1) and monomer / oligomer (B2) obtained as described above were placed in a container equipped with a stirrer, and while stirring, MEK was added in an amount that would result in a final coating with a NV of 40%, followed by the addition of a polymerization initiator (B3). The mixture was stirred for 30 minutes to obtain a clear coating solution.

[0186] <Preparation of protective layer paint> 25.75 parts by weight of hydroxyl-modified urethane resin (Mitsui Chemicals, Inc., trade name Takelac TE-5430, hydroxyl value 22, solids concentration 35%), 0.36 parts by weight of 1% dibutyltin laurate solution, and 6.43 parts of MEK were mixed and stirred to make a homogeneous mixture. To this was added 1.8 parts by weight of hexamethylene diisocyanate (HDI) prepolymer (manufactured by Sumika Covestro Urethane Co., Ltd., trade name Desmodur N3800), and the mixture was stirred until homogeneous, to obtain a protective layer coating material. The viscosity of the resulting protective layer coating was 900 mPa·s.

[0187] [Example of laminated film production] <Preparation of base film> In the case where a release layer was provided, a fluorine-based release agent was applied to one side of the substrate film on which the coating layer was to be formed, to form a release layer.

[0188] <Laminated film production 1> The above clear coating solution was applied onto the base film layer (A) using an applicator so as to obtain a clear coating layer (B) with a dry thickness (hereinafter referred to as "dry film thickness") of 20 μm, and the clear coating layer (B) was formed by drying at 80° C. for 15 minutes. Hereinafter, the clear coating layer (B) formed on the base film layer (A) will be referred to as an (A+B) layer film. Next, the above protective layer paint was applied onto the clear coating layer (B) of the above (A+B) layer film using an applicator and dried at 80°C for 15 minutes to form a protective layer (C) with a dry film thickness of 20 μm. Separately, an adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd.) was applied to a cover film using an applicator so as to obtain an adhesive layer with a dry thickness of 20 μm, and the applied adhesive layer was dried at 80° C. for 15 minutes to form adhesive layer (E). Subsequently, a metal vapor deposition layer (D) made of indium or tin was formed on adhesive layer (E). Furthermore, the obtained metal vapor deposition layer (D) was embossed by any one of methods A, B and C. The films obtained as described above were laminated by lamination so that the protective layer (C) and the metal vapor deposition layer (D) were in contact with each other to obtain a laminated film.

[0189] <Laminated film production 2> The above clear coating solution was applied onto the base film layer (A) using an applicator so as to obtain a clear coating layer (B) with a dry thickness (hereinafter referred to as "dry film thickness") of 20 μm, and the clear coating layer (B) was formed by drying at 80° C. for 15 minutes. Hereinafter, the clear coating layer (B) formed on the base film layer (A) will be referred to as an (A+B) layer film. Next, the above protective layer paint was applied to the opposite side of the above (A+B) layer film from the clear coating layer (B) using an applicator, and dried at 80°C for 15 minutes to form a protective layer (C) with a dry film thickness of 20 μm. Separately, an adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd.) was applied to a cover film using an applicator so as to obtain an adhesive layer with a dry thickness of 20 μm, and the adhesive layer was dried at 80° C. for 15 minutes to form adhesive layer (E). Subsequently, a metal vapor deposition layer (D) made of indium was formed on adhesive layer (E). Furthermore, the obtained metal vapor deposition layer (D) was embossed by the method A. The films obtained as described above were laminated by lamination so that the protective layer (C) and the metal vapor deposition layer (D) were in contact with each other to obtain a laminated film.

[0190] <Embossing of metal vapor deposition layer (D)> Embossing of the metal vapor deposition layer (D) was carried out in the following three ways. Method A: Embossed flat plate Method B: Embossing roll Method C: Embossed film

[0191] <Lamination of protective layers> The above-mentioned protective layer paint was applied using an applicator so as to obtain a protective layer (C) with a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm, and then dried at 80°C for 15 minutes to form a protective layer (C).

[0192] [Example of production of molded article decorated with laminated film] An ABS substrate (molded product) was placed on a vertically adjustable table installed in a double-sided vacuum forming device (product name: NGF-0709, manufactured by Fuse Vacuum Co., Ltd.) consisting of upper and lower boxes. The laminated film obtained above was then set on the sheet clamp frame located above the molded substrate (molded product) of the double-sided vacuum forming device. The vacuum in the upper and lower boxes was then reduced to 1.0 kPa, and the laminated film was heated to 90°C using a near-infrared heater. The molded substrate was then elevated to pressurize the molded substrate and the laminated film together. Compressed air at 200 kPa was then introduced into only the upper box, and the air was maintained for 35 seconds. The upper and lower boxes were then released to atmospheric pressure, yielding a decorated molded product decorated with the laminated film. Furthermore, a 120 W / cm high-pressure mercury lamp was used to irradiate the clear coating layer (B) side of the decorated molded product with 2000 mJ / cm. 2 The clear coating of the clear coating film layer (B) was cured by irradiating it with ultraviolet light at a light intensity of 1000 W, thereby obtaining a UV (ultraviolet) cured molded product.

[0193] The following components were used in the tables below. UV 1700B (Nippon Synthetic Chemical Industry): Urethane acrylate oligomer Lucirin TPO (BASF): 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide Novaclear SG007 (Mitsubishi Plastics): A-PET sheet HBA007P (Mitsubishi Chemical): Acrylic resin film, Acriplene

[0194] The obtained laminated film and molded article were evaluated based on the following criteria, and the results are shown in the table below.

[0195] (breaking elongation) The measurement was performed using an Autograph AG-IS manufactured by Shimadzu Corporation, including the substrate, at a temperature of 80°C and a tension speed of 50 mm / min. The elongation was determined when any layer broke. ○: 200% or more △: 30% or more ×: Less than 30%

[0196] (Moldability) This was confirmed by TOM molding using a double-sided vacuum forming machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd. ◎: Can be molded to follow the highly stretched part of the substrate ○: Can be molded to follow the substrate up to the middle stretched part △: Can be molded to follow the substrate even in the low stretched areas ×: Cannot be molded

[0197] (Hologram feel) The holographic effect was evaluated by visual observation. ○: The hologram is clear and good △: The hologram effect is slightly unclear ×: No holographic effect

[0198] (SW resistance after molding) Using a steel wool resistance tester, 100g / cm 2 The load was passed back and forth 10 times through #0000 steel wool. ◎: No scratches ○: 2 to 3 scratches △: Countable scratches ×: Numerous scratches

[0199] (Impact resistance after molding) Using a DuPont impact resistance tester, a 500g weight was dropped from a height of 20cm to check for cracks in the coating. ○: No cracks △: Slight cracks in the coating ×: Significant cracks in the coating

[0200] (Chemical resistance after molding) A cylindrical poly ring with an inner diameter of 38 mm and a height of 15 mm is fixed to the coating film, and the following solution is dropped onto it. The lid is placed on the film and the film is left to stand under each condition. After the test, the film is washed with water and the initial condition is compared. Acid resistant 0.1N H2SO4 solution 5ml 20℃×24h Alkali resistance 0.1N NaOH solution 5ml 55℃×4h Water resistance: 5ml distilled water, 55℃ x 4h ◎: No change in the coating ○: Slight change in coating appearance (wrinkles, cracks) △: The appearance of the coating film has clearly changed (wrinkles, cracks) ×: Significant change in coating appearance (wrinkles, cracks)

[0201] [Table 1]

[0202] Table 1 shows that the laminated film for decorating three-dimensional molded products of the examples has sufficient SW resistance, impact resistance, and chemical resistance as a coating film while ensuring stretchability and formability during decorative molding. It also shows that it exhibits a good holographic effect. [Industrial Applicability]

[0203] By decorating with the laminate film for decorating three-dimensional molded products of the present invention, distinctive holographic designs can be stably displayed for a long period of time on various three-dimensional molded products without the adhesion of dirt or deterioration over time. [Explanation of symbols]

[0204] (A) Base film layer (B) Clear coating layer (C) Protective layer (D) Metal vapor deposition layer (E) Adhesive layer (F) Release layer

Claims

1. The laminated film has a substrate film layer (A), a clear coating layer (B) made of an energy ray-curable coating film, a protective layer (C) for laminating the metal vapor-deposited surface, a metal vapor-deposited layer (D) made of indium or tin, and an adhesive layer (E), the protective layer (C) contains a reactive resin and a curing agent, the metal vapor deposition layer (D) has a holographic pattern on at least the clear coating layer (B) side; The clear coating layer (B) is formed from an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer / oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3); the reactive resin contained in the protective layer (C) is an epoxy resin or polyurethane resin having a hydroxyl group, the amount of the reactive resin blended in the protective layer (C) is 10 to 70% by weight, and the curing agent contained in the protective layer (C) is at least one curing agent having only a primary isocyanate group; A laminated film for decorating three-dimensional molded products, characterized in that the temperature range in which it exhibits a breaking elongation of 30 to 500% is within the range of 40 to 130°C.

2. 2. The laminated film for decorating three-dimensional molded products according to claim 1, which has a breaking elongation of 30 to 500% at 80°C.

3. 3. A method for decorating a three-dimensional molded product, comprising adhering the adhesive layer of the laminate film for decorating a three-dimensional molded product according to claim 1 or 2 to the three-dimensional molded product under heating conditions.

4. A decorated molded product obtained by adhering the laminated film for decorating three-dimensional molded products according to claim 1 or 2 onto a three-dimensional molded product, The three-dimensional molded product is a decorative molded product that is at least one of an automobile interior part, an automobile exterior part, a housing for a home appliance, and a bathroom vanity.

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