Transfer foil

Abstract

We provide a transfer foil that exhibits a metallizing effect. [Solution] The transfer foil 10 comprises a base film 11 and a transfer laminate 12. The transfer laminate 12 includes a release layer 13 formed on the base film 11, a resin-based protective layer 14 formed on the release layer 13 and having a mesh-like three-dimensional structure, a metal layer 15 formed on the resin-based protective layer 14, and an adhesive layer 16 formed on the metal layer 15.

Description

[Technical Field]

[0001] The present invention relates to a transfer foil, and more specifically to a transfer foil including a modified laminate consisting of a transfer laminate. [Background technology]

[0002] A transfer foil used as a surface decoration for resin-based molded products formed by methods such as hot-press transfer printing includes a protective layer, a release layer, a resin-based protective layer or a color-developing resin-based protective layer, a metal layer, a resin-based protective layer, and an adhesive layer, formed sequentially on a base film. Each layer is formed selectively, while the resin-based protective layer, color-developing resin-based protective layer, etc., are formed by layering and coating them together. In the hot-press transfer method, a film with the transfer lamination is placed on the object to be transferred with the adhesive layer facing it, and pressure and heating are applied from above the base film using a hot-press transfer device to transfer the transfer lamination, after which the base film is peeled off. As a result, the surface of the object to be transferred undergoes a transfer of the transfer lamination (modification lamination), and the object to be transferred becomes a decorated product decorated by the transfer lamination.

[0003] In resin-based molded products and the like, one method of surface decoration involves creating a transfer foil with a base film on which a release layer, a resin-based protective layer, a metal layer, and an adhesive layer are layered and transferred, and then decorating the surface of various transfer targets, including resin-based molded products, using a heat-press transfer method.

[0004] Using a transfer foil with the aforementioned lamination on a base film, the adhesive layer is aligned with the surface layer of the object to be transferred, such as a resin-based molded product, and a transfer machine is used from the base film side. A heat transfer medium such as a rubber-based roll plate, a metal-based flat plate 30, or a relief plate 40 is selected, and pressure and heat are applied to transfer the transfer lamination, consisting of a release layer, a resin-based protective layer, a metal layer, and an adhesive layer, onto the resin-based molded product or onto metals, glass, wood, fibers, paper, or rubber, and then the base film is removed. This allows for the transfer of the design onto the object to be transferred, such as a resin-based molded product, and modifies the surface of the material.

[0005] Japanese Patent Publication No. 56-53086 (Patent Document 1) discloses a transfer foil for protecting an object to be transferred during transfer painting. This transfer foil includes a release layer formed on a base sheet, a first protective layer formed on the release layer, a second protective layer formed on the first protective layer, a colored layer formed on the second protective layer, and an adhesive layer formed on the colored layer. The colored layer contains a thermoplastic acrylic resin, synthetic rubber, and a vinyl chloride resin. The curable first and second protective layers and the plastic colored layer and adhesive layer are layered together. At the interface between the second protective layer and the colored layer, when the object to be transferred and the transfer foil are stretched or contracted during transfer or over time, considering the elasticity of each layer as a transfer burden at the interface between the curable film of the protective layer and the plastic film of the colored layer, the layer constituting the protective film is set as a curable film against the reversible elasticity and contraction of the synthetic rubber incorporated in the colored layer. Regarding the ability of the protective layer's curable film to follow the shrinkage of the colored layer, there remain problems in avoiding the impact on film rupture.

[0006] Furthermore, general-purpose transfer foils have the following configuration. An example of a transfer foil includes a release layer, protective layer, coloring layer, metal layer, and adhesive layer relative to a base film. Various problems exist both during transfer and over time after transfer. Problems that occur during hot-press transfer include poor rupture accuracy of the transfer film, cracks, breaks, poor interlayer adhesion, and poor heat resistance during transfer. Changes that occur over time after transfer are influenced by environmental factors such as temperature and humidity under exposure, resulting in peeling, cracking, and blistering. There is also a risk of discoloration and deterioration due to light.

[0007] In the heat-pressure transfer method using a transfer machine, heating and pressurizing create stress on the base film, release layer, resin-based protective layer, color-developing resin-based protective layer, metal layer, resin-based protective layer, adhesive layer, etc. Differences in response occur due to the expansion, contraction, and pressure caused by the heat and pressure during transfer lamination and transfer of the object to be transferred. Resin-based layers are easily expanded, while metal layers are not. Expansion of the resin-based layers places tensile stress on the metal layers, and the metal layers with high elastic modulus undergo cohesive failure, resulting in cracks, fractures, and blisters. This defect impairs and reduces the brightness of the metal layer as a light-reflecting layer. There is a risk that the decorative gloss will be impaired.

[0008] In terms of peeling the transfer layer from the base film, the layer through the film exhibits a peeling effect by making it sensitive to heat and pressure absorption during heat and pressure propagation, thereby reducing its heat and pressure sensitivity. The adhesive layer selectively employs a resin that excels in low-temperature sensitization under heat and pressure conditions. The resin-based protective layer enhances the film's durability to eliminate physical and chemical influences on the transfer surface after transfer. The colored resin-based protective film contains a colorant to exhibit a coloring effect and forms a film structure that prevents fading and discoloration. The metal layer has a metallizing effect, exhibiting luminescence as a film reflection of the deposited metal used, or it can be formed by dotting the metal in a sea-island pattern or by multi-layer formation. The peeling layer and adhesive layer are at lower temperatures, while the protective layer, vapor-deposited protective layer, and vapor-deposited layer are at higher temperatures. As a result, the transfer lamination, including the base film, does not exhibit uniform expansion and contraction of the transferred object due to heat and pressure propagation caused by heat and pressure transfer. The increased load on the highly elastic metal layer may lead to cracks, fractures, and blisters in the transfer layer, potentially resulting in a decrease in brightness and a reduction in gloss.

[0009] If the metal layer has low tensile strength, the cohesiveness of the metal layer is destroyed by the stretching that occurs in the transfer layer during the transfer process. As a result, cracks, fractures, and blisters appear in the transfer layer with the modified layer. If the resin-based protective layer has high tensile strength, the effect on the cohesiveness of the metal layer can be mitigated, but the stretching of the protective layer caused by heating and pressurizing during the transfer process acts as tensile stress on the metal layer, resulting in fracture and thus a reduction in the gloss and brightness of the modified layer. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 56-53086 [Patent Document 2] Japanese Patent Publication No. 2002-192895 [Patent Document 3] Japanese Patent Publication No. 2016-124289 [Overview of the project] [Problems that the invention aims to solve]

[0011] The object of the present invention is to provide a transfer foil that exhibits a metallizing effect. [Means for solving the problem]

[0012] The transfer foil according to the present invention comprises a base film and a transfer laminate. The transfer laminate includes a release layer formed on the base film, a first resin-based protective layer formed on the release layer and having a mesh-like three-dimensional structure, a metal layer formed on the first resin-based protective layer, and an adhesive layer formed on the metal layer. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 is a cross-sectional view showing the structure of the transfer foil according to Embodiment 1. [Figure 2] Figure 2 is a cross-sectional view showing the structure of the transfer foil according to Embodiment 2. [Figure 3]FIG. 3 is a cross-sectional view showing the structure of the transfer foil according to Embodiment 3. [Figure 4] FIG. 4 is a schematic diagram showing plate making by an up-down type transfer foil press using a lithographic plate. [Figure 5] FIG. 5 is a schematic diagram showing plate making by an up-down type transfer foil press using a relief plate. [Figure 6] FIG. 6 is a schematic diagram showing plate making by a roll type hot press transfer machine. [Figure 7] FIG. 7 is a schematic diagram showing a gravure printing machine and a two-zone drying furnace. [Figure 8] FIG. 8 is a magnified photograph of the protrusion shape on the surface of the polyester film. [Figure 9] FIG. 9 is a photograph showing the stretchability of the transfer laminate. [Figure 10] FIG. 10 is a photograph showing the three-dimensional film of the transfer laminate. [Figure 11] FIG. 11 is a photograph showing cracks, fractures, and bulges in the transfer laminate. [Figure 12] FIG. 12 is a photograph showing the cross-section of the transfer laminate. [Figure 13] FIG. 13 is a photograph showing the surface of the metal layer (surface metal particles of aluminum evaporation). [Figure 14] FIG. 14 is a photograph showing the surface of the metal layer. [Figure 15] FIG. 15 is a photograph showing the surface of the metal layer. [Figure 16] FIG. 16 is a photograph of the transfer laminate taken from the substrate film side. [Figure 17] FIG. 17 is a photograph of the transfer laminate taken from the substrate film side. [Figure 18] FIG. 18 is a photograph of the transfer laminate taken from the release layer side. [Figure 19] FIG. 19 is a photograph of the transfer laminate taken from the release layer side. <00^0109>FIG. 20 is a photograph of the transfer laminate taken from the release layer side. [Figure 21] FIG. 21 is a diagram showing the position of lightness, color, and hue. [Figure 22] Figure 22 is a photograph of the transfer layer taken from the release layer side. [Figure 23] Figure 23 is a photograph of the transfer layer taken from the release layer side. [Figure 24] Figure 24 is a photograph of the transfer layer taken from the release layer side. [Figure 25] Figure 25 is a photograph of the transfer layer taken from the release layer side. [Figure 26] Figure 26 shows the positions of lightness, color, and hue. [Figure 27] Figure 27 is a photograph of the transfer layer taken from the surface. [Figure 28] Figure 28 is a photograph of the transfer layer taken from the surface. [Figure 29] Figure 29 is a photograph of the transfer layer taken from the surface. [Figure 30] Figure 30 is a photograph of the transfer layer taken from the surface. [Figure 31] Figure 31 is a photograph of the transfer layer taken from the surface. [Figure 32] Figure 32 is a photograph of the transfer layer taken from the surface. [Figure 33] Figure 33 is a photograph of the transfer layer taken from the surface. [Modes for carrying out the invention]

[0014] [Summary of the Embodiment] A transfer foil according to an embodiment of the present invention comprises a base film and a transfer laminate. The transfer laminate includes a release layer formed on the base film, a first resin-based protective layer formed on the release layer and having a mesh-like three-dimensional structure, a metal layer formed on the first resin-based protective layer, and an adhesive layer formed on the metal layer.

[0015] With this transfer foil, the first resin-based protective layer has a mesh-like three-dimensional structure (hereinafter sometimes referred to as the "mesh structure"). Therefore, incident light passes through the mesh (gaps in the mesh) (hereinafter sometimes referred to as "voids") in the first resin-based protective layer, is reflected by the metal layer, passes through the mesh again in the first resin-based protective layer, and then exits. At this time, in the first resin-based protective layer, the incident light is scattered by the linear parts that make up the mesh. As a result, this transfer foil exhibits a special metallizing effect.

[0016] The first resin-based protective layer may contain a coloring agent.

[0017] In this case, the emitted light exhibits color due to the coloring agent.

[0018] The colorant may contain pigments having a particle size of 2 nm or larger.

[0019] The transfer lamination may further include a second resin-based protective layer formed between the release layer and the first resin-based protective layer.

[0020] The second resin-based protective layer may have a mesh-like three-dimensional structure.

[0021] In this case, in the second resin-based protective layer, incident light that passes through the mesh is scattered even by the linear parts that make up the mesh. As a result, this transfer foil exhibits an even more special metallizing effect.

[0022] The transfer lamination may further include a third resin-based protective layer formed between the metal layer and the adhesive layer.

[0023] The mesh size in the lattice-like three-dimensional structure can be varied up to a continuous coating.

[0024] The second and third resin-based protective layers function as compounding layers that enhance the resistance of the metal layer.

[0025] [Details of the embodiment] The embodiments will be described in detail below with reference to the attached drawings. Note that identical or corresponding parts in the drawings will be denoted by the same reference numerals to avoid repetition in their description.

[0026] [Embodiment 1] As shown in Figure 1, the transfer foil 10 according to Embodiment 1 comprises a base film 11 and a transfer laminate (hereinafter sometimes referred to as "modification laminate") 12. The transfer laminate 12 includes a release layer 13 formed on the base film 11, a resin-based protective layer (hereinafter sometimes simply referred to as "protective layer") 14 formed on the release layer 13 and having a mesh-like three-dimensional structure, a metal layer 15 formed on the resin-based protective layer 14, and an adhesive layer 16 formed on the metal layer 15. The protective layer 14 contains a plasticizer.

[0027] [Embodiment 2] As shown in Figure 2, the transfer foil 20 according to Embodiment 2 comprises a base film 11 and a transfer laminate 21. The transfer laminate 21 includes a release layer 13 formed on the base film 11, a resin-based protective layer 14 formed on the release layer 13 and having a mesh-like three-dimensional structure, a metal layer 15 formed on the resin-based protective layer 14, a resin-based protective layer 23 formed on the metal layer 15, and an adhesive layer 16 formed on the resin-based protective layer 23. The transfer foil 20 according to Embodiment 2 includes, in addition to the configuration of the transfer foil 10 according to Embodiment 1, another resin-based protective layer 23 formed between the metal layer 15 and the adhesive layer 16.

[0028] [Embodiment 3] As shown in Figure 3, the transfer foil 30 according to Embodiment 3 comprises a base film 11 and a transfer laminate 21. The transfer laminate 21 includes a film protective layer 22 formed on the base film 11, a release layer 13 formed on the film protective layer 22, a resin-based protective layer 17 formed on the release layer 13 and having a mesh-like three-dimensional structure, a resin-based protective layer 14 formed on the resin-based protective layer 17 and having a mesh-like three-dimensional structure, a metal layer 15 formed on the resin-based protective layer 14, a resin-based protective layer 23 formed on the metal layer 15, and an adhesive layer 16 formed on the resin-based protective layer 23. The transfer foil 30 according to Embodiment 3 includes, in addition to the configuration of the transfer foil 10 according to Embodiment 2, a film protective layer 22 formed between the base film 11 and the release layer 13, and another resin-based protective layer 17 formed between the release layer 13 and the resin-based protective layer 14.

[0029] The details of the transfer foil 10 according to Embodiment 1 will be explained below, but unless otherwise specified, the explanation is also applicable to the transfer foil 20 according to Embodiment 2 and the transfer foil 30 according to Embodiment 3.

[0030] The colorants used in the resin-based protective layers 14 and 17 and the adhesive layer 16 can be selected from animal dyes, plant dyes, mineral dyes (inorganic pigments), organic dyes, organic pigments, organosols, metal oxide particles, etc.

[0031] The polyvinyl chloride resin includes, for example, one or more selected from the group prepared by mixing with acrylic resins such as acrylic acid ester copolymers, ethylene vinyl acetate copolymer resins, chlorinated polyethylene resins, acrylonitrile / butadiene / styrene resins, thermoplastic polyurethane copolymer resins, methyl methacrylate / butadiene / styrene copolymer resins, polyester resins / thermoplastic elastomer resins, etc., or by polymer alloying methods.

[0032] The polyvinyl chloride resin is preferably a mixture or modified resin containing one or more selected from the group consisting of ethylene vinyl acetate copolymer resin, thermoplastic polyurethane, acrylonitrile / butadiene / styrene resin, and polyester thermoplastic elastomer.

[0033] The content of polyvinyl chloride resin in the resin-based protective layers 14, 17, and 23 is, for example, 0.01 to 20% by weight. The preferred lower limit of this content is 10% by weight, and more preferably 5 to 10% by weight. On the other hand, the preferred upper limit of this content is 10% by weight.

[0034] The thickness of the resin-based protective layers 14, 17, and 23 is, for example, 1 to 20 μm.

[0035] The resin-based protective layers 14, 17, and 23 may contain urethane resin, melamine resin, or acrylic resin.

[0036] The resin-based protective layers 14, 17, and 23 may contain a hardening agent.

[0037] The colorant can be dyes or pigments. The particle size may include particles with a particle size of 2 nm or larger, pigments, or metal oxide particles.

[0038] The resin-based protective layers 14 and 17 may contain a light stabilizer.

[0039] The resin-based protective layers 14 and 17 may contain ultraviolet absorbers.

[0040] The resin-based protective layers 14, 17, and 23 contain polyvinyl chloride resin. As described above, the arrangement of the transfer lamination can be selected, and the metal layer 15 can be removed. Spacing is also possible, and the addition of a colorant to the resin-based protective layers 14, 17, and 23 and the adhesive layer 16 is optional. The concentration of the metal layer 15 can be selected from between 150 and 800 Å. Multiple layers of the metal layer 15 can also be added. Furthermore, the spacing of the resin-based protective layers 14, 17, and 23, the metal layer 15, etc. can also be selected.

[0041] In the resin-based protective layers 14, 17, and 23, the inclusion of polyvinyl chloride resin in the formulation can be selected.

[0042] The properties shown in Figures 3, 2, and 1 respectively have the function of suppressing the occurrence of cracks, fractures, and blisters in terms of grade resistance.

[0043] In the resin-based protective layers 14, 17, and 23, the respective thicknesses are 1 to 20 μm.

[0044] The resin-based protective layers 14, 17, and 23 may contain urethane resin, acrylic resin, or melamine resin. Methods such as primary curing and secondary curing can be introduced.

[0045] The transfer foil 10 described above includes a metal layer 15 in Figures 1, 2, and 3, but the metal layer 15 is optional. The layering order can be selected using the base film 11, resin-based protective layer 17, resin-based protective layer 14, metal layer 15, and resin-based protective layer 23 to create decorative effects.

[0046] The vinyl chloride resin used in the resin-based protective layer is not particularly limited, but it may include one or more selected from among the resin-based protective layers 14, 17, and 23, which are mixtures with acrylic resins such as acrylic acid ester copolymers, ethylene vinyl acetate copolymer resins, chlorinated polyethylene resins, acrylonitrile / butadiene / styrene resins, acrylonitrile / butadiene / styrene resins, thermoplastic polyurethane copolymer resins, methyl methacrylate / butadiene / styrene copolymer resins, polyester resins / thermoplastic elastomer resins, etc., or modified materials prepared by the resin-based protective layer remaralloy method.

[0047] The content of polyvinyl chloride resin in the resin-based protective layers 14, 17, and 23 is not particularly limited, but is 5 to 10% by weight. The thickness of each resin-based protective layer is not particularly limited, but is 1 to 20 μm. The resin-based protective layers 14, 17, and 23 are not particularly limited, but contain urethane resin, acrylic resin, or melamine resin in their formulations. Each resin-based protective layer is not particularly limited, but contains a curing agent. Hereinafter, a resin-based protective layer containing a coloring agent may be specifically referred to as a "coloring resin-based protective layer." The resin-based protective layer is not particularly limited, but contains a light stabilizer. The resin-based protective layer is not particularly limited, but contains an ultraviolet absorber.

[0048] The transfer foil 10 described above is transferred to the object to be transferred using the transfer apparatus shown in Figures 4, 5, and 6. During this process, heating, pressurization, and residence time are used to peel and transfer the transfer lamination from the base film to the object to be transferred via each metal plate and rubber-like roll.

[0049] Figure 3 is a schematic diagram showing plate making using a vertical transfer foil stamping machine 31 with a flat plate 30. The foil stamping machine 31 transfers the transfer laminate 12 to a transfer target 32 ​​such as a flexible polyvinyl chloride sheet by pressing the transfer foil 10 with the flat plate 30. Figure 4 is a schematic diagram showing plate making using a vertical transfer foil stamping machine 41 with a relief plate 40. The foil stamping machine 41 transfers the transfer laminate 12 to a transfer target 32 ​​such as a flexible polyvinyl chloride sheet by pressing the transfer foil 10 with the relief plate 40. Figure 5 is a schematic diagram showing plate making using a hot press transfer machine (hereinafter sometimes referred to as a "roll-type transfer machine") 51 with a roll plate 50. The hot press transfer machine 51 and the roll plate 50 transfer the transfer laminate 12 to a transfer target 32 ​​such as a resin molded product by pressing the transfer foil 10.

[0050] The transfer foil 10 described above is manufactured using the gravure printing press and drying oven shown in Figure 6 or Figure 7. Figure 6 is a schematic diagram showing the gravure printing press 60 and a first-type drying oven 61. Figure 7 is a schematic diagram showing the gravure printing press 60 and a second-type drying oven 62. The film protective layer 22, release layer 13, resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16 are coated by the machine.

[0051] A gravure printer can form and create coating films using a solvent-solute mixture, and can also use its drying function to select the completed layers and intervene in a dry film baking operation involving heating, hot air, pressurization, and cooling at any stage of film formation.

[0052] As shown in Figure 7, the gravure printing press 60 includes a film unwinding unit 63, a film control roll 64, and a gravure coating head unit 65. Downstream of the gravure printing press 60 shown in Figure 7, a first-type drying furnace 61 is provided. The first-type drying furnace 61 includes a drive metal roll 66, a far-infrared heater 67, an exhaust device 68, and a hot air device 69. Downstream of the first-type drying furnace 61, a film control roll 70, a pressurizing device 71, a cooling device 72, and a film winding unit 73 are provided. Downstream of the gravure printing press 60 shown in Figure 7, a second-type drying furnace 62 is provided. In addition to the configuration of the first-type drying furnace 61 described above, the second-type drying furnace 62 includes an ultraviolet irradiation device 74. Downstream of the second-type drying furnace 62, a film control roll 70, a pressurizing device 71, a cooling device 72, and a film winding unit 73 are provided.

[0053] This embodiment describes the creation of a transfer foil for heat-sensitive pressure transfer that prevents cracking, splitting, and blistering, and reduces discoloration, for a heat-sensitive pressure transfer film that modifies the shape of a transfer object by forming a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16 on the surface of a base film 11.

[0054] The film protective layer 22, release layer 13, resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16 are formed using a gravure printing machine. The metal layer is formed using a two-chamber semi-continuous deposition apparatus. As a vacuum deposition apparatus, for example, the apparatus shown in Figure 4 of Japanese Patent Application Publication No. 2002-192895 (Patent Document 2) can be used. The first and second resin-based protective layers, prepared from polyvinyl chloride resin, are heated, dried with hot air, and formed on the release layer 13 using a gravure printing machine to form the metal layer 15. Afterwards, a baking treatment can be performed using a gravure machine drying oven. Inside the oven, the formed film is heated by irradiation with far-infrared rays, dried with hot air using a hot air treatment device, and then heated, pressurized, and cooled by passing through a connected pressurizing device and cooling device. This operation strengthens the adhesion between the resin-based protective layer 14 and the metal layer 15, and the film's properties change from a hard state to a flexible one. Subsequently, the adhesion between the resin-based protective layer 23 and the metal layer 15 is strengthened, and then the resin-based protective layer 23 and the adhesive layer 16 are formed to complete the transfer lamination.

[0055] The transfer lamination of the transfer foil has a laminate with a flat film structure.

[0056] During transfer lamination, the release of residual stress during film formation, the transfer, peeling, and fixing processes, and the influence of the substrate film 11, transfer lamination, transfer surface, structure, material, and shape on the transfer lamination affect the formation of the film on the low-elasticity metal vapor-deposited film. Regardless of the metal aggregation structure of the metal layer, such as the metal deposition structure layer or metal island structure layer, the influence of heat and pressure propagation during transfer on the cohesiveness of the metal layer is expressed. Cohesive breakdown of the metal layer 15 results in the formation of cracks, fissures, and blisters on the metal layer and adjacent resin protective layers, affecting the modification properties, leading to a decrease in brightness and accelerated film degradation.

[0057] The objective of this embodiment is to avoid the above-mentioned problems and improve the function of transfer lamination. In this embodiment, polyvinyl chloride resin is added to the resin-based protective layer, and heat treatment, hot air treatment, pressurization treatment, and cooling treatment are performed using a gravure printing machine, followed by the drying oven of the gravure printing machine. Because the resin-based protective layer contains polyvinyl chloride resin, the flexibility of the resin-based protective layer exhibits affinity with the metal layer, and the resin-based protective layer and the metal layer exhibit adhesion. The flexibility of the polyvinyl chloride resin promotes the integration of the resin-based protective layer and the metal layer, improving the stretch resistance and shrinkage resistance of the resin-based protective layer and the metal layer.

[0058] Resolving the aforementioned problem also leads to a reduction in brightness degradation. Furthermore, by micronizing the particulate colorant and incorporating it into the resin-based protective layer 14, the coloring effect and the reflectivity of the metal layer can be enhanced while maintaining the transparency of the resin-based protective layers 14, 17, and 23. By selecting the particles, weather resistance can be obtained along with coloring, transparency, a metallic feel with metallic reflectivity, and metal reflective properties.

[0059] Regarding the use of particles, taking silica nanofine particle formulations for resin-based protective layers as an example, the mixed solution remains transparent when the particle size is 20 nm or less. When the particle size is 40 nm or more, the mixed solution becomes semi-transparent. When the particle size is 100 nm or more, the solution becomes opaque. In the formulation of resin-based protective layers, if the above conditions are met, the use of particulate colorants is selected from particles with a diameter of 1 nm or more. Even with coloring particles that maintain a particle size of 100 nm or more, selective use can enhance the coloring effect.

[0060] The adhesive forming the adhesive layer 16 is selected from various materials, taking into consideration its adhesive properties, film rupture properties, melting point, and film stability. It is activated when pressure or heat is applied, and adheres to the transfer target by softening of the film, or by mechanical adhesion.

[0061] Examples of adhesives include polyacrylic acid ester resins, polyvinyl acetate resins, vinyl chloride vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyester resins, polystyrene resins, polyamide resins, ethylene propylene resins, polypropylene resins, ethylene-vinyl acetate resins, vinyl chloride-vinyl acetate resins, polyvinyl chloride resins, polyvinylidene chloride resins, cellulose resins, rosin resins, organic and inorganic pigments, resin-based granular materials, metal-degrading granular materials, extender pigments, and the like.

[0062] For adhesion, it is desirable to select from polypropylene, polyester, vinyl, etc. To ensure film stability, it is desirable to include a cellulose-based adhesive. Regarding the film rupture resistance of the adhesive layer 16, weather resistance can be obtained along with color, transparency, a metallic feel with metallic reflectivity, and so on. It is desirable to select from rosin-based pigments or pigments from the group of organic, inorganic, or extender pigments.

[0063] The resin-based protective layer 17 or resin-based protective layer 14 preferably contains one or more acrylic resins and has weather resistance. Ultraviolet degradation due to natural light causes a decrease in physical properties and changes in appearance. Direct and scattered sunlight causes hydrogen atoms in the polymer and colorants of the transfer laminate to be cleaved, generating radicals. These radicals combine with oxygen in the atmosphere to generate peroxy radicals. Peroxy radicals extract hydrogen atoms from the polymer, generating radicals and hydroperoxides. Hydroperoxides accelerate the degradation of the polymer. To improve the resistance of the resin-based protective layer, acrylic resins with long-term shielding effects, ultraviolet shielding agents such as inorganic pigments, ultraviolet absorbers (UVA) that convert ultraviolet light into thermal energy, light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides generated when peroxy radicals extract hydrogen atoms from the polymer are used. One of the acrylic resins included in the resin-based protective layer formulation contains UV-absorbing groups and UV-stabilizing groups (HALS) within its resin backbone, and is expected to provide long-term UV shielding effects that inactivate reactive oxygen species by generating radicals in the surface peel layer 13 and the resin-based protective layer after transfer due to light. Another acrylic resin is a silicone acrylic resin containing UV-absorbing groups and UV-stabilizing groups (HALS), and having silyl groups, and containing alkyl silicate, resulting in a hard and highly UV-resistant coating. Yet another acrylic resin has reactive functional groups attached and is cross-formed into a hard film by selecting an amino-based resin, a urethane-based resin, a catalyst, a cross-linking agent, a chain extender, etc.

[0064] The resin-based protective layers 14 and 17 are thermosetting films containing an amino resin, a urethane resin, an acrylic resin, and a curing agent. The amino resin is selected from among melamine resins. The curing agent is selected from among organic acids, inorganic acids, and isocyanates. The acrylic resin is selected from among those with added ultraviolet stabilizing groups (HALS), those with attached functional groups such as silyl groups, amino groups, methylol groups, hydroxyl groups, oxadrine groups, and cyclocarbonate groups, copolymers with trialkoxyvinylsilane, etc., those that have undergone addition reactions with isocyanate groups or unsaturated groups, those that have undergone reactions with amines, and those with attached epoxy groups, etc.

[0065] A release layer 13 and a resin-based protective layer 14 containing a colorant are formed on a base film 11 using a gravure printing machine. A metal layer 15 is then created using a two-chamber semi-continuous vacuum deposition apparatus, and an adhesive layer 16 is formed on top of it using a gravure machine to create a transfer foil including a pressure-sensitive, heat-sensitive hot-pressure transfer laminate. In this transfer foil, a pigment is used as the colorant for the resin-based protective layer 14. If the amount of pigment in the formulation is small, there is transparency but no coloring effect. If the content is large, it hides the reflectivity of the metal layer. A pigment is selected as the colorant for the resin-based protective layer. The thickness of the resin-based protective layer is 1 to 10 μm, the formulation solution contains 60 to 80% by weight of solvent, 20 to 40% by weight of solute, and a pigment content of 5 to 15% by weight, with the pigment particle size being finely milled to a range of 1 nm or larger. By selecting these finely milled particles, including the pigment, and using them in the formulation of the resin-based protective layer 14, the particle size and content can be selected, resulting in a coloring effect with transparency similar to that of dyes and pigments. The resin-based protective layer 14 becomes transparent, and the reflectivity of the metal layer 15 appears. Lightfastness is generated by the selection of pigments. This provides the reflectivity of the metal layer 15 and generates a metallic appearance due to this metallizing effect. By selecting selected particle sizes and content of pigments, a coloring effect can be achieved while obtaining the reflectivity of the metal layer 15. Lightfastness is obtained in the resin-based protective layer 14 by selecting particle size materials, including organic and inorganic pigments.

[0066] As colorants, inorganic pigments such as titanium white, carbon black, iron oxide, lead yellow, and ultramarine, organic pigments such as aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue, extender pigments, metal oxide fine particles, fluorescent pigments, and pigments are selected and granulated to approximately 2-500 nm using a bead mill type disperser. Further, chlorides are used to create fine particles of 1 nm or more, which are then washed and dried and used as colorants in the preparation. As a colorant, the transparency of the pigment and the visibility as a color effect can be enhanced. Furthermore, resistance can be increased by selecting pigments with excellent lightfastness. Examples include fine oxide particles such as TiO2, SO2, Al2O3, and Fe2O3. Furthermore, by adding light stabilizers, UV absorbers, and light shielding agents, fading of the resin-based protective layer can be suppressed. Furthermore, by using a polymerization agent composed of light stabilizers, silicones, silicates, etc. in the acrylic resin skeleton, resistance can be further enhanced.

[0067] In the resin-based protective layer 14, a light stabilizer is added to the formulation. This contributes to photostability by capturing and neutralizing radicals generated by ultraviolet light. A non-basic, neutral type of hindered amine-based light stabilizer is selected to avoid problems in the formation of the thermosetting film of the resin-based protective layer 14.

[0068] In the resin-based protective layer 14, an ultraviolet absorber is added. The ultraviolet absorber to be added is selected from those that can suppress photo-induced reactions that lead to photodegradation of the resin-based protective layer 14. In order to stabilize the resin-based protective layer 14 by absorbing ultraviolet light and converting it into low thermal energy and releasing it, a hydroxyphenyltriazine-based material with ultraviolet absorption wavelengths of 280-350 nm and 310-330 nm is selected.

[0069] In transfer lamination, to suppress chemical reactions caused by light that lead to discoloration and film degradation, the transfer lamination absorbs light and enters a state of higher energy than the absorbed energy. Some of this energy becomes photosensitized and is converted back into light energy. Some of it is used for chemical reactions. In addition, excess energy is transferred to other molecules and reacts with polymers. The ultraviolet wavelength range of 200-300 nm has a significant chemical effect. As a countermeasure in the resin-based protective layer 14 containing a colorant, in addition to a preparation to obtain a transparent fine pigment, acrylic resin, a polymer with hinderamine bonded to the structure of the acrylic resin, a hindered amine-based light stabilizer, and a hydroxyphenyltriazine-based ultraviolet absorber, a photoinhibitor is selected from salicylic acid esters, 4-t-butylphenyl salicylate, phenyl salicylate, etc., and phenyl salicylate, which is an ultraviolet shielding agent, is selected and added as a photoinhibitor.

[0070] As means of forming the metal layer 15, vapor phase deposition methods include PVD (Physical Vapor Deposition), such as vacuum deposition and sputtering. Chemical vapor deposition (CVD) methods include thermal CVD, atomic layer deposition (ALD), plasma CVD, metal-organic chemical vapor deposition, two-flow MOCVD, and catalytic chemical vapor deposition (Cat-CVD). Liquid phase deposition methods include melt methods such as liquid phase epitaxy, and plating methods such as wet plating, chemical plating, and sol-gel methods. Coating methods include spin coating, printing, and inkjet. The metals used include Au, Ag, Cu, Sn, Al, Ni, Pt, Rh, Pd, Zn, Cr, and Si, as well as oxides such as In2O3, CdO, CdIn2O4, Cd2SnO4, TiO2, SnO2, ZnO, SiO2, and ZrO2, sulfides such as ZnS, and fluorides such as MgF2. One or more of these can be selected. Alloys can also be used. Layering is possible. It is also possible to set the spacing between layers, such as a metal layer on top of a resin-based protective layer, another resin-based protective layer, and another metal layer. Metal oxide particles can also be used. The metal layer can be formed into various shapes, such as a sea-island film structure where the metal layer is isolated, or a deposited film structure showing the deposition state of the metal. In any structure, regardless of the metal used or the state of the metal film formation, it is possible to suppress the expansion and contraction, cracks, fractures, and blisters caused by pressure during the transfer layering process.

[0071] Furthermore, the thickness of the metal layer 15 is 10-40 nm in the case of isolated island-like structures and 20-80 nm in the case of continuous film deposition. In either case, a uniform luster can be maintained as a metallic coloration. This enhances the decorative, design, and visibility aspects of the image display created by heat transfer printing.

[0072] [Manufacturing Method 1] As the base film 11, any film can be used as long as no abnormalities are observed in heat resistance during manufacturing, resistance to solute solvents, transfer heat resistance during use, and pressure resistance. For example, there are polyester-based, polyamide-based, polyolefin-based, acrylic-based, imide-based, various engineering-based, styrene-based, and cellulose-based films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexa-sanedimethanol-ethylene glycol copolymer, and polyethylene terephthalate-polyethylene naphthalate co-extruded film. Among these, biaxially oriented films are preferable for maintaining physical and chemical strength. When considering hot-pressure transfer, if the film is hot, both heat conduction and pressure propagation will be insufficient. On the other hand, if the film is thin, the mechanical strength will be insufficient, and it will deviate from the control of transfer heat and pressure, making it difficult to clearly display the transferred image. It is best to use a film thickness in the range of 12 to 75 μm, which should be suitable for the shape and material of the object to be transferred. It is necessary to consolidate factors such as film selection, film thickness, setting of release properties for transfer lamination, selection of transfer equipment, and the shape and material of the object to be transferred.

[0073] In accordance with the above, the film protective layer 22, release layer 13, resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16 are formed by gravure printing. A far-infrared heater and a hot air drying device are used for drying. Figure 7 shows a schematic of the gravure printing machine and drying oven. Using the drying oven, the machine is run and remains in an atmosphere of 90-210°C for 20-50 seconds to produce films with a thickness of 0.1-20 μm. In addition, a two-chamber semi-continuous vacuum deposition apparatus is used to form a metal layer with a thickness of 30-80 nm. After that, an adhesive layer is formed.

[0074] Regarding the settings and functions of the protective film layer 22 on the base film 11: Films can be selected from chemical films, paper films, etc. Since they are used for transfer, it is desirable that the surface of the film has excellent smoothness. There are no restrictions on the use of any film as long as no abnormalities are observed in heat resistance, solute solvent resistance during transfer foil manufacturing, and transfer heat resistance and pressure resistance during use. For example, among films made from polyester, polyamide, polyolefin, acrylic, imide, various engineering materials, styrene, cellulose, etc., such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol copolymer, and polyethylene terephthalate-polyethylene naphthalate co-extruded films, biaxially oriented films are preferable to maintain physical and chemical strength. Polyethylene terephthalate film is the preferred choice. When considering heat-sensitive and pressure-sensitive transfer, if the film is too thick, both heat conduction and pressure propagation will be insufficient. If the film is too thin, it will lack sufficient mechanical strength, deviating from the control of transfer heat and pressure, making it difficult to clearly display the transferred image. It is best to choose a film thickness in the range of 9 to 75 μm that is suitable for the shape and material of the object to be transferred. Each layer of the transfer foil to be coated is a thin film layer, forming a total thickness of 5 nm to 40 μm including all layers. There are operations that involve peeling from the film, and the uniformity of the peeling function is required. In the case of chemical films, if unwinding and winding operations are performed on the film alone on the coating equipment, the contact surface between smooth films becomes wide, and sliding between films induces static electricity, resulting in operational failure due to static electricity. To avoid this, chemical films are used by selecting various lubricating fine particles from among them and mixing them into the main resin component of the film.Regarding the surface texture of the film, taking a polyester film as an example, protrusions are formed discontinuously across the entire surface of the film, with protrusions having a peak height of approximately 8 nm. These protrusions are not precisely aligned, but rather irregularly arranged. This can lead to uneven charging zones caused by sliding friction during contact with the film itself, hindering the formation of a smooth coating. During coating, sliding between the charged areas of the film and the coating can lead to damage to the film. Furthermore, during the formation of the polyester film, stretching can occur, resulting in an uneven distribution of areas with densely packed fine lubricating particles and areas with coarse texture. This phenomenon also hinders the uniformity of coating application. The uneven distribution of charged areas and the irregularity of protrusion formation in the film contribute to uneven thickness of the coating film, leading to uneven thickness of the release agent. When performing a large-area simultaneous transfer and peeling process of the film, the load on the release agent layer is significant, and the release function may fail in some areas with uneven thickness. In the protective layer 22, the surface layer of the substrate film is modified by setting the coating film to perform qualitative coating, leading to the formation of a uniform peelability phenomenon. The materials used can be selected from the following. The film is formed using a gravure machine. Furnace volume: 5.28 m³. 3The film is formed in the range of 0.005 to 20 μm with a temperature set between 100 and 200°C and a residence time of 10 to 50 seconds. To modify the surface layer of the film, the following can be selected: Infrared thermosetting resins, thermoplastic resins, various additives, ultraviolet curing resins, etc. In the case of infrared thermosetting resins, the following can be selected. Melamine resin, guanamine resin, sulfamide resin, urea resin, aniline resin, cyanate resin (cyanate ester resin), isocyanate resin, urethane resin, polyurea resin, thiourethane resin, polyimide resin, all-aromatic polyimide resin, thermosetting polyimide resin (addition polymerization polyimide), maleimide resin, bismaleimide BMI resin, polyaminobismaleimide resin, bismaleimide triazine resin (BT resin), reactive multiple bond-terminated compounds (addition curing type), nadiimide resin, bismaleimide and alkenylphenol resin, alicyclic polyimide resin, aromatic polycarbodiimide resin, fluorine-containing polyimide resin, solvent-soluble (varnish) polyimide resin, epoxy resin, phenoxy resin, vinyl ester resin (modified epoxy, epoxy acrylate resin), oxet A selection of resins is available, including polyvinyl acetate resins, polyester resins, alkyd resins, phthalic acid resins, unsaturated polyester resins, maleic acid resins, allyl resins, phenolic acid resins (Bakelite, carbolic acid resins), benzoxazine resins, xylene resins, ketone resins / formaldehyde resins, furan resins, COPNA resins (thermosetting condensed polycyclic polynuclear aromatic resins), silicon resins (silicone resins), condensation reaction curing type silicone resins, addition reaction curing type silicone resins, dicyclopentadiene resins (polydicyclopentadiene resins), BCB (benzocyclobutene resins), CYCLOTENE resins, ebisulfide resins, enethiol resins, polyadmethine resins, polyvinyl benzyl ether compounds, acenaphthylene resins, thermosetting acrylic resins, thermosetting polyphenylene ethers, and UV-curing resins. Addition polymerization agents such as unsaturated double bonds (those with acrylic or methacryloyl groups), vinyl groups, and allyl groups, as well as functional groups such as cyclic ethers (ring-opening polymerization of epoxy and oxetane, etc., and addition polymerization of vinyl ethers) are utilized.In addition, a UV-curable resin film can be constructed by selecting materials consisting of monomers, oligomers, reactive diluents, and photopolymerization initiators, which utilize radicals and ions generated by activation using a photopolymerization initiator, with the ions mainly being cations. Furthermore, silicone adjuvants, waxes, etc., may be selected and added to achieve a smooth film.

[0075] Figure 8 is a magnified view of the protrusion shape on the surface of the polyester film (photograph 1).

[0076] [Manufacturing Method 2] After forming the release layer 13 and the resin-based protective layers 14 and 17, the film is prepared by running and staying in an atmosphere of 90 to 210°C for 20 to 50 seconds using the drying oven of the gravure printing machine shown in Figure 7, to produce films with a thickness of 0.1 to 20 μm. Then, a metal vapor-deposited film is formed to create a metal layer 15 with a thickness of 30 to 80 nm. Subsequently, the drying oven equipment of the gravure machine shown in Figure 7 is subjected to heating operations using infrared heaters and hot air, and interposed by a pressurizing device and a cooling device directly connected to the outside of the oven. This operation is called baking. After that, the adhesive layer 16 is formed.

[0077] The transfer foil according to this embodiment includes a base film 11, a film protective layer 22 and 3, a release agent, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16, and is transferred to the object to be transferred by peeling the transfer laminate from the base film 11 via the heat and pressure time of the transfer machine. During the transfer operation, the transfer laminate peeled from the base film 11 is transferred to the object to be transferred by the transfer action, requiring a heat source supplied from the transfer machine, pressure, and transfer residence time. The effects of heat and pressure received are not uniform depending on the shape and hardness of the object to be transferred. Compared to the base film 11 and the object to be transferred, the transfer laminate is a thin film with peelability and is fragile when peeled off. The peelability of the film is a peel resistance value of 1 to 100 g / cm². 2 This is the starting point for film delamination (using a delamination resistance tester manufactured by Asahi Sokki Co., Ltd.). Film rupture resistance is 500g to 10kg / cm². 2·This is the starting point of film rupture due to transfer pressure at 0.5 seconds (using the Ikeda-type transfer device). The transfer lamination is easily peeled off and is prone to rupture. The objects to be transferred have various shapes, both two-dimensional and three-dimensional, and are made of various materials such as leather, paper, paper containers, printing paper, special paper, wood, textile products, resin sheets, resin molded products, metal products, and glass products. When considering the transfer lamination added to the base film in terms of transfer stretchability with respect to the object to be transferred, the transfer lamination is more prone to cracks, breaks, and blisters due to the stretchability and rupture of the transfer lamination in response to the heat and pressure supplied during transfer, compared to the base film 11 and the object to be transferred. Here, flexibility can be provided by selecting resin-based protective layer 17, resin-based protective layer 14, and resin-based protective layer 23 and adding polyvinyl chloride resin. Furthermore, by going through the process with a gravure printing machine, the affinity and adhesion between the resin-based protective layer 14 and the metal layer will be further enhanced by incorporating the above baking operation. The effects of far-infrared heating, hot air heating, pressurization, and cooling operations performed by gravure printing machines on lamination include the addition of polyvinyl chloride resin to the resin-based protective layer, which transforms flexibility into extensibility. The enhanced adhesion between the resin-based protective layer and the metal layer, along with improved heat resistance, maintains resistance to cracks, fissures, and blistering. This structural transformation, which allows the resin-based protective layer and the metal layer to coexist under load and stress, results in a change in the transfer lamination capabilities.

[0078] [Manufacturing Method 3] The film protective layer 22, release layer 13, resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16 are formed by gravure printing. A far-infrared heater and a hot air device are used for drying. Figure 7 shows a schematic of the gravure printing machine and drying oven. Using the drying oven, each film with a thickness of 0.1 to 20 μm is produced by running it in an atmosphere of 90 to 210°C for 20 to 50 seconds. In addition, a two-chamber semi-continuous vacuum deposition apparatus is used to form a metal layer with a thickness of 30 to 60 nm. After that, the resin-based protective layer 23 and adhesive layer 16 are formed.

[0079] [Manufacturing Method 4] Following the above, after forming the film protective layer 22, release layer 13, resin-based protective layer 17, resin-based protective layer 14, and metal layer 15, the following operation can be added. This improves the adhesion at the interface between the resin-based protective layer and the metal layer. This operation can be selectively introduced. This is a novel means that can improve the durability quality of the transfer lamination and is a new method for adding durability functionality. Performing the operation in the gravure printing machine shown in Figure 7, the lamination up to the metal layer is placed in a drying oven in an atmosphere of 90 to 210°C for 20 to 50 seconds to intervene in the transfer lamination baking operation. In the drying oven, processes such as heating treatment with a far-infrared heater and a hot air device, and pressurization and cooling devices directly connected to the outside of the oven can be added. The introduction of these processes can be selective.

[0080] [Manufacturing Method 5] The transfer foil according to this embodiment includes a base film 11 and a transfer process consisting of a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16. The transfer laminate is peeled off the base film 11 via the heat and pressure of the transfer machine and transferred to the object to be transferred. During the transfer process, the transfer laminate peeled off from the base film is transferred to the object to be transferred by the transfer action, requiring heat, pressure, and transfer residence time supplied by the transfer machine. The effects of heat and pressure received are not uniform depending on the shape and hardness of the object to be transferred. Compared to the base film 11 and the object to be transferred, the transfer laminate is a thin film with peelability and is fragile when peeled off. The peelability of the film is a peel resistance value of 1 to 100 g / cm². 2 This is the starting point for film delamination (using a delamination resistance tester manufactured by Asahi Sokki Co., Ltd.). Film rupture resistance is 500g to 10kg / cm². 2This is the starting point of film rupture due to transfer pressure at 0.5 seconds (using the Ikeda automatic transfer device). The transfer lamination is easily peeled off and is prone to rupture. The transfer target has various shapes, including 2D and 3D, and the materials are also diverse, including leather, paper, paper containers, printing paper, specialty paper, wood, fibers, resin sheets, resin molded materials, metals, and glass. When considering the transfer lamination mounted on the base film 11 in terms of transfer stretchability with respect to the transfer target, compared to the base film 11 and the transfer target, the transfer lamination is more prone to cracks, fractures, and blisters due to the stretchability and rupture of the transfer lamination in response to the heat and pressure supply during transfer. Here, it is possible to add the additive to all formulations of the resin-based protective layer 17, resin-based protective layer 14, and resin-based protective layer 23, or to the formulation of a selected resin-based protective layer, or to supplement with an additive. The agent to counteract stretchability can be selected from polyvinyl chloride resins. The compounding of the resin-based protective layer 14 and resin-based protective layer 23 creates an effect that makes them resistant to the addition of additives.

[0081] [Manufacturing Method 6] Using the drying oven shown in Figure 7, a flat film with a thickness of 0.1 to 20 μm is prepared by running and staying in an atmosphere of 100 to 210°C for 20 to 50 seconds. Next, a metal layer 15 is formed using a vacuum deposition machine, and then using the drying oven shown in Figure 7, it is stayed in an atmosphere of 150 to 210°C for 20 to 50 seconds. After heating, continuous pressurizing and cooling treatments are performed to complete the flat film. The coated flat film undergoes heating, hot air, pressurizing, and cooling treatments. After that, an adhesive layer is formed.

[0082] The following new film-forming environments can be established during film formation using transfer lamination with a gravure printing press. (1) Adhesion: Adhesion due to the layering of resin protective layer 17 and 6 metal layer vapor deposition layer, and interlayer adhesion between the release layer 13 film, resin protective layer 17, resin protective layer 14, metal layer 15, resin protective layer 23, and adhesive layer 16. (2) Stretchability: Stretchability including the resin protective layer 14 and metal layer 15, and the resin protective layer 23. (3) Resistance: Avoidance of cracks, fissures, and blisters during and after transfer layering. (4) Metal reflectance: The reflectance of the Al metal layer is 82.15% (spectral reflectance %). When fine pigments are used in the resin-based protective layer, it is excellent in ensuring brilliance. In a transfer laminate comprising a mold release layer, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16, the reflectance of the Al metal vapor-deposited film when a transmissive coloring operation is performed using fine pigments in the resin-based protective layers 14 and 17. (5) Morphology of the vapor-deposited film: Regardless of whether the morphology of the 15 metal layers is a sea-island film structure or a deposited film structure, the resin-based protective layer and the metal layers maintain affinity and exhibit stretchability. This can prevent cracks, fractures, and blisters in transfer layers resulting from cohesive fracture of metals. (6) Heat resistance: In heat resistance tests conducted after transfer of the transfer laminate, there was no decrease in luster, and it exhibited excellent resistance to cracking, fissures, and blistering. (7) Resin-based protective layers 14, 17: Thermoplastic resin, thermosetting resin, UV-curing resin, or a layer of UV-curing resin and thermosetting resin can be used. Since all of them contain a resistance modifier that constitutes the resin-based protective layer, including the polyvinyl chloride resin mentioned above, they exhibit heat resistance and extensibility, and can achieve adhesion with the metal layer 15. (8) Metal layer: Options include the formation of a transparent metal layer, a semi-transparent metal layer, a reflective film, or no layer at all. (9) Resin-based protective layer: A cure-type UV-curing resin can be used. Alternatively, an after-cure type UV-curing resin can be used. (10) Resin-based protective layer: When using UV-curing resin, hot stamping and cold stamping methods can be used as transfer methods. (11) Resin-based protective layer: When a layer of UV-curing resin and thermosetting resin is used, the UV-curing resin increases the film strength, while the thermosetting resin increases the film fracture resistance. A polyvinyl chloride-based resin agent is added to both resins. (12) Extensibility: There are three-dimensional objects to be transferred as resin-based processed products using resin-based molding machines, etc. In this case, when the transfer laminate film is formed into the mold of the molding machine during the formation of the molded product, and bonded by the heat and pressure of the molten resin, and then the excess film is peeled off, the transfer laminate can maintain sufficient resistance to withstand the stretching it undergoes.

[0083] For surface modification of molded products, a modification laminate consisting of a transfer laminate peeled off from the base film 11 can be transferred and peeled off using a transfer machine to perform the modification, or the modification can be performed by transfer transfer in the molding machine. After bonding a resin-based protective layer containing polyvinyl chloride resin, a resin-based protective layer that exhibits coloration, or a shaped color-forming resin-based protective layer to the base film 11, a resin-based protective layer, a metal layer, a resin-based protective layer, and an adhesive layer are formed, and the adhesive layer is brought into contact with the object to be transferred via a transfer device, and bonded by heat and pressure supplied from the base film 11, allowing it to be mounted on the object to be transferred together with the base film 11. This manufacturing method enables multi-layer lamination with excellent heat resistance and stretchability. With such a multi-layer structure, transfer lamination using the base film 11 and the modification-shaped film integrated with the base film 11 can be applied regardless of whether it is hot-pressure transfer, out-molding, or in-molding.

[0084] For the production of two-dimensional and three-dimensional molded products using resin-based materials with molding machines, molding methods using thermoplastic resins and thermosetting resins include injection molding, blow molding (hollow molding, suction molding), extrusion molding, casting, vacuum molding, pressure molding, compression molding, press molding, hand lay-up, T-die method, inflation method, calendering, co-extrusion multilayer T-die method, biaxial stretching method, lamination method, shape extrusion, extrusion coating, co-extrusion, etc. After the molded product is formed, there are means for transfer lamination as a post-processing modification, such as transfer lamination, and primary processing methods within the mold of the molding machine, such as peeling and transfer of the image from the base film 11 in the in-mold to the molded product, and film lamination where the base film 11 is bonded to the molded product. The material to be transferred by simultaneous transfer of molded products, simultaneous bonding of molded products, and post-processing transfer can be leather, and as described above, it is possible to use a modified laminated structure film that has been shaped and colored by selecting from a wide variety of molding methods and modification means.

[0085] When a selected polyvinyl chloride resin is incorporated into the resin-based protective layers 14, 17, and 23 and manufactured through the above-described manufacturing structure, the resulting transfer laminate and film lamination, when bonded together with the base film 11, exhibit improved quality in terms of stretchability, heat resistance, interlayer adhesion, maintenance of reflectivity of the metal layer 15, maintenance of light resistance and luster, and prevention of cracks, fractures, and blisters.

[0086] In a transfer laminate consisting of a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16, the film is produced by gravure printing and a metal vapor deposition apparatus. Depending on the gravure printing method, the film formation process involves heating with a far-infrared heater in the drying oven, hot air heating with a hot air system, a pressurizing device directly connected to the outside of the oven, and a cooling device. Drying of the preparation consisting of solvent and solute is achieved by a film formation method using an infrared heater and a hot air drying apparatus, and in the post-film formation process of the resin-based protective layer and metal layer. There is a means to incorporate a reheating method for the dry film. Means for improving the film quality are provided. The dry film, which has been formed with a release layer, a resin-based protective layer, and metal vapor deposition, is further re-dried in a gravure machine's drying oven. This process involves baking the film using far-infrared heaters and hot air heating treatment within the oven, followed by a pressurizing device directly connected to the drying oven, and then a cooling device. This process strengthens the adhesion of the transferred film through pressurization, and then the cooling device ensures the adhesion and fixation of the laminations. The temperature inside the drying oven during the re-drying method is in the range of 150 to 210°C. By incorporating this high-temperature re-drying method for the dry film in metal vapor deposition films, the adhesion of the metal layer to the resin-based protective layer is further enhanced, resulting in a higher quality of fixation. The metal layer may be a film with an isolated island structure or a deposited structure. Each resin-based protective layer contains thermosetting resins, including polyvinyl chloride resins, along with a hardener. The resin-based protective film hardens through a continuous process of heating, hot air, pressurization, and cooling. Simultaneously, the resin-based protective layer containing added polyvinyl chloride resin exhibits flexibility, resulting in improved hardness and flexibility in the film formation. Between the resin-based protective layer 14 and the metal layer 15, baking is performed using a dry film reheating process. This generates flexibility in the resin-based protective layer 14 due to heat exposure, and the propagation of this flexibility occurs. In the furnace, the heated and softened resin layer, the softened state of the resin-based protective layer 14, and the metal deposition particles near the interface with the metal layer 15 are simultaneously excited and activated by heat exposure. While this interface state between the two layers is occurring in the furnace, pressure is applied via an external pressurization device directly connected to the drying furnace.As a result, both layers are pressurized. The activated metal particles at the interface tip of the metal layer 15 are subjected to external pressurization, and their adhesion to the resin protective layer 14 interface is improved as the pressurization is carried out while the resin film softens and the metal layer's interface particles are activated. At the interface between the two layers, the state of fixation of the metal particles exceeds that of adhesion. The quality of the flexibility of the resin protective layer is transferred to the metal particles through this interface state. This quality transfer then occurs via the connected cooling device. Through this cooling device, the interface between both layers, the resin protective layer and the metal layer, becomes fixed with an adhesion layer of metal particles that have received the resin quality transfer. The metal layer highly accepts the quality of the resin protective layer. The metal layer 15 may have an isolated island structure where the metal layer is like an island in the sea, or a deposited structure where it is like a deposit.

[0087] A baking process is incorporated into the drying process of the gravure coating. Through heating treatment in the drying oven, pressurization outside the oven, and cooling operations, the viscosity of the resin-based protective layer becomes more flexible, and the miscible adhesion between the resin-based protective layer and the metal deposition is enhanced with the metal deposition particles interposed. The effects of residual stress accumulation due to film shrinkage during the curing of the resin-based protective layer are reduced by the addition of polyvinyl chloride resin to the formulation. The fracture shear stress on the metal layer is reduced, and the load of cohesive fracture on the metal layer is attenuated.

[0088] In a transfer laminate consisting of a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16, layering the metal layer 15 and performing far-infrared heating, hot air heating, pressurization, and cooling treatments using the drying oven of a gravure printing press is a necessary process for propagating and fixing the flexible film quality of the resin-based protective layer to the metal particles at the interface with the metal layer. Both the resin-based protective layer and the metal layer become hard, flexible, and viscous films when heated, pressurized, and cooled. Furthermore, the transfer of the flexible film quality of the resin-based protective layer 14 to the metal layer 15 results in both layers exhibiting the hardened film and toughness of the resin-based protective layer, as well as the extensibility derived from the flexibility of the polyvinyl chloride resin. Residual stress in the resin-based protective layer 14 leads to cohesive failure of the metal layer 15, causing film rupture, which can trigger the rupture of the transfer lamination and become a factor in the occurrence of cracks, fractures, and blisters. To suppress this, the film quality is modified to improve the heat resistance, flexibility, adhesion, and extensibility between the two layers. To enhance the adhesion between the resin-based protective layer 14 and the metal layer 15, the formulation of the resin-based protective layer 14 includes heat-resistant polyvinyl chloride resin and acrylic resin, which are used to transfer and adhere the film quality to the metal layer 15, followed by baking treatments such as heating, pressurization, and cooling. The correlation between the resin-based protective layer 14 and the 6 metal layer vapor deposition layer is checked to see if the relationship between heat resistance, flexibility, adhesion, and extensibility is expressed in relation to the adhesion between the two layers.

[0089] A film protective layer 22 and a release layer 13 are formed on a base film 11, and a resin-based protective layer 14 containing polyvinyl chloride resin is produced using a gravure printing press drying oven. Next, a metal layer 15 is formed on top, and the dry film is baked in the gravure printing press drying oven while still in layers. Heating treatment is performed using a far-infrared heater, a hot air device, a pressurizing device, and forced cooling is performed using a cooling device. By applying the maximum load of heating, pressurizing, and cooling in this overloaded state, the flexibility of the plastic portion of the polyvinyl chloride resin in the resin-based protective layer 14 is activated, resulting in stretchability, and the particles of the metal layer 15 adhere to the interface, induced by the stretchability of the resin-based protective layer. In order to confirm the degree of synchronized stretching of the metal particle group of the metal vapor-deposited film, the flexibility and stretchability as a transfer foil, which are the result of the above heating, pressurizing, and cooling treatments, are confirmed, and after the above treatments on the metal layer, an adhesive layer 16 is formed to complete the transfer lamination. This transfer laminate was transferred onto a flexible PVC sheet, and the surface layer of the transfer laminate was examined. The hot-press transfer layer was transferred onto a flexible PVC sheet, and the surface layer of the transfer laminate was examined. Hot-press transfer conditions: Using an upper and lower type transfer foil stamping machine, temperature 160°C, pressure 5 kg / cm² 2 With a transfer residence time of 0.5 seconds, no cracks, fractures, or blisters were observed when using a relief stamp, and no changes were seen in the metallizing effect. Both the resin-based protective layer containing polyvinyl chloride resin and the metal layer are synchronized with the expansion of the film. Through heating, pressurizing, and cooling treatments, the flexibility, affinity, and migration induction properties of the resin-based protective layer 14, along with the metal layer 15 with low cohesive force and the resin-based protective layer 14 released from residual stress, induce plastic deformation in the metal thin film through in-furnace and out-of-furnace processes using a gravure printing machine, resulting in plasticity. The metal layer establishes adhesion that surpasses mere adhesion to structures having a fine particle film structure, such as a deposited particle film or a metal vapor-deposited film band in an isolated island state.

[0090] Based on manufacturing method 6, a transfer foil is created. After forming the metal layer 15, a baking process is performed, followed by high-temperature treatment, pressurization, and cooling in a gravure drying oven in the region where the expanded film is formed. This process maximizes the adhesion and fixation between the resin protective layer 14 and the metal layer 15, thereby creating an elongated surface for both layers. When the resin protective layer 14 and the metal layer 15 are synchronized, no cracks, fractures, or blisters occur. However, if the metal layer 15 fails to follow the resin protective layer 14, the resulting problems are diverse and can stem from stress loads from the transfer load, the object being transferred, or twisting from the transfer foil, object being transferred, or transfer jig. Figures 9 and 10 show that the function of the coating follows the elongation during the interface adhesion improvement operation by baking the resin protective layer 14 and the metal layer 15.

[0091] In the above section, a transfer laminate is fabricated by sequentially forming the base film 11, release layer 13, resin-based protective layer 17, second seed-based protective layer 5, and metal layer 15. Subsequently, a baking process is performed using a gravure oven, involving heating, hot air treatment, and pressurization and cooling devices connected to the oven. After that, an adhesive layer 16 is formed to complete the transfer laminate. Photo 2 shows a magnified view of the surface of a transfer foil subjected to an experiment based on manufacturing method 5, after transfer using an up-and-down transfer foil stamping machine. The metal layer 15, made of aluminum, had a film thickness of 40 nm, a valley width of 1.4 to 1.76 μm, a peak width of 0.99 to 1.2 μm, and a height of 11 to 15 μm.

[0092] [Manufacturing Method 7] Figure 9 is a photograph showing the stretchability of the transfer laminate. The photograph shows the stretchability of the transfer foil in a magnified view. It is a photograph of the stretched surface of the test work-in-progress up to the Al deposition stage, during heating, pressurizing, and cooling. The transfer structure consists of a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, and a metal layer 15, and is subjected to heating, pressurizing, and cooling. The upper part of the work-in-progress surface is magnified to confirm the surface of the transfer foil. The transfer laminate follows the stretching of the heat-treated transfer laminate. There are no signs of failure. A gold-containing dye is used as the coloring agent for the resin-based protective layer 14. Al is used as the metal for deposition. After the baking operation described above, the adhesive layer 16 is treated, and the stretched surface is confirmed along with the transferred object after transfer. The surface of the transfer laminate is confirmed by magnification. Adhesive is applied to the above work-in-progress, and the transfer is confirmed using a transfer device. The surface layer after transfer is confirmed, and the presence or absence of failure of the transfer laminate is checked.

[0093] The details of the photograph shown in Figure 9 are as follows: Elongation length: Peak length 2.3 μm Transfer target material: Flexible polyvinyl chloride sheet Transfer conditions: 160°C, 0.5 seconds, 5 kg / cm³ 2 pressure Width of the peak: 0.99~1.2 μm (length of the chord) Valley width: 1.4–1.76 μm Mountain height: 1.5 μm (height) Digital microscope VHX-8000 manufactured by Keyence Corporation used.

[0094] confirmation (1) Confirm the length of the peak to be 2.3 μm. (2) Based on the above, confirm the stretching due to the development of flexibility through baking. (3) No abnormalities such as cracks, fissures, or blisters are observed on the surface of the transfer layer. (4) The transfer foil follows the stretching of the flexible polyvinyl chloride sheet. There are no cracks, breaks, or blisters due to stress. (5) There is no change in luster. (6) No defects due to factors in the metal layer 15 were detected.

[0095] This embodiment aims to improve defects that occur in the transfer lamination during the heat-pressure transfer process and over time after the transfer. External and internal stresses from the heat-pressure load on the transfer lamination and the object to be transferred, such as cracks, fissures, blisters, and discoloration, cause deformation interactions such as elongation, contraction, shearing, twisting, and bending in the transfer lamination and the object to be transferred. The deformation effects on the object to be transferred and the transfer lamination resulting from these derived phenomena reduce the modifiable properties on the object to be transferred. This necessitates obtaining a maintenance means that can individually address these deformation effects as a burden to be accepted by the transfer lamination.

[0096] Transfer lamination offers various functions, including peelability, fracture resistance, adhesion, heat resistance, gloss resistance, color development, image display, and decorative properties. In addition to these, to address the morphological changes that occur during and after transfer, the following must be added as means of transfer lamination: By selecting a material from the resin system that exhibits heat resistance, flexibility, and migration induction properties, and adding it to the resin protective layer, the function of the resin protective layer can be enhanced, and the function of the metal layer can be transmitted. Furthermore, by using a gravure printing machine for drying, which involves heat treatment, hot air treatment, pressurization treatment, and cooling treatment, the heat resistance and flexibility functions of the resin protective layer, along with the material's migration induction properties to the metal layer, are transmitted through affinity to the metal layer interface, resulting in enhanced adhesion and the intersection and fixation of the two interfaces. The intersection zone, which is a physical intersection, is a mixed layer of fine particles of the resin-based protective layer and the metal layer. The fine metal particles in the resin film are in a mixed state. When impacts such as transfer loads or stresses are applied to the transfer lamination, these metal vapor-deposited particles absorb the impact energy and prevent the transfer lamination from failing. The resin-based protective layer simultaneously assists in expansion and contraction. This creates elasticity in both the resin-based protective layer and the metal layer. The resin-based protective layer and the metal layer share transfer breakability and stretchability. The transfer lamination becomes a modified lamination that can cope with cracks, fractures, and blisters during and after the transfer process.

[0097] The goal is to determine the optimal amount of flexibility transfer inducer within the resin-based protective layer. This involves exploring how to set a specific amount that does not lead to delamination at the protective layer interface. The selection of a material that can be guided to the vicinity of the interface of the protective layer having a thermosetting resin system, and that does not become sealed within the thermosetting resin and does not cause interface delamination, is necessary. Simultaneously, when performing transfer lamination film formation by dispersing a stretchable material that is linked and synchronously induced, the resin-based protective layer exhibits a softened state, and the interface zone of the fine metal particles in the metal layer is affected by a series of baking operations using a gravure oven, including heating, hot air, pressurization, and cooling. This creates a mechanical intersection state in the affinity between the resin-based protective layer and the metal layer, and the adhesion and fixation of the metal layer are enhanced interlayer. In terms of stretchability, the stretchability, which is a quality of the resin-based protective layer, is achieved by the interface alignment of the material and the stretchable material in the curable film, and the physical intersection zone is created between the resin-based protective layer interface and the activation excitation operation of the fine particles in the metal layer. The metal layer undergoes a grade transfer between itself and the resin-based protective layer, providing resistance to various loads caused by adhesion, transfer loads, and stresses. Physical crossings provide a novel function to protect the metal layer from various loads. The metal layer's fine particle group undergoes functional modification.

[0098] A transfer foil consists of a base film and a transfer-peelable modification laminate. It is formed by sequentially laminating a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16 onto a base film 11 selected from chemical films. The film protective layer 22, resin-based protective layer 17, and metal layer 15 are optional. The resin-based protective layer 17 and resin-based protective layer 14 can be selected, and multiple layers of each are possible. One or more resin-based protective layers 14 and 17 may be added, selected from among interfacial guides and expansion / contraction agents of the resin coating. By excluding the metal layer 15, the resin-based protective layers 14 and 17 can be colored using dyes, pigments, etc.

[0099] The resin-based protective layers 14 and 17 are composed of acrylic resin, amino resin, curing agent, plasticizing resin including ketone resin, colorant, light stabilizer, light blocking agent, UV absorber, plasticizer, solvent, etc. These are formed as a transfer laminate using a gravure printing machine. During transfer, expansion, contraction, pressure, and heat are applied. To withstand the formation of cracks, fissures, and blisters, the transfer laminate is carried out by imparting elasticity to the cured film and selecting an interface guide material. By incorporating heating, pressurization, and cooling using the gravure method, the affinity of the interface between the resin-based protective layer and the metal layer is enhanced. As a result, the transfer laminate can produce a laminated structure with high elasticity.

[0100] The resin-based protective layers 14 and 17 contain light stabilizers, light blocking agents, ultraviolet absorbers, etc., which suppress the fading of dyes, pigments, resin-based particles, extender pigments, etc.

[0101] The transfer laminate is formed by sequentially laminating a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16 on a base film 11. The film protective layer 22 contains one or more resins selected from the group consisting of phenolic resin, epoxy resin, urea resin, unsaturated polyester resin, silicone resin, melamine resin, aniline resin, sulfonamide resin, alkyd resin, silicone resin, melamine resin, aniline resin, sulfonamide resin, alkyd resin, polyurethane resin, diallyl phthalate resin, and thermosetting polyimide resin. The film protective layer 22 is smoothly coated and bonded to the base film 11 with a thickness of 0.3 to 1 μm by a gravure printing machine. The film protective layer has the function of providing uniformity of release to the release layer 13 during hot pressure transfer. In addition, it maintains the uniformity of heat pressure propagation to the base film 11 and the transfer laminate caused by the heat pressure during transfer. Furthermore, the effects of expansion and contraction caused by the heat and pressure during transfer on the base film 11 can be suppressed. This helps maintain the uniformity of the transfer lamination peeling and the stability of the heat transfer process.

[0102] Because the resin-based protective layers 14 and 17 contain interfacial guides and expansion / contraction agents, even if the transfer lamination expands and contracts due to thermal transfer, the metal layers do not undergo cohesive failure, and therefore cracks, fissures, and blisters do not occur in the transfer lamination.

[0103] The transfer foil is heated and pressurized on a film that supports the transfer laminate, which is passed between the foil and the object to be transferred via a hot-pressure transfer device. The transfer laminate is peeled and broken from the base film 11 to the object to be transferred, and the selected hieroglyphic image is transferred onto the object to be transferred. The surface layer of the object to be transferred is broken and the selected hieroglyphic image is transferred onto the object to be transferred. This results in modification of the surface layer of the object to be transferred. The modification laminate, which is the transfer laminate, has an adhesive film protective layer 22 on the base film 11 for protection of the base film 11 and interface modification. By adhering it to the base film 11 and forming a cured film, it prevents the expansion and contraction of the base film 11 during hot-pressure transfer and prevents the propagation of expansion and contraction to the transfer laminate. It also provides peel stability when the transfer laminate is peeled off. It is formed using a well-known thermosetting resin with a film thickness in the range of 0.3 to 5 μm. Next, a release layer 13 is provided. The materials can be selected from known materials and preferably contain selected acrylic resins such as methyl methacrylate, ethyl methacrylate, butyl acrylate, vinyl chloride resin, vinyl chloride vinyl acetate copolymer, vinyl butyral, polyester resin, urethane resin, epoxy amino resin, amino alkyd resin, silicone wax, silicone resin, silicone modified resin, fluororesin, fluoromodified resin, polyvinyl alcohol, nitrocellulose and other cellulose-based materials, as well as silica as a hardening agent, polyethylene wax and various other waxes. It can be formed from a mixture of one or more selected materials. The release agent, heat transfer agent, hardening agent, breaking agent, interlayer bonding agent, pressure-resistant agent, lubricating agent, heat-resistant agent, gloss agent, and peeling in the form of interfacial peeling with the base film 11 or film protective layer 22, or cohesive fracture and fracture peeling during transfer within the release layer 13 due to transfer heat pressure, result in the formation of a cover of the release agent on the next layer of resin protective layer 17 and assistance in physical and chemical resistance after transfer, which are necessary elements for the release layer 13 to be established along with its peeling ability. For this purpose, the release layer 13 may be layered. Alternatively, it may be multilayered with differentiated functions. The release layer 13 is formed by drying a prepared solution using a known film-forming machine such as a gravure printing machine. The film thickness is 0.1 to 20 μm, preferably 0.1 to 10 μm.

[0104] The transfer lamination, consisting of a base film 11, a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16, can be configured by selecting and discarding each layer from 2 to 8. The film protective layer 22 allows for modification of the surface properties of the base film 11, such as fine irregularities, uneven polarity of the film surface, and the establishment of bands with varying levels of charge. The release layer 13 is configured to avoid any abnormalities during peeling and detachment during transfer lamination, even when directly applied to the base film 11. The film protective layer 22 offers superior applicability to a wider range of transfer targets. In the resin-based protective layer 17, the compounding agent consists of a curable resin, a curing agent, a breaking agent, a softening agent, a coloring agent, etc. In the resin-based protective layer 14, the same compounding agent can be used as in the resin-based protective layer, but in order to incorporate a novel means of interlayer fixing between the resin-based protective layer and the subsequent metal layer, the lamination compounding agent can include a polyvinyl chloride-based resin with film curing properties that re-softens the film when heated, a material that maintains heat resistance when heated, and a material that induces these to form at the interface with the metal layer 15 when heated. Next, the metal layer 15 is formed, and any known material that can be used in a vacuum deposition apparatus that uses metal can be used. The resin-based protective layer 23 uses a plastic urethane-based resin, and the urethane material absorbs and converges the effect on the cohesiveness of the metal layer 15 caused by the propagation of load and stress during transfer to the metal layer 15. Next, an adhesive is prepared and made into a transfer foil. These measures include setting interface guides, expansion and contraction agents, film re-softening agents during heating, and film curing time settings for the resin-based protective layer. With this structure of the resin-based protective layer, heating, hot air, pressurizing, and cooling operations are performed using a gravure oven. At the interface between the resin-based protective layer 14 and the metal layer 15, activated fine particles of the metal layer at the metal deposition interface penetrate the softening surface of the resin-based protective layer. An intersection of the resin layer and metal particles is created. Softening and capture of the resin-based protective layer occur, metal particle penetration occurs, and a transfer of quality of the resin-based protective layer occurs in the metal particle layer through the baking operation.These methods utilize a resin-based protective layer containing various compounding agents, which, along with the metal layer, effectively adapt to the expansion and contraction and pressure loads that occur during the heat transfer process.

[0105] The film protective layer 22 is formed under the following conditions: During heat-pressure transfer, the base film 11 expands or contracts due to the propagation of heat and pressure during the transfer. To suppress these effects, a rigid film protective layer is formed. To ensure stable and uniform peeling of the release layer 13 during transfer, a rigid and smooth film protective layer is formed between the base film 11 and the release layer 13. This allows for equal propagation of pressure and heat during transfer, improving transfer peeling, transfer fixation, and breakage properties, such as image transfer during transfer.

[0106] During heat transfer, the base film 11, as well as the resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16, exhibit stretching. When the metal layer 15 is subjected to the stretching tensile stress of the resin-based protective layer 17, resin-based protective layer 14, resin-based protective layer 23, and adhesive layer 16, cracks, fissures, and blisters may occur between the metal layer 15 or 6 and the resin-based protective layer 14. This results in a decrease in the brightness of the transferred layer due to a reduction in the luster of the metal layer 15 and blistering of the resin-based protective layer 14 due to heat yielding during transfer.

[0107] In a transfer laminate on a base film 11, the layers consist of a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16. In the resin-based protective layer 14, polyvinyl chloride resin is added to the formulation. All layers except the metal layer 15 are coated and formed using a gravure printing machine. Each step is dried in the drying oven of the gravure printing machine using a far-infrared heater and a hot air drying device. During heat treatment, the resin-based protective layer 14 and resin-based protective layer 23 undergo film shrinkage, and the stress of shrinkage accumulates inside the film. In the resin-based protective layer 14, the film formation process incorporates the setting of a curing time for the hardened film, along with functional materials such as polyvinyl chloride resin, an interfacial guide, and a heat-resistant stretch material. This is a means of inducing the promotion of softening of the resin layer by reheating, thereby improving the interfacial adhesion with the metal layer 15. During heat treatment, the film protective layer 22 undergoes thermal shrinkage together with the base film 11. The stress of shrinkage accumulates inside the film. In the resin-based protective layer 14, the film formation process incorporates the setting of curing time for the hardened film, along with functional materials such as polyvinyl chloride resin, an interfacial induction agent, and a heat-resistant stretching material. The resin-based protective layer 23 employs a plastic urethane resin to provide absorbent properties against stretching. The resin-based protective layer 14 and resin-based protective layer 23, which are sandwiched between the metal layer 15, have a buffering effect against the generation of stress from external and internal forces. As a result, the deformation due to expansion and contraction of the lamination can be reduced. The impact on film fracture or shear properties of each resin-based protective layer and the metal layer can be reduced or avoided.

[0108] The laminate to which the coloring agent is added can be specified as a resin-based protective layer 17, a resin-based protective layer 14, a resin-based protective layer 23, or an adhesive layer 16, allowing for individual development. The laminate can be selected as a transfer laminate. The coloring material can be dye, inorganic pigment, organic pigment, extender pigment, fluorescent dye, fluorescent pigment, metal oxide particles, etc. The coloring means can be selected from the above transfer laminates, and the coloring means, amount of additive, and means of forming the image can be selected and adopted, depending on the degree of coloring, such as high transmittance, semi-transparent transmittance, opaque brightness, and the degree of light reflectivity of light sources when a light-reflective film such as a metal layer is set. In addition, one or more allyl resins containing a hindered amine-based material, which is a light stabilizer, are added as weather-resistant materials. One or more hydroxyphenyltriazine-based materials, which are ultraviolet absorbers, are added. By including phenyl salicylate as a light-blocking agent, the fading and deterioration of the transfer laminate 21 can be suppressed and its resistance can be extended.

[0109] The transfer shape of the object to be transferred ranges from planar to three-dimensional, and its material ranges from hard to soft. During heating and pressing during transfer, tensile and compressive stresses are applied between the object to be transferred and the transfer layer. Simultaneously, in the metal layer, the vapor-deposited layer, which is a layer of metal granules, is stretched, creating a force that inhibits the cohesiveness of the metal. As a result of the tensile stress of the resin-based protective layer 14, the load on the cohesive force of the metal deposition layer or metal island layer is concentrated, leading to cohesive failure. Starting from this point, the transfer layer may progress to cracks, fissures, blisters, peeling, poor interlayer adhesion, foil detachment due to poor interlayer adhesion, poor heat resistance, poor gloss, poor weather resistance, etc.

[0110] To improve this situation, numerous experiments were conducted, revealing that selective addition of polyvinyl chloride resin to the prepared liquid formulation of the resin-based protective layer 14 results in affinity between the resin-based protective layer 14 and the metal layer 15. This enhances the interfacial fixation between the resin-based protective layer 14 and the metal layer 15, contributing to the suppression of cracks, fissures, and blisters, and provides a means to resist the elongation of the transfer lamination during transfer. By incorporating processes such as adding polyvinyl chloride resin to the resin-based protective layer 14, and performing heat treatment, hot air treatment, pressurization, and cooling treatment with the resin-based protective layer 14 and the metal layer together, the transfer lamination becomes heat-resistant, flexible, and stretchable, and can withstand and suppress the stress during hot-pressure transfer.

[0111] [Manufacturing Method 8] After forming a release layer 13 on the base film 11 by a gravure printing machine, the resin-based protective layer 14 containing polyvinyl chloride resin becomes a thermosetting resin layer formed by amino resin, curing agent, and acrylic resin. Because polyvinyl chloride resin is added, the resulting film is flexible. The mixture is heated in the drying oven of the gravure printing machine by an infrared heater and a hot air device, and the film is formed. Next, a metal layer 15 is formed by a vacuum deposition device, and an adhesive is added.

[0112] [Manufacturing Method 9] After forming a release layer 13 on the base film 11 by a gravure printing machine, the resin-based protective layer 14 containing polyvinyl chloride resin becomes a thermosetting resin layer formed by amino resin, curing agent, and acrylic resin. Because polyvinyl chloride resin is added, the resulting film is flexible. The mixture is heated in the gravure printing machine's drying oven by an infrared heater and a hot air device to form the film. Subsequently, a metal vapor deposition film is formed, and the dry film, which consists of the base film 11, release layer 13, resin-based protective layer 14 containing the polyvinyl chloride resin layer, and metal layer 15, is subjected to a baking process in the gravure machine's drying oven at a temperature of 100-210°C and a time of 20-50 seconds, passing through a pressurizing device and cooling device directly connected to the rear of the gravure machine's drying oven. The heating, pressurizing, and cooling processes are performed in a continuous sequence. The purpose of this series of operations is to activate the interface between the resin-based protective layer and the metal layer and thereby enhance adhesion between the interfaces. Subsequently, an adhesive layer 16 is formed. After heat treatment, pressure treatment, and cooling treatment, the resin-based protective layer 14 hardens, becoming a hard, tough thermosetting film, and forming a flat film structure in which a viscous, flexible, and stretchable film property is propagated to the metal layer. Subsequently, the adhesive layer 16 is added. A transfer foil containing a transfer laminate that can modify the surface layer of the object to be transferred is obtained.

[0113] [Manufacturing Method 10] In the gravure drying oven described above, the oven temperature was set between 140 and 210°C during the baking operation between 100 and 210°C, and further, the temperature was selected and set between 180 and 210°C for the operation. The transfer lamination used consisted of a base film 11, a release agent layer, a resin-based protective layer 14, and a metal layer 15. Furthermore, the film was subjected to heat exposure between 200 and 210°C. The expansion and fixation of the film formed by the heat, pressure, and cooling operations of the performed transfer lamination were confirmed. The film formed had an uneven surface, and the transfer lamination was stretched. The unevenness had a height of 13.87 μm, and peaks were observed at various points within the width. The transfer lamination was stretched and fixed. Upon examination of the surface, no phenomena such as cracks, fissures, or blistering leading to cracking were observed.

[0114] Figure 10 is a photograph showing the stretched transfer foil lamination. The details of the photograph shown in Figure 10 are as follows: Digital microscope VHX-8000 manufactured by Keyence Corporation used.

[0115] [Manufacturing Method 11] Between the resin-based protective layer 14 containing polyvinyl chloride resin and the metal layer 15, the resin-based protective layer 14 contains a flexible material, an elastic material, an interfacial guide material, a heat-resistant material, a curable resin, a curing means, and a curing time until the resin film hardens. The process for hardening the film involves triggering hardening with an amino resin and setting a curing time with a urethane resin. Subsequently, the hardened film is enhanced by adding flexibility and heat resistance, elasticity and heat resistance, and improving the quality of the resin-based protective layer on the metal layer. The means for developing the film structure within the resin-based protective layer proceeds in the following order. The formulation of the resin-based protective layer 14 was selected from amino resins, curing agents, guides for the film interface, stretch / flexibility maintaining materials, heat-resistant materials, flexible materials, urethane resins, etc., to set the curing time for the resin-based protective layer, activate various components during re-heating and softening of the interface between the two layers by heat treatment to enhance the adhesion function between the resin-based protective layer and the metal layer, enhance adhesion by pressurizing and cooling the gravure machine, and maintain film hardening and flexibility upon completion of the curing time of the resin-based protective film. The formulation of the resin-based protective layer, the incorporation of heating, pressurizing, and cooling methods for the formed film, the incorporation of curing time for the progress of film formation to hardening film, the setting of film-forming materials and functionalities, the discovery of activation of the interface of each film-forming, and the discovery of means to enhance the adhesion between the resin-based protective layer and the metal layer were all carried out. By combining these means, a novel method for adhesion between the resin-based protective layer and the metal layer was devised.

[0116] [Manufacturing Method 12] In the resin-based protective layer 14, the composition is made by combining an interface guide, a stretchable heat-resistant material, a flexible material, a thermosetting material, a curing material, a curing time setting material, a film heat-softening material, and materials that provide both heat resistance and stretchability, thereby preventing a loss of affinity with the interface of the metal layer 15. Through heating, pressurizing, and cooling operations, both interfaces are activated and excited. When heated, the resin film softens, and the tips of the metal particles at the interface of the metal layer are also activated by heat. The metal layer 15 undergoes metal plastic modification, and the metal fine particles become heat-activated along the interface of its metal deposit-like structure or metal island-like structure. Functional materials such as the interface guide, flexible stretchable material, and heat-resistant material in the resin-based protective layer 14 become heat-softened when heated. At the interface of the metal layer, the tips of the metal fine particles penetrate the resin layer between the resin-based protective layer 14 and the metal layer 15, causing intersection between the resin layer and the metal particles, resulting in the appearance of intersection zones. The contact between these two interfaces is fixed by a series of operations involving high-temperature heating, pressurization, and cooling. The flexibility, heat resistance, and stretchability functions of the resin protective layer 14 are propagated and fixed to the intersections of the fine particles of the metal layer, resulting in the propagation of the resin layer's functions to the intersections of the metal layer 15. This phenomenon provides resistance to various defects in the metal layer caused by the various loads generated during transfer, stresses received from the transferred object, transfer loads, and twisting resulting from stress, such as the appearance of cracks, fractures, and blisters. This also results in the metal layer 15 gaining elasticity. The data on the expansion and contraction of the transfer lamination shown in Figure 8 shows that even with the stretching of both the resin protective layer 14 and the metal layer 15, neither layer fractured or sheared, and no defects were observed.

[0117] Defects in transfer foils include poor release properties, poor film rupture accuracy, crack formation, splitting, peeling, blistering, poor interlayer adhesion, foil detachment due to poor interlayer adhesion, poor transfer heat resistance, poor luster, poor weather resistance, foil detachment due to poor adhesion, poor slipperiness of the foil surface, discoloration, and poor film permeability that diminishes the metallic effect. Of these, cracks, splitting, and blistering occur during the transfer process and can lead to a decrease in luster, foil detachment over time, and damage to the aesthetic appearance. The object being transferred also undergoes dimensional changes over time due to humidity, temperature, and climate. These factors can also impair the decorative properties of the transfer lamination, cause damage, and lead to foil detachment.

[0118] Figure 11 shows photographs of cracks, fissures, and blistering in the transfer layer. The details of the photograph shown in Figure 11 are as follows: Cracks, fissures, and blisters on the surface of transfer-laminate (modified-laminate) flat films. (200x magnification VHX-8000 / microscope) (Transfer laminated surface including release layer, resin-based protective layer, metal layer, and adhesive layer) Using general transfer materials Transfer lamination is a form of defect caused by the heat-press transfer of a flat film-shaped transfer foil.

[0119] Transfer lamination consists of layers with different functions, formed by selecting and filling them with materials. Each layer, acting as a transfer foil, obtains the necessary transfer conditions of heat, pressure, and time, and the transfer lamination peels off from the base film 11, resulting in all layers exhibiting the same fundamental properties in terms of film fracture, and accurately transferring the shape of the image on the printing plate. The objects to be transferred include general printed materials, paper containers, bookbinding materials, film sheets, electrical wire tubes, resin processed and molded products, leather products, textiles, wood products, glass products, metal products, etc., and their forms and shapes are diverse. The transferred shapes range from planar to three-dimensional, and during transfer, a load is applied between the object to be transferred and the transfer foil, and stress is generated in response from the object to be transferred. Furthermore, a twisting phenomenon occurs on the transfer foil between the transfer machine, transfer medium, transfer foil, and object to be transferred, and the transfer lamination is subjected to loads on film cohesion due to twisting phenomena, stretching conditions, etc. In the resin-based protective layer 14 and the metal layer 15, the ratio of the adhesion level of the metal layer to the resin-based protective layer is a critical factor. In the resin-based protective layer 14, a curing time is set using a thermosetting resin. During this time, reheating, pressurizing, and cooling operations are intervened to activate the resin-based protective layer during reheating of the in-progress transfer lamination, activate the metal particle group at the interface of the metal layer, and enhance adhesion between the layers. This reactivation of the metal deposition at both interfaces causes the resin film to soften due to reheating of the resin-based protective layer. The interface of the activated metal particle group from the metal layer penetrates into the softened resin-based protective layer interface due to the pressurizing operation, creating an intersection state. Here, the metal layer interface particles penetrate into the resin-based protective layer interface, resulting in the formation of an intersection zone of the metal particle group in the resin-based protective layer. In this intersection zone, the elasticity of the resin-based protective layer propagates within the curable film of the resin-based protective layer. In this case, the resin-based protective layer takes on the functionality of the metal layer in terms of its resistance to stretching and shrinking. The resin-based protective layer and the metal layer work in sync to prevent the metal layer from failing due to transfer load, stress from the transferred object, twisting, etc.

[0120] In view of the above, this embodiment suppresses cracks, fissures, and blistering in the transfer foil, and improves heat resistance and light resistance by selecting materials used for transfer lamination, improving the adhesion strength between layers, improving stretchability, and controlling the transfer load and stress in each film. Repeated experiments were conducted to find countermeasures for problems that occur between the transfer equipment and the object to be transferred 3 during transfer lamination, and details are given below. This invention was newly devised with the aim of improving the stretchability resistance of the metal layer in the event of such problems occurring during transfer lamination. The curing time of the resin protective layer, the appearance of softening during reheating, the development of a stretchable cured film and the setting of the curing period, the baking effect of reheating both the resin protective layer and the metal layer by heat treatment with a gravure machine, and subsequently the ratio of the level of fixation to the resin protective layer due to the penetration of metal vapor-deposited particles into the resin protective layer interface by pressurization treatment are all important. In the resin protective layer 14, by setting a period for the thermosetting resin, it is possible to set the maintenance of stretchability and the imparting of heat resistance in the cured film. The transfer of properties such as elasticity and heat resistance of the resin-based protective layer occurs through the interface intersection with the metal layer. This transfer of properties from the resin-based protective layer to the metal layer helps to avoid defects in the modification properties of the transfer lamination.

[0121] [Experiment 1] Forming means for enhancing interlayer adhesion between resin-based protective layer and metal layer

[0122] In the stretchable environment of the transfer lamination described above, this invention seeks to find a method for creating resistance in both layers to various loads applied during transfer to the resin protective layer and the metal layer, stresses generated from the material being transferred, stretching loads, stresses, torsional loads, and stresses applied to the transfer lamination. A polyester film with a thickness of 12 μm was used for the base film 11. A release layer 13 was formed on the base film 11. Specifically, a release agent consisting of 71.1% by weight of toluene (Idemitsu Kosan Co., Ltd.), 25% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Holdings Corporation), 0.03% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd. Kyoto), 1.04% by weight of Fischer Trophic Wax (Sador; A859), and 0.9% by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301) was prepared and applied and dried using a gravure printing press 60 to form a release layer 13 with a thickness of 0.5 μm. The release layer 13 with a thickness of 0.5 μm was prepared by using the drying oven of the gravure printing press and staying in a heating temperature of 100-140°C for 20-50 seconds.

[0123] Next, a resin-based protective layer 14 was prepared on the release layer 13, a film was formed, and the layer was coated and dried in a gravure printing machine to form a resin-based protective layer 14 with a thickness of 1 μm. The resin-based protective layer 14 consists of 42.9% by weight of toluene (Idemitsu Kosan Co., Ltd.), 26.6% by weight of MEK (methyl ethyl ketone) (Idemitsu Kosan Co., Ltd.), 23.7% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Chemical Holdings Co., Ltd.), 0.04% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 12.3% by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301), 7.02% by weight of acrylic resin (Alpha Kaken Co., Ltd.: Acrylic silicone silicate resin UVHA), and 0.71% by weight of acrylic resin (Wilba - Ellis Co., Ltd.: Paraloid AT-740), melamine resin 0.89 wt% (Nippon Carbide Co., Ltd.: MS-001), ketone resin 4.4 wt% (Wally Co., Ltd.: Polyton K-97), UV absorber 0.08 wt% (BASF: Tinuvin 1600), UV absorber 0.08 wt% (BASF: Tinuvin 249), light stabilizer 0.08 wt% (BASF: Tinuvin 249), light blocking agent 0.08 wt% (Tokyo Chemical Industries, Ltd.: Phenyl salicylate), curing agent 0.08 wt% (Tokyo Chemical Industries, Ltd.: p-toluenesulfonic acid), polyvinyl chloride acetate copolymer resin 3.75% by weight (Earth Corporation: Earth Enabond #380), flexibility and heat resistance imparting agent 1.25% by weight (Daicel Hirss Toluene Sulfonamide: MPY720), interface inducer 0.05% by weight (Mitsui Petrochemical Co., Ltd.: Ethylene-α-olefin oligomer: A-5515), hardening agent / breaking shear agent 5.0% by weight (Nippon Kasei Co., Ltd.: (Triallyl isocyanurate TAIC), isocyanate / curing accelerator 1.5% by weight (Hyrs: Isophoron D A film was formed by combining socianate (T-1890), 3.0% by weight of acrylic ladder silicone resin (Showa Denko K.K.: LS230), 0.6% by weight of hardening and breaking shearing agent (Colcoat Co., Ltd.: ethyl silicate sol HAS-1), 1.9% by weight of iron particle yellow pigment (Mikuni Shikiso Co., Ltd.: 8197M), 3.75% by weight of iron particle red pigment (Mikuni Shikiso Co., Ltd.: 8196M), and 0.375% by weight of reaction accelerator (Kusumoto Kasei Co., Ltd.: organic bismuth compound). The iron particle pigment was selected from the color group with a diameter of 40-80 nm.

[0124] The resin-based protective layer 17 can be formed using the same formulation as the resin-based protective layer 14. In the case of a flat film structure, it is possible to produce films such as a transparent layer without a coloring agent, a colored image, or a single colored layer, and the resin-based protective layer can be layered or made into a single layer. Transfer lamination can be performed using a base film 11, a film protective layer 22, a release layer 13, a resin-based protective layer 17, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16. Each layer can be arbitrarily selected and discarded for the transfer substrate. For example, in the case of a transfer substrate related to printed paper packaging, the base film 11, release layer 13, resin-based protective layer 14, metal layer 15, and adhesive layer 16 can be selected to form the transfer laminate.

[0125] The resin-based protective layers 14 and 17 have a time delay before the film hardens after film formation. A curing time of 5 to 10 days is provided. The functions of the resin-based protective layers are provided during this time. Primarily, this is to ensure a certain level of hardening during heat drying by the gravure machine during film formation, and secondaryly, to create a compound that induces softening of the resin-based protective layer when the film is heated again in the gravure machine.

[0126] In resin-based protective layers, melamine resin and curing agent, and isocyanate and organic bismuth compound materials govern the curing process. If the film is reheated in a gravure printing machine, the resin film softens during the curing time. Interfacial particles in the metal layer become activated.

[0127] When the resin-based protective layer softens upon heat, ethylene-α-olefin oligomer acts as an interfacial inducer, toluenesulfonamide can induce flexibility and heat resistance, and polyvinyl chloride acetate copolymer resin softens, resulting in easy adhesion. To maintain the lightfastness of the color band of the resin-based protective layer, light-absorbing, stability-maintaining, and shielding agents are added. The resin-based protective layer 14 contains an organosol-based silicate sol material. This material has high bonding energy and excellent adhesion. When the film is reheated and plasticized, the bonding of the interfacial particles of the metal layer, such as the aluminum layer, to the substrate is excellent, and the fixation in the resin-based film can be enhanced. In addition to improved interfacial bonding, heat resistance and acid resistance are imparted.

[0128] The composition of the resin-based protective layer is set to allow for curing time. When the dry film is reheated using a gravure machine or the like, a film softening response occurs, which is intended to further improve the adhesion between the layers in contact at the interface, such as resin films applied by a gravure machine or metal vapor-deposited films. The curing time of the resin-based protective layer and the reheating of the layered dry film cause thermal activity at the interface between the two layers.

[0129] For example, in a setup consisting of a base film 11, a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16, during the process up to the metal vapor deposition film, when baking the dry film using the drying oven of a gravure machine, the resin of the resin-based protective layer 14 softens during the curing period. At the interface, the activated metal particles of the metal layer penetrate along the resin layer as they are heated and warmed. In the gravure machine, the interlayers are continuously pressed, and the physical penetration of the metal particles into the resin-based protective layer progresses. Subsequently, the film is cooled. A portion of the metal vapor deposition particle layer intersects with the resin-based protective layer film and becomes fixed. For the formation of the metal layer, aluminum is used as the metal, and a coating thickness of 30-80 nm is achieved using a two-chamber semi-continuous vacuum deposition apparatus and a high-frequency induction heating metal melting heat source.

[0130] Next, an adhesive layer 16 was formed on the metal layer 15. Films with thicknesses of 1 μm and 2 μm were fabricated using a gravure coater with 50.0% by weight toluene (Idemitsu Kosan Co., Ltd.), 37.7% by weight ethyl acetate (Showa Denko K.K.), 1.5% by weight butyl acetate (Standard Petroleum Corporation), 0.07% by weight ethyl silicate (Colcoat Co., Ltd.; Ethyl Silicate 100), 2.7% by weight acrylic resin (Mitsubishi Chemical Corporation; Corponil N2147), 2.7% by weight ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), and 3.0% by weight ketone resin (Wally Co.; Polyton K-97). Volume: 5.28 m³ 3 Using a drying oven, the material was kept in a heated environment of 100-120°C for 20-50 seconds to produce an adhesive layer 16 with a thickness of 1 μm.

[0131] The formulation settings for the resin-based protective layer 17 and resin-based protective layer 14 described above include a time interval for the curing of the resin-based protective layer film. The aim is to achieve the desired functionality of the resin-based protective layer. The formulation settings for the resin-based protective layer 17 and resin-based protective layer 14 govern the curing level of the resin film during solution formulation, application, and drying. The degree of curing is determined by the curing time. As a primary curing agent, melamine resin and a 40-50% curing agent are mixed to achieve 40-50% curing. A curing time of 5-10 days is maintained until curing. Furthermore, as a secondary curing agent, a curing time for resin film curing is set between the urethane-based resin and the organic bismuth-based material to achieve 50-70% curing. A curing time of 5-10 days is maintained.

[0132] The purpose of allowing the resin-based protective layer to undergo changes over time and providing a curing time is to impart functionality to the film before it reaches a hardened state. Specifically, within 5 to 10 days, 30 to 40% of the resin in the resin-based protective layer will be in a plasticized state. In this area, the quality of the resin-based protective layer can be changed, and the following functionalities can be added: adhesion activity within the plasticity due to polyvinyl chloride acetate copolymer resin, film softening of the plasticized portion upon reheating, function as an interfacial inducer due to ethylene-α-olefin oligomer, and heat resistance and extensibility due to toluenesulfonamide.

[0133] The above resin-based protective layers have resins attached that act as functional agents. These are resin-based protective layers 17 and 14. The main film-forming component is acrylic resin, with melamine resin and urethane resin to induce curing, and it also contains a lightfastener and a coloring agent.

[0134] In the case of a double layer of resin-based protective layer 17 and resin-based protective layer 14, or in the case of a single layer, a metal layer 15 is then applied. Subsequently, using the drying oven of the gravure machine, a baking operation is performed using up to 6 metal vapor-deposited films. The dry film is reheated to a high temperature using far-infrared heaters and hot air equipment in the drying oven at 140-210°C.

[0135] In the above process, the resin-based protective layer exhibits softening of its plastic portion due to the heat applied during baking, while the metal particles in the metal layer become activated. At the interface between the two layers, a bilayer interface is formed between the heat-softened resin film and the heated, activated metal particles.

[0136] During the curing period, the resin-based protective layer exhibits properties such as stretchability, heat resistance, interfacial induction, adhesion, thermal re-softening, and resin film curing. The remaining 30-40% of the curing time is spent in the opposing portion of the film.

[0137] The resin-based protective layer and the metal layer are formed by a dry film baking operation. Heating causes changes in both layers and the interface between them. The resin-based protective layer is in a state where it has not yet hardened and has areas that can be plasticized. Furthermore, the functional materials in the resin film include ethylene-α-olefin oligomer as an interface inducer, toluenesulfonamide for flexibility, heat resistance and extensibility, silicate sol for bonding, heat resistance and permeability to maintain the film's spatial structure, and polyvinyl chloride resin with good softening and adhesion properties. Reheating by baking activates these functions and makes them work effectively. In the metal layer, the particles at the deposition layer interface, which are in the form of metal particulate matter, are activated.

[0138] At this time, pressurization is applied via a pressurizing device directly connected to the gravure drying oven, which is installed in a continuous manner. At this time, the resin film is in a softened state, and the metal layer is in a state where the metal particles are activated. The affinity and adhesion of the polyvinyl chloride resin, the flexibility and heat resistance of the sulfonamide, and the bonding and heat resistance of the silicate sols to the metal particles cause a transfer of quality at the interface of the metal layer along the interface inducer. The pressurization operation forces the metal vapor-deposited particles onto the resin protective layer, and the metal vapor-deposited particles penetrate the softened resin protective layer. Crossover phenomena occur between the constituent materials at both interfaces. The flexibility of the resin-based protective layer is transferred and propagated to a portion of the metal layer, resulting in the development of the metal layer's resistance to stretching and contraction.

[0139] Following the above operation, a cooling device directly connected to the pressurizing device is used to fix the interfacial cross-section configuration resulting from the pressurizing operation between the layers.

[0140] Figure 12 shows a cross-section of the transfer layer. The transfer foil lamination consists of a release layer 13, a resin-based protective layer 14, and a metal layer 15 made of aluminum. In Figure 12, P1 indicates the position of the intersection of the interface between the resin-based protective layer 14 and the metal layer 15 in the cross-section of the transfer lamination.

[0141] The details of the photograph shown in Figure 12 are as follows: Keyence microscope Using VHX-8000

[0142] Figure 13 is a photograph showing the surface of the metal layer (surface metal particles of aluminum deposition). The details of the photograph shown in Figure 13 are as follows: Surface of aluminum deposition in metal layer 15 It consists of a release layer 13, a resin-based protective layer 14, and a metal layer 15. Radiation from the surface of the metal layer x20 enlargement Keyence Microscope Using VHX-8000 Coaxial ring incident light source Surface radiation of a metal layer (Al material)

[0143] The details of the photograph shown in Figure 14 are as follows: x40 enlargement Keyence microscope Using VHX-8000 Coaxial ring incident light source Surface radiation of a metal layer (Al material)

[0144] The details of the photograph shown in Figure 15 are as follows: x200 enlargement Keyence microscope Using VHX-8000 Coaxial ring incident light source Surface radiation of a metal layer (Al material)

[0145] Schematic diagram of cross-zone generation in transfer layering. Formation of an intersection between the resin-based protective layer 14 and the metal layer 15 Lamination setup: Base film 11, release layer 13, resin-based protective layer 14, metal layer 15, baking process. Baking: Using a gravure oven, the dry film is baked by passing it through a heat treatment of 150-210°C, far-infrared radiation, and hot air, followed by a direct pressurization device and cooling device outside the oven. The duration of stay should be between 20 and 50 seconds.

[0146] Elements of the means of forming cross bands (1) The resin protective layer 14 has a curing time of 5 to 10 days for the resin film. This is intended to induce film plasticization in response to reheating. (2) The resin-based protective layer 14 is assembled with an initial curing level of 50% when the amino resin is coated. (3) The resin-based protective layer 14 is designed to facilitate the progress of the reaction as a secondary curing level between the isophorone diisocyanate and the organobismuth compound, with a resin film curing level of 80%. (4) During the baking process, the resin layer becomes plasticized and softened when heated, and is activated. At that time, the organic bismuth compound and the metal vapor-deposited particles bond together and adhere tightly. (5) During the baking operation, the resin layer becomes plasticized, softened, and activated when heated. In the case of silicate sol, an interlocking state is formed between it and the metal vapor-deposited particles. (6) During the baking operation, the drying oven of the gravure machine will create a high-temperature zone using far-infrared heaters and hot air treatment. Maintain a maximum drying temperature of 210°C, and the residence time, including transfer lamination, will be 20 to 50 seconds. (7) During the baking operation, the pressurizing device directly connected to the drying oven of the gravure machine is exposed to high temperatures, and at the interface between the transfer laminate, the resin-based protective layer 14 and the metal layer 15, each layer is heat-softened and activated. Under these conditions, both the base film 11 and the laminate are pressurized. The 6 metal vapor-deposited particles penetrate under pressure into the interface of the organic bismuth compound, isophorone diisocyanate, silicate sol, and plasticized resins of the resin-based protective layer 14. Some of the metal vapor-deposited particles form an intersecting state with the interfacial resin layer. During the heat treatment and pressurization treatments of (8), (6), and (7), the curing level of the resin protective layer 14 progresses to 80%. (9) The penetration and crossing state of metal vapor-deposited particles into the resin layer is due to the capture of metal vapor-deposited particles that have penetrated the resin film, which occurs during pressurization and reheating by baking the resin film, and then to the immobilization of the metal vapor-deposited particles by hardening of the resin film. (10) The curing level of the resin-based protective layer 14 is preferably 80% or less. (11) The unreacted portion is caused by the transfer load during transfer, stresses caused by the object being transferred, torsional loads and stresses on the base film and transfer lamination. This is necessary to maintain the stretch resistance. (12) In order to maintain the interface between the resin protective layer 14 and the metal layer 15, the cooling device is passed through to fix the function.

[0147] Morphology of the crossing zone (1) Film forming order In the transfer laminate 12 shown in Figure 1, silicate sol particles in the resin protective layer 14 are scattered within the resin layer. Interfacial adhesion of metal particles in metal layer 15 (2) Baking operation Through the intervention of the baking operation, the morphology of the metal layer on the resin-based protective layer changes from an attached state to one in which metal particles at the metal deposition interface penetrate the resin layer, and an intersection state with the resin material and silicate sol material is created and fixed between the resin layer and the metal layer under heating, hot air, pressurization, and cooling operations. The quality of the resin system is transmitted to the metal layer from the formation of the intersection zone. The interface particles of the metal layer at the intersection zone correspond to the load-fracture stress of the metal layer. (3) Genesis of the crossing zone In the transfer layer 12 shown in Figure 1, after the baking and heating operation, the layer interface intersection zone is generated by pressurization and cooling. (4) An intersection is formed between the resin protective layer and the metal layer. Loads from the transfer equipment, stresses from the object to be transferred, tensile stress, compressive stress, shear stress, bending stress, torsional load and shear stress affect the object to be transferred and the transfer laminate. In the metal layer, resistance under load decreases, cracks, fractures, and blisters occur, leading to the destruction of the cohesiveness of the metal film. The resin protective layer 14 has excellent flexibility, extensibility, and heat resistance. Its quality is propagated through the above intersection. (5) During baking, in the resin protective layer 14, the continuous film at the interface tip of the metal layer (AL material) with metal vapor-deposited particles of 0.1 to 0.3 nm in diameter is formed by the re-heat softening of the resins and co-activation of organosilicate sols with a particle size of 12 to 80 nm, and the heat-activated interface is pressurized in a high-temperature vortex of the furnace. The heat-activated metal fine vapor-deposited particles of the metal layer penetrate the heat-activated and softened resin protective layer 14 under pressure. Under pressure, inorganic material-containing acrylic resin, organosilicate, triallyl isocyanurate, toluenesulfonamide, polyvinyl chloride acetate copolymer resin, etc., are forced to conjugate the metal vapor-deposited particles in the metal layer 15 (Al example), resulting in the formation of crossbands. Subsequently, the crossbands are fixed and set using a cooling device. (6) In the metal film deposition layer, the quality of the resin-based protective layer is transmitted to the intersections through which the properties of flexibility, heat resistance, and stretchability are imparted. The metal layer will satisfy the stretchability requirements by being able to withstand various loads, stresses, torsions, and other loads. (7) The organic bismuth compound contained in the resin protective layer 14 exhibits excellent low-temperature sensitization when heated and has excellent adhesion at the interface with metal vapor-deposited particles (Al material). During baking in the gravure machine, the affinity of these materials increases under heating and pressurizing treatment. (8) After baking, the adhesive layer 16 is formed. (9) No abnormalities were detected in the transfer layering after the baking operation, regarding transfer function, metallic luster, brightness, discoloration, or interlayer adhesion. No abnormalities were found in the transfer function either.

[0148] Perform the baking operation once. Repeat it again to perform the second time. The purpose is to confirm the functions and resistance of the transfer laminate. The confirmation of functions is to confirm incidental properties such as flexibility, heat resistance, stretchability, etc. For functionality, it was to confirm the presence or absence of film breakage accompanying the stretchability of the transfer laminate. The specimens adopted the same settings as those of the base film 11, release layer 13, resin-based protective layer 14, and metal layer 15. The purpose is to confirm whether the flexibility, heat resistance, and stretchability of the resin-based protective layer 14 are transferred to the quality propagation to the metal layer 15 through the crossover zone. It is to confirm whether the metal layer 15 can show corresponding resistance in synchronization with the stretching of the film formation of the transfer laminate. In the operation of the dry film of the transfer laminate in the gravure machine, it was carried out as follows. The drying furnace temperature was 150 - 210 °C, and heat sources such as far-infrared heaters and hot air drying devices were heated. The generation of the crossover zone between the resin layer and metal particles due to the intrusion of metal vapor deposition particles by the pressurizing device, and the operation of fixing and fixing the crossover zone by the cooling device were carried out twice with a residence time of 20 - 60 seconds. The two implementations were to confirm whether the generation of film breakage of the transfer coating due to overloading on the transfer laminate would occur, or whether the brilliance due to heating would cause breakage due to stretchability. Regarding the film by the heating operation of the transfer laminate, it is to confirm whether phenomena such as cracks, fractures, and bulges will appear. It is also to confirm whether the function of the crossover zone of the film formation control, which is a new means, is effective, and whether the resistance propagation to the metal layer occurs by applying a stretching load. It was to confirm the appearance of cracks, fractures, bulges, loss of brilliance of the metal layer 15, loss of metallic feeling of the metal layer reflection, loss of interlayer adhesion, incomplete peeling of the release layer 13, and malfunction of the contour shearing property. After baking, the adhesive layer 16 is formed. Using a transfer device, transfer using a relief metal plate under the conditions of a temperature of 160 °C, a residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2 Under these conditions, use a transfer machine of Taihei Machinery Co., Ltd. to transfer a soft vinyl chloride sheet with a thickness of 2 mm as the transfer body.

[0149] [Result 1] Figure 16 is a photograph taken of the surface of the base film 11, release layer 13, resin-based protective layer 14, and metal layer 15 directly above the film. The transfer laminate is stretched. No film breakage is seen. The transfer laminate including the release layer, resin-based protective layer, and metal layer is stretched in a waveform.

[0150] The details of the photograph shown in Figure 16 are as follows: Height 0.99~1.4μm x5000VHX-8000 / microscope KEYENCE Corporation

[0151] [Result 2] Figure 17 shows the process of forming a base film 11, a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16, and then transferring them to a flexible polyvinyl chloride sheet using a transfer machine. The flexible polyvinyl chloride sheet is stretched by applying heat and pressure at 160°C. The flexible polyvinyl chloride sheet stretches. When the heat and pressure are released, the sheet shrinks. The transfer lamination follows the expansion and contraction. No defects are observed. The transfer lamination, including the release layer, resin-based protective layer, metal layer, and adhesive layer, stretches in a corrugated shape.

[0152] The details of the photograph shown in Figure 17 are as follows: Height 0.99~1.4μm x5000VHX-8000 / microscope KEYENCE Corporation

[0153] [Result 3] Confirmation of the transfer layer after stretching. [Table 1]

[0154] evaluation (1) No failure occurs during stretching of the intersecting state of the resin layer and metal layer during baking. (2) Adjustments will be made when the transfer layer expands or contracts. (3) It accommodates the elongation of the object being transferred during the transfer process. (4) The metal layer exhibits tensile properties in response to transferred loads and stresses. (5) No defects were observed in the transfer lamination, transfer machine, or the object to be transferred due to load, stress, or torsion. (6) Peelability, contouring, heat resistance, and light resistance are maintained. (7) The interlayer properties of the transfer layer are maintained.

[0155] Control operation The formation of the intersection between the resin-based protective layer and the metal layer can be controlled by adjusting the levels of heating, hot air, pressurization, and cooling during the baking process on the dry film.

[0156] [Experiment 2] A method for obtaining the light reflectivity of a metal layer in a metal layer by using a pigment in the formulation of a colorant in a resin-based protective layer of a transfer laminate.

[0157] A transfer laminate was fabricated. A polyester film with a thickness of 12 μm was used as the base film 11. A release layer 13 was formed on the base film 11. Specifically, a release agent consisting of 71.1% by weight of toluene (Idemitsu Kosan Co., Ltd.), 25% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Holdings Corporation), 0.03% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd. Kyoto), 1.04% by weight of Fischer Trophic Wax (Sador; A859), and 0.9% by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UVG301) was prepared, applied and dried using a gravure printing machine, and a release agent with a thickness of 0.5 μm was prepared, applied and dried using a gravure printing machine, to form a release layer 13 with a thickness of 0.5 μm. Using the drying oven of the gravure printing machine, the film was kept in a heated temperature of 100~140°C for 20~50 seconds to produce a release layer 13 with a thickness of 0.5 μm.

[0158] The resin-based protective layer preferably contains one or more acrylic resins and has light resistance. UV degradation due to natural light causes a decrease in physical properties and changes in appearance. Direct sunlight, scattered sunlight, etc., causes hydrogen atoms in the polymer and colorant of the transfer laminate to be cleaved, generating radicals. These radicals combine with oxygen in the atmosphere to generate peroxy radicals. Peroxy radicals remove hydrogen atoms from the polymer, generating radicals and hydroperoxides. Hydroperoxides accelerate the degradation of the polymer. To improve the resistance of resin transfer protective layers 14, 17, etc., acrylic resins with long-term shielding effects, organic and inorganic UV shielding agents, UV absorbers (UVA) that convert ultraviolet light into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose the hydroperoxides generated when peroxy radicals remove hydrogen atoms from the polymer, generating radicals and hydroperoxides are used. One of the acrylic resins included in the formulations of resin-based protective layers 14 and 17 contains ultraviolet absorbing groups and ultraviolet stabilizing groups (HALS) in its resin backbone, and after transfer, radicals are generated by light on the surface peel layer 13, resin-based protective layer 17, resin-based protective layer 14, etc., and a long-term ultraviolet shielding effect that inactivates reactive oxygen species is expected. Another acrylic resin contains ultraviolet absorbing groups and ultraviolet stabilizing groups (HALS), is a silicone acrylic resin having silyl groups, contains alkyl silicate, and forms a hard and highly ultraviolet resistant film. Yet another acrylic resin has hydroxyl groups attached with reactive functional groups that contribute to cross-linking film formation.

[0159] Next, a resin-based protective layer 14 was prepared on the release layer 13, a film was formed, and the layer was coated and dried in a gravure printing machine to form a resin-based protective layer 14 with a thickness of 1 μm.The resin-based protective layer 14 consists of 42.9% by weight of toluene (Idemitsu Kosan Co., Ltd.), 26.6% by weight of MEK (methyl ethyl ketone) (Idemitsu Kosan Co., Ltd.), 23.7% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Chemical Holdings), 0.04% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 12.3% by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301), 7.02% by weight of acrylic resin (Alpha Kaken Co., Ltd.: Acrylic silicone silicate resin UVHA), and 0.71% by weight of acrylic resin (Wilbur Ellis Ltd.: Paraloid AT-740), melamine resin 0.89 wt% (Nippon Carbide Co., Ltd.: MS-001), ketone resin 4.4 wt% (Wally Co., Ltd.: Polyton K-97), UV absorber 0.08 wt% (BASF: Tinuvin 1600), UV absorber 0.08 wt% (BASF: Tinuvin 249), light blocking agent 0.08 wt% (Tokyo Chemical Industries, Ltd.: Phenyl salicylate), curing agent 0.08 wt% (Tokyo Chemical Industries, Ltd.: p-toluenesulfonic acid), polyvinyl chloride acetate copolymer resin 3.75 wt% (Earth Co., Ltd.: Earth Enabond #380), 1.25% by weight of flexibility and heat resistance imparting agent (Daicel Hirss Toluene Sulfonamide: MPY720), 0.05% by weight of interface inducer (Mitsui Petrochemical Co., Ltd.: Ethylene-α-olefin oligomer: A-5515), 5.0% by weight of hardening agent and fracture shearing agent (Nippon Kasei Co., Ltd.: Triallyl Isocyanurate TAIC), 1.5% by weight of isocyanate and curing accelerator (Hürss: Isophorone Diisocyanate: T-1890), 3.0% by weight of acrylic ladder silicone resin (Showa Denko K.K.: LS230) Film formation was carried out by combining 0.6 wt% hard / fracture shearing agent (Colcoat Co., Ltd.: ethyl silicate sol HAS-1), 1.9 wt% iron particle yellow pigment (Mikuni Pigment Co., Ltd.: 8197M), 3.75 wt% iron particle red pigment (Mikuni Pigment Co., Ltd.: 8196M), 0.9836 wt% red pigment (DiPont: Shinshaka Red B), 0.9340 wt% yellow pigment (BASF: Paliotol Yellow 1070, DiPont: Shinshaka Red B), and 0.375 wt% reaction accelerator (Kusumoto Chemical Co., Ltd.: organic bismuth compound). The iron particle pigment was selected from the color group within the particle size range of 40 to 100 nm.Red and yellow pigments were dispersed and granulated using a bead mill type granule disperser, model KD-5, manufactured by DYNO-MIL Co., Ltd.

[0160] As means of forming the metal layer 15, examples of vapor phase deposition methods include PVD (Physical Vapor Deposition), such as vacuum deposition and sputtering. Examples of chemical vapor deposition (CVD) methods include thermal CVD, atomic layer deposition (ALD), plasma CVD, metal-organic chemical vapor deposition, two-flow MOCVD, and catalytic chemical vapor deposition (Cat-CVD). Examples of liquid phase deposition methods include solution-based methods such as liquid phase epitaxy, and examples of plating methods such as wet plating, chemical plating, and sol-gel plating. Examples of coating methods include spin coating, printing, and inkjet. The metals used include Au, Ag, Cu, Sn, Al, Ni, Pt, Rh, Pd, Zn, Cr, and Si, as well as oxides such as In2O3, CdO, CdIn2O4, Cd2SnO4, TiO2, SnO2, ZnO, SiO2, and ZrO2, sulfides such as ZnS, and fluorides such as MgF2. One or more of these can be selected. Alloys can also be used. Layering is also possible. The film structure of the metal layer 15 can be an island-sea film structure where the metal layer 15 is in an isolated island state, or a deposited film structure showing the deposition state of the metal. Regardless of the structure, regardless of the metal used or the film structure of the metal, it is possible to suppress the expansion and contraction, cracks, fractures, and blistering caused by pressure on the transfer layer 12 during thermal pressure transfer.

[0161] Furthermore, the thickness of the metal layer 15 is 10-30 nm in the case of isolated island states and 20-60 nm in the case of continuous film deposition states. In either case, a uniform luster can be maintained as a metallic coloration. This enhances the decorative and design aspects of the image display using thermal transfer printing. Aluminum was used as the metal, and a coating thickness of 30-80 nm was achieved using a two-chamber semi-continuous vacuum deposition apparatus and a high-frequency induction heating metal melting heat source.

[0162] Next, an adhesive layer 16 was formed on the metal layer 15. Films with thicknesses of 1 μm and 2 μm were fabricated using a gravure coater with 50.0% by weight toluene (Idemitsu Kosan Co., Ltd.), 37.7% by weight ethyl acetate (Showa Denko K.K.), 1.5% by weight butyl acetate (Standard Petroleum Corporation), 0.07% by weight ethyl silicate (Colcoat Co., Ltd.; Ethyl Silicate 100), 2.7% by weight acrylic resin (Mitsubishi Chemical Corporation; Corponil N2147), 2.7% by weight ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), and 3.0% by weight ketone resin (Wally Co.; Polyton K-97). Volume: 5.28 m³ 3 A drying oven was used. The material was kept in a heating temperature of 100-120°C for 20-50 seconds to create an adhesive layer 16 with a thickness of 1 μm to 2 μm.

[0163] As described above, pigments are used as colorants in the resin-based protective layer 14. The pigments used are: 1.9% by weight of iron particle yellow pigment (Mikuni Pigment Co., Ltd.: 8197M), 3.75% by weight of iron particle red pigment (Mikuni Pigment Co., Ltd.: 8196M), 0.9836% by weight of red pigment (DiPont: Shinshaka Red B), and 0.9340% by weight of yellow pigment (BASF: Paliotol Yellow 1070). Here, solvent-soluble dyes are used to produce the desired color in the preparation. The comparison is based on solvent solubility, and the goal is to find a way to obtain identical results when comparing the metallic reflection characteristics of the metal layer 15 when dyes are used versus when pigments are used, when applied to the resin-based protective layer 14. The preparation of the resin-based protective layer 14 using dyes was formulated as described above. The dyes used were yellow dye: 0.0375% by weight (Chuo Gosei Kagaku Co., Ltd.: Yellow93) and orange dye: 0.025% by weight (Chuo Gosei Kagaku Co., Ltd.: Orange826N), used as substitute colorants for pigments. The transfer lamination of the base film 11, release layer 13, resin-based protective layer 14, metal layer 15, and adhesive layer 16 was carried out using the same configuration as described above.

[0164] In the resin-based protective layer 14, the color development from the surface layer when dyes are used as described above is confirmed. Coloration in the resin-based protective layer 14 (metallic gold color when dye is used) Gold coloration of resin-based protective layer 14 using dyes Laminated base film 11, release layer 13, resin-based protective layer 14 (coloring is done using dyes), metal layer 15

[0165] The details of the photograph shown in Figure 18 are as follows: Dye coloring surface (gold coloring) x20 enlargement Keyence microscope Using VHX-8000 Coaxial and ring-shaped incident light sources Vision from the delamination layer side

[0166] The details of the photograph shown in Figure 19 are as follows: Dye coloring surface (gold coloring) x40 enlargement Keyence microscope Using VHX-8000 Coaxial and ring-shaped incident light sources Vision from the delamination layer side

[0167] The details of the photograph shown in Figure 20 are as follows: Dye coloring surface (gold coloring) x2500 magnification Keyence microscope Using VHX-8000 Light source ring incident light source Vision from the delamination layer side P2: Dye dissolving part P3: Core of dye-dissolved residue Color development of resin-based protective layer 14 using dyes (dye preparation) Transfer laminate structure: release layer 13, resin-based protective layer 14, metal layer 15 Figure 21 shows the position of lightness, color, and hue (indicated by X marks). L*a*b Brightness Red Yellow Dye coloration L 84.59 Spectral reflectance of Al (lightness) a -1.09 hue saturation b 22.10 Hue Saturation Spectrocalorimeter measurement Nippon Denshoku Industries Co., Ltd. SZS-Σ90 JISZ8781-4 Spatial chromaticity L*a*b Thickness of resin-based protective layer: 1 μm Solid content of compounded medicine (%) 25% by weight Preparation coloring material content 5~10% by weight Color development using the above dyes

[0168] In the resin-based protective layer 14, the color development from the surface when the above-mentioned pigment is used is confirmed. Coloration in the resin-based protective layer 14 (metallic gold color using pigment) The golden coloration of the resin-based protective layer 14 using pigments. Lamination: Release layer 13, resin-based protective layer 14 (coloring is done using pigments), metal layer 15

[0169] The details of the photograph shown in Figure 22 are as follows: Pigment coloring surface Vision from the delamination layer side x20 enlargement Coaxial and ring-shaped incident light sources Keyence microscope Using VHX-8000

[0170] The details of the photograph shown in Figure 23 are as follows: Pigment coloring surface Vision from the delamination layer side x40 enlargement Coaxial and ring-shaped incident light sources Keyence microscope Using VHX-8000

[0171] The details of the photograph shown in Figure 24 are as follows: Vision from the delamination layer side x2500 magnification Light source: Single ring incident light source Keyence microscope Using VHX-8000

[0172] The details of the photograph shown in Figure 25 are as follows: Light source: Single ring incident light source Keyence microscope Using VHX-8000 In this photograph, the particle size (nm) of the pigments is as follows: [1] 510nm [2] 330nm [3] 380nm [4] 420nm [5] 450nm [6] 380nm The average particle size mentioned above is 410 nm. Color development of resin-based protective layer 14 using pigments (pigment formulation) Release layer 13, resin-based protective layer 14, metal layer 15 Position of lightness, color, and hue (indicated by an X mark) L*a*b Lightness Red Yellow Pigment Color L 81.33 Spectral reflectance of Al (lightness) a -0.16 hue saturation b 24.37 hue saturation Spectrocalorimeter, Nippon Denshoku Industries Co., Ltd. SZS-Σ90 JISZ8781-4 Spatial chromaticity L*a*b Thickness of resin-based protective layer: 1 μm Solid content of compounded medicine (%) 25% by weight Preparation coloring material content 5~10% by weight

[0173] In the resin-based protective layer 14 of the transfer laminate, it was found that the coloration and state of the coating surface differed depending on whether dyes or pigments were used. In the case of dye use, traces of dissolved and undissolved dye residue were observed, but in terms of light transmittance of the coating film and light reflectivity of the metal layer, the spatial chromaticity was L=84.59, indicating that the reflectivity of the metal layer (using Al) was maintained.

[0174] In the resin-based protective layer 14 of the transfer laminate, it was found that the coloration of the coating surface differed depending on whether dyes or pigments were used. When pigments were used, the light transmittance of the coating film and the light reflectivity of the metal layer were L=81.33 in terms of spatial chromaticity, maintaining the reflectivity of the metal layer (using Al).

[0175] In terms of color hue range, the spatial chromaticity of the dyes is a=-1.09 and b=22.10.

[0176] In terms of color and hue range, the spatial chromaticity of the pigments is a=-0.16 and b=24.37.

[0177] In the color contrast measured by the spectrocalorimeter and the spatial chromaticity L*a*b* results, the color produced by dyes and pigments, and the spatial chromaticity in the resin-based protective layer 14, show approximate values ​​for light reflectivity and spatial chromaticity, as previously described. The color difference is then confirmed through comparison. [Table 2]

[0178] When confirming the light transmittance of the resin-based protective layer 14 and the light reflectivity of the metal layer 15 (Al layer), the above ΔE, as determined from the photograph, shows that the dye-used surface is superior in light transmittance and reflection. However, on the pigment-forming surface, the dispersion state and aggregation of the pigment create unique connections due to the kinetic energy between particles, forming secondary aggregates. This creates spaces and ensures the incidence of light paths. Even in light reflection, reflected light is emitted from the pigment aggregation spaces. The incoming and outgoing light hitting the pigment aggregates emits scattered light of the pigment's color, resulting in coloration. The amount of pigment added determines whether the spatial areas are formed as aggregation areas. The multiplicity of secondary aggregates of pigment particles can be controlled by adjusting the concentration of the resin-based protective layer 14. Pigments of 1 nm or larger can be used, and a transfer foil with a laminate that maintains a colored state that obtains transmittance similar to that of the dye added to the resin-based protective layer 14 can be composed. The resin-based formulation and pigment used in the resin-based protective layer 14 have the same composition as described above. The characteristics of the color development of dyes and pigments are that dyes can provide both color development and transparency, while pigments can provide both color development and opacity. In the use of pigment formulations, the primary focus is on coloring that prioritizes opacity. The main purpose of this invention is to utilize the repulsive force of pigment particles to form pigment aggregates in a gravure coating film, thereby creating spatial regions. This allows light to enter and exit the film in these spatial regions, returning the reflected light from the metal layer 15 after the resin-based protective layer 14, and exhibiting scattered light and metallic color development equivalent to that of dyes. The images shown are comparative photographs of the above using dyes, pigments, and the above using the above as a coloring agent. Regarding means for aligning the spatial areas of pigment particles in the resin-based protective layer 14 (1) The repulsive force of the pigment is fixed and maintained during the first curing process. (2) Damping is stopped by adding an additive to the repulsive force. (3) Measures are taken to stop the secondary aggregation of pigment dispersion and to maintain spatial area. (4) Creating spatial areas for pigment particles and aligning the network are achieved by repulsive forces, and maintaining the structure is achieved by adding a film-forming agent to isolate the particles. (5) For the resin-based protective layer 14, one-component, two-component, and three-component formulations are prepared. (6) The resin-based protective layer 14 is provided with various curing means such as resin. (7) The resin-based protective layer 14 has the property of pigments to aggregate and adhere to the porous rings. (8) The size of the vacancy rings in the fabricated film is adjusted by adding a glass transition temperature. (9) The size of the porous rings in the film is adjusted by adjusting the inter-crosslinking chains. The following elements were used to formulate the resin-based protective layer 14 using a gravure printer. The composition of the film-forming elements is as described above. [Table 3]

[0179] Comparison of the use of colorants, dyes, and pigments in resin-based protective layer 14. A photograph comparing the reflected light from a metal layer on a surface colored using dyes and a surface colored using pigments. The color development of dyes and pigments is measured, and the reflected light is compared as brightness.

[0180] The details of the photograph shown in Figure 27 are as follows: Formation of a resin-based protective layer 14 and a metal layer 15 in the case of coloring with dyes, and viewing from the top of the film. Visual rendering from the surface of the transfer layer Light source: Coaxial ring incident radiation Keyence microscope VHX-8000 used x20 There are areas where the dye dissolved and traces of residue are visible.

[0181] The details of the photograph shown in Figure 28 are as follows: Formation of a resin-based protective layer 14 and a metal layer 15 in the case of coloring with pigments, and viewing from the top of the film. Visual rendering from the surface of the transfer layer Light source: Coaxial ring incident radiation Keyence microscope VHX-8000 used x20 Pigment aggregates were observed. Regarding the above two points, the color former of the resin-based protective layer 14 of the transfer laminate is compared with each dye and pigment. The reflected light of the metal layer (when Al is used) is measured for light reflection using the lightness term in the International Commission on Illumination (CIE), JIS Z8781-4 space colorimetry L*a*b*, and the hiding power of the color formers of the dye and pigment is compared. The measuring instrument uses a spectrocolorimeter, the SZ-Σ90 of Nippon Denshoku Industries Co., Ltd. The transfer laminate is as described above

[0182] The lamination up to the metal layer (using Al material) is carried out from the upper part of the base film. The film thickness of the resin-based protective layer 14 is 1 μm, the solid content of the formulation is 25% by weight, and the color former content of the formulation is 5 - 15% by weight. When using a dye, the reflectance lightness L = 84.59 When using a pigment, the reflectance lightness L = 81.33 From these results, the light reflectance when using a pigment is in the vicinity of the light reflectance with light transmittance when using a dye. This indicates that in the aggregated state where the pigment colors, it does not inhibit or form hiding of the light reflection of the metal layer.

[0183] [Experiment 3] Make a laminate of the structure of the transfer foil. The base film 11, release layer 13, resin-based protective layer 14, metal layer 15, and adhesive layer 16 are configured to form a transfer foil laminate. Regarding the mesh structure of the resin-based protective layer 14.

[0184] In the formulation of the resin-based protective layer 14, a pigment is used as a color former. Using pigment particles, a pore structure is created to enable the entry and exit of light, and through the light reflection path from a reflective base material such as a metal layer, a manufacturing method has been found that can form light reflection, light absorption, and light diffusion of the colorant pigment within the resin-based protective layer 14. It becomes a transfer laminate using pigment particles with color formation and light reflectance. It has found a means to eliminate the light hiding power of the pigment film formation of the color former and obtain the means of the light reflectance of the color forming means and the metal layer, resulting in a metallic color formation using a pigment material. When colorants and pigments are used in paints, the resulting film has opacity from light, and the resulting color cannot be expressed from the substrate. The transfer laminate structure of the present invention uses a pigment as a colorant in a resin-based protective layer 14. A metal layer is then provided, but if the resin-based protective layer is formulated using a general-purpose pigment, the metal layer is obscured and the metallic luster is not retroreflected to the surface of the transfer laminate. The reflection of the metal layer is neutralized. In contrast to this situation, the newly discovered method is a laminate structure that uses a pigment as a colorant and allows light incidence to the metal reflective layer and retroreflection of light. Furthermore, a means has been found for the light source to return to the surface of the transfer laminate as reflected light via the metal layer. This has resulted in the creation of a mechanism that allows for coloring by pigment or other particles in the resin-based protective layer 14 and the emission of reflected light from the metal layer.

[0185] The pigment-forming film of the resin-based protective layer 14 is formed into a network structure by irreversibly agglomerating it. By finding a link between the resin-based film structure and the agglomeration properties of particles such as pigments, a network structure is created in the film, forming a spatial region. This spatial region is light-transmitting. This transparent portion allows light and light sources to enter and exit. When a post-processing metal layer is applied, the network structure of the resin-based protective layer allows reflected light from the metal vapor-deposited film of the light source to pass through and be guided to the upper part of the transfer layer. Furthermore, because the alignment of pigments and particles in the network structure of the resin-based protective layer is in a fine form, and when reflected light from the metal layer passes through the pores of the network structure, light irradiation of the pigments occurs as it passes through the network structure formed by the pigments, and scattered light such as reflected and retroreflective light is emitted from the pigment surface. When light enters and exits, the pigment body walls absorb and reflect light in multiple directions, leading to color development and obtaining a metallic color.

[0186] A transfer laminate is constructed comprising a base film 11, a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16. A transfer laminate with a color-developing structure and a metallic feel is created. All layers except the resin-based protective layer are treated according to the previously described formulation. In the resin-based protective layer 14, a composition that combines both color-developing and metallic-feeling properties is realized in the coating film, as described below.

[0187] The formulation for the resin-based protective layer 14 is as follows. Using a gravure printing machine, the coating is applied and dried, and a 1 μm thick layer is formed and dried at 160°C for a 20-40 second stay in a 15 m long drying oven using far-infrared heating and a hot air heating device. The coating solution was prepared as follows. A one-component and a two-component coating solution were prepared. After preparation, the one-component and two-component solutions were mixed. The one-component solution serves as the core material for creating the network structure. The two-component solution is formulated to maintain the dispersion of the pigment and release the aggregated state, maintaining a diffusive mixed state. The film formation of the two-component solution is configured to undergo primary curing, which occurs when the coating is heated, and secondary curing, which progresses over time with a curing period.

[0188] This formulation is used for the resin-based protective layer 14. A one-component formulation, a two-component formulation, and a three-component formulation are prepared. The one-component formulation is a formulation that acts as a nucleating agent for the formation of a network-structured coating. The two-component formulation is a formulation for creating the cured resin-based protective layer. The three-component formulation is a mixture of the one-component and two-component formulations. The one-component and two-component formulations are prepared individually, but after preparation, they are combined to form the three-component formulation.

[0189] In primary curing, the composition of the amino-based resin and acid is important. The degree of curing of the resin-based protective layer film is set to 50%. The composition of the one-component compound is prepared. Mix 31% by weight of toluene (Idemitsu Kosan Co., Ltd.), 19% by weight of methyl ethyl ketone (Idemitsu Kosan Co., Ltd.), 17% by weight of methyl isobutyl ketone (Mitsubishi Chemical Holdings), 0.06% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 17% by weight of acrylic resin (Alpha Kaken Co., Ltd.: Acrylic silicone silicate resin: UVHA), 2% by weight of melamine resin (Nippon Carbide Co., Ltd.: MS-001), 3% by weight of flexibility and heat resistance imparting agent (Daicel Fils Co., Ltd.: Toluene sulfonamide: MPY720), 0.12% by weight of interface inducer / dispersant (Mitsui Oil Co., Ltd.: Ethylene-α-olefin oligomer: A-5515), 7% by weight of acrylic ladder silicone resin (Showa Denko K.K.: LS-230), and 1.4% by weight of void nucleating agent (Colcoat Co., Ltd.: Ethyl silicate HAS-1), and stir and granulate for 30 minutes at high speed using a bladed agitator. The volume may be increased. The above amount will be used as the standard for the one-component mixture. Combination will be carried out with an amino-based resin and an acid. The acid will be used in conjunction with the two-component mixture. For primary curing, the three-component mixture, a combination of the one-component and two-component mixtures, will be allowed to proceed to a film with a curing degree of 50% in actual gravure printing.

[0190] Prepare a two-component compound. Toluene 28% by weight (Idemitsu Kosan Co., Ltd.), methyl ethyl ketone 17% by weight, methyl isobutyl ketone 15% by weight, ethylene glycol 1% by weight, acrylic resin 11% by weight (Nippon Shokubai Co., Ltd.: UV-G301), acrylic resin 0.6% by weight (Wilbur Ellis Company: Paraloid AT-740), ketone resin 4% by weight (Wally Company: Polyton K-97), UV absorber 0.07% by weight (BASF: Tinuvin 1600), UV absorber 0.07% by weight (BASF: Tinuvin 249), light blocking agent 0.07% by weight (Tokyo Chemical Industries, Ltd.: Phenyl salicylate), curing agent 0.07% by weight (Tokyo Chemical Industries, Ltd.: p-toluene) A mixture of sulfonic acid, polyvinyl chloride copolymer resin (3% by weight: Earth Corporation: Earth Enabond #380), hardening agent, fracture shearing agent (4% by weight: Nippon Chemical Corporation: Triallyl isocyanurate), isocyanate (1.5% by weight: Hürss: Isophorone diisocyanate: T-1890), iron particle yellow pigment (1.7% by weight: Mikuni Pigment Co., Ltd.: 8197M), iron particle red pigment (3.5% by weight: Mikuni Pigment Co., Ltd.: 8196M), red pigment (1.7% by weight: DiPont: Shinshaka Red B), yellow pigment (0.3% by weight: BASF Paliotol Yellow), and reaction accelerator (0.35% by weight: Kusumoto Chemical Co., Ltd.: Organic bismuth compound) was used as the basis for the two-component formulation.

[0191] Mix the above 1-component and 2-component formulations and stir them using a mixer with blades at room temperature for 20 to 40 minutes. The resulting mixture will be the 3-component formulation.

[0192] As a three-component compound, the following components contribute to the formation of the pores: primary curing with amino resin and acid to reach 50% curing, secondary curing with isophorone diisocyanate and organic bismuth compound to allow for curing time, curing progression with acrylic ladder silicone resin, curing progression with hydroxyl group attachment of acrylic resin, nucleating agent for the network structure with ethyl silicate, nucleating agent for the network structure with acrylic resin-based acrylic:silicone:methyl silicate, ethylene-α-olefin oligomer which maintains the pores of the network structure, and toluenesulfonamide which attaches to the silicate ring and adsorbs pigment particles. These components form a network structure, causing pigment to adhere to the pore frame, organizing the dispersion and aggregation of pigment particles, and maintaining the pores.

[0193] To create a spatial structure in the resin-based protective layer and observe the alignment of pigments and the generation of color, the following composition is carried out: A material with a network structure is selected for the coating agent to adhere and fix the dispersion of pigments. Secondary aggregation of pigments is restricted to create voids. With a pigment particle size of ~500 nm and voids of ~40 μm, the screen ruling and depth of the gravure printing machine are selected, and the dispersion and aggregation of pigments on the network structure are controlled using the far-infrared heater and hot air drying means attached to the gravure printing machine's drying oven. This enables the formation of a network structure film and the alignment of pigments, resulting in light entry and exit into the spatial areas, reflection, color scattering of pigments, and generation of a metallic feel.

[0194] The above three-component mixture is coated as a resin-based protective layer 14 using a gravure printing press. The process involves a gravure machine drying oven 15m, a heat source equipped with a far-infrared heater and a hot air device, with an oven temperature of 140-210°C, an oven stay time of 20-60 seconds, a grid-type engraved roll plate making of 180 lines, a plate depth of 40-60 μm, and a film thickness of 0.5-8 μm / dry.

[0195] By treating the resin-based protective layer 14 with a three-component compound, a transfer laminate consisting of the base film 11, release layer 13, resin-based protective layer 14, metal layer 15 (using Al material), and adhesive layer 16 is fabricated. The base film 11 is a polyester film #12μm thick. In all cases, visual confirmation is performed from the top of the film side. Vacancies of the colorant pigment in the resin-based protective layer 14 (Use of pigment) Gold coloration of the resin-based protective layer 14 using a pigment Release layer 13 + Resin-based protective layer 14 + Metal layer 15 Vacant spaces are appearing in parallel with the pigment.

[0196] The details of the photograph shown in Fig. 29 are as follows. Vacant spaces are generated in the pigment layer Keyence microscope Using VHX-8000, single-sided illumination of the light source link Pigment of the resin-based protective layer Dispersion state of the liquid mixture coating film Detection of vacant spaces

[0197] The details of the photograph shown in Fig. 30 are as follows. Confirmation of the particle size of the pigment particles Keyence microscope Using VHX-8000, single-sided illumination of the light source link In this photograph, the particle size (nm) of the pigment is as follows. [1] 510 nm [2] 330 nm [4] 420 nm [6] 380 nm The particle size is 330 - 510 nm.

[0198] The details of the photograph shown in Fig. 31 are as follows. Mesh structure of the pigment alignment Length of the spatial domain Keyence microscope Using VHX-8000, double-sided illumination of the light source link x80 In this photograph, the mesh length (μm) is as follows.

[19] 50 μm

[20] 30 μm

[21] 70 μm

[22] 40 μm

[23] 40 μm

[24] 40 μm The length of the spatial domain is 30 - 70 μm.

[0199] The details of the photograph shown in Figure 32 are as follows: Color development and metallic feel of the pigment layer (using a metal vapor-deposited layer of aluminum) Surface layer confirmation using incident light from a light source (pigment) Keyence microscope Single incident light source using VHX-8000 Actual size

[0200] The details of the photograph shown in Figure 33 are as follows: Color development and metallic feel of the pigment layer (using aluminum in the metallic layer) Confirmation of metallic appearance by reflected light (pigment) Keyence microscope Using VHX-8000, reflected light source x40 Confirmation by spectrocalorimeter Nippon Denshoku Industries Co., Ltd. SZS-Σ90 JISZ8781-4 spatial chromaticity L* 81.33 a* -0.16 b* 24.37

[0201] A method for forming a metallic-looking transfer foil by setting the spatial arrangement using pigments as colorants for transfer lamination, thereby obtaining the light reflectivity of the metal layer. The pore area of ​​the resin-based protective layer in the transfer laminate is set using pigment concentration, particle size, and film thickness in the color formulation. Pigments were used as the colorants. Experiments revealed that the selection and addition state of the colorant pigment particles during film formation of the resin-based protective layer 14, as well as the film formation method, are involved in obtaining a color with excellent metallic feel through the light reflectivity of the metal film in the transfer laminate that supports the metal layer. The composition of the transfer laminate used in the experiment consisted of a base film 11, a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16. Pigments were selected as the colorants in the formulation of the resin-based protective layer 14. The transfer laminate with metallic luster obtained from the metal layer, in conjunction with the color of the colored layer containing the pigment layer, was confirmed by utilizing the light reflectivity of the metal layer 15 (using Al material). In resin-based protective layers, the range of coloration using pigments and the range of film formation using metal layers (Al) In the base film 11, release layer 13, resin-based protective layer 14, metal layer 15, and adhesive layer 16, the color effect was confirmed based on the amount of pigment used in the resin-based protective layer 14 and the pigment occupancy rate based on the light reflectance of the metal layer. The formulation of the resin-based protective layer 14 follows the description for the three-component formulation. Measure the spatial color lab. L=*81.33, a=*-0.16, b=*24.37 Based on a pigment particle size of 380-400 nm and an air gap length of 30-40 μm in the resin-based protective layer, the formulation used should be based on the three-component formulation used when pigment particles are utilized. Table 4 shows the details of each item in the resin-based protective layer 14 and the metal layer 15. [Table 4]

[0202] 1: Appropriate value for pore length, based on a 66.4% pore ratio in the mesh structure of the aggregated space resin protective layer. 2: Pigment addition amount: Based on the amount of pigment added to the three-component formulation of the resin-based protective layer (303.0g), adhesion to the void ring. 3: Opening of voids, based on a metal layer reflection aggregation space of 66.4%. 4: Based on a 30% pigment reflection rate. 5: Pigment particle size based on a particle size of 450 nm. 6: Use a color difference of L=*81.33, a=*-0.16, and b=*24.37 as the base (spatial chromaticity L*a*b*). 7: Use a color difference of L=*81.33, a=*-0.16, and b=*24.37 as the base (spatial chromaticity L*a*b*). 8: Use a color difference of L=*81.33, a=*-0.16, and b=*24.37 as the base (spatial chromaticity L*a*b*). [Explanation of Symbols]

[0203] 10, 20, 30: Transfer foil 11: Base film 12,21: Transfer Lamination 13: Exfoliation layer 14,17,23: Resin-based protective layer 15: Metal layer 16: Adhesive layer 22: Film protective layer

Claims

1. A base film and Equipped with transfer lamination, The aforementioned transfer layering is A release layer formed on the base film, A first resin-based protective layer is formed on the release layer and has a mesh-like three-dimensional structure including linear portions and voids formed between the linear portions, A metal layer formed on the first resin-based protective layer, A transfer foil comprising an adhesive layer formed on the metal layer.

2. A transfer foil according to claim 1, The first resin-based protective layer is a transfer foil containing a coloring agent.

3. A transfer foil according to claim 2, The colorant is a transfer foil containing a pigment having a particle size of 2 nm or more.

4. A transfer foil according to claim 1, The aforementioned transfer stacking further, A transfer foil comprising a second resin-based protective layer formed between the release layer and the first resin-based protective layer.

5. A transfer foil according to claim 4, The transfer foil has a second resin-based protective layer having a mesh-like three-dimensional structure including linear portions and voids formed between the linear portions.

6. A transfer foil according to claim 1, The aforementioned transfer stacking further, A transfer foil comprising a third resin-based protective layer formed between the metal layer and the adhesive layer.

Images