Transfer foil

Abstract

To provide a transfer foil capable of preventing cracking, breaking, blistering, or the like.SOLUTION: A 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 an adhesive layer 16 formed on the resin-based protective layer 14. The resin-based protective layer 14 contains a plasticizer.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] A transfer foil for surface decoration of a resin molded article formed by a hot press transfer method or the like includes a protective layer, a release layer, a resin-based protective layer or a color-forming resin-based protective layer, a metal vapor deposition layer, a resin-based protective layer, and an adhesive layer, which are sequentially formed on a base film. Each layer is selectively formed, and the resin-based protective layer, the color-forming resin-based protective layer, etc. are formed by applying them in a superposed manner together. According to the hot press transfer method, a film having a transfer laminate is placed on a transfer object with the adhesive layer facing it, pressure and heat are applied by a hot press transfer device from the base film side, and after the transfer laminate is transferred, the base film is peeled off. As a result, the surface of the transfer object is transferred by the transfer laminate (modified laminate), and the transfer object becomes a decorated product decorated by the transfer laminate.

[0003] In a resin molded article or the like, as a surface decoration method, a transfer foil having a release layer, a resin-based protective layer, a metal vapor deposition layer, and an adhesive layer stacked on a base film to form a transfer laminate is produced, and the surface layer of various transfer objects such as resin molded articles is decorated by hot press transfer means.

[0004] Using a transfer foil having the above laminate on a base film, an adhesive layer is combined with the surface layer of a resin molded article or the like as a transfer object, and from the base film side, by a transfer machine. Select an image heating medium such as a rubber roll plate, a metal flat plate 30, or a relief plate 40, apply pressure and heat, and transfer the transfer laminate composed of a release layer, a resin-based protective layer, a metal vapor deposition layer, and an adhesive layer onto a resin molded article or the like, or onto metals, glasses, woods, fibers, papers, or rubbers, and then remove the base film. As a result, transfer to the surface decoration on a transfer object such as a resin molded article can be achieved, and the surface decoration of the material can be modified.

[0005] Japanese Patent Application Laid-Open No. Sho 56-53086 (Patent Document 1) discloses a transfer foil for protecting a transfer object in 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 coloring layer formed on the second protective layer, and an adhesive layer formed on the coloring layer. The coloring layer contains a thermoplastic acrylic resin, a synthetic rubber, and a vinyl chloride-based resin. The curable first and second protective layers and the plastic coloring layer and adhesive layer are laminated. At the interface between the second protective layer and the coloring layer, when the transfer object and the transfer foil are about to stretch or contract during transfer or over time, considering the elasticity of each layer as a transfer load at the interface between the curable film of the protective layer and the plastic film of the coloring layer, the layer constituting the protective film against the reversible elasticity and shrinkage of the synthetic rubber incorporated in the coloring layer is set as a curable film. Regarding the followability of the curable film of the protective layer to the shrinkage of the coloring layer, there remains a problem in avoiding the influence on film breakage.

[0006] Also, a general-purpose transfer foil has the following configuration. Taking an example of a transfer foil, in a transfer foil including a release layer, a protective layer, a coloring layer, a metal vapor deposition layer, and an adhesive layer with respect to a base film, various defects exist both during transfer and over time after transfer. Defects occurring during thermocompression transfer include poor transfer film breakage accuracy, cracks, fractures, poor interlayer adhesion, and poor transfer heat resistance. Regarding the changes occurring over time after transfer, peeling, cracking, swelling, etc. are generated as being affected by the temperature, humidity, etc. of the environment under exposure. There is also a possibility of fading degradation due to light.

[0007] According to the thermal transfer method using a transfer machine, heating and pressing cause loads on the base film, release layer, resin-based protective layer, color-forming resin-based protective layer, metal vapor deposition layer, resin-based protective layer, adhesive layer, etc. There are differences in response due to the stretching, contraction, and pressure applied during the transfer of the transfer laminate and the object to be transferred. Resin-based layers are prone to stretching, while metal layers are difficult to stretch. The stretching of the resin-based layer subjects the metal layer to tensile stress, and the metal layer with a high elastic modulus undergoes cohesive failure, resulting in cracks, breaks, bulges, etc. This defect impairs and attenuates the brightness of the metal vapor deposition layer as a light reflection layer. There is a risk of impairing the decorative glossiness.

[0008] In terms of peeling the transfer layer from the base film, as a layer through the film, it shows a peeling effect by making the heat pressure absorption sensitive during the heat pressure propagation and reducing the thermosensitivity and pressure sensitivity. The adhesive layer selectively employs a resin that is excellent in low-temperature sensitization with heat and pressure to function. In the resin-based protective layer, the resistance of the film is enhanced to eliminate the physical and chemical effects on the transfer surface layer after transfer. The color-forming resin-based protective film contains a color former, forms a film structure that exhibits a color-forming effect and prevents fading and discoloration. The metal vapor deposition layer has a metallic luster as a film reflection of the deposited layer of the metal used as a metallizing effect, or there are those with an island-like dispersed film formation or a multilayer film formation. The release layer and the adhesive layer are shifted to lower temperatures, while the protective layer, vapor deposition protective layer, and vapor deposition layer are shifted to higher temperatures. As a result, the stretching and contraction of the transfer laminate, including the base film, due to the heat pressure propagation caused by thermal transfer are not uniform. The load on the highly elastic metal vapor deposition layer increases, leading to cracks, breaks, bulges, etc. in the transfer layer, and there is a risk of progressing to a decrease in brightness and attenuation of gloss.

[0009] When the ductility of the metal in the metal vapor deposition layer is low, the cohesion of the metal layer is destroyed by the elongation that occurs in the transfer laminate formed on the transfer layer during transfer. Therefore, cracks, breaks, and bulges occur in the transfer layer with the modified laminate. When the ductility of the resin-based protective layer is high, the influence on the cohesion of the metal vapor deposition layer can be mitigated. However, tensile stress acts on the metal layer due to the elongation of the protective layer caused by heating and pressurization during transfer, and as a result, breakability occurs, leading to a decrease in the gloss and brightness of the modified laminate.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] An object of the present invention is to provide a transfer foil capable of preventing the occurrence of cracks, breaks, bulges, etc.

Means for Solving the Problems

[0012] The transfer foil according to the present invention includes 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 an adhesive layer formed on the first resin-based protective layer. The first resin-based protective layer contains a plasticizer.

Brief Description of the Drawings

[0013]

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Mode for Carrying Out the Invention

[0014] [Outline of Embodiment] The transfer foil according to an embodiment of the present invention includes 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 an adhesive layer formed on the first resin-based protective layer. The first resin-based protective layer contains a plasticizer.

[0015] According to this transfer foil, since the first resin-based protective layer contains a plasticizer, the release layer, the first resin-based protective layer, and the adhesive layer can stretch in synchronization with the transfer. As a result, the occurrence of cracks, cracks, bulges, etc. can be prevented.

[0016] The transfer laminate may further include a metal layer formed between the first resin-based protective layer and the adhesive layer.

[0017] The transfer laminate may further include a second resin-based protective layer formed between the metal layer and the adhesive layer.

[0018] The transfer foil may further include a film protective layer formed between the base film and the release layer.

[0019] In this case, the second resin-based protective layer functions as a compounding agent layer that raises the resistance of the metal layer.

[0020] The plasticizer includes one or more selected from the group consisting of, for example, chlorinated paraffin, butyl adipate, 2-ethylhexyl adipate, dioctyl adipate, 2-ethylhexyl azelate, phthalic acid esters, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, citrate esters, the ester of succinic acid and triethylene glycol monomethyl ether, the ester of adipic acid and diethylene glycol monomethyl ether, tricarboxylic acid esters such as trioctyl trimellitate, the ester of 1,3,6-hexanetricarboxylic acid and butyl diglycol, tricresyl phosphate, triphenyl phosphate, tri-2-ethylhexyl phosphate, trixylenyl phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxidized linseed oil, epoxyoctyl stearate, epoxidized fatty butyl, butyl epoxidized linseed oil fatty acid, trimellitic acid ester, pyromellitic acid ester, sebacic acid ester, azelaic ester, maleic acid ester, benzoic acid ester, methyl adipate, butyl oleate, oxy acid ester, dibasic alcohol ester, aliphatic dibasic acid ester series, triphenyl phosphate, dinonylnaphthalene, tributyl acetyl citrate, P-toluenesulfonamide, toluenesulfonamide, toluenesulfonethylamide, aminobenzenesulfonamide compounds, aminotoluenesulfonamide compounds, N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, dinonylnaphthalene, tributyl acetyl citrate, and ethylene olefin oligomers.

[0021] The plasticizer preferably includes one or more selected from the group consisting of P-toluenesulfonamide, toluenesulfonamide, toluenesulfonethylamide, aminotoluenesulfonamide compounds, and N-ethyl-o-toluenesulfonamide.

[0022] The content rate of the plasticizer with respect to the first resin-based protective layer is, for example, 0.01 to 20 wt%. The preferable lower limit of the content rate is 0.1 wt%, and the more preferable lower limit is 1 wt%. On the other hand, the preferable upper limit of the content rate is 10 wt%, and the more preferable upper limit is 5 wt%.

[0023] The thickness of the first resin-based protective layer is, for example, 1 to 20 μm.

[0024] The first resin-based protective layer may contain one or more acrylic resins.

[0025] The first resin-based protective layer may contain a curing agent.

[0026] The first resin-based protective layer may contain a color former.

[0027] The color former may contain a pigment having a particle size of 10 to 120 nm. Here, the particle size is the geometric mean particle size obtained by averaging the major axis diameter and the minor axis diameter.

[0028] The first resin-based protective layer may contain a light stabilizer.

[0029] The first resin-based protective layer may contain an ultraviolet absorber.

[0030] [Details of Embodiment] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and the description thereof will not be repeated.

[0031] [Embodiment 1] As shown in FIG. 1, the transfer foil 10 according to Embodiment 1 includes a base film 11 and a transfer laminate (hereinafter, may be referred to as a “modifying laminate”). The transfer laminate 12 includes a release layer 13 formed on the base film 11, a resin-based protective layer (hereinafter, may be simply referred to as a “protective layer”) 14 formed on the release layer 13, 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.

[0032] [Embodiment 2] As shown in FIG. 2, the transfer foil 20 according to Embodiment 2 includes 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 14 formed on the release layer 13, 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, a film protective layer 22 formed between the base film 11 and the release layer 13 and another resin-based protective layer 23 formed between the metal layer 15 and the adhesive layer 16.

[0033] [Other Embodiments] Although the transfer foils 10 and 20 described above include the metal layer 15, the metal layer 15 may not be provided.

[0034] Hereinafter, taking the transfer foil 10 according to Embodiment 1 as an example, its details will be described. However, unless otherwise particularly restricted, the description is also applicable to the transfer foil 20 according to Embodiment 2.

[0035] The plasticizer is not particularly limited, and includes one or more selected from the group consisting of chlorinated paraffin, butyl adipate, 2-ethylhexyl adipate, dioctyl adipate, 2-ethylhexyl azelate, phthalic acid ester, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, citrate esters, ester of succinic acid and triethylene glycol monomethyl ether, ester of adipic acid and diethylene glycol monomethyl ether, tricarboxylic acid esters such as trioctyl trimellitate, ester of 1,3,6-hexanetricarboxylic acid and butyl diglycol, tricresyl phosphate, triphenyl phosphate, tri-2-ethylhexyl phosphate, trixylenyl phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxidized linseed oil, octyl epoxidized stearate, epoxidized fatty butyl, butyl epoxidized linseed oil fatty acid, trimellitic acid ester, pyromellitic acid ester, sebacic acid ester, azelaic ester, maleic acid ester, benzoic acid ester, methyl adipate, butyl oleate, oxyacid ester, dibasic alcohol ester, aliphatic dibasic acid ester series, triphenyl phosphate, dinonylnaphthalene, tributyl acetylcitrate, p-toluenesulfonamide, toluenesulfonamide, toluenesulfonethylamide, aminobenzenesulfonamide compound, aminotoluenesulfonamide compound, N-butylbenzenesulfonamide, N-ethyl-o(ortho)-toluenesulfonamide, dinonylnaphthalene, tributyl acetylcitrate, and ethylene olefin oligomer.

[0036] The content rate of the plasticizer with respect to the resin-based protective layer 14 is not particularly limited, but is 1 to 20% by weight. The thickness of the resin-based protective layer 14 is not particularly limited, but is 1 to 20 μm. The resin-based protective layer 14 contains, although not particularly limited, one or more acrylic resins. The resin-based protective layer 14 contains, although not particularly limited, a curing agent. The resin-based protective layer 14 contains, although not particularly limited, a color former. Hereinafter, the resin-based protective layer containing a color former may be particularly referred to as a "color-forming resin-based protective layer". The resin-based protective layer 14 contains, although not particularly limited, a light stabilizer. The resin-based protective layer 14 contains, although not particularly limited, an ultraviolet absorber.

[0037] The transfer foil 10 described above is transferred onto a transfer object using the transfer device shown in FIG. 3, FIG. 4 or FIG. 5. FIG. 3 is a schematic diagram showing plate making by an up-and-down type transfer foil press 31 using a lithographic plate 30. The foil press 31 transfers the transfer laminate 12 onto a transfer object 32 such as a soft vinyl chloride sheet by pressing the transfer foil 10 with the lithographic plate 30. FIG. 4 is a schematic diagram showing plate making by an up-and-down type transfer foil press 41 using a relief plate 40. The foil press 41 transfers the transfer laminate 12 onto a transfer object 32 such as a soft vinyl chloride sheet by pressing the transfer foil 10 with the relief plate 40. FIG. 5 is a schematic diagram showing plate making by a hot pressure transfer machine (hereinafter sometimes referred to as a "roll type transfer machine") 51 using a roll plate 50. The transfer laminate 12 is transferred onto a transfer object 32 such as a resin molded product by pressing the transfer foil 10 with the hot pressure transfer machine 51 and the roll plate 50.

[0038] The transfer foil 10 described above is manufactured using the gravure printing machine and the drying furnace shown in FIG. 6 or FIG. 7. FIG. 6 is a schematic diagram showing a gravure printing machine 60 and a first type drying furnace 61. FIG. 7 is a schematic diagram showing a gravure printing machine 60 and a second type drying furnace 62.

[0039] As shown in FIGS. 6 and 7, the gravure printing machine 60 includes a film unwinding unit 63, a film control roll 64, and a gravure coating head unit 65. Downstream of the gravure printing machine 60 shown in FIG. 6, a drying furnace type 1 furnace 61 is provided. The drying furnace type 1 furnace 61 includes a driving metal roll 66, an infrared heater 67, an exhaust device 68, and a hot air device 69. Downstream of the drying furnace type 1 furnace 61, a film control roll 70, a pressing device 71, a cooling device 72, and a film winding unit 73 are provided. Downstream of the gravure printing machine 60 shown in FIG. 7, a drying furnace type 2 furnace 62 is provided. The drying furnace type 2 furnace 62 includes an ultraviolet irradiation facility 74 in addition to the configuration of the above-described drying furnace type 1 furnace 61. Downstream of the drying furnace type 2 furnace 62, a film control roll 70, a pressing device 71, a cooling device 72, and a film winding unit 73 are provided.

[0040] In this embodiment, a transfer laminate 12 including a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16 is formed on the surface of the base film 11, and the transfer foil 10 for thermosensitive and pressure-sensitive transfer that can prevent cracks, breaks, swelling, and reduce fading with respect to the thermocompression transfer film for image decoration of the transfer object 32.

[0041] The release layer 13, the resin-based protective layer 14, and the adhesive layer 16 are formed by film formation using the gravure printing machine 60. The metal layer 15 is formed by film formation using a two-chamber semi-continuous vacuum deposition apparatus. As the vacuum deposition apparatus, for example, the apparatus shown in FIG. 4 of Japanese Patent Application Laid-Open No. 2002-192895 (Patent Document 2) can be used. The resin-based protective layer 14 prepared with a plasticizer is heated and hot air dried by the gravure printing machine 60 to form a film on the release layer 13, and the metal layer 15 and the adhesive layer 16 are formed. Since the resin-based protective layer 14 contains a plasticizer, flexibility is obtained. The dry film of the resin-based protective layer 14 formed on the release layer 13 is heated in the drying furnaces 61 and 62 of the gravure printing machine 60, annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled, whereby the film quality is modified from a hard one to a flexible one. Thereafter, the metal layer 15 and the adhesive layer 16 are formed into films.

[0042] Instead of the method described above, the transfer foil 10 can also be manufactured by the following method. After forming the metal layer 15 on the resin-based protective layer 14 containing a plasticizer, the laminated release layer 13, protective layer 14, and metal layer 15 are heated by the hot air device 69 of the drying furnaces 61 and 62, and an annealing process of heating and baking the laminated dry film is performed. By passing through the pressure device 71 and cooling device 72 outside the furnace connected to the drying furnaces 61 and 62, the resin-based protective layer 14 and the metal layer 15 become flexible from a hard film, and the interface between the resin-based protective layer 14 and the metal layer 15 progresses in bondability to obtain stretchability.

[0043] The transfer laminate 12 has a flat film structure, but it can also be manufactured to have a three-dimensional structure by coating through heating, hot air, pressure, and cooling using a gravure printing machine 60 or the like.

[0044] The transfer laminates 12 and 21, during hot press transfer, the release of residual stress during film formation, and during transfer, peeling, and fixing during hot press transfer, the influence on the transfer laminate 12 due to the base film 11, transfer laminate 12, transfer surface, structure, material, shape, etc. affects the metal forming film with low elasticity. Without being restricted by the aggregation structure of the metal in the metal deposition structure layer or metal island structure layer which is the metal layer 15, the influence on the aggregability of the metal layer 15 is manifested by the heat pressure propagation during transfer. The aggregation failure of the metal layer 15 is generated and appears in forms such as cracks, splits, and bulges. The generation on the metal layer 15 and the adjacent protective layer 14 leads to an influence on the decorativeness, a drop in brightness, and an acceleration of film deterioration.

[0045] The object of this embodiment is to avoid the above problems and improve the transfer ability of the transfer laminates 12 and 21. In this embodiment, a plasticizer is added and formulated into the resin-based protective layer 14, and heat treatment, hot air treatment, pressure treatment, and cooling treatment are performed using a gravure printing machine 60 or the like, and the drying furnace 1 type furnace 61 or 2 type furnace 62 of the gravure printing machine 60 is used. Since the resin-based protective layer 14 contains a plasticizer, the flexibility of the protective layer 14 exhibits affinity for the metal layer 15. During the process of bonding between the protective layer 14 and the metal layer 15, the flexibility of the plasticizer promotes the integration of the protective layer 14 and the metal layer 15, and the stretch resistance and shrink resistance of the protective layer 14 and the metal layer 15 are improved.

[0046] The elimination of the defect is also connected to the attenuation of luminance degradation. Further, if the particulate color former is made into fine particles and contained in the resin-based protective layer 14, the coloring effect and the reflectance of the metal layer 15 can be enhanced while maintaining the transparency of the protective layer 14. By selecting the particles, it is possible to obtain light resistance along with a metallic feeling with coloring, transparency, and metallic reflectivity.

[0047] Regarding the adhesive for forming the adhesive layer 16, an appropriate one is selected from various materials in consideration of adhesiveness, film breakability, and film stability.

[0048] Examples of the adhesive include polyacrylate 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, polyvinylidene chloride, cellulose resins, rosin resins, organic pigments, inorganic pigments, and the like.

[0049] Regarding adhesiveness, it is preferably selected from polypropylene-based, polyester-based, vinyl-based, etc. For the purpose of achieving film formation stability, a cellulose-based one is preferred. Regarding the film breakability of the adhesive layer 16, it is preferably selected from rosin-based, or organic, inorganic, or extender pigments.

[0050] The resin-based protective layer 14 preferably contains one or more acrylic resins and has weather resistance. Ultraviolet degradation by natural light causes a decrease in physical properties and a change in appearance. Due to direct solar radiation and scattered solar radiation, hydrogen atoms in the polymer and color former of the transfer laminate 12 are cleaved to generate radicals. The radicals combine with atmospheric oxygen to generate peroxy radicals. The peroxy radicals extract hydrogen atoms from the polymer to generate radicals and hydroperoxides. The hydroperoxides cause the polymer to deteriorate. To improve the resistance of the protective layer 14, ultraviolet shielding agents such as acrylic resins and inorganic pigments with a long-term expected shielding effect, ultraviolet 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 antioxidants that decompose hydroperoxides generated when peroxy radicals extract hydrogen atoms from the polymer are used. One of the acrylic resins contained in the formulation of the protective layer 14 contains an ultraviolet absorption group and an ultraviolet stability group (HALS) in the resin skeleton. After transfer, radicals are generated by light in the release layer 13, the resin-based protective layer 14, etc. on the surface layer, and a long-term shielding effect of ultraviolet light that inactivates active oxygen is expected. Another acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylic resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet light. Yet another acrylic resin has an attached reactive functional group and forms a crosslinked film with an amino resin and a catalyst to form a hard film.

[0051] The resin-based protective layer 14 is a thermosetting resin containing an amino resin, a curing agent, and an acrylic resin. The amino resin is selected from melamine-based resins. The curing agent is selected from organic acids or inorganic acids. Acrylic refers to acrylic or methacrylic. The acrylic resin is one to which an ultraviolet stabilizer (HALS) is added, one with functional groups such as a silyl group, an amino group, a methylol group, a hydroxyl group, an oxazolidine group, a cyclocarbonate group, a cyclocarbonate group, etc. attached thereto, a copolymer with trialkoxyvinylsilane, etc., an addition reaction with an isocyanate group or an unsaturated group, a reaction with an amine, and one selected from materials with an epoxy group, etc. attached thereto.

[0052] On the base film 11, a release layer 13 and a resin-based protective layer 14 containing a color former are formed by a gravure printer 60, and then a metal layer 15 is made by a two-chamber semi-continuous vacuum evaporation device. An adhesive layer 16 is formed thereon by the gravure printer 60 to produce a transfer foil 10 including a pressure-sensitive and heat-sensitive thermal transfer laminate 12. In this transfer foil 10, a pigment is used as the color former for the resin-based protective layer 14. When the content of the pigment is small, there is permeability but no color-forming effect. When the content is large, there is a color-forming effect but the reflectivity of the metal layer 15 is concealed. A pigment is selected as the color former for the protective layer 14. The thickness of the protective layer 14 is refined in the range of 1 to 10 μm, the liquid preparation solvent is 60 to 80% by weight, the solute is 20 to 40% by weight, the pigment content rate is 5 to 15% by weight, and the pigment particle size is 10 to 120 nm. Further, the pigment is sized to a particle size of 10 to 80 nm. By using this refined pigment in the preparation of the protective layer 14, a color-forming effect similar to that of a dye is produced, the permeability of the protective layer 14 is produced, the reflectivity of the metal layer 15 appears, and light resistance is generated. Thereby, the reflectivity of the metal layer 15 is obtained, and the metallic feeling due to this metallizing effect can be expressed as a color-forming effect by using the pigment. The resin-based protective layer 14 obtains light resistance by using a color former such as an organic pigment.

[0053] As color formers, inorganic pigments such as titanium white, carbon black, chrome yellow, lead yellow, ultramarine blue, etc., organic pigments such as aniline black, quinacridone red, isoindolinone yellow, phthalocyanine blue, etc. are selected, and those sized to around 10 to 80 nm using a bead mill type disperser are used. As the color former, the transparency of the pigment and the visibility as the color forming image effect can be enhanced. Furthermore, a pigment excellent in light resistance can be selected to improve the resistance. For example, there are fine particle oxides such as TiO2, SO2, Al2O3, Fe2O3, etc. Furthermore, by additionally containing a light stabilizer, an ultraviolet absorber, and a light shielding agent, fading of the protective layer 14 can be suppressed. Furthermore, by adopting a polymer material in which a light stabilizer, silicon, silicate, etc. are combined in the skeleton of the acrylic resin, the resistance can be promoted and improved.

[0054] In the resin-based protective layer 14, a light stabilizer is added to the formulation. It contributes to the light stability by capturing and detoxifying the radicals generated by ultraviolet rays. A non-basic neutral type hindered amine-based light stabilizer is selected. The occurrence failure of the thermosetting film of the protective layer 14 is avoided.

[0055] In the resin-based protective layer 14, an ultraviolet absorber is added. The addition is selected from ultraviolet absorbers that can suppress the photoinduced reaction leading to the photo-degradation of the protective layer 14. In order to achieve the stability of the protective layer 14 by absorbing ultraviolet rays and converting them into low thermal energy and releasing them, among the hydroxyphenyltriazine-based materials, those with ultraviolet absorption wavelengths of 280 to 350 nm and 310 to 330 nm are selected.

[0056] In the transfer laminate 12, in order to suppress the chemical reaction caused by light that causes fading and film deterioration, the transfer laminate 12 absorbs light and becomes a higher energy state by the absorbed energy. Part of it becomes a photosensitization phenomenon and then becomes light energy again. Part of it reaches a chemical reaction. Also, excessive energy transfers to other molecules and reacts with polymers. The ultraviolet wavelength range of 200 to 300 nm has a significant chemical effect. As a countermeasure in the resin-based protective layer 14 containing a color preservative, in addition to a transparent fine pigment, an acrylic resin, a polymer having a hindered amine bonded in the structure by an acrylic resin, a hindered amine-based light stabilizer, and a preparation for obtaining a hydroxyphenyltriazine-based ultraviolet absorber, as a light action inhibitor, select from salicylic acid esters, 4-t-butylphenyl salicylate, phenyl salicylate, etc., and select and add phenyl salicylate, which is an ultraviolet blocker, as a light action inhibitor.

[0057] As means for forming the metal layer 15, among the physical vapor deposition methods (PVD) as the vapor deposition method, there are vacuum evaporation, sputtering, etc. Among the chemical vapor deposition methods (CVD), there are thermal CVD, atomic layer deposition (ALD), plasma CVD, metalorganic chemical vapor deposition, two-flow MOCVD, catalytic chemical vapor deposition (Cat-CVD), etc. As the liquid phase deposition method, among the melt methods, there are liquid phase epitaxy, plating methods such as wet plating and electroless plating, sol-gel methods, and coating means such as spin coating, printing, and inkjet. As the metal to be used, in addition to Au, Ag, Cu, Sn, Al, Ni, Pt, Rh, Pd, Zn, Cr, Si, as oxides, In2O3, CdO, CdIn2O4, Cd2SnO4, TiO2, SnO2, ZnO, SiO2, ZrO2, etc., as sulfides, ZnS, etc., and as fluorides, MgF2, etc., select one or more from among them. Also, alloys can be used. Layers can also be stacked. As the film formation shape of the metal layer 15, there are shapes such as an island film structure in which the metal layer 15 is in an island state and a deposited film structure showing the deposition state of the metal. However, in any structure, without being restricted by the metal employed or the film formation state of the metal, it is possible to suppress expansion and contraction, cracks, fractures, swelling, etc. that the transfer laminate 12 undergoes during thermal transfer.

[0058] In addition, the thickness of the metal layer 15 is 10 to 30 nm in the case of an island state and 20 to 60 nm in the case of the deposition state of a continuous film. In either case, the metallic luster can be uniformly maintained as the metallic color tone. This enhances the decorativeness and design quality as the image display of the thermal transfer.

[0059] [Manufacturing Method 1] As the base film 11, any film may be used as long as it shows no abnormality in heat resistance during manufacturing, resistance to solute solvents, heat resistance during transfer during use, and pressure resistance. For example, there are films such as polyester-based, polyamide-based, polyolefin-based, acrylic-based, imide-based, various engineering-based, styrene-based, and cellulose-based films like polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, and polyethylene terephthalate-polyethylene naphthalate coextruded film. Among them, a biaxially stretched film is good for maintaining physical and chemical strength. It is good to select a polyethylene terephthalate film from these. Considering thermal transfer, when the film is thick, both heat conduction and pressure propagation are insufficient. On the other hand, when the film is thin, the mechanical strength is insufficient, and it deviates from under the control of the transfer heat pressure, making it difficult to clearly display the transfer image. It is good to use it within the range of a film thickness of 12 to 75 μm in accordance with the shape and material of the object to be transferred 32.

[0060] In accordance with the above, the release layer 13, the resin-based protective layer 14, and the adhesive layer 16 are formed by the gravure method. As the drying means, a far-infrared heater 67 and a hot air device 69 are used. Fig. 6 shows an overview of the gravure printing machine 60 and the drying furnace 61 of one type. Using the drying furnace 61 of one type, it travels and stays in the furnace atmosphere of 90 to 210 °C for 20 to 50 seconds to produce each film with a thickness of 0.1 to 20 μm. Also, a two-chamber semi-continuous vacuum evaporation device is used to form the metal layer 15 with a thickness of 30 to 60 nm. Then, the adhesive layer 16 is formed.

[0061] [Manufacturing Method 2] After forming the release layer 13 and the resin-based protective layer 14, the two-zone drying oven 62 with a volume of 2.64 m shown in FIG. 7 of the gravure printing machine 60 is used, and it travels and stays in an atmosphere of 100 to 210°C for 20 to 50 seconds to perform an annealing process for baking the dry film. Then, the metal layer 15 and the adhesive layer 16 are formed. 3 After that, the metal layer 15 and the adhesive layer 16 are formed.

[0062] [Manufacturing Method 3] The drying means for the release layer 13 and the resin-based protective layer 14 uses the far-infrared heater 67 and the hot air device 69 in the drying oven 61 of the first type shown in FIG. 6, travels and stays in an atmosphere of 90 to 210°C for 20 to 50 seconds, and produces a flat film with a thickness of 0.1 to 20 μm. Next, after forming the metal layer 15 with an evaporator, the two-zone drying oven 62 in the gravure printing machine 60 shown in FIG. 7 is used, and it travels and stays in an atmosphere of 150 to 210°C for 20 to 50 seconds to perform an annealing process for baking the dry film composed of the release layer 13, the resin-based protective layer 14, and the metal layer 15 laminated on the base film 11. Then, the adhesive layer 16 is formed.

[0063] [Manufacturing Method 4] The drying means for the resin-based protective layer uses the far-infrared heater 67 and the hot air device 69. The drying oven 61 of the first type shown in FIG. 6 is used, and it travels and stays in an atmosphere of 90 to 210°C for 20 to 50 seconds to produce a flat film with a thickness of 0.1 to 20 μm. Next, after forming the metal layer 15 with an evaporator, the gravure printing machine 60 having the two-zone drying oven 62 shown in FIG. 7 is used, and it travels and stays in an atmosphere of 150 to 210°C for 20 to 50 seconds and is heated in the oven. A pressing process is performed by the pressing device 71 directly connected outside the oven, followed by a cooling process by the cooling device 72 installed. Then, the adhesive layer 16 is formed.

[0064] [Manufacturing Method 5] Using the drying furnace type 1 furnace 61 shown in FIG. 6, stay in an atmosphere of 90 to 210 ° C for 20 to 50 seconds to produce a flat film with a thickness of 0.1 to 20 μm. Next, after forming the metal layer 15 with a vapor deposition machine, use the drying furnace type 2 furnace 62 shown in FIG. 7, and stay in a heating atmosphere of 150 to 210 ° C for 20 to 50 seconds to perform annealing treatment for baking the dry film. After heating in the furnace, continuous pressure and cooling treatments are carried out by the external pressure device 71 and the cooling device 72 connected to the furnace to complete a three-dimensional structure film including the release layer 13, the resin-based protective layer 14, and the metal layer 15. Then, the adhesive layer 16 is formed.

[0065] [Manufacturing Method 6] Using the drying furnace type 1 furnace 61 shown in FIG. 6, stay in an atmosphere of 100 to 210 ° C for 20 to 50 seconds to produce a flat film with a thickness of 0.1 to 20 μm. Next, after forming the metal layer 15 with a vacuum vapor deposition machine, use the drying furnace type 2 furnace 62 shown in FIG. 7, stay in an atmosphere of 150 to 210 ° C for 20 to 50 seconds, and after heating, perform continuous pressure and cooling treatments to complete a flat film or a three-dimensional film. The separation between the production of the flat film and the three-dimensional film can be carried out by changing the levels of heating, hot air, pressure, and cooling treatments. Then, the adhesive layer 16 is formed.

[0066] The transfer foil 10 according to this embodiment includes a base film 11 and a transfer laminate 12 composed of a release layer 13, a protective layer 14, a metal layer 15, and an adhesive layer 16, and the transfer laminate 12 is peeled off from the base film 11 through the pressure-heat time of the transfer machine and transferred to the object to be transferred 32. During the transfer operation, the transfer laminate 12 peeled off from the base film 11 requires a heat source, pressure, and transfer residence time supplied from the transfer machine and is transferred to the object to be transferred 32 by the transfer action. Due to the shape and hardness / softness of the material of the object to be transferred 32, the actions of being heated and being pressured received are not uniform. The transfer laminate 12 is a thin film body with peelability compared to the base film 11 and the object to be transferred 32, and has breakability during transfer peeling. The film peelability is the starting point of film peeling (using a peel resistance tester manufactured by Asahi Measuring Instruments Co., Ltd.). The film breakability is 500 g to 10 Kg / cm 2 (when using a peel resistance tester manufactured by Asahi Measuring Instruments Co., Ltd.). The film breakability is 500 g to 10 Kg / cm 2·It is the starting point of film breakage due to transfer pressure at 0.5 seconds (using Ikeda type transfer device). The transfer laminate 12 is easy to peel off and has breakability. The object to be transferred 32 has various two-dimensional, three-dimensional shapes, and the materials are various, such as leather, paper, paperware, printed paper, special paper, wood, fiber, resin sheet, resin molding, metal, and glass. Considering the transfer stretchability of the transfer laminate 12 mounted on the base film 11 with the object to be transferred 32, compared with the base film 11 and the object to be transferred 32, the transfer laminate 12 is more likely to generate cracks, cracks, and bulges due to the stretchability and breakability of the transfer laminate 12 with respect to the thermal pressure supply during transfer. Here, flexibility can be imparted by adding a plasticizer to the protective layer 14. Furthermore, through the process by the gravure printing machine 60, the adhesion between the protective layer 14 and the metal layer 15 is enhanced to bonding. The effects of heating, hot air, pressurization, and cooling by the gravure printing machine 60 are such that the flexibility due to adding a plasticizer to the protective layer 14 becomes stretchability, and the heat resistance of 380 °C maintains resistance to the occurrence of cracks, cracks, and bulges, and the ability of the protective layer 14 and the metal layer 15 to coexist is manifested, resulting in a change in the ability as the transfer laminate 12 due to the structural transformation of the resistance.

[0067] As newly manifested during the film formation of the transfer laminate 12 by the gravure printing machine 60, the following film formation environment can be prepared. (1) Adhesion: Bonding by the lamination of the resin-based protective layer 14 and the metal layer 15 (2) Stretchability: Stretchability of the resin-based protective layer 14 and the metal layer 15 (3) Resistance: Avoidance of the occurrence of cracks, cracks, and bulges during and after the transfer of the transfer laminate 12 (4) Metal reflectivity: Reflectivity of the Al metal layer 15 is 82.15% (spectral reflectivity %) When a pigment is used for the protective layer 14, it is excellent in ensuring gloss. In the base film 11, release layer 13, protective layer 14, Al metal layer 15, and adhesive layer 16, the Al film reflectivity of the colored layer using fine pigments for the protective layer 14 (5) Morphology of the vapor deposition film: Regardless of whether the morphology of the metal layer 15 is a sea-island film structure or a deposited film structure, the protective layer 14 and the metal layer 15 maintain bonding properties and exhibit stretchability. Cracks, cracks, and bulges of the transfer laminate 12 caused by cohesive failure of the metal can be avoided. (6) Heat resistance: In the heat resistance test after transfer of the transfer laminate 12, it is excellent in resistance to cracking, cracking, and swelling of the transfer laminate 12 at 380°C. (7) Resin-based protective layer 14: A thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or a laminate of an ultraviolet curable resin and a thermosetting resin can be used. All contain the above-described plasticizer, and a film having heat resistance and stretchability and having adhesiveness to the metal layer 15 can be formed by the above-described manufacturing process. (8) Resin-based protective layer 14: A cure type can be used as the ultraviolet curable resin. (9) Resin-based protective layer 14: An after-cure type can be used as the ultraviolet curable resin. (10) Resin-based protective layer 14: When an ultraviolet curable resin is used, a hot stamping method and a cold stamping method can be used as the transfer method. (11) Resin-based protective layer 14: When a laminate of an ultraviolet curable resin and a thermosetting resin is used, the ultraviolet curable resin increases the film strength, and the thermosetting resin increases the film breakage resistance. A plasticizer is added to both resins. (12) Stretchability: There is a three-dimensional transfer object 32 as a resin processed product by a resin molding machine or the like. In this case, when the transfer laminate film is shaped in the mold of the molding machine at the time of forming the molded product, bonded by the heat and pressure of the molten resin, and then the excess film is peeled off, the transfer laminate 12 can maintain the resistance corresponding to the stretch it receives.

[0068] Regarding the surface modification of the molded product, in addition to performing the modification by transferring and peeling off the modified laminate composed of the transfer laminate 12 peeled from the base film 11 using a transfer machine, the modification may also be performed by transfer transfer in the molding machine. After adhering the resin-based protective layer 14 containing a plasticizer, or the colored resin-based protective layer 14, or the colored resin-based protective layer 14 with an image formed thereon to the base film 11, a metal layer 15, a resin-based protective layer 23, and an adhesive layer 16 are formed on the resin-based protective layer 14. The adhesive layer 16 is brought into contact with the object to be transferred 32 via a transfer device, and is adhered by the thermal pressure supplied from above the base film 11, and can be mounted on the object to be transferred 32 together with the base film 11. According to this manufacturing method, a multi-layer laminate excellent in heat resistance and stretchability can be obtained. According to such a multi-layer laminate structure, the transfer laminate 12 using the base film 11 and the modified visualization film integrated with the base film 11 can be applied regardless of the distinction between thermal pressure transfer, outmold, and inmold.

[0069] Regarding the production of two-dimensional and three-dimensional molded products by a molding machine using a resin-based material, the molding methods using thermoplastic resins and thermosetting resins include injection molding, blow molding (hollow molding, suction molding), extrusion molding, casting molding, vacuum molding, pressure-air molding, compression molding, press molding, hand lay-up, T-die method, inflation method, calender molding, co-extrusion multi-layer T-die method, biaxial stretching method, lamination method, profile extrusion, extrusion coating, co-extrusion, etc. After being formed as a molded product, as a modified laminate by post-attachment, there are means such as the transfer means of the transfer laminate 12 and the peeling transfer of the image from the base film 11 in the mold of the molding machine to the molded product as a primary processing method in the mold, and film bonding for bonding the film to the molded product together with the base film 11. For the object to be transferred 32 by simultaneous transfer of the molded product, simultaneous bonding of the molded product, and post-attachment transfer, although there are various molding methods and modification means as described above including leather, the use of a modified laminate structure film with an image formed by being colored can be selected from among them.

[0070] When the selected plasticizer is introduced into the protective layer 14 and the above-described manufacturing process is carried out, together with the produced transfer laminate 12 and the film for laminating to the base film 11, etc., the functionality of extensibility, heat resistance, interlayer adhesion, maintenance of the reflectance of the metal layer 15, light resistance, prevention of cracks, fractures, and swelling will show an improvement in quality.

[0071] In the three-dimensional structure of the transfer laminate 12 including the resin-based protective layer 14, in the transfer laminate 12 consisting of the base film 11, the release layer 13, the resin-based protective layer 14, the metal layer 15, and the adhesive layer 16, by means of drying using the drying furnace 1 type furnace 61 of the gravure printing machine 60 and the drying furnace 2 type furnace 62 of the gravure printing machine 60, the coating film using the heat sources of the far-infrared heater 67 and the hot air device 69 in the range of 150 to 210 °C each is heated and dried, pressed, and cooled to form a flat film and a three-dimensional film separately. At this time, the release layer 13, the resin-based protective layer 14, the metal layer 15, and the adhesive layer 16 are sequentially formed on the base film 11 to complete the transfer laminate 12. However, during the treatment of the resin-based protective layer 14, heating and drying, hot air treatment, pressing treatment, and cooling treatment are continuously carried out using the drying furnace 1 type furnace 61 of the gravure printing machine 60. While the protective layer 14 is hardened into a hard film by the preparation of an amino resin-based material containing a plasticizer and a curing agent by heating and drying, the resin-based material becomes hard by performing continuous operations of heating, hot air, pressing, and cooling. The protective layer 14 containing a plasticizer exhibits flexibility. After the formation of the protective layer 14, the metal layer 15 is formed, and baking of the dry film is carried out using the gravure printing machine 60 having the drying furnace 2 type furnace 62 in a state where the release layer 13, the protective layer 14, and the metal layer 15 are in a multilayer state. As a result, the propagation of flexibility appears in the protective layer 14. When the interface between the protective layer 14 and the metal layer 15 is heated, pressed, and cooled, affinity is generated between the protective layer 14 and the metal layer 15 by the heating and pressing operations, and fixation between the layers is ensured by the cooling operation to form the transfer laminate 12. The metal layer 15 may be in an island structure where the metal is in an island shape or in a deposition structure where it is in a deposited state.

[0072] In the drying process of the gravure coating, by continuously providing heating in the two - type furnace 62 of the drying furnace, external - furnace pressurization, and external - furnace cooling, the protective layer 14 and the metal layer 15 pass through this process, and the resin - based protective layer 14 has film stickiness. Compatibility occurs between the resin in the protective layer 14 and a part of the metal particles in the metal layer 15. The influence caused by the accumulation of residual stress due to film shrinkage during the curing of the protective layer 14 is reduced by the co - packaging preparation of the plasticizer. The shear stress on the metal layer 15 is reduced, and the load on the destruction of the cohesiveness of the metal layer 15 is attenuated.

[0073] Treating the release layer 13 and the resin - based protective layer 14 in the one - type furnace 61 of the drying furnace of the gravure printing machine 60, laminating the metal layer 15, heating in the two - type furnace 62 of the drying furnace of the gravure printing machine 60, and continuously performing external - furnace pressurization and external - furnace cooling are necessary processes for propagating and fixing the flexible film quality of the resin - based protective layer 14 to the interface with the metal layer 15. Both layers of the protective layer 14 and the metal layer 15 become hard and sticky film qualities when heating, pressurization, and cooling are applied. Furthermore, the transfer of the flexible film quality of the protective layer 14 to the metal layer 15 results in a combination of the cured film, toughness of the protective layer 14, and the extensibility from the flexibility containing the plasticizer for both layers. The film breakage caused by the manifestation of the residual stress of the protective layer 14 and occurring from the cohesive failure of the metal layer 15 is triggered by the shear of the transfer laminate 12 and becomes a factor for the occurrence of cracks, breaks, bulges, etc. To suppress this, in order to raise the properties between the two layers to those with heat resistance, flexibility, adhesion, and extensibility, film quality modification is carried out. The protective layer 14 contains a heat - resistant plasticizer and an interface - transfer - inductive plasticizer in its formulation to enhance the fixing with the metal layer 15, transfer and bond the film quality to the metal layer 15, and perform annealing treatment such as heating, pressurization treatment, and cooling treatment. Confirmation is made as to whether the correlation between the protective layer 14 and the metal layer 15 is manifested within the context of the bonding of the two layers in terms of heat resistance, flexibility, adhesion, and extensibility.

[0074] In the following-described embodiments, when observing the surface of the transfer laminate 12 after transfer, the formed three-dimensional structure had a cross-section showing a chord of 1 μm, a height of 13 μm, and an arc of 26 μm as shown in FIG. 8 in the radiation bow-shaped cross-section. It was expressed as a three-dimensional structure film of a ridged and wrinkled continuous layer with unevenness. Further scrutiny and enlarged confirmation of the surface change of the surface layer after thermal pressure transfer revealed no phenomena such as cracks, fractures, or bulges.

[0075] FIGS. 8 to 10 are photographs showing the three-dimensional structure film. FIGS. 11 to 14 are photographs showing cracks, fractures, and bulges on the flat film structure film of the transfer laminate 12.

[0076] A release layer 13 is formed on the base film 11, and a gravure printing machine 60 having a drying furnace 1 type furnace 61 is used to coat a resin-based protective layer 14 containing a plasticizer to produce a flat film. Next, a metal layer 15 is formed by overlaying, and while in the multilayer state, a gravure printing machine 60 having a drying furnace 2 type furnace 62 is used to perform baking of the dry film, and heating, pressurization, and cooling are performed using a far-infrared heater 67 and hot air. Generation of a ridged and continuous three-dimensional structure band where the transfer laminate 12 bulged and stretched together was observed. Next, an adhesive layer 16 was formed to complete the transfer laminate 12. This transfer laminate 12 was transferred onto a soft vinyl chloride sheet, and the surface layer of the transfer laminate 12 was confirmed. Using a thermal pressure transfer condition and an up-down type transfer foil press, at a temperature of 160°C, a pressure of 5 Kg / cm 2 and a transfer residence time of 0.5 seconds, using a relief plate 40, as a result, there was no occurrence of cracks, fractures, bulges, etc., and no change was observed in the metallizing effect either. The resin-based protective layer 14 containing a plasticizer and the metal layer 15 were both synchronized with the stretching of the film. Through the processes of heating, pressurization, and cooling, together with the metal layer 15 with low cohesive force and the protective layer 14 released from the residual stress, the flexibility, affinity, and migration inductivity of the protective layer 14 induced plastic deformation in the metal thin film and brought about plasticity through the in-furnace and out-of-furnace processes by the gravure printing machine 60. The metal layer 15 has a structure of a deposited particle film or an island-shaped particle film, and its film quality propagates to the protective layer 14. As a result, both layers of the protective layer 14 and the metal layer 15 exhibited bondability and fixed the interface between the two layers.

[0077] The photograph in Fig. 10 shows the surface layer of the transfer foil 10, which was subjected to the experiment based on Production Method 5, after transfer using an up-down type transfer foil press, and enlarged to a three-dimensional structured image. The metal layer 15 used aluminum with a film thickness of 40 nm, a valley width of 1.4 to 1.76 μm, a peak width of the convex portion of 0.99 to 1.2 μm, and a height of the convex portion of 11 to 14 μm.

[0078] This embodiment aims to improve the defects that occur in the transfer laminate 12 over time after transfer when the transfer foil 10 is hot-press transferred. For the external force and internal stress of the thermal pressure load on the transfer laminate 12 and the object to be transferred 32, such as cracks, fractures, bulges, and fading that occur, deformation interactions such as elongation, contraction, displacement, torsion, and bending are caused in the transfer laminate 12 and the object to be transferred 32. The action on the deformation during transfer on the object to be transferred 32 and the transfer laminate 12 resulting from this derived phenomenon reduces the decorativeness on the object to be transferred 32. It is necessary to obtain a maintenance method that can individually face this deforming action as the acceptance burden of the transfer laminate 12.

[0079] The functions of the transfer laminate 12 include peeling, breaking, adhesion, heat resistance, brilliance resistance, color development, image display, decorativeness, etc. In addition to this, in order to cope with the morphological transformation that occurs during and after the above transfer, the following need to be added as means of the transfer laminate 12. By obtaining a material that functions by expressing extensibility due to flexibility using heat resistance, flexibility, and migration inductivity from plasticizers and adding it to the protective layer 14, the function of the protective layer 14 can be enhanced, and the function can be propagated to the metal layer 15. Furthermore, by passing the drying means by the gravure printing machine 60 through heat treatment, hot air treatment, pressure treatment, and cooling treatment, together with the material having migration inductivity of the protective layer 14 to the metal layer 15, the functions of heat resistance and flexibility become function propagation from the affinity of the metal layer 15 interface and join and fix. As a result, extensibility of both the resin-based protective layer 14 and the metal layer 15 is generated. The protective layer 14 and the metal layer 15 share transfer breakability, extensibility, and heat resistance. The transfer laminate 12 becomes a modified laminate that can cope with cracks, fractures, and bulges during and after transfer.

[0080] Among the plasticizers, the setting of the flexibility transfer inducer is measured. The specific amount within the range where delamination does not occur at the interface of the protective layer 14 is explored. It will have the function of transferring the property of flexibility of the formulation containing the plasticizer up to the vicinity of the interface of the thermosetting resin-based protective layer 14. The flexible interface due to the plasticizer of the thermosetting resin-based protective layer 14 is dispersed in the film without being sealed in the curable film structure, and thus is fixed to the interface even in a trace amount. When forming the protective layer 14 by the gravure method, the affinity between the protective layer 14 and the metal layer 15 is enhanced by continuously introducing means such as heating, hot air, pressurization, and cooling during film formation.

[0081] For the plasticizer, materials with heat resistance, flexibility, and transfer induction properties are specified, and the addition of the formulation to the protective layer 14 is planned. The specification of each material and the setting of the formulation amount are determined through experiments, and it is connected to the generation of affinity for the film formation adjacent to the interface of the protective layer 14 while maintaining heat resistance, flexibility, and transfer induction properties. The plasticizer capable of generating these functions can be selected from one or more of the above-mentioned plasticizers.

[0082] After forming the release agent film on the base film 11 by the gravure method, the formation of the protective layer 14 is carried out by a film formation method using heating by the far-infrared heater 67, heating of one type of drying furnace 61, hot air treatment, and the directly connected external furnace pressurizing device 71 and external furnace cooling device 72. Alternatively, the execution of the film formation operation by the external furnace pressurizing device 71 and external furnace cooling device 72 directly connected to the heating and hot air treatment using the two types of drying furnace 62, or the annealing treatment of baking the dry film of the protective layer 14 by the one type of furnace 61 and two types of furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and external furnace cooling device 72, the modification treatment by the lamination of both the protective layer 14 and the metal layer 15, and further, the modification treatment for each layer is appropriately combined with the selection of the plasticizer for the formulation of the protective layer 14, the setting of the input amount and the effect, the interface modification treatment of the laminated film of the protective layer 14 and the metal layer 15, etc., so that the flat film structure or three-dimensional structure of the transfer laminate 12 can be formed.

[0083] In each of the heating, hot air, pressurizing, and cooling devices, the resin-based protective layer 14 can be obtained by curing and hardening the resin film through heating and hot air treatment. The pressurizing treatment relieves the compressive residual stress of the resin film, and the cooling treatment aims to soften and fix the resin film, thereby fixing the protective layer 14 and the metal layer 15. In the heating, hot air, pressurizing, and cooling treatments of the resin-based protective layer 14, and in the annealing treatment of baking the dry film during heating, hot air, pressurizing, and cooling after the lamination of the resin-based protective layer 14 and the metal layer 15, the protective layer 14 and the metal layer 15 have improved affinity and become a softer and stickier film quality.

[0084] The transfer foil 10 is composed of a film serving as a base material and a decorative laminate that is laminated and peeled off therefrom. On the base material film 11 selected from among chemical conversion films, the film protective layer 22, the release layer 13, the resin-based protective layer 14, the metal layer 15, the resin-based protective layer 23, and the adhesive layer 16 are selected and laminated in sequence as the laminate. The film protective layer 22 and the metal layer 15 may be omitted. The resin-based protective layer 14 can also be laminated. One or more of the plasticizers listed above are added to the resin-based protective layer 14. Excluding the metal layer 15, the colored resin-based protective layer 14 can also be used as a colored layer with a color former such as a dye or a pigment.

[0085] The film protection layer 22, the release layer 13, the resin-based protection layer 14, the adhesive layer 16, etc. are formed into films by the gravure method. The metal layer 15 is formed into a vapor deposition layer using a two-chamber semi-continuous vacuum vapor deposition apparatus. The drying equipment used for gravure coating has a far-infrared heater 67 installed in the furnace and can be heated and dried together with the hot air device 69. The transfer laminate 12 in the heating and warming vortex can be pressurized by a pressurizing device 71 provided just outside the drying furnaces 61 and 62 together with the base film 11. Furthermore, it can be rapidly cooled by passing through a continuously installed cooling device 72 to form a film. Also, only heat treatment can be performed by the far-infrared heater 67 and the hot air device 69. The gravure printing machine 60 is equipped with a drying furnace type 1 furnace 61 shown in FIG. 6 or a drying furnace type 2 furnace 62 shown in FIG. 7. The drying equipment can perform dry film formation from the wet state of the liquid preparation through drying means. Also, annealing treatment for baking the dry film through heating and hot air treatment of the formed dry film can be performed. Furthermore, the film formed by heating treatment and swollen and softened into a soft state by the pressurizing device 71 can be compressed under pressure. And the fixing property between each layer can be enhanced by rapidly cooling the formed film by the subsequent cooling device 72. Each means can be implemented alone for the device and film formation. Also, they can be used in combination in a coordinated manner. They can be selectively combined.

[0086] Together with the blending of the plasticizer into the resin-based protection layer 14, the heat treatment with the addition of each device for heating, hot air, pressurization, and cooling by the gravure method makes the flexible state of the protection layer 14 between the protection layer 14 and the metal layer 15 have a tendency for the affinity at each interface to become more prominent in terms of bonding property after undergoing the heat treatment. The compatibility between the resin-based layer and the metal-based layer is forced and the bonding property is enhanced through the processes via each device such as heating, hot air, pressurization, and cooling by the gravure printing machine 60. The influence from the heating and pressurization from the transfer device during thermocompression transfer on the transfer laminate 12 causes the resin-based protection layer 14 and the metal layer 15 to both respond to the expansion and contraction with respect to the load of expansion and contraction occurring from the description of the transfer laminate 12 including the base film 11 and the object to be transferred 32, thereby preventing the transfer laminate 12 from cracking, splitting, swelling, etc.

[0087] The resin-based protective layer 14 is composed of an acrylic resin, an amino resin, a curing agent, a ketone resin, a color former, a light stabilizer, a light blocker, an ultraviolet absorber, a plasticizer, a solvent, etc. These are formed into a film by a gravure printing machine 60 as the transfer laminate 12. During transfer, a load of stretching, shrinking, pressure, and heat is applied. In order for the transfer laminate 12 to withstand the generation of cracks, breaks, bulges, etc., flexibility is imparted to the cured film by selecting a plasticizer, and heating, pressurization, and cooling are incorporated by the gravure method to enhance the affinity at the interface between the protective layer 14 and the metal layer 15. As a result, the transfer laminate 12 can be separately produced into a flat film structure or a three-dimensional film structure rich in stretchability.

Example

[0088] Among the modified laminates, in the three-dimensional structure film, the surface layer of the transfer laminate 12 forms a continuous film formation with a three-dimensional structure having ridge-like irregularities. This is shown in the photograph of FIG. 8. It has a continuous three-dimensional shape with a chord of 22.30 μm, a height of 13.87 μm, and an arc of 37.25 μm in the parabolic arc cross-section, and has a continuous three-dimensional film structure with a valley width of 1.1 to 1.14 μm in the concave part and a peak width of 0.7 to 0.9 μm in the convex part.

[0089] The photographs in FIGS. 8 to 10 show the three-dimensional image of the modified laminate after transfer. Regarding the flat film structure of the modified laminate, as a result of the test in the heat resistance test after transfer in the cycle of sequentially increasing the temperature from room temperature to reach 380° C. and then decreasing the temperature to room temperature, there was no occurrence of cracks, breaks, bulges, etc., no change in the reflectance of the metal layer 15, and no abnormality was observed regarding delamination between the layers of the laminated film.

[0090] As described above, the formation of the three-dimensional structure film forms a continuous coating with fine irregularities on the surface layer by the transfer laminate 12. The incident light on the metal layer 15 in the film reaches the surface layer by reflection by the metal layer 15. The light by diffraction light returns to the surface layer part, light interference appears, and an interference metallizing effect is generated. In addition, the light reception by the fine three-dimensional layer on the surface layer causes light interference on the surface layer.

[0091] The surface layer of the fine three-dimensional structure of the transfer laminate 12 is under a pressure of 5 to 10 Kg / cm during thermocompression transfer 2, when the transfer peel resistance value and film breakage were confirmed under the conditions of a temperature of 150 to 200 °C and a transfer residence time of 0.5 seconds, no change was observed. No change was also observed in terms of the glow property.

[0092] The color-forming resin-based protective layer 14 contains a light stabilizer, a light blocker, an ultraviolet absorber, etc., and suppresses the fading of dyes, pigments, resins, etc.

[0093] In the resin-based protective layer 14, the film has strength as a cured film, contains a plasticizer, and has flexibility. By performing heating, hot air, pressurization, and cooling by means of the drying means of the gravure method, the film toughness and adhesiveness are expressed in the transfer laminate 12. In the film formation in which the flat film structure or three-dimensional structure shape of the transfer laminate 12 can be stretched in a state including the metal layer 15, the transfer breakage is maintained by the ketone-based material added to the formulation. When the base film 11 is peeled from the transfer body 32 after transfer, the broken end face of the contour of the transferred image is clearly displayed, and the transfer laminate 12 has shearability. Regarding the transfer breakage of the transfer laminate 12, a vertical transfer foil press using the metal transfer relief plate 40 shown in the photograph of Fig. 16 was used, with a temperature of 120 to 150 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2 , and transfer was performed using a 1-mm-thick PP sheet as the transfer body 32. The breakage after transfer is shown in the photograph of Fig. 15. The transfer laminate 12 transferred onto the PP sheet is broken and transferred precisely as the image of the metal plate making, as shown in the photograph of Fig. 16.

[0094] The transfer laminate 21 is formed by laminating, in order, a film protective layer 22, a release layer 13, 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 selected from the group consisting of a phenol resin, an epoxy resin, a urea resin, an unsaturated polyester resin, a silicone resin, a melamine resin, an aniline resin, a sulfonamide resin, an alkyd resin, a polyurethane resin, a diallyl phthalate resin, and a thermosetting polyimide resin. The film protective layer 22 is smoothly coated on the base film 11 with a thickness of 0.3 to 1 μm by a gravure printing machine 60 and adhered. The film protective layer 22 has a function of imparting peeling uniformity to the release layer 13 during thermal transfer. In addition, it maintains the uniformity of the thermal pressure propagation to the base film 11 and the transfer laminate 21 caused by the thermal pressure during transfer. Furthermore, it can suppress the influence of the expansion and contraction movement of the base film 11 caused by the thermal pressure during transfer. By these, the peeling uniformity of the transfer laminate 12 can be maintained, and the stability of the thermal transfer can be maintained.

[0095] Since the resin-based protective layer 14 contains a plasticizer, even if the transfer laminate 12 expands and contracts due to thermal transfer, the metal layer 15 does not cause cohesive failure, so cracks, cracks, and bulges do not occur in the transfer laminate 12.

[0096] The transfer foil 10 is heated and pressed on a transfer film on which a transfer laminate 12 is placed between it and the object to be transferred 32 through a thermal transfer device. As a result, the transfer laminate 12 is peeled off and broken from the base film 11 and transferred onto the object to be transferred 32 as a selected pictorial image, thereby modifying the surface layer of the object to be transferred 32. The modification laminate of the transfer laminate 12 is provided with a resin-based protective layer 14 having adhesiveness on the base film 11 for protecting the base film 11 and modifying the interface. By adhering to the base film 11 and forming a cured film, it serves as a measure to prevent the expansion and contraction of the base film 11 during thermal transfer of the base film 11, and prevents the propagation of expansion and contraction to the transfer laminate 12. In addition, it provides peel stability when the transfer laminate 12 is peeled off. It is formed in the range of 0.3 to 5 μm in film thickness using a well-known thermosetting resin. Next, a release layer 13 is provided. The material can be selected from known materials and preferably contains one or more selected from methyl methacrylate, ethyl methacrylate, butyl acrylate of acrylic resin, 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, fluorine-modified resin, polyvinyl alcohol, cellulose-based materials such as nitrocellulose, silica as a hardening agent, and various waxes including polyethylene wax. It can be formed by selecting and formulating from one or more of them. As a result of the peeling of the release layer 13, which can be in the form of interface peeling with the release material, heat transfer material, hard material, breaking material, interlayer bonding material, pressure-resistant material, lubricity material, heat-resistant material, gloss material, base film 11 or film protective layer 22, or breaking peeling due to cohesive failure within the release layer 13 by transfer heat pressure, the formation of a cover of the release agent on the next resin-based protective layer 14 and the assistance of physical and chemical resistance after transfer are established as the release layer 13, which is an essential element together with the release ability. Therefore, the release layer 13 may be laminated or may be multi-layered with differentiated functions. The release layer 13 is formed by drying using a prepared liquid using a known film forming machine such as a gravure printing machine 60. The film thickness is 0.1 to 20 μm, preferably 0.1 to 10 μm.

[0097] In order, on the base film 11, a film protective layer 22, a release layer 13, a resin-based protective layer 14 containing a plasticizer or a color-forming resin-based protective layer 14 containing a plasticizer, a metal layer 15, a resin-based protective layer 23 containing a plasticizer, and an adhesive layer 16 are sequentially laminated, and a transfer laminate 12 of the transfer foil 10 is formed. Each layer can be selectively adopted and combined to constitute the transfer foil 10. For example, in order, any selection of the base film 11, the release layer 13, the resin-based protective layer 14 containing a plasticizer or the color-forming resin-based protective layer 14 containing a plasticizer, the setting of the metal layer 15 and the adhesive layer 16, or the setting of the base film 11, the film protective layer 22, the release layer 13, the resin-based protective layer 14 containing a plasticizer or the color-forming resin-based protective layer 14 containing a plasticizer, the metal layer 15, and the adhesive layer 16, or the setting of the base film 11, the release layer 13, the resin-based protective layer 14 containing a plasticizer or the color-forming resin-based protective layer 14 containing a plasticizer, the metal layer 15, the resin-based protective layer 14 containing a plasticizer, and the adhesive layer 16 can be formed. These means are effective in adapting to the expansion and contraction and the pressure load generated during thermocompression transfer with the metal layer 15 by means of each resin-based protective layer 14 containing a plasticizer.

[0098] The film protective layer 22 shown in FIG. 2 is formed under the following conditions. During heat and pressure transfer, the base film 11 expands or contracts under the propagation of heat and pressure. In order to suppress this, a hard film protective layer 22 is formed. In order to realize stable and uniform peeling of the release layer 13 during transfer, a hard and smooth film protective layer 22 is formed between the base film 11 and the release layer 13. Thereby, pressure and heat can be propagated equally during transfer, and transfer peeling such as image transfer during transfer, transfer fixing property, and breakability are improved.

[0099] During thermocompression transfer, first, when the base film 11, the resin-based protective layer 14, the color-forming resin-based protective layer 14, and the adhesive layer 16 show film expansion at that time, and when tensile stress for the expansion of the resin-based protective layer 14 and the adhesive layer 16 is applied to the metal layer 15, cracks, breaks, bulges, etc. occur between the metal layer 15 or between the metal layer 15 and the resin-based protective layer 14, and the brightness of the transfer laminate 12 drops due to the attenuation of the brightness of the metal layer 15 and the bulge due to the heat resistance yield during transfer of the resin-based protective layer 14.

[0100] In a transfer lamination 21 for forming a thermal transfer layer by sequentially laminating a film protective layer 22, a release layer 13, 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, a plasticizer is added to the resin-based protective layer 14 to make a coating solution. Together with the film protective layer 22 and the adhesive layer 16, it is formed by coating using a gravure printing machine 60. Each process is dried by a far-infrared heater 67 and a hot air device 69 in the drying furnaces 61, 62 of the gravure printing machine 60. The protective layer 14 causes film shrinkage during heat treatment. The stress of shrinkage is accumulated inside the film. A plasticizer is formulated in the protective layer 14. The plasticizer in the mesh structure film of film formation has flexibility in the curable film. The protective layer 14 has the buffering property of the generation of stress of external force and internal force received. Therefore, the deformation of the protective layer 14 against expansion and contraction can also be reduced. The influence of breakage or shear caused by the expansion and contraction of the interface between the protective layer 14 and the metal layer 15 or the protective layer 14 on the metal layer 15 can be reduced or avoided.

[0101] The color-developing resin-based protective layer 14 can use dyes, inorganic pigments, organic pigments, etc. as color-developing materials as a layer having light resistance. In addition, as a weather-resistant material, one or more acrylic resins containing a hindered amine-based material which is a light stabilizer are added. One or more hydroxy phenyl triazine-based materials which are ultraviolet absorbers are added. By containing phenyl salicylate as a light-blocking agent, the fading deterioration of the transfer lamination 21 can be suppressed and the durability can be extended.

[0102] The transfer shape of the transfer body 32 ranges from a planar shape to a three-dimensional shape, and its material ranges from hard to soft. During heat and pressure transfer, tensile and compressive stress due to heat and pressure is applied between the transfer body 32 and the transfer laminate 12. At the same time, in the metal layer 15, the vapor deposition layer, which is a metal granular deposition layer, is stretched, generating a force that inhibits the cohesion of the metal. As a result, the load on the cohesive force of the metal deposition layer or the metal island layer is concentrated with respect to the tensile stress of the protective layer 14, leading to cohesive failure. Starting from this, the transfer laminate 12 may progress to cracks, fractures, bulges, cracks, peeling, poor interlayer adhesion, foil peeling due to interlayer defects, poor heat resistance, poor gloss, poor weather resistance, etc.

[0103] In order to improve such a situation, after conducting various experiments, by selectively adding a plasticizer to the formulation of the resin-based protective layer 14, affinity is expressed in the correlation between the resin-based protective layer 14 and the metal layer 15. This enhances the interfacial fixation of the protective layer 14 and the metal layer 15, which contributes to suppressing the occurrence of cracks, fractures, bulges, etc., and provides a means to exhibit resistance to the elongation of the transfer laminate 12 during transfer. By incorporating methods such as adding a plasticizer to the protective layer 14, heat treatment of the protective layer, heat treatment, hot air treatment, pressure treatment, cooling treatment, annealing treatment, etc. in the state of combining the protective layer 14 and the metal layer 15 during the process, the transfer laminate 12 comes to have heat resistance, flexibility, and stretchability, and can confront and suppress the stress during heat pressure transfer.

[0104] [Manufacturing Method 7] After forming the release layer 13 coated by the gravure printing machine 60 on the base film 11, the resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since a plasticizer is added, a film with flexibility is formed. The formulation is heated by an infrared heater and a hot air device 69 in the drying furnace 61 of the gravure printing machine 60 to form a film. Next, the metal layer 15 is formed by a vacuum deposition device, and an adhesive is added later.

[0105] [Manufacturing Method 8] After forming a release layer 13 coated on a base film 11 by a gravure printing machine 60, a resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since the plasticizer is added, a film with flexibility is formed. The formulation is heated by an infrared heater and a hot air device 69 in a drying furnace 1 type furnace 61 of the gravure printing machine 60 to form a film. Next, in the gravure printing machine 60 having a drying furnace 2 type furnace 62, a dry film in a state where the release layer 13 and the protective layer 14 containing a plasticizer are laminated on the base film 11 has a volume of 2.64 m 3 , and an annealing treatment for baking is carried out by an operation at a temperature of 100 to 210 °C and an in-furnace residence time of 20 to 50 seconds. Thereafter, a metal layer 15 and an adhesive layer 16 are formed. A transfer foil 10 including a transfer laminate 12 that modifies the surface layer of the transfer body 32 having a flat film layer structure is obtained.

[0106] [Manufacturing Method 9] After forming a release layer 13 coated on a base film 11 by a gravure printing machine 60, a resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since the plasticizer is added, a film with flexibility is formed. Thereafter, a metal layer 15 is formed. Thereafter, a baking treatment is performed in the gravure printing machine 60 having a drying furnace 2 type furnace 62 in the same manner as the above heat treatment. Thereafter, an adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 that modifies the surface layer of the transfer body 32 having a flat film layer structure is obtained.

[0107] [Manufacturing Method 10] After forming the release layer 13 coated on the base film 11 by the gravure printer 60, the resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since a plasticizer is added, a film with flexibility is formed. Then, the metal layer 15 is formed. After that, a baking process is performed in the gravure printer 60 having two drying furnaces 62 in the same manner as the above heat treatment. Through the furnace external pressure device 71 directly connected to the drying furnaces 61 and 62 and the furnace external cooling device 72, heat treatment, pressure treatment, and cooling treatment are performed, and the protective layer 14 is cured into a hard and tough thermosetting film, and a flat film structure with stickiness, flexibility, and stretchability is formed and propagated to the metal layer 15. Then, the adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 for modifying the surface layer of the transfer body 32 is obtained.

[0108] [Production Method 11] After forming the release layer 13 coated on the base film 11 by the gravure printer 60, the resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since a plasticizer is added, a film with flexibility is formed. Then, the metal layer 15 is formed. After that, in the gravure printer 60 equipped with two drying furnaces 62, in-furnace heating and hot air treatment are performed, pressure is applied by the connected furnace external pressure device 71, and cooling is performed by the furnace external cooling device 72. Annealing treatment for baking the dry film of the laminate including the base film 11, the release layer 13, the protective layer 14, and the metal layer 15 is performed. At this time, by setting the heating and hot air heat treatment states of the drying furnaces 61 and 62 in the high temperature region and passing through pressure and cooling, the release layer 13, the protective layer 14, and the metal layer 15 form a continuous three-dimensional structure layer with a ridge and wrinkle shape having fine irregularities. Then, the adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 for modifying the surface layer of the transfer body 32 is obtained.

[0109] [Production Method 12] After forming a release layer 13 coated by a gravure printing machine 60 on a base film 11, a resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin layer formed by an amino resin, a curing agent, and an acrylic resin. Since a plasticizer is added, it becomes a film with flexibility. In a drying furnace 1 type furnace 61 of the gravure printing machine 60, a far-infrared heater 67 and hot air treatment are performed at a high temperature region. Then, a metal layer 15 is formed. Further, in a drying furnace 2 type furnace 62 of the gravure printing machine 60, a far-infrared heater 67 and hot air treatment are performed at a high temperature region, and then, by performing a pressure treatment and a cooling treatment, a fine ridged continuous three-dimensional structure layer is formed. Then, an adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 that modifies the surface layer of a transfer body 32 is obtained.

[0110] By setting the temperature control of the 1 type furnace 61 and the 2 type furnace 62 to be divided into a process set between 100 - 160°C in a low temperature region and a process set between 140 - 210°C in a high temperature region, in the low temperature region, a flat film structure is formed, and in the high temperature region, a three-dimensional film structure is formed. The film structure can be produced separately as a flat film structure and a three-dimensional structure. The resin-based protective layer 14 is formed by the treatment of the gravure printing machine 60. Through the treatment by the 1 type furnace 61 and the 2 type furnace 62, the treatment by the far-infrared heater 67, hot air treatment, pressure treatment, and cooling treatment, drying of the liquid preparation, annealing, film modification, and film bonding can be carried out.

[0111] [Manufacturing Method 13] The above three-dimensional structure becomes a continuous film structure presenting a ridged shape. It forms a continuous three-dimensional film with a bow-shaped cross-section. It forms a continuous three-dimensional structure with a cross-section having a chord length of 10 - 70μm, a height of 10 - 270μm, and an arc length of 40 - 550μm.

[0112] The photograph shown in FIG. 8 shows the surface of the transferred transfer laminate 12. The right photograph shown in FIG. 9 shows the surface of the transfer laminate 12 including the resin-based protective layer 14 containing a plasticizer. The left photograph shown in FIG. 9 shows the surface of the transfer laminate 12 including the resin-based protective layer 14 not containing a plasticizer. The photograph shown in FIG. 10 shows an enlarged view of the uneven portion of the surface shown in FIG. 9.

[0113] The formation is carried out as follows. The release layer 13 is formed by heating and drying on the base film 11 in the drying furnace 61 of the gravure printing machine 60. Next, the resin-based protective layer 14 containing a plasticizer is formed by heating and drying in the drying furnace 61. Then, the metal layer 15 is formed using a two-chamber semi-continuous vacuum evaporator via a high-frequency excited plasma activation reactive device. Next, annealing treatment is performed in the drying furnace 62 of the gravure printing machine 60 at a high temperature in the range of 150 to 210 °C for the film formed with the release layer 13, the protective layer 14, and the vapor deposition film on the base film 11, and continuous hot air treatment, external furnace pressurization treatment, and external furnace cooling treatment are carried out. In this machine, the release layer 13, the protective layer 14, and the vapor deposition layer are integrated and stretched and raised to exhibit a fine three-dimensional structure without damage. Next, the adhesive layer 16 is heated and dried using the drying furnace 61 of the gravure printing machine 60 to complete the three-dimensional film of the transfer laminate 12.

[0114] In the formation of the three-dimensional film, the interface between the protective layer 14 and the metal layer 15 has a film formation with excellent bonding properties for affinity-based interface fixing. In the above example, it has a continuous three-dimensional structure with a bow-shaped or arc-shaped cross-section of 20 to 550 μm. When the area of the film after vapor deposition film formation and the area after the process of the drying furnace 62 were compared and measured in a state including the film, they were of the same area. After the operations of heat treatment, hot air treatment, pressurization treatment, and cooling treatment of the resin-based protective layer 14 containing a plasticizer and the metal layer 15, a three-dimensional film was formed, and the cross-section of the bow-shaped arc showed 20 to 550 μm, representing the stretching ratio. No cracks, fractures, bulges, etc. were observed in either the protective layer 14 or the metal layer 15 after stretching. There was no change in the brightness after transfer.

[0115] The resin-based protective layer 14 containing a plasticizer becomes a thermosetting resin film by heating, hot air, pressurization, and cooling treatment with the drying furnaces 61 and 62 of the gravure printing machine 60, and the film is hardened. The plasticizer in the mesh structure film imparts flexibility to the film quality. Furthermore, by using a plasticizer that migrates and induces into the film within a limit, a plurality of plasticizers having flexibility and migration inductivity are formulated and attached into the cured film of the protective layer 14. As a result, the protective layer 14 is imparted with a film quality from a hard and tough film quality to flexibility and interfacial inductivity. The protective layer 14 having hard and tough properties in the film becomes sticky, and the flexibility becomes stretchable. The interfacial inductivity of the plasticizer guides the interfacial portion of the protective layer 14 having an affinity for the metal deposition layer and the grain boundaries of the island-like layers of the metal layer 15. The plasticizer needs to maintain the heat resistance of the transfer laminate 12 in combination with the performance showing flexibility. The transfer laminate 12 needs to withstand the heat load of transfer prior to the generation of the flexibility of the protective layer 14 during thermocompression transfer. The flexibility of the protective layer 14 is manifested during external furnace pressurization, and together with the agent having migration inductivity, the affinity for the metal layer 15 is promoted, and the fixing at the interface between the protective layer 14 and the metal layer 15 is enhanced by external furnace cooling. The number of plasticizers added to the resin-based protective layer 14 needs to be one or more for the function to be established.

[0116] Furthermore, through the continuous operations of heating, hot air, pressurization, and cooling by the gravure printing machine 60, the resin-based protective layer 14 containing a plasticizer has heat resistance as a thermosetting resin film, the stress is removed by annealing treatment and pressurization for baking the dry film, and it also has the generation of flexibility by the plasticizer. The plasticizer having interfacial inductivity in the film guides to the interface of the metal layer 15 together with the flexible plasticizer. The heat resistance, flexibility, and stretchability of the protective layer 14 are enhanced from the generation of interfacial affinity to further adhesion fixing by forced pressurization and forced cooling. The protective layer 14 and the metal layer 15 have heat resistance, flexibility, and stretchability in addition to a hard and tough film quality, and a film is formed that maintains the adhesion between the layers.

[0117] Between the resin-based protective layer 14 containing a plasticizer and the metal layer 15, a plasticizer that imparts flexibility to the protective layer 14 and a plasticizer that acts as a migratory agent are selected. Further, the plasticizer maintains heat resistance during transfer. By preventing the lack of affinity with the interface of the metal layer 15, when operations such as heating, hot air, pressurization, and cooling are performed, the metal layer 15 undergoes metal plastic deformation, and due to the induction by the plasticizer in the formulation of the protective layer 14 along its metal deposition structure or metal island structure, the affinity increases. Furthermore, by intervening in the metal layer 15, it progresses to bondability, and the fixing between layers further proceeds.

[0118] Defects of the transfer foil 10 include incomplete peelability, poor film breakage accuracy, occurrence of cracks, occurrence of splits, cracks, peeling, swelling, poor interlayer adhesion, foil peeling due to interlayer defects, poor transfer heat resistance, poor glossiness, poor weather resistance, foil peeling due to poor adhesion, incomplete slipperiness of the foil surface layer, decolorization, poor film permeability causing attenuation of the metallic effect, etc. Among these, for cracks, splits, and swelling, as phenomena occurring during transfer, they lead to a drop in gloss, a factor for foil peeling over time, and damage to the aesthetic feeling. In the object to be transferred 32, dimensional changes also occur over time due to humidity, temperature, and climate. Due to these effects, the transfer laminate 12 also loses its decorative property, gets damaged, and undergoes foil peeling.

[0119] Figs. 11 to 14 are photographs of cracks, splits, and swelling of the transfer laminate 12.

[0120] The transfer laminate 12 has layers with different functions and is formed by selecting and assigning materials. Each layer obtains heat-sensitive, pressure-sensitive, and time transfer conditions as the transfer foil 10, and the transfer laminate 12 peels off from the base film 11, resulting in the same root property of film breakability for all layers, and accurately transferring and transferring the shape of the image of the plate-making material. Also, in the object to be transferred 32, there are general printed materials, paper products, bookbinding products, film sheets, electric wire tubes, resin processed and molded products, leather products, fiber products, wood products, glass products, metal products, etc., and the morphological shapes are diverse. The transfer shape ranges from a planar shape to a three-dimensional shape, and during transfer, due to the influence on the difference in stress correspondence and cohesive force between the object to be transferred 32 and the transfer foil 10, it concentrates as expansion and contraction in the transfer laminate 12. This leads to the above-mentioned defects in the transfer foil 10.

[0121] In view of the above, in this embodiment, in order to suppress cracks, cracks, swelling, etc. in the transfer foil 10 and improve heat resistance, light resistance, etc., the material selection for the transfer laminate 12 is improved, the adhesion strength between layers is improved, the stretch resistance is improved, and the stress in each film is controlled. In order to find countermeasures for the problems that occur between the transfer laminate 12, the transfer equipment, and the object to be transferred 32, repeated experiments have been carried out, and the details are given below.

[0122] [Experiment 1] 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 composed 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-Tropsch wax (Sadole Co.; A859), and 0.9% by weight of an acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301) was prepared, coated and dried by a gravure printing machine 60, and a release layer 13 with a thickness of 0.5 μm was formed. Using a single-zone furnace 61 of the gravure printing machine 60, it was allowed to stay in a heating temperature of 100 to 120 °C for 20 to 50 seconds to produce a flat film (release layer 13) with a thickness of 0.5 μm.

[0123] Next, a resin-based protective layer 14 was formed on the release layer 13, formulation was carried out, coating and drying were performed using a gravure printing machine 60, and a resin-based protective layer 14 with a thickness of 1 μm was formed. The resin-based protective layer 14 consists of 26.9% by weight of toluene (Idemitsu Kosan Co., Ltd.), 16.7% by weight of MEK (methyl ethyl ketone) (Idemitsu Kosan Co., Ltd.), 14.9% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Chemical Holdings), 0.04% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd., Kyoto), 20.6% by weight of an acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301), 11.7% by weight of an acrylic resin (Alpha Kaken Co., Ltd.; Silicon Acrylic Silicate UVHA), 1.19% by weight of an acrylic resin (Wilbur-Ellis Co.; Paraloid AT740), 1.49% by weight of a melamine resin (Nippon Carbide Industries Co., Ltd.; MS-001), 4.4% by weight of a ketone resin (Worley Co.; Polytone K-97), 0.08% by weight of an ultraviolet absorber (BASF; Tinuvin1600), 0.08% by weight of an ultraviolet absorber (BASF; Tinuvin479), 0.08% by weight of a light stabilizer (BASF; Tinuvin249), 0.08% by weight of a light blocking agent (Tokyo Chemical Industry Co., Ltd.; phenyl salicylate), 0.03% by weight of a curing agent (Tokyo Chemical Industry Co., Ltd.; p-toluenesulfonic acid), etc., and was formulated as a thermosetting resin-based protective layer 14.

[0124] The thermoplastic resin-based protective layer 14 was composed of the above excluding the melamine resin and the curing agent. Using a single furnace 61 with a volume of 5.28 m 3 and staying for 20 to 50 seconds in a heating temperature range of 150 to 210 °C, a flat film (thermoplastic resin-based protective layer 14) with a thickness of 1 μm was produced.

[0125] Next, a metal layer 15 was formed. Aluminum was used as the metal, and the coating film thickness was set to 30 to 80 nm using a two-chamber semi-continuous vacuum evaporation apparatus and a high-frequency induction heating metal melting heat source.

[0126] Next, an adhesive layer 16 was formed on the metal layer 15. A film with a thickness of 1 μm and 2 μm was prepared by gravure coating using 50.0% by weight of toluene (Idemitsu Kosan Co., Ltd.), 37.7% by weight of ethyl acetate (Showa Denko K.K.), 1.5% by weight of butyl acetate (Standard Oil Co., Ltd.), 0.07% by weight of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7% by weight of an acrylic resin (Mitsubishi Chemical Corporation; Corponil N2147), 2.7% by weight of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), and 3.0% by weight of a ketone resin (Wally Co., Ltd.; Polytone K-97). Volume 5.28 m 3 A single furnace 61 of was used and the sample was left to stand for 20 - 50 seconds at a heating temperature of 100 - 120 °C to produce flat films (adhesive layer 16) with thicknesses of 1 μm and 2 μm.

[0127] As described above, a transfer foil 10 including a thermosetting resin-based protective layer 14 and a transfer foil 10 including a thermoplastic resin-based protective layer 14 were produced. Also, a transfer foil 10 including an adhesive layer 16 with a thickness of 1 μm and a transfer foil 10 including an adhesive layer 16 with a thickness of 2 μm were produced. Using a hot press transfer machine 51, the occurrence of cracks in the transfer foil 10 was evaluated.

[0128] Confirmation was carried out when the resin-based protective layer 14 was thermosetting or thermoplastic, and when the adhesive layer 16 had a thickness of 1 μm or 2 μm. Also, using an up-down type transfer foil press 31 with a brass flat plate 30 or an up-down type transfer foil press 41 with a brass relief plate 40, a soft vinyl chloride sheet with a thickness of 0.9 mm was used as the transfer body 32, and the occurrence of cracks after transfer was confirmed. The photographs shown in Fig. 11 show cracks, breaks, and bulges in the transfer foil 10. The photograph shown in Fig. 12 shows cracks in the transfer foil 10 on the uneven transfer body 32. The photographs shown in Figs. 13 and 14 are magnifications of the openings of the cracks in the transfer foil 10.

[0129] For each of the thermosetting and thermoplastic transfer laminates 12, an up-down type transfer foil press 31 or 41 was used, the transfer temperature was 120 °C or 160 °C, and the transfer pressure was 5 Kg / cm 2, Transfer was carried out under the condition that the transfer residence time was 0.5 seconds. In both the thermosetting and thermoplastic resin-based protective layers 14, the plasticizer content was set to 3.0%. As a result, no cracks were observed on any of the transfer foils 10. No elongation of the soft vinyl chloride sheet was also observed. The results are shown in Table 1. In the table, "○" indicates good, and "×" indicates bad. The same applies to the following tables.

[0130]

Table 1

[0131] [Experiment 2] Also, by changing the transfer residence time, the change in the elongation of the transfer target 32 and the influence on the transfer foil 10 were set and confirmed as follows. The transfer residence time was divided into three stages: 0.5 seconds, 0.75 seconds, and 1.00 seconds. The transfer temperature was 160°C, and the transfer pressure was 5 Kg / cm 2 . An up-down type transfer foil press 41 using a relief plate 40 (vertical 3 mm × horizontal 6.75 mm × height 2 mm) was used as the transfer machine. The thickness of the adhesive layer 16 was 1 μm. The transfer laminate 12 was composed of a release layer 13, a resin-based protective layer 14, a metal layer 15, and an adhesive layer 16. However, the resin-based protective layer 14 was a thermosetting or thermoplastic resin. The formulation was the same as in Experiment 1 above. After transfer, when the elongation of the soft vinyl chloride sheet was confirmed, when the transfer residence time was 0.5 seconds, there was no elongation of the soft vinyl chloride sheet. When the transfer residence time was 0.75 seconds, the soft vinyl chloride sheet showed an elongation of 2% of the original transfer size. When the transfer residence time was 1.00 seconds, the elongation showed an increase of 8.2%. When the cracks in the transfer foil 10 were confirmed, no cracks were confirmed in the case of 0.5 seconds. Cracks were confirmed in the cases of 0.75 seconds and 1.00 seconds. The crack state of the transfer foil 10 was recorded in Table 2. Here, the protective layer 14 was divided into thermosetting and thermoplastic, and the transfer residence time was divided into 0.5 seconds, 0.75 seconds, and 1.00 seconds.

[0132] Also, regarding the elongation during the transfer of the soft vinyl chloride sheet, the elongation ratio (%) obtained by expressing the measured value of the elongation part of the soft vinyl chloride sheet from the transfer plate and the transfer plate end face as a ratio, and the crack opening width (μm) obtained by measuring the opening width of the cracked part are shown in Table 2. When the transfer residence time was 0.5 seconds, no cracks occurred. When the transfer residence time was 0.75 seconds, the soft vinyl chloride sheet elongated by 2%, and the opening width was 7 μm. When the transfer residence time was 1.00 seconds, the soft vinyl chloride sheet elongated by 8.2%, and the opening width was 282 μm. From these results, transfer conditions involving heating, pressurization, and time onto the soft vinyl chloride sheet as the object to be transferred 32 were applied, and due to the cycle until the pressure was released and it returned to normal temperature, the metal layer 15 of the transfer laminate 12 was affected by the tensile stress and compressive stress of the soft vinyl chloride sheet expanding and contracting, and the cohesive failure of the metal layer 15 with weak cohesive force progressed. The stress of the break advanced from the break of the metal layer 15 to the interface of the protective layer 14 and then to the protective layer 14, resulting in the generation of cracks. The resin-based protective layer 14 cracked in both cases of thermosetting and thermoplastic when the transfer residence time was either 0.75 seconds or 1.00 seconds. The results are shown in Table 2. When the protective layer 14 did not contain a plasticizer, both the crack opening width and the elongation ratio became extremely large.

[0133]

Table 2

[0134] [Experiment 3] From the results of the above Experiment 2, it was found that cracks occurred when the transfer residence time was 0.75 to 1.00 seconds. In order to improve this, it is necessary to equip the transfer foil 10 with means for coping with the expansion and contraction of the object to be transferred 32. The object to be transferred 32 has material shapes covering a wide range of materials such as flat surfaces, three-dimensional surfaces, hard materials, soft materials, organic materials, and inorganic materials. Between the object to be transferred 32 and the transfer laminate 12, it is necessary to cope with deformations such as strain, elongation, contraction, displacement, torsion, bending, and inclination due to various stresses such as external forces and internal forces generated during transfer. The transfer laminate 12 cannot withstand the interfering deformation and expansion and contraction generated between the transfer operation and the object to be transferred 32, leading to film breakage and shearing. It is difficult to maintain the film properties of the transfer laminate 12 with respect to the effects received from the film having transfer breakage properties, the expansion and contraction of the object to be transferred 32, and the action of various stresses due to transfer. Here, a form that can withstand cracks and the like while maintaining the breakage and shearing properties of the transfer laminate 12 and also maintaining stretchability was examined.

[0135] Selected from among the aforementioned plasticizers, as the deformation of the transfer laminate 12 caused by the transfer expansion of the flexible vinyl chloride sheet, the selection of additive materials was carried out in the formulation of the resin-based protective layer 14 for maintaining resistance to the influence on the generation of cracks in the transfer foil 10. As the functions obtained when introduced as compounding additives such as the resin-based protective layer 14 and the color-developing resin-based protective layer 14, there are flexibility, stretchability, transparency, good mixing affinity, no inhibition of interlayer adhesion, no whitening phenomenon and interface alteration after component migration, no change over time, no change in heat resistance, and no influence on the breakage of the film, etc. For the selection of these, each layer was sequentially laminated on the base film 11 to produce the transfer foil 10.

[0136] In the lamination of the release layer 13, the resin-based protective layer 14, the metal layer 15, the adhesive layer 16, etc. on the base film 11, there are the resin-based protective layer 14 and the adhesive layer 16 at the interface of the metal layer 15 with weak cohesiveness. If the stretchability of the resin-based protective layer 14 is improved, the deformation of the transfer laminate 12 can be prevented. A thermosetting film was used as an inhibitor for cracks caused by plastic deformation of the film, and a plasticizer was added to obtain flexibility and stretchability and to prevent a decrease in the softening point and shearing of the film.

[0137] On a base film 11 made of a polyester film with a thickness of 12 μm, a release layer 13 was formed in the same manner as in Experiment 1 above, and then a resin-based protective layer 14 was formed thereon. With respect to the resin-based protective layer 14, 26.9% by weight of toluene (Idemitsu Kosan Co., Ltd.), 17.2% by weight of MEK (Idemitsu Kosan Co., Ltd.), 14.9% by weight of MIBK (methyl isobutyl ketone) (Mitsubishi Chemical Holdings), 0.04% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 20.6% by weight of an acrylic resin (Nippon Shokubai; UV-G301), 11.7% by weight of an acrylic resin (Alfa Chemical Research; UVHA), 1.19% by weight of an acrylic resin (Wilber-Ellis Co.; Paraloid AT-740), 1.49% by weight of a melamine resin (Nippon Carbide Industries Co., Ltd.; MS001), 4.4% by weight of a ketone resin (Worley Co.; Polytone K97), 0.08% by weight of an ultraviolet absorber (BASF; Tinuvin 1600), 0.08% by weight of an ultraviolet absorber (BASF; Tinuvin 479), 0.08% by weight of a light stabilizer (BASF; Tinuvin 249), 0.08% by weight of a light blocking agent (Tokyo Chemical Industry Co., Ltd.; phenyl salicylate), 0.03% by weight of a curing agent (Tokyo Chemical Industry Co., Ltd.; p-toluenesulfonic acid), and 1.0% by weight of a plasticizer were added.

[0138] As the plasticizer, the following (1) to (5) were selected. (1) Paraffins (Nippon Seiro Co., Ltd.; Paraffin Wax 115) (2) Low molecular weight polyesters (Mitsubishi Chemical Corporation; adipic acid polyester D620) (3) Phosphate esters (Tokyo Chemical Industry Co., Ltd.; phosphate ester PO271) (4) Sulfonamides (Fujifilm Wako Pure Chemical Corporation; benzenesulfonamide) (5) Ethylene olefins (Idemitsu Kosan Co., Ltd.; Linearene 6)

[0139] As the coating film conditioner, one type of furnace 61 (volume 5.28 m 3) was used to form a film by passing through and staying in an atmosphere of 150 to 210 °C for 20 to 50 seconds. The film thickness was set to 1 μm. Next, in the same manner as in Experiment 1 above, a metal layer 15 and an adhesive layer 16 were formed, and thereby a transfer foil 10 having a flat film structure was produced. Next, using an up-down type transfer foil press 41 equipped with a relief plate 40, hot pressure transfer was performed on a soft vinyl chloride sheet, the base film 11 was peeled off, and the transferred state was confirmed.

[0140] As evaluation items of the plasticizer, the following functions were determined. 1: Mixability in the formulation (affinity with other materials during mixing in the formulation) 2: Transparency of film formation (permeability of the coating film during coating) 3: Flexibility of film formation (cracks in the foil due to relief plate platemaking of the transfer device, soft vinyl chloride sheet as the material to be transferred) 4: Flexibility of the transfer laminate 12 (cracks in the foil due to relief plate platemaking of the transfer device, soft vinyl chloride sheet as the material to be transferred) 5: Heat resistance of the transfer laminate 12 (relief plate platemaking of the transfer device, temperature 160 °C, transfer residence time 0.5 seconds, transfer pressure 5 Kg / cm 2 , material to be transferred, soft vinyl chloride sheet, attenuation of luster) 6: Breakability of the transfer laminate 12 (breakage of the transfer film of the pictorial image during transfer, state of the shearing posture) 7: Compatibility at both interfaces of the protective layer 14 (affinity at the adjacent layer interfaces, by peeling with an adhesive tape) 8: Stretchability of the transfer laminate 12 (relief plate platemaking of the transfer device, temperature 160 °C, transfer residence time 0.75 seconds, transfer pressure 5 Kg / cm 2 , presence or absence of cracks in the pictorial image on the soft vinyl chloride sheet as the material to be transferred) 9: Interlayer adhesion at both interfaces of the protective layer 14 (confirmed by the peeling state of the interface by setting upper and lower adhesive tapes inside the transfer layer and performing a 180 °C peel test) 10: Migration property of the added plasticizer (putting the transfers on the soft vinyl chloride sheet together, applying a load of 500 g, after passing 48 hours at 160 °C in a thermo-hygrostat, returning to room temperature, and confirming by peeling)

[0141] Table 3 shows the determination contents and results.

[0142] [Table 3]

[0143] (a) Paraffin-based and (b) low-molecular-weight polyester-based are particularly lacking in flexibility, so they may be excluded from the selection targets. (c) Phosphate ester-based lacks flexibility, so it may be excluded from the selection targets. (d) Toluene sulfonamide-based showed no abnormalities in all evaluation items. Specifically, characteristics were recognized in flexibility and heat resistance, but no abnormalities were recognized in extensibility, stretchability, interlayer adhesion, and migration. (e) Ethylene olefin-based showed abnormalities in extensibility, stretchability, interlayer adhesion, and migration, but characteristics of interfacial induction were recognized in migration. The use of this material was determined by the addition amount so that the affinity to the metal layer 15 of the protective layer 14 was improved, and the effect was confirmed. As a result, (d) toluene sulfonamide-based was good in all evaluation items. (e) Ethylene olefin-based was selected to reconfirm the interfacial induction. As described above, it is preferable to select (d) toluene sulfonamide-based and (e) ethylene olefin-based.

[0144] [Experiment 4]

[0145] (d) The protective layer 14 added with a toluene sulfonamide-based and (e) an ethylene olefin-based plasticizer was selected. In these two points, in order to confirm the change in the heat-affected transfer laminate 12, a transfer laminate 12 with a flat film structure was produced and a heat resistance test was conducted. As the test content, through the evaluation of the heat resistance test, it was determined whether it would lead to cracks, breaks, swelling, etc. of the transfer foil 10 resulting from results such as transfer pressure, transparency, heat resistance, stretchability, interlayer adhesion, and migration.

[0146] The heat resistance evaluation was conducted as follows. On a transparent glass with a length of 10 cm × width of 10 cm × thickness of 0.5 cm, an acrylic binder film with a length of 10 cm × width of 3 cm × thickness of 1 μm was printed and coated by silk screen and dried to obtain a resin film as the object to be transferred 32.

[0147] A transfer foil 10 was produced, which included a thermosetting protective layer 14 provided with a release layer 13 on a base film 11 and containing a (d) toluenesulfonamide plasticizer. Further, a transfer foil 10 including a protective layer 14 containing an (e) ethylene olefin plasticizer was also produced in the protective layer 14.

[0148] Using the roll-type hot press transfer machine 51 shown in Fig. 5, the above two types of transfer foils 10 were hot press transferred. The transfer machine 51 used a silicon rubber roller as a heat and pressure application medium, and transferred to an acrylic resin layer formed on glass with a transfer line pressure of 0.5 Kg / cm 2 , at a foil feeding speed of 2.5 m / sec and a roller heated temperature of 200°C. After 2 hours had passed since the transfer, five specimens of each of the above two types transferred to a glass substrate were placed in a constant temperature bath. After heating from room temperature to 380°C over 200 minutes, staying for 5 minutes, and then cooling to room temperature over 150 minutes. After 12 hours had passed since the cooling, it was taken out and the transfer laminate 12 on the specimen was confirmed. The visual results were used to identify and evaluate the effects of the plasticizers added from items such as gloss attenuation due to changes in transparency, influence on the metallizing effect, inhibition of adhesion due to migration of the plasticizer within the protective layer 14, cracks generated in the transfer laminate 12, cracks generated between the transfer body 32 and the transfer laminate 12, and swelling generated in the transfer laminate 12.

[0149] Regarding the (d) toluenesulfonamide plasticizer, no problems such as brilliance, adhesion, crack generation, crack occurrence, or swelling occurrence were observed. Regarding the (e) ethylene olefin plasticizer, in terms of adhesion, a partial delamination phenomenon occurred between the release layer 13 and the protective layer 14 and between the protective layer 14 and the metal layer 15 in the cellophane tape peel test. The (d) toluenesulfonamide plasticizer remained within the protective layer 14, and the (e) ethylene olefin plasticizer showed migratability in the thermosetting film of the protective layer 14.

[0150] The above evaluation results are shown in Table 4.

[0151]

Table 4

[0152] Five specimens were prepared respectively. All the evaluation results were the same as those in Table 4.

[0153] [Evaluation Method] Heat resistance: Using the thermal transfer machine 51, transfer was carried out at a temperature of 160°C, a transfer line pressure of 0.5 Kg / cm 2 , and a transfer residence time of 0.5 seconds. Luminosity: After transfer was carried out at a temperature of 160°C, a transfer line pressure of 0.5 Kg / cm 2 , and a transfer residence time of 0.5 seconds, visual confirmation was made. Adhesion: Using an adhesive tape with a width of 15 mm, confirmation was made by a 180-degree peel test. Crack occurrence: The specimen was magnified 500 times and visually confirmed. Fracture occurrence: The specimen was magnified 500 times and visually confirmed. Swelling occurrence: The specimen was magnified 500 times and visually confirmed.

[0154] [Evaluation Results] (d) Toluene sulfonamide-based: No problems were found in the heat treatment. (e) Ethylene olefin-based: A problem of delamination occurred in terms of adhesion.

[0155] [Experiment 5] Regarding the results of the above Experiment 4, for the (e) ethylene olefin-based plasticizer, a phenomenon of partial delamination occurred at both interfaces of the protective layer 14. The protective layer 14 in which the plasticizer was formulated is a thermosetting film, indicating that the (e) ethylene olefin-based plasticizer migrated to and reached both interfaces of the release layer 13 and the metal layer 15 without being blocked by the aggregated resin chains in this film.

[0156] As for the film structure, in order to complement functions such as reducing the elasticity of the protective layer 14, maintaining the breakability, increasing the stretchability, maintaining the migration inductivity, imparting flexibility, and maintaining the interface adhesion, the addition amount was specified.

[0157] The amount of (e) ethylene olefin plasticizer added to the protective layer 14 was set at 0.075 wt%, 0.05 wt%, and 0.025 wt% to prepare formulations, form the transfer laminate 12, and produce the transfer foil 10 having a flat film structure.

[0158] As described above, resin processing was performed on the glass substrate, roll transfer was performed, the substrate was left in a constant temperature bath, taken out, and performance was confirmed in the order described above. The results are shown in Table 5. In the table, "Δ" indicates that it is not defective but contains defects.

[0159] Regarding the (e) ethylene olefin plasticizer, when the upper limit of its addition amount was set at 0.025 wt%, it was found to be effective without change in adhesion. It can be used as an interlayer propagator of the flexibility of the resin-based protective layer 14 together with other plasticizers as a flexibility propagator for material migration inductivity and the like.

[0160] The above evaluation results are shown in Table 5.

[0161]

Table 5

[0162] [Evaluation method] Heat resistance: Confirmed visually. Adhesion: After taking out from the constant temperature bath, a 180-degree peel test was performed using a 15-mm wide adhesive tape. Crack generation: The specimen was magnified 500 times and visually confirmed. Fracture generation: The specimen was magnified 500 times and visually confirmed. Bubble generation: The specimen was magnified 500 times and visually confirmed.

[0163] [Evaluation results] Heat resistance: There was no change in brilliance, and all showed good results. Interlayer adhesion: When the addition amount was 0.075 wt%, it showed poor results; when it was 0.05 wt%, it showed that it contained defects; when it was 0.025 wt%, it showed good results. (e) The ethylene olefin plasticizer was added at 0.025% by weight. As a result of visually observing the adhesion, crack generation, cracking, and swelling after the heat resistance test, it was confirmed that it was not related to film deterioration and the resistance could be maintained.

[0164] [Experiment 6] Due to the above process, the (e) ethylene olefin plasticizer migrated to the interface of the layer in the curable resin film in the protective layer 14 of the thermosetting resin film. This led to the peeling of the interface of the protective layer 14. Furthermore, as a result of attempting to adjust the addition amount, with the addition amount of 0.025% by weight as the upper limit, there was no abnormal occurrence regarding the peeling of the interlayer adhesion, and it became possible to be involved in the migration induction in the protective layer 14.

[0165] Regarding the phosphate ester-based, toluenesulfonamide-based, and ethylene olefin plasticizers as the plasticizers contained in the protective layer 14, it has been confirmed in Experiment 3 that they can be used for heat resistance.

[0166] As the effect of adding the plasticizer, it is predicted that by inducing the generation of flexibility in the protective layer 14 and the propagation of flexibility to the interface of the protective layer 14, the affinity of the interface of the protective layer 14 for the bonding property with the metal layer 15 can be increased. By performing interface modification of the protective layer 14 through heat treatment by the gravure printing machine 60 with the addition of the plasticizer, miscibility, transparency, breakability, compatibility, flexibility, heat resistance, and migration induction are generated in the thermosetting film. The spread of the temperature range of the protective layer 14 containing the plasticizer reaches the interface in the curable film of the protective layer 14. When the tough film with thermosetting property of the protective layer 14 is modified into a flexible film of the resin-based protective layer 14 and the metal layer 15 while maintaining heat resistance, migration induction is a necessary condition as the plasticizer to be contained.

[0167] In the preparation of the thermosetting resin-based protective layer 14 in Experiment 1, 1% by weight of the plasticizer benzenesulfonamide (Fuji Film Wako Pure Chemical Industries, Ltd.) and 0.025% by weight of the plasticizer ethylene olefin-based resin (Idemitsu Kosan Co., Ltd.; Linearlene 6) were additionally added to impose the expression of flexibility, heat resistance, and migration inductivity, and the release layer 13, the protective layer 14, the metal layer 15, and the adhesive layer 16 were formed to fabricate the transfer laminate 12 having a flat film structure.

[0168] It was carried out according to the processing on the glass substrate described in Experiment 4. Thermocompression transfer using a roll-type transfer device was performed, a heat resistance test of staying in a constant temperature bath was carried out, and it was taken out and confirmed. No phenomena of cracks, fractures, or swelling were observed. The results are shown in Table 8. For the coating film formation using the drying furnace 1 type furnace 61 of the gravure printing machine 60, by adding (d) toluenesulfonamide-based plasticizer and (e) ethylene olefin-based plasticizer into the tough thermosetting resin film, flexibility, heat resistance, and the migration inductivity of flexibility were taken into account.

[0169] The above evaluation results are shown in Table 6.

[0170]

Table 6

[0171] [Evaluation method] A resin coat was applied to a glass substrate. After transfer by the roll-type transfer method, it was stored in a constant temperature bath, heated from room temperature to 380 °C, stayed for 5 minutes, cooled to room temperature, and then the resistance was confirmed. In addition, it was carried out in the same manner as in Experiment 2 above. Interface adhesion after the heat resistance test: A 180-degree peel test was performed using an adhesive tape with a width of 15 mm. Crack generation: The specimen was magnified 500 times and visually confirmed. Fracture generation: The specimen was magnified 500 times and visually confirmed. Swelling generation: The specimen was magnified 500 times and visually confirmed.

[0172] [Evaluation results] As shown in Table 6, as a result of the heat resistance test, no problem was found with the interfacial adhesion between the protective layer 14 and the release layer 13 or the metal layer 15. No change was observed in the phenomena of cracks, fractures, or swelling either.

[0173] [Experiment 7] A protective layer 14 was prepared by adding 1% by weight of a benzenesulfonamide-based plasticizer and 0.025% by weight of an ethylene olefin-based plasticizer. Using this, a resin-based protective layer 14 was formed. On the base film 11, a transfer laminate 12 having a flat film structure composed of a release layer 13, a protective layer 14, a metal layer 15, and an adhesive layer 16 was formed to prepare a specimen. Using this specimen, hot stamping was performed on a flexible vinyl chloride sheet with a relief plate 40 (3 mm in length × 6.75 mm in width × 2 mm in height of the convex portion) using an up-down type transfer foil press 41. The transfer temperature was 160°C, the transfer pressure was 5 Kg / cm 2 , and the transfer residence time was carried out in each case. The followability of the transfer laminate 12 with respect to the elongation of the flexible vinyl chloride sheet was confirmed. Table 7 shows the results of the elongation during transfer to the flexible vinyl chloride sheet and the occurrence of cracks.

[0174] At a transfer residence time of 0.5 seconds, no elongation of the flexible vinyl chloride sheet was confirmed, no opening was observed, and no phenomena of cracks or fractures were found either. At a transfer residence time of 0.75 seconds, there was an elongation of 2.4%, and the opening width of the crack was 8.4 μm. At a transfer residence time of 1.00 seconds, there was an elongation of 11.48%, and the opening width of the crack was 394 μm.

[0175] Furthermore, during thermal transfer, in order to confirm the elongation of the flexible vinyl chloride sheet and the occurrence of openings and cracks in the transfer laminate 12, the transfer residence time was set in intervals from 0.5 seconds to 0.75 seconds at 0.58 seconds, 0.66 seconds, and 0.74 seconds. As a result, at a transfer residence time of 0.58 seconds, the elongation of the sheet was 0.8% and the opening width was 0 μm. At a transfer residence time of 0.66 seconds, the elongation of the sheet was 1.6% and the opening width was 5.6 μm. At a transfer residence time of 0.74 seconds, the elongation of the sheet was 2.4% and the opening width was 8.4 μm. The transfer laminate 12 having a flat film structure including the protective layer 14 containing a plasticizer was found to withstand up to 0.8% of the elongation occurring in the flexible vinyl chloride sheet at a transfer residence time of 0.58 seconds with respect to the followability of the transfer laminate 12 to the elongation of the flexible vinyl chloride sheet.

[0176] The above evaluation results are shown in Tables 7 to 9.

[0177]

Table 7

[0178]

Table 8

[0179]

Table 9

[0180] For the protective layer 14, one or more plasticizers were selected and added to the formulation. It has both heat resistance and flexibility, and the adhesion between the protective layer 14 and the metal layer 15 is good. The elongation of both layers is shown in Table 7 when observing the progress of Experiment 7 above. At a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride flexible sheet was 0.8%, and no crack openings were observed in the transfer foil 10 to which two types of plasticizers were added. It was found that this was the effect of the plasticizer received by the resin-based protective layer 14 and it follows the elongation of the object to be transferred 32.

[0181] The flexibility of the protective layer 14 containing a plasticizer can weaken the internal stress applied during film formation, thereby simultaneously weakening film breakage and film shearing with respect to the metal layer 15. During transfer, it is possible to relieve cracks, breaks, bulges, etc. of the transfer laminate 12 that appear due to cohesive failure occurring in the metal layer 15 caused by the stretching that occurs in the transfer body 32 and the stretching that occurs in the transfer laminate 12. When the transfer body 32 exhibits a stretch of 0.8% or more, the internal stress and fracture shear stress applied to the protective layer 14 and the metal layer 15 cannot be weakened, and there is a risk of a decrease in brilliance and peeling from the transfer body 32 over time.

[0182] Figures 11 to 14 are photographs of cracks, breaks, bulges, etc.

[0183] Examples of the base film 11 include polyesters such as polyethylene terephthalates, polypropylene, polycarbonate, vinyl chloride, polystyrene, polyethylene, polyimide, etc. The thickness of the film is selected from 12 to 75 μm. A release layer 13 is provided between the base film 11 and the protective layer 14. It is a layer made of resins and waxes, and polyethylene-based resins, polypropylene-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, acrylic-based resins, urethane-based resins, melamine-based resins, epoxy-based resins, fluorine-based resins, waxes, etc. can be used, and it can be a single product or a mixture of one or more. The thickness of the release layer 13 is preferably 0.1 to 10 μm. The protective layer 14 is a preparation using one or more of acrylic resins, melamine resins, ketone resins, curing agents, ultraviolet absorbers, light stabilizers, light blockers, dyes, pigments, inorganic agents, and plasticizers. The thickness is preferably 1 to 20 μm. The metal layer 15 can use an alloy using one or more metals such as Ag, Cu, Sn, In, Al, Ni, Cr, Si, Zn, In2O3, CdO, CdIn2O4, Cd2SnO4, TiO2, SnO2, ZnO, SiO2, ZrO2, ZnS, MgF2. The thickness of the metal layer 15 is preferably 20 to 60 nm. The metal layer 15 can be formed by wet plating, dry plating, or electroless plating. Considering the adhesion between the resin-based protective layer 14 and the metal layer 15, dry plating is selected. Specifically, vapor deposition such as vacuum vapor deposition, electron beam vapor deposition, chemical vapor deposition, and sputtering, etc. can be mentioned. The adhesive layer 16 has the function of adhering the transfer object 32 and the transfer laminate 12 (modified laminate). Examples of the adhesive include acrylic resins, chlorinated polypropylene-based resins, vinyl chloride acetate-based resins, and polyester-based resins. It can also be a preparation mixed with one or more. The thickness of the adhesive layer 16 is preferably between 1 and 10 μm. Examples of the transfer object 32 include resins, metals, metals, wood, leather, fibers, etc. The release layer 13, the protective layer 14, and the adhesive layer 16 use a gravure printing machine 60. The metal layer 15 uses a two-chamber semi-continuous vacuum vapor deposition apparatus.

[0184] Transfer laminate (modified laminate) 12 A film protective layer 22 may be provided between the base material film 11 and the release layer 13. It is applied using a gravure printing machine 60 with a melamine resin and a sulfonic acid curing agent selected from amino resins and curing agents. It is used to ensure the smoothness of the surface of the base material film 11 and the uniformity of peelability. The film formation adheres to the base material film 11. A thickness between 0.5 and 5 μm is preferable.

[0185] A resin-based protective layer 14 can be provided between the metal layer 15 and the adhesive layer 16. In the structure of the base material film 11, release layer 13, resin-based protective layer 14, metal layer 15, resin-based protective layer 14, and adhesive layer 16, further avoiding cohesive failure of the metal layer 15 by using the same protective layer 14 for both. A color-forming resin-based protective layer 14 using a color former can be provided between the release layer 13 and the metal layer 15. Further, the resin-based protective layer 14 can also be laminated. The metal layer 15 can also be a transfer laminate 12 with the metal layer removed.

[0186] [Experiment 8] A base film of a polyester film with a thickness of 12 μm was used for the base material film 11, and a release layer 13 was formed thereon. A gravure printing machine 60 having one type of drying furnace 61 (volume 5.28 m 3 ) was used to form a film with a thickness of 0.5 to 0.8 μm within a range of 100 to 140 °C and a residence time of 20 to 50 seconds in the furnace by a far-infrared heater 67 and a hot air device 69. The liquid preparation was the same as in Experiment 1. The protective layer 14 was formed using one type of drying furnace 61 (volume 5.28 m 3Using the gravure printing machine 60 having [[ID=]], the flat film with a thickness of 1 to 2 μm was produced by traveling for a residence time of 20 to 50 seconds within the furnace temperature range of 150 to 210 °C by the far-infrared heater 67 and the hot air device 69. The liquid preparation of the protective layer 14 was made into a thermosetting resin film as in Experiment 1. As plasticizers, 1% by weight of benzenesulfonamide (Fuji Film Wako Pure Chemical Industries, Ltd.) and 0.025% by weight of ethylene olefin resin (Idemitsu Kosan Co., Ltd., Linearene 6) were added. Then, the metal layer 15 was formed. Using a two-chamber semi-continuous vacuum evaporation apparatus and a high-frequency induction heating metal melting heat source, the protective layer 14 was coated with aluminum having a thickness of 40 to 60 nm. Next, the adhesive layer 16 was formed. The formulation was the same as in Experiment 1. Film formation was carried out with a thickness of 1 μm at a furnace temperature of 80 to 110 °C and a residence running time of 20 to 50 seconds in the drying furnace 61 of the gravure printing machine 60.

[0187] Using this transfer foil 10 with a flat film structure, 10 glass test pieces described in Experiment 4 were produced and transferred using a roll-type transfer machine 51, and then stored in a constant temperature bath for a heat resistance test. After heating from room temperature to 380 °C over 200 minutes, it was allowed to stay for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours at a constant temperature, it was taken out and the transfer laminate 12 on the specimen was confirmed. Visual inspection was carried out for cracks, fractures, swelling, and loss of gloss, and no abnormalities were observed in any of them.

[0188] [Experiment 9] As the base film of the polyester film with a thickness of 12 μm, the base film was used for the substrate film 11, and the release layer 13 was formed thereon. The drying furnace 61 of the first type (volume 5.28 m 3 ) The gravure printing machine 60 having [[ID=]] formed a film with a thickness of 0.5 μm to 0.8 within the furnace temperature range of 100 to 140 °C and a furnace running residence time range of 20 to 50 seconds by the far-infrared heater 67 and the hot air device 69. The liquid preparation was equivalent to that in Experiment 1. The protective layer 14 was formed in the drying furnace 61 of the first type (volume 5.28 m 3Using the gravure printing machine 60 having [[ID=]], the flat film with a thickness of 1 - 2 μm was produced by running it for 20 - 50 seconds within the furnace temperature range of 150 - 210°C with the far - infrared heater 67 and the hot - air device 69. The liquid preparation of the protective layer 14 was made into a thermosetting resin film as in Experiment 1. As plasticizers, 1 wt% of benzenesulfonamide (Fuji Film Wako Pure Chemical Industries, Ltd.) and 0.025 wt% of ethylene - olefin - based resin (Idemitsu Kosan Co., Ltd., Linerene 6) were added. Then, using the gravure printing machine 60 having two types of drying furnaces 62, an annealing process was carried out to bake the dry film that requires a furnace residence time of 20 - 50 seconds within the furnace temperature range of 100 - 210°C. After that, the metal layer 15 was formed. Using a two - chamber semi - continuous vacuum evaporation device and a high - frequency induction heating metal melting heat source, the protective layer 14 was coated with aluminum having a thickness of 40 - 60 nm. Next, the adhesive layer 16 was formed. The formulation was the same as in Experiment 1. A film with a thickness of 1 μm was formed in the single - type drying furnace 61 of the gravure printing machine 60 at a furnace temperature of 80 - 110°C for a residence running time of 20 - 50 seconds.

[0189] Using this transfer foil 10 with a flat - film structure, 10 glass test pieces shown in Table 2 were produced and transferred using the roll - type transfer machine 51, and then stored in a thermostatic chamber for a heat - resistance test. After heating from room temperature to 380°C over 200 minutes, it was left to stand for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours at a constant temperature, it was taken out and the transfer laminate 12 on the specimen was confirmed. Visual inspection was carried out in terms of cracks, fractures, bulges, and loss of gloss, and no abnormalities were observed in any of them.

[0190] [Experiment 10] A base film of a polyester film with a thickness of 12 μm was used for the base material film 11, and a release layer 13 was formed thereon. A resin-based protective layer 14 was formed by a gravure printing machine 60 having one type of drying furnace 61. Then, a metal layer 15 was formed of aluminum. Thereafter, using the second type of drying furnace 62 of the gravure printing machine 60, with the base material film 11, release layer 13, protective layer 14, and metal layer 15 formed, heating was performed under the conditions of an in-furnace temperature of 150 to 210 °C and an in-furnace running residence time of 20 to 50 seconds for annealing treatment. Thereafter, an adhesive layer 16 was formed according to the above. A transfer laminate 12 having a flat film structure was obtained. A heat resistance test was performed according to the above. Visual inspection results were carried out in terms of cracks, fractures, swelling, and gloss attenuation, and no abnormalities were observed in any of them.

[0191] [Experiment 11] A base film of a polyester film with a thickness of 12 μm was used for the base material film 11, and a release layer 13 was formed thereon. A resin-based protective layer 14 was formed by a gravure printing machine 60 having one type of drying furnace 61. Then, a metal layer 15 is formed of aluminum. Thereafter, using the second type of drying furnace 62 of the gravure printing machine 60, with the base material film 11, release layer 13, protective layer 14, and metal layer 15 formed, heating was performed under the conditions of an in-furnace temperature of 150 to 210 °C and an in-furnace running residence time of 20 to 50 seconds for baking treatment. In addition to the heat treatment by the far-infrared heater 67 in the furnace, hot air at 100 to 140 °C was blown into the furnace by a hot air device 69. Further, using a pressure device 71 outside the furnace directly connected to the furnace, a transfer line pressure of 10 to 50 Kg / cm 2 while an EPDM roll was being pressed against the obtained metal roll. Subsequently, using an external cooling device 72 outside the furnace, the base material film 11, release layer 13, protective layer 14, and metal layer 15 were all passed through the space between the rolls where a Si roll was being pressed against a metal roll maintained at 5 to 15 °C. Thereafter, an adhesive layer 16 was formed according to the above. A transfer laminate 12 having a flat film structure was obtained. A heat resistance test was performed according to the above. Visual inspection results were carried out in terms of cracks, fractures, swelling, and gloss attenuation, and no abnormalities were observed in any of them.

[0192] [Experiment 12] In the film-forming operation according to Experiment 11, by annealing, pressurizing, and cooling with the heating temperature of the two types of drying furnaces 62 of the gravure printing machine 60 set at 180 to 210 °C and the hot air at 120 to 140 °C, a continuous three-dimensional structure with uneven ridged wrinkles was formed. The heat resistance test was carried out according to the above. The visual results were examined for cracks, fractures, swelling, and loss of gloss, and no abnormalities were observed in any of them.

[0193] Photographs showing an enlarged view of the surface after transfer of the transfer laminate 12 having a three-dimensional structure are shown in FIGS. 23 to 25. The parabolic arc-shaped cross-section was as follows. That is, in FIG. 23, the chord length was 22.30 μm, the height was 13.87 μm, and the arc length was 37.25 μm. In FIG. 24, the chord length was 21.96 μm, the height was 35.98 μm, and the arc length was 66.29 μm. In FIG. 25, the chord length was 66.29 μm, the height was 267.30 μm, and the arc length was 542.70 μm.

[0194] The formed films of the release layer 13, the protective layer 14, the metal layer 15, and the adhesive layer 16 were subjected to the addition of a plasticizer, heating by the gravure printing machine 60, hot air, pressurization, and cooling processes, resulting in the generation of film modification leading to layer-to-layer bonding, and no problems occurred even when facing the load of film stretching.

[0195] [Experiment 13] In the film-forming operation according to Experiment 11, by annealing, pressurizing, and cooling with the heating temperature of the two types of drying furnaces 62 of the gravure printing machine 60 set at 120 to 160 °C and the hot air at 80 to 100 °C, a transfer laminate 12 presenting a flat film was obtained. In the treatment of Experiment 12, a three-dimensional structure was formed, but in the treatment of this Experiment 13, a flat film structure was formed. The heat resistance test was carried out according to the above. The visual results were examined for cracks, fractures, swelling, and loss of gloss, and no abnormalities were observed in either the flat film structure or the three-dimensional structure.

[0196] Table 10 shows the evaluation results for cracks, fractures, swelling, and gloss by the heat resistance tests of Experiments 8 to 13.

[0197]

Table 10

[0198] In dealing with cracks, fractures, and bulges in 12 transfer laminates, any manufacturing method in Experiments 8 to 13 can be adopted. In the manufacturing method of Experiment 8, as shown in Table 9, a flat-film transfer laminate 12 that follows the elongation of the transfer object 32 up to 0.8% is shown. In the manufacturing method of Experiment 12, as described above, the elongation of the three-dimensional film transfer laminate 12 shows the length of the cross-section of the arcuate parabolic arc of 40 to 550 μm. As described above, the means to obtain this extensibility can be made into a flat-film or three-dimensional film structure. By means of the first drying furnace 61 of the gravure printing machine 60 and the second drying furnace 62 of the gravure printing machine 60, through processes such as heating, drying of the liquid mixture by hot air, annealing treatment of the dry film of the protective layer 14, and treatment by the pressing device 71 and the cooling device 72, the hardening, softening, and stress modification of the protective layer 14 and the metal layer 15 are achieved, and the extensibility followability of the flat-film and three-dimensional film transfer laminates 12 can be achieved without losing the metallic luster. According to Experiments 8 to 12, (1) drying of the release layer 13 and the protective layer 14 by the first drying furnace 61, annealing drying by the second drying furnace 62, the metal layer 15, the adhesive layer 16, (2) drying of the release layer 13 and the protective layer 14 by the first drying furnace 61, the metal layer 15, annealing treatment by the second drying furnace 62, the adhesive layer 16, or (3) drying of the release layer 13 and the protective layer 14 by the first drying furnace 61, annealing treatment including hot air treatment by the second drying furnace 62, pressing treatment, cooling treatment, the adhesive layer 16. Up to this point, the film can be formed flat by controlling each process. Furthermore, in the high-temperature drying of the release layer 13 and the protective layer 14 by the first drying furnace 61, high-temperature annealing treatment including hot air treatment by the second drying furnace 62, pressing treatment, cooling treatment, the adhesive layer 16, and the high-temperature treatment of the protective layer 14 and the metal layer 15, the film can be formed three-dimensionally.

[0199] Tables 11 to 13 show the processing, processing sequence, resistance, and elongation of the resin-based protective layer 14 and the metal layer 15.

[0200]

Table 11

[0201]

Table 12

[0202] In the table, ○ indicates good and × indicates bad.

[0203]

Table 13

[0204] [Experiment 14] After forming the release layer 13 and the resin-based protective layer 14 on the base film 11, the metal layer 15 was formed using a two-chamber semi-continuous vacuum evaporation machine. Specifically, metal layers 15 of Al, Cr, and Sn were formed in the range of 20 to 65 nm in thickness. Then, the adhesive layer 16 was formed, thereby producing the transfer laminate 12. Next, using a hot press transfer machine 51, onto the calendered glossy paper, at a transfer temperature of 100 to 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2 After transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured for its surface layer using a spectrophotometer calorimeter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance L of Al was 89.44, the spectral reflectance L of Cr was 62.36, and the spectral reflectance L of Sn was 68.31.

[0205] [Experiment 15] The transfer laminate 12 was produced by forming a release layer 13, a color-forming resin-based protective layer 14 containing a gold-containing dye, a metal layer 15 of Al with a thickness of 20 to 65 nm, and a pressure-sensitive and heat-sensitive adhesive layer 16 with a thickness of 1 μm on the base film 11. Next, using a hot press transfer machine 51, onto the calendered glossy paper, at a transfer temperature of 100 to 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2Then, after transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured through the color-forming resin-based protective layer 14 on its surface using a spectrophotocolorimeter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance of Al was L = 80.21. The spatial chromaticity L*a*b* according to JIS Z8781-4 was measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The lightness chromaticity was L = 80.21, a = 3.86, and b = 28.54. The transfer laminate 12 has a flat film structure that obtains the reflection of the metal layer 15 and exhibits a permeable metallized golden color.

[0206] [Experiment 16] On the base film 11, a release layer 13, a color-forming resin-based protective layer 14 containing micronized permeable pigments, a metal layer 15 of Al with a thickness of 20 to 65 nm, and a pressure-sensitive and heat-sensitive adhesive layer 16 with a thickness of 1 μm were formed to produce the transfer laminate 12. Next, using a hot-press transfer machine 51, onto the calendared glossy paper, at a transfer temperature of 100 to 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2 Then, after transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured through the color-forming resin-based protective layer 14 on its surface using a spectrophotocolorimeter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance of Al was L = 82.15. The spatial chromaticity L*a*b* according to JIS Z8781-4 was measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The lightness chromaticity was L = 82.15, a = -0.04, and b = 24.49. The transfer laminate 12 has a flat film structure that obtains the reflection of the metal layer 15 and exhibits a permeable metallized golden color.

[0207] [Experiment 17] On the base film 11, a release layer 13, a color-forming resin-based protective layer 14 containing general-purpose pigments, a metal layer 15 of Al with a thickness of 20 to 65 nm, and a pressure-sensitive and heat-sensitive adhesive layer 16 with a thickness of 1 μm were formed to produce the transfer laminate 12. Next, using a hot-press transfer machine 51, onto the calendared glossy paper, at a transfer temperature of 100 to 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2After transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured through the color-forming resin-based protective layer 14 using a spectrophotometer (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90) on its surface. The lightness and chromaticity were measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90) according to the spatial chromaticity L*a*b* defined in JIS Z8781-4. Due to the appearance of the hiding property of the color-forming resin-based protective layer 14 containing the pigment, the reflectance of Al decreased. The spectral reflectance L of Al was L = 43.99 when containing a blue pigment, L = 61.28 when containing a pink pigment, L = 45.84 when containing a red pigment, L = 81.85 when containing a yellow pigment, and L = 31.63 when containing a black pigment.

[0208] [Experiment 18] After forming a release layer 13, a color-forming resin-based protective layer 14 containing a gold-containing dye, and a metal layer 15 of Al with a thickness of 20 to 65 nm on the base film 11, two types of drying furnaces 62 of a gravure printing machine 60 were used to perform heat treatment, hot air treatment, pressure treatment, and cooling treatment by annealing, and the laminate up to the metal layer 15 was made into a three-dimensional film. Further, by forming an adhesive layer 16 thereon, a transfer laminate 12 was produced. Next, using a hot press transfer machine 51, onto the calendared glossy paper, the transfer temperature was 100 to 140 °C, the transfer residence time was 0.5 seconds, and the pressure was 5 Kg / cm 2 After transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured through the color-forming resin-based protective layer 14 using a spectrophotometer (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90) on its surface. The spectral reflectance L of Al was 75.40. The spatial chromaticity L*a*b* according to JIS Z8781-4 was measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The lightness and chromaticity were L = 75.40, a = 3.06, and b = 28.67. The transfer laminate 12 has a three-dimensional structure that obtains the reflection of the metal layer 15 and exhibits a transparent metallized gold color.

[0209] [Experiment 19] After forming a release layer 13, a transparent resin-based protective layer 14, and an Al metal layer 15 with a thickness of 20 to 65 nm on a base film 11, two types of furnaces 62 of a drying furnace of a gravure printing machine 60 were used to perform heat treatment by annealing, hot air treatment, pressure treatment, and cooling treatment, and the lamination up to the metal layer 15 was made into a three-dimensional film. Further, by forming an adhesive layer 16 thereon, a transfer laminate 12 was produced. Next, using a hot press transfer machine 51, on the calendered glossy paper, at a transfer temperature of 100 to 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm 2 2 After transferring the transfer laminate 12, the reflectance of the metal layer 15 was measured through the transparent resin-based protective layer 14 using a spectrophotometer (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance L of Al was 87.74. The spatial colorimetric values L*a*b* according to JIS Z8781-4 were measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The lightness colorimetric values were L = 87.74, a = -0.17, and b = 0.76. The transfer laminate 12 has a three-dimensional structure that exhibits a transmissive metallized silver color by obtaining the reflection of the metal layer 15.

[0210]

Table 14

[0211] The attenuation of the reflectance of the protective layer 14 was confirmed from the spectral reflectance of the metal layer 15. In Experiment 16, a state with good permeability due to the micronized pigment was found. In Experiment 19, it was found that the reflectance of the Al metal layer 15 does not change even in the film formation of the three-dimensional structure. In Experiment 16, it was found that the pigment of the protective layer 14 exhibits color development and permeability equivalent to those of the gold-containing dye. In Experiment 17, all of the general-purpose pigments shielded the reflection of the Al metal layer 15. In Experiments 18 and 19, no attenuation of the spectral reflectance due to the three-dimensional structure was observed.

[0212] [Experiment 20] A transfer laminate 12 composed of a base film 11 as a frame support, a release layer 13, a color-forming resin-based protective layer 14 using a permeable pigment, an Al metal layer 15, and an adhesive layer 16 was formed. The release layer 13 was set as follows. That is, as solvents, 72.2% by weight of toluene (Idemitsu Kosan Co., Ltd.), 25.4% by weight of MIBK (Mitsubishi Chemical Holdings), and 0.03% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.) were used. As solutes, 1.07% by weight of Fischer-Tropsch wax (Sadole Co.; A859), 0.04% by weight of fatty acid ester (NOF Corporation; WEP), and 0.9% by weight of an acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301) were used, and these were formulated. Using a gravure printing machine 60, a film was formed under the conditions of a drying temperature in the furnace of 90 to 140°C, a residence time in drying furnaces 61, 62 of 20 to 60 seconds, and a thickness of 0.1 to 20 μm. For the resin-based protective layer 14, a pigment was adopted as a color former. Specifically, 14.6% by weight of toluene (Idemitsu Kosan Co., Ltd.), 8.7% by weight of butyl acetate (Standard Oil Co., Ltd.), 17.0% by weight of MEK (Idemitsu Kosan Co., Ltd.), 17.0% by weight of MIBK (Mitsubishi Chemical Holdings Corporation), 0.004% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 20.5% by weight of an acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301), 1.1% by weight of an acrylic resin (Wilbur-Ellis; AT740), 1.3% by weight of a melamine resin (Nippon Carbide; MS-001), 4.3% by weight of a ketone resin (Worley Co.; K-95), 0.1% by weight of a curing agent (Tokyo Chemical Industry Co., Ltd.; p-toluenesulfonic acid), 1.0% by weight of red iron oxide (Mikuni Shikiso Co., Ltd.; 8196M), 0.05% by weight of yellow iron oxide (Mikuni Shikiso Co., Ltd.; 8197M), 1.0% by weight of a red pigment (DuPont; Synkashared Red B), and 0.95% by weight of a yellow pigment (BASF Japan Ltd.; Paliotol Yellow 1070) were arranged to form a preparation liquid. For the release layer 13 and the resin-based protective layer 14, using a gravure printing machine 60, a film was formed under the conditions of a temperature in drying furnaces 61, 62 of 100 to 180°C, a residence time of 20 to 60 seconds, and a thickness of 0.5 to 20 μm. It is even better that the thickness of the resin-based protective layer 14 is in the range of 1 to 10 μm.Setting the particle size of the pigment in the range of 10 to 80 nm is necessary for using the pigment as a colorant by obtaining color rendering property, transparency, and reflectivity from the metal layer 15 to exhibit metallic property. The pigments were sized for fine particle dispersion using a bead mill type pigment disperser KD-5 manufactured by DYNO-MIL. The metal layer 15 was vapor-deposited with aluminum having a thickness of 40 to 60 nm. The thickness of the adhesive layer 16 was 1 to 10 μm, the drying temperature was 80 to 140 °C, and the residence time in the furnace was 10 to 40 seconds. The formulation used 51.7% by weight of toluene (Idemitsu Kosan Co., Ltd.), 37.7% by weight of ethyl acetate (Showa Denko K.K.), 1.5% by weight of butyl acetate (Standard Oil Co., Ltd.), 0.7% by weight of ethyl silicate (Colcoat Co., Ltd.; HAS-10), 2.7% by weight of an acrylic resin (Mitsubishi Chemical Corporation; N2147), 2.7% by weight of an ethylene vinyl acetate resin (Mitsubishi Chemical Corporation; D2908), and 3.0% by weight of a ketone resin (Worley Co., Ltd.; K-95).

[0213] Despite using a pigment, the color rendering of the resin-based protective layer 14 of the completed transfer foil 10 was highly transparent. Transfer was performed using an up-down type hot press transfer machine 51 onto ball paper that had been smoothly calendered and surface resin-coated to produce a specimen (transferred transfer laminate 12). After 800 hours had elapsed, the specimen was taken out using a xenon arc type lightfastness tester (Suga Test Instruments Co., Ltd.; XT1500), and the color displacement ΔE of the color rendering was measured using a spectroscopic color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The results of the presence or absence of exposure are shown in Table 15. The transfer laminate 12 having a metallic layer with a resin-based protective layer 14 containing a refined pigment and obtaining a transparent gold color rendering and metallic reflection was excellent in lightfastness.

[0214]

Table 15

[0215] [Experiment 21] In Experiment 20, since the transfer laminate 12 using the micronized transparent pigment has the metal layer 15, a metallic coloration was shown and one having light resistance was obtained. In Experiment 22, a known material was further used to measure the promotion of the resistance to light resistance.

[0216] It was intended to add a supplementary note on the light resistance of the transfer laminate 12 in which the micronized and transparent pigment exhibits color-developing properties and the reflection of the metallizing-like metal layer 15 is obtained. In the transfer laminate 12 formed by forming the release layer 13, the color-developing resin-based protective layer 14, the metal layer 15, and the adhesive layer 16 on the base film 11, the following were added to the release layer 13 and the color-developing resin-based protective layer 14 to attempt to improve the light resistance.

[0217] The colored resin-based protective layer 14 that has received ultraviolet rays has its hydrogen atoms of the polymer cleaved to become hydroperoxides, which promotes the deterioration of the polymer. To prevent this, a hindered amine-based material is used. Polymer deterioration occurs as a chain reaction of radical generation by photodegradation, and this is suppressed. An acrylic resin that scarcely absorbs ultraviolet rays is selected, and an acrylic polymer material in which silicon with good light resistance, a silicate-based material with light-shielding properties, and a hindered amine as a light stabilizer are polymerized is selected. For the acrylic resin, HALS Hybrid UV-G301 manufactured by Nippon Shokubai in which a hindered amine is polymerized is selected, and for the acrylic resin, UVH manufactured by Alpha Kaken Co., Ltd. in which silicon, silicate, and a hindered amine are polymerized is selected. Also, as a stabilizer against the photodegradation action of ultraviolet rays on the resin, Tinuvin 249 manufactured by BASF, which is a neutral monomer hindered amine, is selected. A hydroxyphenyltriazine-based material is selected as the ultraviolet absorber. Specifically, Tinuvin 479 and 1600 are selected by choosing the wavelength range from among the Tinuvin types manufactured by BASF. As the light-shielding agent, iron oxides, titanium oxides, and organic pigments with good light resistance that are refined to a particle size of 10 to 80 nm are selected. As the inhibitor of the light action, phenyl salicylate that does not transfer ultraviolet light quanta with a blocking effect to the polymer chain is selected. In the release layer 13, titanium oxide, iron oxide, and phenyl salicylate are used as the ultraviolet shielding agent, and an acrylic resin in which a hindered amine is used as the polymerizing material is selected as the binder. The formulation of the release layer 13 is 72.2% by weight of toluene (Idemitsu Kosan Co., Ltd.), 25.4% by weight of MIBK (Mitsubishi Chemical Holdings), 0.03% by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd., Kyoto), 1.07% by weight of Fischer-Tropsch wax (Sadole A859), 0.04% by weight of fatty acid ester (NOF Corporation; WEP), 0.91% by weight of acrylic resin (Nippon Shokubai Co., Ltd.), HALS Hybrid UV-G301 in which a hindered amine is polymerized, 0.05% by weight of iron oxide (Mikuni Shikiso Co., Ltd.; 8197M), 0.062% by weight of titanium oxide (Ishihara Techno Co., Ltd.; TTO-55D), and 0.081% by weight of phenyl salicylate (Tokyo Chemical Industry Co., Ltd.).The formulation of the color-forming resin-based protective layer 14 is as follows: toluene 14.65% by weight (Idemitsu Kosan Co., Ltd.), butyl acetate 8.57% by weight (Standard Oil Co., Ltd.), MEK 17% by weight (Idemitsu Kosan Co., Ltd.), MIBK 17% by weight (Mitsubishi Chemical Holdings Corporation), ethylene glycol 0.0039% by weight (Wako Pure Chemical Industries, Ltd.), acrylic resin 1.08% by weight (Wilbur-Ellis; AT740), amino resin 1.37% by weight (Nippon Carbide Industries Co., Ltd.; MS-001), ketone resin 4.32% by weight (Worley; K95), acrylic resin 20.5% by weight (Nippon Shokubai Co., Ltd.; UV-G301), acrylic resin 11.7% by weight (Alpha Kaken Co., Ltd.; UVHA), ultraviolet absorber 0.078% by weight (BASF; Tinuvin1600), ultraviolet absorber 0.078% by weight (BASF; 479), cerium oxide 0.157% by weight (Taki Chemical Co., Ltd.; B10), titanium oxide 0.157% by weight (Ishihara Techno Co., Ltd.; TTO-55T), iron oxide 0.049% by weight (Mikuni Shikiso Co., Ltd.; 8197M), iron oxide 0.9836% by weight (Mikuni Shikiso Co., Ltd. 8196M), red pigment 0.9836% by weight (DuPont; Cinschakared B), yellow pigment 0.934% by weight (BASF; Paliotol Yellow 1070), phenyl salicylate 0.078% by weight (Tokyo Chemical Industry Co., Ltd.). The particle size of cerium oxide is 10 - 30 nm, the particle size of titanium oxide is 10 - 40 nm, the particle size of iron oxides is 40 - 100 nm, and the particle size range of 60 - 100 nm for the color-forming pigment leads the transparency and is good as a color-forming effect. For the metal layer 15 and the adhesive layer 16, film formation was carried out according to the above. For the release layer 13, the color-forming resin-based protective layer 14, and the adhesive layer 16, a gravure printing machine 60 was used, with a drying temperature of 90 - 180°C, a residence time of 20 - 60 seconds in the drying furnaces 61, 62, a thickness of 0.1 - 20 μm, and one type of drying furnace 61 (volume 5.28 m. 3 ) and film formation was carried out.

[0218] [Experiment 22] Based on the specifications described in Experiment 20, the light resistance test described in Experiment 21 was conducted. In this Experiment 22, the transfer laminate 12 from Experiment 21 was used as the specimen. The results of the light resistance test are shown in Table 16.

[0219]

Table 16

[0220] As for the coloring effect of the resin-based protective layer 14, the reflectance of the original Al metal layer 15 was 81.33%, and it became highly permeable. Even after 1400 hours, the reflectance of the metal layer 15 was 81.53%, which was at the same level as the original state. Regarding the change in the spatial chromaticity Lab value after 1400 hours, ΔE was 1.23, and the coloring was equivalent to the original state. The reflectance of the metal layer 15 containing a pigment with high transparency and subjected to miniaturization processing became high. For the preparation of the release layer 13, an acrylic resin containing a hindered amine, finely processed iron oxide, titanium oxide, and phenyl salicylate which is a light-shielding agent were added. For the preparation of the coloring resin-based protective layer 14, an acrylic resin in which a hindered amine was polymerized, a hindered amine, silicon, silicate, an acrylic resin in which a hindered amine was polymerized, an ultraviolet absorber, cerium oxide, titanium oxide, phenyl salicylate, iron oxides as coloring materials, and organic pigments with excellent light resistance were selected and arranged to improve the light resistance in the laminate of the release layer 13 and the protective layer 14. In the light resistance test, the confirmation after 1400 hours showed that ΔE = 1.23 in the spatial chromaticity L*a*b*, and the light resistance of the organic pigment used in the preparation of the protective layer 14 by Experiment 20 was maintained.

Explanation of Reference Signs

[0221] 10: Transfer foil 11: Substrate film 12, 21: Transfer laminate 13: Release layer 14, 23: Resin-based protective layer 15: Metal layer 16: Adhesive layer 22: Film protective layer

Claims

1. A base film and a transfer laminate, wherein the transfer laminate includes a release layer formed on the base film, a first resin-based protective layer formed on the release layer, and an adhesive layer formed on the first resin-based protective layer, and the first resin-based protective layer contains a plasticizer, a transfer foil.

2. The transfer foil according to Claim 1, wherein the transfer laminate further includes a metal layer formed between the first resin-based protective layer and the adhesive layer, a transfer foil.

3. The transfer foil according to Claim 2, wherein the transfer laminate further includes a second resin-based protective layer formed between the metal layer and the adhesive layer, a transfer foil.

4. The transfer foil according to Claim 1, further comprising a film protective layer formed between the base film and the release layer, a transfer foil.

5. The transfer foil according to Claim 1, The plasticizer includes one or more selected from the group consisting of chlorinated paraffin, butyl adipate, 2-ethylhexyl adipate, dioctyl adipate, 2-ethylhexyl azelate, phthalic acid ester, dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, citric acid esters, the ester of succinic acid and triethylene glycol monomethyl ether, the ester of adipic acid and diethylene glycol monomethyl ether, tricarboxylic acid esters such as trioctyl trimellitate, the ester of 1,3,6-hexanetricarboxylic acid and butyl diglycol, tricresyl phosphate, triphenyl phosphate, tri(2-ethylhexyl) phosphate, trixylenyl phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxidized linseed oil, octyl epoxidized stearate, epoxidized fatty butyl, butyl epoxidized linseed oil fatty acid, trimellitic acid ester, pyromellitic acid ester, sebacic acid ester, azelaic ester, maleic acid ester, benzoic acid ester, methyl adipate, butyl oleate, oxy acid ester, dibasic alcohol ester, aliphatic dibasic acid ester series, triphenyl phosphate, dinonylnaphthalene, tributyl acetylcitrate, P-toluenesulfonamide, toluenesulfonamide, toluenesulfonethylamide, aminobenzenesulfonamide compounds, aminotoluenesulfonamide compounds, N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, dinonylnaphthalene, tributyl acetylcitrate, and ethylene olefin-based oligomers, a transfer foil.

6. The transfer foil according to claim 1, wherein the plasticizer includes one or more selected from the group consisting of P-toluenesulfonamide, toluenesulfonamide, toluenesulfonethylamide, aminotoluenesulfonamide compounds, and N-ethyl-o-toluenesulfonamide.

7. The transfer foil according to claim 1, wherein the content of the plasticizer with respect to the first resin-based protective layer is 0.01 to 20% by weight.

8. The transfer foil according to claim 1, wherein the thickness of the first resin-based protective layer is 1 to 20 μm.

9. The transfer foil according to claim 1, wherein the first resin-based protective layer contains one or more acrylic resins, the transfer foil.

10. The transfer foil according to claim 1, wherein the first resin-based protective layer contains a curing agent, the transfer foil.

11. The transfer foil according to claim 1, wherein the first resin-based protective layer contains a color former, the transfer foil.

12. The transfer foil according to claim 11, wherein the color former includes a pigment having a particle size of 10 to 120 nm, the transfer foil.

13. The transfer foil according to claim 12, wherein the first resin-based protective layer contains a light stabilizer, the transfer foil.

14. The transfer foil according to claim 12, wherein the first resin-based protective layer contains an ultraviolet absorber, the transfer foil.

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