Transfer foil

Abstract

To provide a transfer foil which can prevent the occurrence of cracks, fractures, swelling, etc.SOLUTION: A transfer foil 10 comprises a base material film 11 and a transferring laminate 12. The transferring laminate 12 comprises a release layer 13 formed on the base material film 11, a resin protective layer 14 formed on the release layer 13, and an adhesive layer 16 formed on the resin protective layer 14. The resin protective layer 14 contains a plasticizer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a transfer foil, more particularly to a transfer foil comprising a modified laminate consisting of a transfer laminate. do. [Background technology]

[0002] Transfer foils, which are used to decorate the surface of resin-based molded products formed by thermal transfer printing, etc., are made of a base film. A protective layer, a release layer, a resin-based protective layer or a color-changing resin-based protective layer, a metal vapor deposition layer, and a film are formed in this order on the film. Each layer is selectively formed, and the resin-based protective layer is The color-developing resin-based protective layer and the like are formed by coating them together in layers. Then, the film with the transfer layer is placed on the transferee with the adhesive layer facing the substrate, and the transfer layer is Then, pressure and heat are applied using a thermal transfer device to transfer the transfer laminate, and the base film is then peeled off. This causes the surface of the transferred object to be transferred by transfer lamination (modification lamination), The object becomes a decorative item that is decorated by transfer lamination.

[0003] In resin-based molded products, the surface modification method involves adding a release layer to the base film, a resin-based protective layer, A transfer foil with a transfer laminate is produced by layering a protective layer, a metal deposition layer, and an adhesive layer, and then used to attach resin-based molded products, etc. There is a method for modifying the surface of various transfer objects, including those described above, by heat and pressure transfer means.

[0004] Using a transfer foil with the above laminate on a base film, the transfer target is a resin-based molded product or other The adhesive layer is placed on the surface of the substrate, and the substrate is transferred onto the substrate using a transfer machine. Select a heat transfer medium such as a flat plate 30 or a letterpress 40, and apply pressure and heat to the resin molded product, etc. For use on metals, glass, wood, textiles, paper, or rubber as a release layer or resin-based protection After transferring the transfer laminate composed of a layer, a metal vapor deposition layer, and an adhesive layer, the base film is removed. Thereby, transfer onto the surface of a transfer target such as a resin molded product is achieved, and the surface of the material can be decorated.

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

[0006] Defects occurring during hot press transfer include poor transfer film breakage accuracy, cracks, fractures, and poor interlayer adhesion. During hot press transfer and over time after transfer, various defects exist. In a transfer foil including a release layer, a protective layer, a color developing layer, a metal vapor deposition layer, and an adhesive layer with respect to a base film, Also, general-purpose transfer foils have the following configuration. Checking an example of a transfer foil,

[0006]

[0005] , there are occurrences such as poor heat resistance in transfer. Regarding the changes that occur over time after transfer, peeling, cracking, swelling, etc. are generated as being affected by factors such as the temperature and humidity of the environment under exposure. There is a possibility of fading degradation due to light.

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

[0008] In terms of peeling the transfer layer from the base film, as a layer through the film, the heat absorption of the heat pressure is made sensitive during the heat pressure propagation, reducing the thermosensitivity and pressure sensitivity to show a peeling effect. The adhesive layer selectively uses a resin that is excellent in low-temperature sensitization with heat and pressure to function. In the resin protective layer, the resistance of the film is increased to eliminate the physical and chemical effects on the transfer surface layer after transfer. The color-forming resin protective film contains a color former, forms a film structure that exhibits a color-forming effect and prevents fading and color change. The metal vapor deposition layer has the luster of 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 at a lower temperature, while the protective layer, vapor deposition protective layer, and vapor deposition layer are at a higher temperature. It is protruding. As a result, the transfer lamination including the base film is caused by heat and pressure transfer The expansion and contraction of the transfer lamination and the object to be transferred caused by the heat and pressure propagation that occurs are not uniform. The highly elastic The load on the metal vapor deposition layer increases, leading to cracks, breaks, bulges, etc. in the transfer layer, There is a risk of progression to a decrease in brightness and attenuation of gloss.

[0009] When the extensibility of the metal in the metal vapor deposition layer is low, the expansion that occurs in the transfer layer during transfer causes the aggregation of the metal layer to be destroyed. Therefore, cracks, breaks, and bulges occur in the transfer layer with the modified lamination. When the extensibility of the resin-based protective layer is high, the influence on the aggregability of the metal vapor deposition layer can be mitigated, but the tensile stress acts on the metal layer due to the expansion of the protective layer caused by heating and pressurization during transfer, and the breakability occurs, resulting in the attenuation of the gloss and brightness of the modified lamination.

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. 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 are included. The first resin-based protective layer contains a plasticizer.

Brief Description of the Drawings

[0013]

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DETAILED DESCRIPTION OF THE INVENTION

[0014] [Overview of the Embodiment] The transfer foil according to the 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, breaks, bulges, etc. can be prevented.

[0016] The transfer laminate further includes a metal layer formed between the first resin-based protective layer and the adhesive layer. is also good.

[0017] The transfer laminate further includes a second resin-based protective layer formed between the metal layer and the adhesive layer. is also good.

[0018] The transfer foil further includes a film protective layer formed between the base film and the release layer. That's fine.

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

[0020] The plasticizer may be, for example, chlorinated paraffin, butyl adipate, 2-ethylhexyl adipate, etc. Dioctyl adipate, 2-ethylhexyl azelaate, phthalates, Dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisonyl phthalate Nyl, diisodecyl phthalate, citrate esters, succinic acid and triethylene glycol Esters of adipic acid and diethylene glycol monomethyl ether Tricarboxylate esters such as trioctyl trimellitate, 1,3,6 -Ester of hexatricarboxylic acid and butyl diglycol, tricresyl phosphate , triphenyl phosphate, tri-2-ethylhexyl phosphate, trixylenyl phosphate phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxy Epoxidized Linseed Oil, Epoxidized Octyl Stearate, Epoxidized Fatty Butyl, Epoxidized Linseed oil fatty acid butyl, trimellitate, pyromellitate, sebacic acid Esters, azelaic esters, maleic esters, benzoic esters, azithinic acid Methyl, butyl oleate, oxy acid ester, dihydric alcohol ester, aliphatic dibasic acid ester series, triphenyl phosphate, dinonylnaphthalene, triacetyl citrate butyl, P-toluenesulfonamide, toluenesulfonamide, toluenesulfonylethyl amide, aminobenzenesulfonamide compound, aminotoluenesulfonamide compound , N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, dinonylnaphthalene, tributyl acetyl citrate, and ethylene olefin oligomer selected from the group consisting of one or more of the above.

[0021] The plasticizer preferably contains one or more selected from the group consisting of P-toluenesulfonamide, toluenesulfonamide, tolu enesulfonylethylamide, aminotoluenesulfonamide compound, and N-ethyl-o-tol uenesulfonamide.

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

[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 Embodiments] 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, a transfer foil 10 according to Embodiment 1 includes a base film 11 and a transfer laminate layer (hereinafter, may be referred to as "modified 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 "protective layer") 14 formed on the release layer 13, a gold 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, a 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 2 2 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, and a layer formed on the metal layer 15 ​It includes the resin-based protective layer 23 and the adhesive layer 16 formed on the resin-based protective layer 23. Embodiment The transfer foil 20 according to Embodiment 2, in addition to the configuration of the transfer foil 10 according to Embodiment 1, includes a film protective layer 22 formed between the base material 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 above-described transfer foils 10 and 20 are provided with 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, but examples include chlorinated paraffin, butyl adipate, 2- ethylhexyl adipate, dioctyl adipate, 2-ethylhexyl azelate, ethyl phthalate ester, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, phthal ate diisononyl, phthalate diisodecyl, citrate esters, the ester of succinic acid and triethylene glycol monomethyl ether, the ester of adipic acid and diethylene glycol mono methyl 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, tri xylenyl phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxidized linseed oil, octyl epoxidized stearate, epoxidized fatty butyl ​, epoxidized linseed oil fatty acid butyl, trimellitic acid ester, pyromellitic acid ester , sebacic acid ester, azelaic acid 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, acetyl tributyl citrate, p-toluenesulfonamide, toluenesulfonamide, toluene sulfonylethylamide, aminobenzenesulfonamide compound, aminotoluenesulfon amide compound, N-butylbenzenesulfonamide, N-ethyl-o(ortho)-tolu enesulfonamide, dinonylnaphthalene, tributyl acetyl citrate, and ethylene olef in-based oligomers, and contains one or more selected from the group consisting of.

[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 There is. The thickness of the resin-based protective layer 14 is not particularly limited, but is 1 to 20 μm. The resin-based protection The layer 14 is not particularly limited, but contains one or more acrylic resins. The resin-based protective layer 14 is not particularly limited, but contains a curing agent. The resin-based protective layer 14 is not particularly limited However, it contains a color former. Hereinafter, the resin-based protective layer containing a color former may be particularly referred to as the "colored resin-based protection layer". The resin-based protective layer 14 is not particularly limited, but contains a light stabilizer . The resin-based protective layer 14 is not particularly limited, but contains an ultraviolet absorber.

[0037] The above-described transfer foil 10 is transferred onto a transfer target 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-down type transfer foil press 31 using a lithographic plate 30. There is. The foil pressing machine 31 presses the transfer foil 10 with the flat plate 30, so that the transfer laminate 12 is soft It transfers to the transfer body 32 such as a vinyl chloride sheet. Fig. 4 is a schematic diagram showing plate making by the up-down type transfer foil pressing machine 41 using the relief plate 40. The foil pressing machine 41 presses the transfer foil 10 with the relief plate 40 to transfer the transfer laminate 12 to the transfer body 32 such as a soft vinyl chloride sheet. Fig. 5 is a schematic diagram showing plate making by the hot pressure transfer machine (hereinafter sometimes referred to as "roll type transfer machine". ) 51 using the roll plate 50. By pressing the transfer foil 10 with the hot pressure transfer machine 51 and the roll plate 50 the transfer laminate 12 is transferred to the transfer body 32 such as a resin molded product.

[0038] The above-mentioned transfer foil 10 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 the gravure printing machine 60 and the drying furnace type 1 furnace 61. Fig. 7 is a schematic diagram showing the gravure printing machine 60 and the drying furnace type 2 furnace 62.

[0039] As shown in Figs. 6 and 7, the gravure printing machine 60 includes a film unwinding section 63, a f ilm control roll 64, and a gravure coating head section 65. Downstream of the gravure printing machine 60 shown in Fig. 6 is provided with a drying furnace type 1 furnace 61. 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 are provided a film control roll 70, a pressing device 71, and a cooling device 72 and a film winding section 73. Downstream of the gravure printing machine 60 shown in Fig. 7 is provided with a drying furnace type 2 furnace 62. The drying furnace type 2 furnace 62, in addition to the configuration of the above-mentioned drying furnace type 1 furnace 61, includes an ultraviolet irradiation facility 74. Downstream of the drying furnace type 2 furnace 62 is a f A rum control roll 70, a pressing device 71, a cooling device 72, and a film winding section 73 are provided. It is done.

[0040] In this embodiment, a transfer laminate 12 including a release layer 13, a resin-based protective layer 14, a metal layer 1 5, and an adhesive layer 16 is formed on the surface of the base film 11, and the transfer film for thermosensitive pressure transfer that can prevent cracks, cracks, and swelling and reduce fading is used for the heat and pressure transfer for image decoration of the transfer body 32. It is 10. It is.

[0041] The release layer 13, the resin-based protective layer 14, and the adhesive layer 16 are formed by film formation using a gravure printing machine 60. The metal layer 15 is formed by film formation using a two-chamber semi-continuous vacuum evaporation device. As the vacuum evaporation device, for example, the device shown in FIG. 4 of JP-A-2002-192895 (Patent Document 2) can be used. The resin-based protective layer 14 prepared with a plasticizer is heated by the gravure printing machine 60 and dried with hot air 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It is done. The metal layer 15 is formed by film formation using a two-chamber semi-continuous vacuum evaporation device. As the vacuum evaporation device, for example, the device shown in FIG. 4 of JP-A-2002-192895 (Patent Document 2) can be used. The resin-based protective layer 14 prepared with a plasticizer is heated by the gravure printing machine 60 and dried with hot air 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. For example, the device shown in FIG. 4 of JP-A-2002-192895 (Patent Document 2) can be used. The resin-based protective layer 14 prepared with a plasticizer is heated by the gravure printing machine 60 and dried with hot air 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It can be used. The resin-based protective layer 14 prepared with a plasticizer is heated by the gravure printing machine 60 and dried with hot air 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It is heated by the gravure printing machine 60 and dried with hot air 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. 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 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It is heated in the drying furnaces 61 and 62 of the gravure printing machine 60 and annealed with hot air, and then passed through the connected pressing device 71 and cooling device 72 to be pressed and cooled. As a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It is pressed and cooled, and as a result, the film quality changes from hard to flexible. Then, the metal layer 15 and the adhesive layer 16 are formed. It is formed.

[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 the laminated layer 14, and metal layer 15 are heated by the hot air device 69 of the drying furnaces 61 and 62, and the laminated An annealing process is performed to heat-bake the i-film, and it is installed in connection with drying furnaces 61 and 62. The resin-based protective layer 14 and the metal layer 1 5 are transformed from a hard film to a flexible one, and the interface between the resin-based protective layer 14 and the metal layer 15 has improved bondability and obtains 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, cooling, etc. by a gravure printing machine 60 or the like. It is possible.

[0044] During the hot press transfer of the transfer laminates 12 and 21, the release of residual stress during film formation and the transfer, peeling, and fixing during hot press transfer cause the base film 11, the transfer laminate 12, the surface to be transferred, the structure , material, shape, etc. affect the transfer laminate 12, which in turn affects the low-elasticity metal-forming film. Without being restricted by the aggregation structure of the metal in the metal deposition structure layer or the metal island structure layer of the metal layer 15, the influence on the aggregation property of the metal layer 15 is manifested by the heat pressure propagation during transfer. The aggregation failure of the metal layer 15 appears in the form of cracks, breaks, bulges, etc. The generation on the metal layer 15 and the adjacent protective layer 14 leads to an impact on the modification property, a decrease in brightness, and an acceleration of film deterioration.

[0045] The purpose of this embodiment is to avoid the above-mentioned 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 by 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 protection The flexibility of the protective layer 14 exhibits an affinity for the metal layer 15, and during the process of the protective layer 14 and the metal layer 15 bonding to each other, the flexibility of the plasticizer promotes the integration of the protective layer 14 and the metal layer 15, and the stretch resistance and shrinkage resistance of the protective layer 1 4 and the metal layer 15 are improved.

[0046] The elimination of the above problems is also related to the attenuation of luminance degradation. Also, if the particulate color former is made into fine particles and contained in the resin-based protective layer 14, the color-forming effect and the reflectance of the metal layer 15 can be increased while maintaining the transparency of the protective layer 14. By selecting particles, light resistance can be obtained along with a metallic feeling with color formation, 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 breakage property, and film stability.

[0048] Examples of the adhesive include polyacrylate-based resins, polyvinyl acetate-based resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyester-based resins, po lystyrene-based resins, polyamide-based resins, ethylene-propylene-based resins, polypropylene-based resins, ethylene-vinyl acetate-based resins, vinyl chloride-vinyl acetate-based resins, polyvinyl chloride, po lyvinylidene chloride, cellulose-based resins, rosin-based 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 improving the stability of film formation, cellulose-based is preferred. Regarding the film breakage property 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. Natural ultraviolet degradation caused by sunlight results in a decrease in physical properties and a change in appearance. Due to direct solar radiation and diffuse solar radiation, the hydrogen atoms of the polymer and color former in the transfer lamination 12 are cleaved to generate radicals. The radicals combine with atmospheric oxygen to generate peroxy radicals. The peroxy radicals extract the hydrogen atoms of the polymer to generate radicals and hydroperoxides. The hydroperoxides promote the degradation of the polymer. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. Another type of acrylic resin is accompanied by a reactive functional group and forms a crosslinked film with an amino resin and a catalyst to form a hard film. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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 rays into thermal energy, etc., light stabilizers (HALS) that capture radicals, phenolic antioxidants that capture peroxy radicals generated by the combination of radicals and oxygen, and phosphorus-based antioxidants that decompose hydroperoxides 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. 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, and a shielding effect of ultraviolet rays that inactivates active oxygen due to radicals generated by light in the release layer 13, resin-based protective layer 14, etc. on the surface layer after transfer is expected to be long-term. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. Another type of acrylic resin contains an ultraviolet absorption group and an ultraviolet stability group (HALS), is a silicone acrylate resin having a silyl group, contains an alkyl silicate, and forms a film with high hardness and high resistance to ultraviolet rays. Another type of 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 having an amino resin, a curing agent, and an acrylic resin, and is formed. The amino resin is selected from melamine 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 light stabilizer group (HALS) is added, a silyl group, an amino group, a methylol group, a hydroxyl group, a functional group such as an oxazoline group, a cyclocarbonate group, a cyclocarbonate group, etc. is attached, a copolymer with trialkoxyvinylsilane, etc., an addition reaction with an isocyanate group or an unsaturated group, a reaction with an amine, and is selected from materials with an attached epoxy group, etc.

[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 printing machine 60, and further, a metal layer 15 is made by a two-chamber semi-continuous vacuum deposition apparatus, and an adhesive layer 16 is generated thereon by a gravure printing machine 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 low, there is permeability but no color-forming effect. When the content is high, 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 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 content rate of the pigment is 5 to 15% by weight, and the pigment particle size is refined to the range of 10 to 120 nm. Furthermore, 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 transparency of the protective layer 14 is produced, the reflectivity of the metal layer 15 appears, and light resistance is generated. Thereby, the metal layer 1 ​To obtain the reflectivity of 5 and express the metallic feeling due to this metallizing effect as a coloring effect by using pigments. It can be expressed as a coloring effect. The resin-based protective layer 14 obtains light resistance by using a color former such as an organic pigment or the like.

[0053] As the color former, inorganic pigments such as titanium white, carbon black, cinnabar, lead yellow, ultramarine blue, etc., and 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. The transparency of the pigment as the color former and the visibility as the coloring image effect can be enhanced. Furthermore, pigments with excellent light resistance are 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 composed of a light stabilizer, silicon, silicate, etc. 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 light stability by capturing and detoxifying the radicals generated by ultraviolet rays. A non-basic neutral type hindered amine-based light stabilizer is selected to avoid problems in the formation of the thermosetting film of the protective layer 14.

[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. By absorbing ultraviolet rays and converting them into low thermal energy and releasing them, the stability of the protective layer 14 is achieved. Therefore, hydroxyphenol Among the nitrotriazine-based materials, those with an ultraviolet absorption wavelength 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 becomes light energy again. Part of it reaches a chemical reaction. In addition, excess energy transfers to other molecules and reacts with the polymer. The ultraviolet wavelength range of 200 to 300 nm has a significant chemical action . As a countermeasure in the resin-based protective layer 14 containing a color preservative, a transparent fine pigment, an acrylic resin, a polymer in which a hindered amine by an acrylic resin is bonded in the structure , a hindered amine-based light stabilizer, and a hydroxyphenyltriazine-based ultraviolet absorber are obtained . In addition to the preparation, as a light action inhibitor, a salicylate ester-based, 4-t-butylphenyl -salicylate, phenyl salicylate, etc. are selected, and as a light action inhibitor, phenyl salicylate, which is an ultraviolet blocking agent, is selected and added.

[0057] As a means for forming the metal layer 15, in the case of physical vapor deposition (PVD) as a vapor deposition method, vacuum evaporation, sputtering, etc. can be mentioned. Among chemical vapor deposition (CVD) methods , thermal CVD, atomic layer deposition (ALD), plasma CVD, metalorganic chemical vapor deposition, two-flow low-pressure MOCVD, catalytic chemical vapor deposition (Cat-CVD), etc. can be mentioned. In the case of liquid phase deposition and the melt method, liquid phase epitaxy, plating methods such as wet plating, electroless plating plating, sol-gel method, and coating means such as spin coating, printing, inkjet, etc. can be mentioned . As the metal to be used, Au, Ag, Cu, Sn, Al, Ni, Pt, Rh, Pd, Z . In addition to n, Cr, and Si, as oxides, In2O3, CdO, CdIn2O4, Cd2Sn O4, TiO2, SnO2, ZnO, SiO2, ZrO2, etc., as sulfides, ZnS, etc., and as flu orides, MgF2, etc., one or more are selected from among them. Also, an alloy can be used. Lamination is also possible. 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 indicating the deposition state of the metal, etc. However, in any structure, without being restricted by the employed metal or the film formation state of the metal, it is possible to suppress the expansion and contraction, cracks, fractures, swelling, etc. that the transfer laminate 12 undergoes during thermocompression transfer.

[0058] Also, 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, it is possible to maintain uniform brilliance as the metallic color tone. It enhances the decorativeness and design quality as an image display of thermocompression transfer.

[0059] [Manufacturing Method 1] As the base film 11, any film can be used as long as there are no abnormalities in heat resistance during manufacturing, resistance to solute solvents, transfer heat resistance during use, and pressure resistance. For example, , polyethylene terephthalate, polybutylene terephthalate, polyethylene naphtha late, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohex anedimethanol-ethylene glycol copolymer, polyethylene terephthalate-polyeth ylene naphthalate coextruded film, etc., polyester-based, polyamide-based, polyolefin -based, acrylic-based, imide-based, various engineering-based, styrene-based, cellulose-based, etc. films. Among them, in order to maintain physical and chemical strength, biaxially stretched films The film is good. Among these, a polyethylene terephthalate film is good. Considering thermal transfer printing, 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 thermal pressure, making it difficult to clearly display the transferred image. It is advisable to use it in accordance with the shape and material of the object to be transferred 32 within the range of a film thickness of 12 to 75 μm.

[0060] Accordingly, the release layer 13, the resin-based protective layer 14, and the adhesive layer 16 are formed by the gravure method. The drying means uses a far-infrared heater 67 and a hot air device 69. FIG. 6 shows an overview of the gravure printer 60 and the drying furnace 1 type furnace 61. Using the drying furnace 1 type furnace 61, it travels and stays in the furnace atmosphere of 90 to 21 0 °C for 20 to 50 seconds to produce each film with a thickness of 0.1 to 20 μm. Also, using a two-chamber semi-continuous vacuum evaporation device, a metal layer 15 with a thickness of 30 to 60 nm is formed. After that, the adhesive layer 16 is formed.

[0061] [Manufacturing Method 2] After forming the release layer 13 and the resin-based protective layer 14, using the drying furnace 2 type furnace 62 with a volume of 2.64 m in the gravure printer 60 shown in FIG. 7, it travels and stays in the atmosphere of 100 to 210 °C for 2 3 0 to 50 seconds to perform an annealing process of baking the dry film. After that, the metal layer 15 and the adhesive layer 16 are formed.

[0062] [Manufacturing Method 3] As the drying means for the release layer 13 and the resin-based protective layer 14, using the drying furnace 1 type furnace 61 shown in FIG. 6 with the far-infrared heater 67 and the hot air device 6 9 in the furnace, it travels and stays in the atmosphere of 90 to 210 °C for 2 Run and stay for 0 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, using two types of drying furnaces 62 in the gravure printer 60 shown in FIG. 7, run and stay in an atmosphere of 150 to 210 °C for 20 to 50 seconds, and perform annealing treatment to bake the dry film composed of the release layer 13, resin-based protective layer 14, and metal layer 15 laminated on the base film 1 1. Then, form the adhesive layer 16.

[0063] [Manufacturing Method 4] As the drying means for the resin-based protective layer, a far-infrared heater 67 and a hot air device 69 were used. Using the one-type drying furnace 61 shown in FIG. 6, run and 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, using the gravure printer 60 having the two-type drying furnace 62 shown in FIG. 7, run and stay in an atmosphere of 150 ~210 °C for 20 to 50 seconds and heat in the furnace. Perform a pressurizing treatment with a pressurizing device 71 directly connected outside the furnace, followed by a cooling treatment with a cooling device 72 installed . Then, form the adhesive layer 16.

[0064] [Manufacturing Method 5] Using the one-type drying 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, using the two-type drying furnace 62 shown in FIG. 7, run 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, and after heating in the furnace, perform continuous pressurizing and cooling treatments with an external furnace pressurizing device 71 and a cooling device 72 connected to the furnace to complete a three-dimensional structure film including the release layer 13, resin-based protective layer 14, and 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 by a vacuum evaporator, using 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. After heating, perform continuous pressing and cooling treatments to complete the flat film or 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, pressing, 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. The transfer laminate 12 is peeled from the base film 11 through the thermocompression time of the transfer machine and transferred to the object to be transferred 32. During the transfer operation the transfer laminate 12 peeled from the base film 11 is transferred to the object to be transferred 32 by the transfer action, requiring a heat source, pressure, and transfer stay time supplied from the transfer machine. Due to the shape and hardness / softness of the material of the object to be transferred 32, the actions of heat and pressure received are not uniform. The transfer laminate 12 is a thin film body with peelability and has breakability during transfer peeling compared to the base film 11 and the object to be transferred 32. The film peelability is the starting point of film peeling in the peel resistance value of 1 to 100 g / cm (using a peel resistance tester manufactured by Asahi Measuring Instruments Co., Ltd.). The film breakability is at 500 g to 1 0 Kg / cm ·0.5 seconds (using Ikeda type transfer device) at the transfer pressure. 2 (Asahi Measuring Instruments Co., Ltd. manufactured peel resistance tester) is the starting point of film peeling. The film breakability is at 500 g to 1 0 Kg / cm 2 ·0.5 seconds (using Ikeda type transfer device) at the transfer pressure for film breakage. It is the starting point. The transfer laminate 12 is easy to peel off and has breakability. The object to be transferred 32 has two-dimensional, three dimensional and various shapes, and the materials are leather, paper, paperware, printed paper, special paper, wood, fiber, resin sheet , resin molding, metal, glass, etc., and there are also various materials. 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, breaks, 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, the adhesion between the protective layer 14 and the metal layer 15 is enhanced to bonding through the process by the gravure printing machine 60. The effects of heating, hot air, pressurization, and cooling by the gravure printing machine 60 result in the flexibility due to the addition of the plasticizer to the protective layer 14 becoming stretchability, and the heat resistance of 380 °C becomes resistance to the occurrence of cracks, breaks, 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 of the transfer laminate 12 due to the structural transformation of the resistance . 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, breaks, and bulges during and after the transfer of the transfer laminate 12 (4) Metal reflectance: Reflectance of the Al metal layer 15 of 82.15% (spectral reflectance%)

[0067] When a pigment is used for the protective layer 14, it is excellent in ensuring gloss. Among the base film 11, the release layer 1 3, the protective layer 14, the Al metal layer 15, and the adhesive layer 16, when a fine pigment is used for the protective layer 14 (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, breaks, and bulges during and after the transfer of the transfer laminate 12 (4) Metal reflectance: Reflectance of the Al metal layer 15 of 82.15% (spectral reflectance%) When a pigment is used for the protective layer 14, it is excellent in ensuring gloss. Among the base film 11, the release layer 1 3, the protective layer 14, the Al metal layer 15, and the adhesive layer 16, when a fine pigment is used for the protective layer 14 Al film reflectance of the colored layer (5) Morphology of the vapor-deposited film: Regardless of whether the morphology of the metal layer 15 is an island film structure or a deposited film structure, the protective layer 14 and the metal layer 15 maintain bondability and exhibit extensibility. It is possible to avoid cracks, breaks, and swelling of the transfer product layer 12 caused by cohesive failure of the metal. (6) Heat resistance: In the heat resistance test after transfer of the transfer laminate 12, it is excellent in resistance to cracks, breaks, 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 plasticizer described above and can form a film having heat resistance and extensibility and bondability with the metal layer 15 by the manufacturing process described above. (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 breakability. Plasticizers are added to both resins. (12) Extensibility: 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 into the mold of the molding machine during the formation of the molded product and bonded by the heat and pressure of the molten resin, and then the excess film is peeled off, the transfer laminate 12 can maintain resistance corresponding to the extension it receives. (13) Extensibility: When a three-dimensional transfer object 32 is a resin processed product by a resin molding machine or the like, during the formation of the molded product, the transfer laminate film is shaped into the mold of the molding machine and bonded by the heat and pressure of the molten resin. After that, when the excess film is peeled off, the transfer laminate 12 can maintain resistance corresponding to the extension it receives. (14) Adhesion: When the resin-based protective layer 14 is bonded to the metal layer 15, the peel strength is 1 N / 25 mm or more. (15) Transfer laminate 12: When the transfer laminate 12 is transferred onto the three-dimensional transfer object 32, the transfer accuracy is within ± 0.1 mm. (16) Transfer laminate 12: When the transfer laminate 12 is transferred onto the three-dimensional transfer object 32, the transfer accuracy is within ± 0.05 mm. (17) Transfer laminate 12: When the transfer laminate 12 is transferred onto the three-dimensional transfer object 32, the transfer accuracy is within ± 0.01 mm.

[0068] Regarding the surface modification of the molded product, the modification is performed by transferring and peeling off the decorative laminate composed of the transfer laminate 12 peeled from the base film 11 using a transfer machine, or by transfer transfer in a molding machine. After adhering the resin-based protective layer 14 containing a plasticizer, 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. Through a transfer device, the adhesive layer 16 is brought into contact with the transfer body 32, and adhered by the hot pressure supplied from above the base film 11, so that it can be mounted on the transfer body 32 together with the base film 11. By this manufacturing method, a multi-layer laminate excellent in heat resistance and stretchability can be achieved. According to such a multi-layer laminate structure, the transfer laminate 12 using the base film 11 and the decorative visualization film integrated with the base film 11 can be applied regardless of the distinction between hot pressure transfer, outmold, and inmold. Regarding the production of two-dimensional and three-dimensional molded products using a molding machine with 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 forming as a molded product, as a post-attachment

[0069] decorative laminate, 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, and film bonding for bonding the film to the molded product together with the base film 11 are available. For the molded product itself, there are means such as peeling and transferring the image from the base film 11 in the inmold to the molded product, and film bonding for bonding the film to the molded product together with the base film 11. After forming as a molded product, as a post-attachment decorative laminate, the transfer means of the transfer laminate 12 and the primary processing method in the mold of the molding machine, such as the peeling transfer of the image from the base film 11 in the inmold to the molded product, and film bonding for bonding the film to the molded product together with the base film 11 are available. 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 forming as a molded product, as a post-attachment decorative laminate, 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, and film bonding for bonding the film to the molded product together with the base film 11 are available. Regarding the transfer of the image from the base film 11 in the inmold to the molded product and the film bonding for bonding the film to the molded product together with the base film 11, etc. For the molded product itself, there are means such as peeling and transferring the image from the base film 11 in the inmold to the molded product, and film bonding for bonding the film to the molded product together with the base film 11. The transfer body 32 by time transfer, simultaneous sticking of molded products, and post - attachment transfer, such as leather, among others, Although there are a wide variety of molding methods and modification means as described above, the modified utilization of the laminated structure film becomes possible.

[0070] When the selected plasticizer is introduced into the protective layer 14 and through the above - mentioned manufacturing process, the produced transfer When laminating 12, together with the base film 11, for film laminating, etc., extensibility, heat resistance, interlayer adhesion, maintenance of the reflectivity of the metal layer 15, light resistance, prevention of cracks, fractures, and swelling The additional functionality shows an improvement in quality.

[0071] The three - dimensional structure of the transfer laminate 12 including the resin - based protective layer 14 is composed of the base film 11, release layer 13, resin - based protective layer 14, metal layer 15, and adhesive layer 16 in the transfer laminate 12. By using the drying means of 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 and using the heat sources of the far - infrared heater 67 and the hot - air device 69 in the range of 150 - 210 °C each, The coating film is heated, dried, pressurized, and cooled to form a flat film and a three - dimensional film separately. At this time, on the base film 11, the release layer 13, resin - based protective layer 14, metal layer 15, and adhesive layer 16 are sequentially formed to complete the transfer laminate 12. During the treatment of the resin - based protective layer 14 heating and drying, hot - air treatment, pressurization treatment are continuously performed using the drying furnace 1 type furnace 61 of the gravure printing machine 60. By heating and drying, the amino resin - based material containing the plasticizer is cured with a curing agent, and while hardening the protective layer 14, through the continuous operations of heating, hot - air, pressurization, and cooling the resin - based material becomes hard. The protective layer 14 containing the plasticizer exhibits flexibility It appears. After forming the protective layer 14, the metal layer 15 is formed, and the release layer 13, the protective layer 14, and the metal layer 15 are in a laminated state. Further, using a gravure printing machine 60 having two types of drying furnaces 62, the baking of the dry film is carried out. 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, pressurized, and cooled, affinity is generated between the protective layer 14 and the metal layer 15 by the heating and pressurizing 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

[0072] During the drying process of the gravure coating, by continuously providing heating in the two types of drying furnace 62, external pressurization outside the furnace, and cooling outside the furnace, the protective layer 14 and the metal layer 15 pass through this process to form a resin-based The protective layer 14 develops film stickiness. Solubility occurs between the resin in the protective layer 14 and a part of the metal particles in the metal layer 15. The influence due to the accumulation of residual stress caused by film shrinkage during the curing of the protective layer 14 is reduced by the co-packaging preparation of

[0073] The release layer 13 and the resin-based protective layer 14 are treated in the single-type drying furnace 61 of the gravure printing machine 60, the metal layer 15 is laminated, heated in the two types of drying furnace 62 of the gravure printing machine 60, and continuously subjected to external pressurization outside the furnace and cooling outside the furnace. This is a necessary process for propagating and fixing the flexible film quality of the resin-based protective layer 14 to the interface with the metal layer 15. Both the protective layer 14 and the metal layer 15 become a hard and sticky film quality when heated, pressurized, and cooled. Further, the and has extensibility due to flexibility containing a plasticizer. The residual stress of the protective layer 14 causing film breakage generated from the cohesive failure of the metal layer 15 becomes a factor for the occurrence of shear, cracks, breaks, swelling, etc. in the transfer laminate 12. To suppress this, the film quality is modified to raise the properties between the two layers to those having heat resistance, flexibility, adhesion, and extensibility. To enhance the fixing to the metal layer 15, a film quality containing a heat-resistant plasticizer and an interface transfer-induced plasticizer is transferred and bonded to the metal layer 15 in the preparation of the protective layer 14, and annealing treatment, pressure treatment, and cooling treatment are performed. Confirmation is made as to whether the correlation between the protective layer 14 and the metal layer 15 is expressed in relation to the bonding of the two layers in terms of heat resistance, flexibility, adhesion, and extensibility. In the examples described later, when observing the surface after the transfer of the transfer laminate 12, the formed three-dimensional structure has a cross-section as shown in FIG. 8 in a radiation bow-shaped cross-section, with a chord of 1 μm, a height of 13 μm, and an arc of 26 μm. It was expressed as a three-dimensional structure film of a concavo-convex ridged continuous layer. Further scrutiny and magnification of the surface change after the thermocompression transfer of the surface layer confirmed that no phenomena such as cracks, breaks, and swelling were observed.

[0074] In the examples described later, when observing the surface after the transfer of the transfer laminate 12, the formed three-dimensional structure has a cross-section as shown in FIG. 8 in a radiation bow-shaped cross-section, with a chord of 1 μm, a height of 13 μm, and an arc of 26 μm. It was expressed as a three-dimensional structure film of a concavo-convex ridged continuous layer. Further scrutiny and magnification of the surface change after the thermocompression transfer of the surface layer confirmed that no phenomena such as cracks, breaks, and swelling were observed.

[0075] Figs. 8 to 10 are photographs showing the three-dimensional structure film. Figs. 11 to 14 are photographs showing cracks, breaks, and swelling 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 printer 60 having a drying furnace 61 is used to coat a resin-based protective layer 14 containing a plasticizer to produce a flat film. Next, ​​​​​​​​​The metal layer 15 is then laminated on the substrate 10 and dried in the laminated state by a gravure printing machine having a drying oven 62. 60 is used to bake the dry film, and then far-infrared heater 67 is used to heat the film with hot air. The transfer laminate 12 was stretched and raised together to form a continuous ridge-like three-dimensional structure band. Next, an adhesive layer 16 was formed to complete the transfer laminate 12. The layer 12 was transferred onto a soft vinyl chloride sheet, and the surface layer of the transfer laminate 12 was confirmed. Conditions: Using a top-bottom transfer foil stamping machine, temperature 160℃, pressure 5Kg / cm 2 , Transcription time 0 After using the 40-inch plate in 0.5 seconds, there were no cracks, breaks, or swelling, and the metallization No change was observed in the coating effect. Both layers 15 are in tune with the expansion of the film, and the cohesive strength is reduced by the processes of heating, pressing, and cooling. The metal layer 15 has a low mechanical strength and the protective layer 14 is free from residual stress. The compatibility and migration inductivity are determined by the plasticity of the metal thin film during the in-furnace and out-furnace processes of the gravure printing machine 60. The metal layer 15 has a structure of a deposited grain film or an isolated grain film. The film quality is transferred to the protective layer 14. As a result, both the protective layer 14 and the metal layer 15 are It exhibits adhesiveness and fixes the interface between the two layers.

[0077] The photograph in Figure 10 shows the transfer foil 10 subjected to the experiment based on the manufacturing method 5, which was applied using a top-bottom transfer foil stamping machine. The metal layer 15 is made of aluminum. The film thickness used is 40 nm, the valley width is 1.4 to 1.76 μm, and the peak width of the convex part is 0.99 to The thickness of the projections was 1.2 μm, and the height of the projections was 11 to 14 μm.

[0078] This embodiment aims to improve the problems that occur in the transfer laminate 12 over time after thermal transfer when the transfer foil 10 is used. Cracks, breaks, bulges, fading, etc. occur in the transfer laminate 12, and external forces and internal stress responses to the thermal pressure load on the transfer laminate 12 and the object to be transferred 32 cause deformation interactions such as elongation, contraction, displacement, torsion, and bending in the transfer laminate 12 and the object to be transferred 32. From this derived phenomenon, the action on the deformation during transfer to the object to be transferred 32 and the transfer laminate 12 will reduce the decorativeness on the object to be transferred 32. It is necessary to obtain a preservation method that can individually face this deforming action as the acceptance burden of the transfer laminate 12. The functions of the transfer laminate 12 include peeling, breaking, adhesion, heat resistance, brilliance resistance, color development, image display, decorativeness, etc. In addition, in order to cope with the morphological changes that occur during and after the above transfer, the following are required as means of the transfer laminate 12. Obtain a functional material with extensibility due to flexibility using heat resistance, flexibility, and migration inductivity from plasticizers and add it to the protective layer 14 to enhance the function of the protective layer 14 and achieve functional propagation to the metal layer 15. Furthermore, by passing the drying means of 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 functional propagation from the affinity at the interface of the metal layer 15 and adhere and fix. As a result, extensibility is generated in both the resin-based protective layer 14 and the metal layer 15. The protective layer 14 and the metal layer 15 share transfer breakage, extensibility, and heat resistance. The transfer laminate 12 becomes a decorative laminate that can cope with cracks, breaks, and bulges during and after transfer. External forces and internal stress responses to the thermal pressure load on the transfer laminate 12 and the object to be transferred 32 cause deformation interactions such as elongation, contraction, displacement, torsion, and bending in the transfer laminate 12 and the object to be transferred 32. From this derived phenomenon, the action on the deformation during transfer to the object to be transferred 32 and the transfer laminate 12 will reduce the decorativeness on the object to be transferred 32. It is necessary to obtain a preservation method that can individually face this deforming action as the acceptance burden of the transfer laminate 12. The functions of the transfer laminate 12 include peeling, breaking, adhesion, heat resistance, brilliance resistance, color development, image display, decorativeness, etc. In addition, in order to cope with the morphological changes that occur during and after the above transfer, the following are required as means of the transfer laminate 12.

[0079] Obtain a functional material with extensibility due to flexibility using heat resistance, flexibility, and migration inductivity from plasticizers and add it to the protective layer 14 to enhance the function of the protective layer 14 and achieve functional propagation to the metal layer 15. Furthermore, by passing the drying means of 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 functional propagation from the affinity at the interface of the metal layer 15 and adhere and fix. As a result, extensibility is generated in both the resin-based protective layer 14 and the metal layer 15. The protective layer 14 and the metal layer 15 share transfer breakage, extensibility, and heat resistance. The transfer laminate 12 becomes a decorative laminate that can cope with cracks, breaks, and bulges during and after transfer. External forces and internal stress responses to the thermal pressure load on the transfer laminate 12 and the object to be transferred 32 cause deformation interactions such as elongation, contraction, displacement, torsion, and bending in the transfer laminate 12 and the object to be transferred 32. From this derived phenomenon, the action on the deformation during transfer to the object to be transferred 32 and the transfer laminate 12 will reduce the decorativeness on the object to be transferred 32. It is necessary to obtain a preservation method that can individually face this deforming action as the acceptance burden of the transfer laminate 12. The functions of the transfer laminate 12 include peeling, breaking, adhesion, heat resistance, brilliance resistance, color development, image display, decorativeness, etc. In addition, in order to cope with the morphological changes that occur during and after the above transfer, the following are required as means of the transfer laminate 12. Obtain a functional material with extensibility due to flexibility using heat resistance, flexibility, and migration inductivity from plasticizers and add it to the protective layer 14 to enhance the function of the protective layer 14 and achieve functional propagation to the metal layer 15.

[0080] Among the plasticizers, measure the setting of the flexibility transfer inducer. Explore the setting of a specific amount within the range where delamination does not occur at the interface of the protective layer 14. 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. Without the interface having flexibility due to the plasticizer in the thermosetting resin-based protective layer 14 being sealed within the cured film structure, it is dispersed in the film and thus adheres to the interface even in trace amounts. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. Explore the setting of a specific amount within the range where delamination does not occur at the interface of the thermosetting resin-based protective layer 14. 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. Without the interface having flexibility due to the plasticizer in the thermosetting resin-based protective layer 14 being sealed within the cured film structure, it is dispersed in the film and thus adheres to the interface even in trace amounts. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. 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. Without the interface having flexibility due to the plasticizer in the thermosetting resin-based protective layer 14 being sealed within the cured film structure, it is dispersed in the film and thus adheres to the interface even in trace amounts. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. Without the interface having flexibility due to the plasticizer in the thermosetting resin-based protective layer 14 being sealed within the cured film structure, it is dispersed in the film and thus adheres to the interface even in trace amounts. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. It is dispersed in the film and thus adheres to the interface even in trace amounts. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced. When forming the protective layer 14 by the gravure method, by continuously intervening means such as heating, hot air, pressurization, and cooling during film formation, the affinity between the protective layer 14 and the metal layer 15 is enhanced.

[0081] Among the plasticizers, select specific heat-resistant materials, flexible materials, and materials with transfer induction properties for formulating and adding to the protective layer 14. Determine the specific selection of each material and the setting of the formulation amount through experiments, and link it 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 plasticizers. Determine the specific selection of each material and the setting of the formulation amount through experiments, and link it 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 plasticizers. Link it 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 plasticizers. The plasticizer capable of generating these functions can be selected from one or more of the above plasticizers. The plasticizer capable of generating these functions can be selected from one or more of the above 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 the film formation method using the heating of the drying furnace 61 of one type by the far-infrared heater 67, hot air treatment, and the directly connected external furnace pressurizing device 71 and the external furnace cooling device 72. Or, the film formation operation is executed by using the heating of the drying furnace 62 of two types, hot air treatment, the directly connected external furnace pressurizing device 71, and the external furnace cooling device 72. Or, the annealing treatment of baking the dry film of the protective layer 14 by the one-type furnace 61 and the two-type furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. 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 the film formation method using the heating of the drying furnace 61 of one type by the far-infrared heater 67, hot air treatment, and the directly connected external furnace pressurizing device 71 and the external furnace cooling device 72. Or, the film formation operation is executed by using the heating of the drying furnace 62 of two types, hot air treatment, the directly connected external furnace pressurizing device 71, and the external furnace cooling device 72. Or, the annealing treatment of baking the dry film of the protective layer 14 by the one-type furnace 61 and the two-type furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. Or, the film formation operation is executed by using the heating of the drying furnace 62 of two types, hot air treatment, the directly connected external furnace pressurizing device 71, and the external furnace cooling device 72. Or, the annealing treatment of baking the dry film of the protective layer 14 by the one-type furnace 61 and the two-type furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. Or, the film formation operation is executed by using the heating of the drying furnace 62 of two types, hot air treatment, the directly connected external furnace pressurizing device 71, and the external furnace cooling device 72. Or, the annealing treatment of baking the dry film of the protective layer 14 by the one-type furnace 61 and the two-type furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. Or, the annealing treatment of baking the dry film of the protective layer 14 by the one-type furnace 61 and the two-type furnace 62, the film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. The film modification treatment of the protective layer 14 by the external furnace pressurizing device 71 and the external furnace cooling device 72, the modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. The modification treatment by the lamination of both layers of the protective layer 14 and the metal layer 15, and the modification treatment for each layer is for the formulation of the protective layer 14. Selection of plasticizer, setting of input amount and its effects, interfacial modification treatment of the multilayer film of protective layer 14 and metal layer 15 By appropriately combining the above at the right time, a flat film structure or a three-dimensional structure of the transfer laminate 12 can be formed .

[0083] In each of the heating, hot air, pressurization, and cooling devices, the resin-based protective layer 14 can be hardened and rigidified by heating the resin film , and can be obtained by hot air treatment. The pressurization treatment relieves the compressive residual stress of the resin film, and the cooling treatment aims to soften and fix the resin film, and can fix the protective layer 14 and the metal layer 15 For the heating, hot air, pressurization, and cooling treatments of the resin-based protective layer 14, and for the annealing treatment of baking the dry film in heating, hot air, pressurization, and cooling after the lamination of the resin-based protective layer 14 and the metal layer 15 , the affinity between the protective layer 14 and the metal layer 15 is improved, and it becomes a softer and stickier film quality .

[0084] The transfer foil 10 is composed of a film serving as a base material and a modified laminate that is laminated and peeled off therefrom . On the base material film 11 selected from among chemical conversion films, in order as a laminate 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 are selected and laminated to form. The film protective layer 22 and the metal layer 15 may be absent . 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, a colorant such as a dye or a pigment can be used to make the colored resin-based protective layer 14 a colored layer .

[0085] The film protective layer 22, the release layer 13, the resin-based protective 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. Gravure ​The drying equipment used for coating has a far-infrared heater 67 installed in the furnace and can perform heating and drying 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 immediately outside the drying furnaces 61 and 62 together with the base film 11. Further, it can pass through the continuously installed cooling device 72 to be rapidly cooled 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 printer 60 is equipped with the drying furnace type 1 furnace 61 shown in FIG. 6 or the 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 the drying means. Also, the dry film of the formed film can be subjected to annealing treatment to bake the dry film through heating and hot air treatment. Further, the film formation that has swelled and softened into a soft material by heat treatment can be pressure-compressed by the pressurizing device 71. And, the film formation can be rapidly cooled by the subsequent cooling device 72 to enhance the fixing property between layers. Each means can be implemented alone for the device and film formation. Also, they can be used in combination in a layered and coordinated manner . They can be selected and combined. With the blending of the plasticizer into the resin-based protective 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 protective layer 14 tend to have a bonding property when the affinity at each interface becomes prominent after the heat treatment. The compatibility between the resin-based layer and the metal-based layer is forced, and the bonding property is enhanced by the processes through each device such as heating, hot air, pressurization, and cooling by the gravure printer 60. The influence from heating and pressurization from the transfer device during thermal pressure transfer on the transfer laminate 12 including the base film 11

[0086] ​​​​​​​​​​ , with respect to the expansion and contraction load resulting from the description of the transfer object 32, the resin-based protective layer 14 and the gold metal layer 15 both respond to expansion and contraction, 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 expansion, contraction, pressure, and heat is applied. In order for the transfer laminate 12 to withstand the generation of cracks, splits, swelling, etc., flexibility is imparted to the cured film by selecting a plasticizer, and heating, pressurization, and cooling are incorporated by the gravure method. This enhances 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 in 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 uneven ridges and wrinkles in a three-dimensional structure. As shown in the photograph of FIG. 8. It has a continuous three-dimensional shape with a chord of 2 2.30 μm, a height of 13.87 μm, and an arc of 37.25 μm in the parabolic cross-section, and has a continuous three-dimensional film structure with a valley width of 1.1 - 1.14 μm in the concave part and a peak width of 0.7 - 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, in the heat resistance test after transfer, the temperature is sequentially increased from room temperature to reach 380 °C and then decreased to room temperature. As a result of the test in the cycle, no cracks, splits, swelling, etc. occurred, and gold There was no change in the reflectivity of the metal layer 15, and no abnormalities such as delamination between the layers of the laminated film were observed. None.

[0090] As described above, the film formation of the three-dimensional structure film forms a continuous film with fine irregularities on the surface by the transfer laminate 12. The incident light on the metal layer 15 in the film reaches the surface by reflection by the metal layer 15. The light by the diffracted light returns to the surface part, optical interference occurs, and an interference metallizing effect is generated. In addition, the light reception by the fine three-dimensional layer on the surface causes optical interference on the surface. None.

[0091] The surface layer of the fine three-dimensional structure of the transfer laminate 12 was subjected to a pressure of 5 to 10 Kg / cm 2 , temperature 150 to 200 °C, and a transfer residence time of 0.5 seconds. When the transfer peel resistance value and film breakage were confirmed, no change was observed. No change was observed in the brilliance either. None.

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

[0093] In the resin-based protective layer 14, the film has strength as a cured film, contains a plasticizer, and has flexibility. By heating, hot air, pressurization, and cooling by 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 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 object to be transferred 32 after transfer, the broken end face of the contour of the transferred image is clearly displayed, and the transfer laminate 12 has shearability. None. Regarding the transfer breakage of the transfer laminate 12, the metal transfer relief plate shown in the photograph of Fig. 16 None. Using a vertical transfer foil press with 40, at a temperature of 120 - 150°C and a transfer residence time of 0.5 seconds , a pressure of 5 Kg / cm 2 , using a 1 - mm - thick PP sheet as the transfer body 32, the transfer was performed. The breakage after transfer is shown in the photo of Figure 15. The transfer lamination 12 transferred onto the PP sheet is exquisitely broken and transferred as shown in the photo of Figure 16, in the shape of a metal - made plate.

[0094] The transfer laminate 21 is formed by laminating, in order on the base film 11, 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. The film protective layer 22 contains one or more selected from the group consisting of phenolic resin, epoxy resin, urea resin, unsaturated polyester resin, silicone resin, melamine resin, aniline resin, sulfonamide resin, alkyd resin, polyurethane resin, diallyl phthalate resin, and thermosetting polyimide resin. The film protective layer 22 is smoothly coated on the base film 11 with a thickness of 0.3 - 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 pressure transfer. In addition, it maintains the uniformity of heat - 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. These can maintain the peeling uniformity of the transfer laminate 12 and the stability of thermal pressure transfer. Since the resin - based protective layer 14 contains a plasticizer, the transfer laminate 12 expands due to thermal pressure transfer

[0095] ​​​​​​Even when shrinkage occurs, the metal layer 15 does not cause cohesive failure, so the transfer laminate 12 does not develop cracks, fractures, or bulges.

[0096] The transfer foil 10 is passed through a thermocompression transfer device to laminate the transfer laminate 12 with the object to be transferred 32, and is heated and pressed on the transfer film. As a result, the transfer laminate 12 peels off from the base film 11, breaks, and is transferred onto the object to be transferred 32 as a selected pictorial image. This decorates the surface layer of the object to be transferred 32. The decorative laminate, i.e., the transfer laminate 12, has a resin-based protective layer 14 with adhesiveness provided thereon for protecting the base film 11 and modifying the interface. By bonding with 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 thermocompression transfer, and also prevents the propagation of expansion and contraction to the transfer laminate 12. Further, it provides peel stability when the transfer laminate 12 peels off. It is formed using a well-known thermosetting resin in the range of a film thickness of 0.3 to 5 μm. Next, a release layer 13 is provided. The material can be selected from known materials and can be formed by blending one or more selected from methyl methacrylate, ethyl methacrylate, butyl acrylate, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl butyral, polyester resin, urethane resin, epoxy amino resin, aminoalkyd resin, silicon wax-based, silicon resin, silicon-modified resin, fluororesin, fluorine-modified resin, polyvinyl alcohol, cellulose-based materials such as nitrocellulose, and various waxes including silica as a hardening agent and polyethylene wax. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. This serves as a measure to prevent the expansion and contraction of the base film 11 during thermocompression transfer of the base film 11 and prevents the propagation of expansion and contraction to the transfer laminate 12. Also, it provides peel stability when the transfer laminate 12 peels off. It is formed using a well-known thermosetting resin in the range of a film thickness of 0.3 to 5 μm. Next, a release layer 13 is provided. The material can be selected from known materials and can be formed by blending one or more selected from methyl methacrylate, ethyl methacrylate, butyl acrylate, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl butyral, polyester resin, urethane resin, epoxy amino resin, aminoalkyd resin, silicon wax-based, silicon resin, silicon-modified resin, fluororesin, fluorine-modified resin, polyvinyl alcohol, cellulose-based materials such as nitrocellulose, and various waxes including silica as a hardening agent and polyethylene wax. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. It can be selected from known materials and used by selecting and containing one or more from methyl methacrylate, ethyl methacrylate, butyl acrylate, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl butyral, polyester resin, urethane resin, epoxy amino resin, aminoalkyd resin, silicon wax-based, silicon resin, silicon-modified resin, fluororesin, fluorine-modified resin, polyvinyl alcohol, cellulose-based materials such as nitrocellulose, and various waxes including silica as a hardening agent and polyethylene wax. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. It can be selected from known materials and used by selecting and containing one or more from methyl methacrylate, ethyl methacrylate, butyl acrylate, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl butyral, polyester resin, urethane resin, epoxy amino resin, aminoalkyd resin, silicon wax-based, silicon resin, silicon-modified resin, fluororesin, fluorine-modified resin, polyvinyl alcohol, cellulose-based materials such as nitrocellulose, and various waxes including silica as a hardening agent and polyethylene wax. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. It is preferably formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. It can be formed by selecting and blending one or more from release materials, heat transfer materials, hard materials, breaking materials, interlayer bonding materials, pressure-resistant materials, lubricious materials, heat-resistant materials, glossy materials, and the base film 11. Or the form of interfacial peeling with the film protective layer 22 or the cohesive failure within the release layer 13 due to transfer hot pressing As a result of peeling by fracture peeling due to peeling, the formation and transfer of the cover of the release agent to the next resin-based protective layer 14 The assistance of physical and chemical resistance after transfer is necessary as the release layer 13 together with the releasability For this purpose, the release layer 13 may be laminated. Also, the functions may be differentiated and may be made into multiple layers. The formation of the release layer 13 is carried out using a known film forming machine such as a gravure printing machine 60 and drying using a prepared liquid. The film thickness is 0.1 to 20 μm, preferably 0.1 to 10 μm is good.

[0097] In order 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 colored resin-based protective layer 14 containing a plasticizer, the metal layer 15, the resin-based protective layer 23 containing a plasticizer, the adhesive layer 16 are sequentially laminated, and the 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 either the selection of the base film 11, the release layer 13, the resin-based protective layer 14 containing a plasticizer or the colored resin-based protective layer 14 containing a plasticizer in sequence, the setting of the metal layer 15, the adhesive layer 16, the setting of the base film 11, the film protective layer 22, the release layer 13, the resin-based protective layer 1 4 or the colored resin-based protective layer 14 containing a plasticizer, the metal layer 15, the adhesive layer 16, the setting of the base film 11, the release layer 13, the resin-based protective layer 14 containing a plasticizer or the colored resin-based protective layer 14 containing a plasticizer in sequence, the metal layer 15, the resin-based protective layer 14 containing a plasticizer, the adhesive layer 16 can be formed. These means use each resin-based protective layer 14 containing a plasticizer to adapt to the expansion and contraction and the load of the pressure applied during thermocompression transfer together with the metal layer 15, and the effect is reflected in the adaptation to the load of the pressure applied during thermocompression transfer together with the metal layer 15 These means are effective in adapting to the expansion and contraction and the load of the pressure applied during thermocompression transfer with each resin-based protective layer 14 containing a plasticizer together with the metal layer 15 will be obtained.

[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. To suppress this, a hard film protective layer 22 is formed. To achieve 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, transfer fixability, and breakability during transfer are improved.

[0099] During heat and pressure transfer, first the base film 11, the resin-based protective layer 14, the color-forming resin-based protective layer 14, The adhesive layer 16 shows film expansion at that time. When a tensile stress that causes expansion is applied to the metal layer 15 from the resin-based protective layer 14 or the adhesive layer 16, cracks, breaks, bulges, etc. occur between the metal layer 15 or between the metal layer 15 and the resin-based protective layer 1 4, resulting in a decrease in the brightness of the transfer laminate 12 due to attenuation of the luster of the metal layer 15 and bulges due to heat yield during transfer of the resin-based protective layer 14. .

[0100] On the base film 11, a transfer laminate 21 for forming a heat and pressure 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. In the resin-based protective layer 14, a plasticizer is added to make a coating solution. The film protective layer 22 and the adhesive layer 16 are formed by coating using a gravure printing machine 60. . Each process is dried by a far-infrared heater 67 and a hot air device 6 9 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 within the film is accumulated in the part. A plasticizer is formulated in the protective layer 14. The plasticizer in the mesh structure film for film formation has imparted flexibility in the curable film. The protective layer 14 has brought in the buffering property of the generation of stress of external force and internal force. Therefore, the deformation of the protective layer 14 against expansion and contraction can also be reduced. The interface between the protective layer 14 and the metal layer 15 or the influence of the breakage or shearing caused by the expansion and contraction of the protective layer 14 on the metal layer 15 can be reduced or avoided .

[0101] The color-developing resin-based protective layer 14 is a layer having light resistance, and dyes, inorganic pigments, organic pigments, etc. can be used as the color-developing material. In addition, as the weather-resistant material, one or more acrylic resins containing a hindered amine-based material which is a light stabilizer are added. One or more hydroxyphenyltriazine-based materials which are ultraviolet absorbers are added. By containing salicylic acid phenyl as a light-blocking agent, the fading deterioration of the transfer laminate 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 heating and pressurization during transfer, an expansion and compression stress due to heating and pressurization 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, a force that inhibits the cohesiveness of the metal is generated, and 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 fracture. Starting from this, the transfer laminate 12 progresses to cracks, breaks, bulges, cracks, peeling, poor interlayer adhesion, foil peeling due to interlayer defects, poor heat resistance, poor glossiness, poor weather resistance, etc ​ There is a risk of occurrence.

[0103] In order to improve such a situation, after conducting various experiments, by selectively adding a plasticizer to the liquid 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. It contributes to suppressing the occurrence of cracks, fractures, swelling, etc., enhances the interfacial fixation of the protective layer 14 and the metal layer 15, and obtains a means to show resistance to the elongation of the transfer laminate 12 during transfer. By adding a plasticizer to the protective layer 14, the method of heat-treating the protective layer, heat treatment, hot air treatment, pressure treatment, cooling treatment, annealing treatment, etc. are incorporated into the process for the combined state of the protective layer 14 and the metal layer 15, so that the transfer laminate 12 comes to have heat resistance, flexibility, and stretchability, and can withstand and suppress the stress during the transfer of thermocompression transfer.

[0104] [Manufacturing Method 7] After forming the release layer 13 coated on the base film 11 by the gravure printing machine 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, it becomes a film with flexibility. 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 and formed into a film. Next, the metal layer 15 is formed by a vacuum deposition device, and an adhesive is supplemented.

[0105] [Manufacturing Method 8] After forming the release layer 13 coated on the base film 11 by the gravure printing machine 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, it becomes a film with flexibility. ​ It is carried out. The coating is heated by an infrared heater and a hot air device 69 in the drying furnace 61 of the gravure printing machine 60 and film formation is performed. Next, in the gravure printing machine 60 having the drying furnace 62 of the second type, a dry film in a state where a release layer 13 and a protective layer 14 containing a plasticizer are laminated on the base film 11 is subjected to an annealing treatment for baking by an operation of a volume of 2.64 m 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 3 are formed. A transfer foil 10 including a transfer laminate 12 for modifying the surface layer of the transfer body 32 having a flat film layer structure is obtained.

[0106] [Production Method 9] After forming a release layer 13 coated on the base film 11 by the gravure printing machine 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 having flexibility is formed. Thereafter, a metal layer 15 is formed. Then, in the gravure printing machine 60 having the drying furnace 62 of the second type, a baking treatment is performed 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 for modifying the surface layer of the transfer body 32 having a flat film layer structure is obtained.

[0107] [Production Method 10] After forming a release layer 13 coated on the base film 11 by the gravure printing machine 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 having flexibility is formed. Thereafter, a metal layer 15 is formed. Then, in the gravure printing machine 60 having the drying furnace 62 of the second type, a baking treatment is performed 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 for modifying the surface layer of the transfer body 32 having a flat film layer structure is obtained. At this point, a baking process is performed in the same manner as the above heat treatment. Through the external pressure device 71 directly connected to the drying furnaces 61 and 62 and the external cooling device 72, a heat treatment, a pressure treatment, and a cooling treatment are carried out, so that the protective layer 1 becomes a cured, hard, and tough thermosetting film with stickiness, flexibility, and extensibility, and a flat film structure in which the film quality is propagated to the metal layer 15 is formed. Then, the adhesive layer 16 is added . A transfer foil 10 including a transfer laminate 12 that modifies the surface layer of the transfer body 32 is obtained.

[0108] [Manufacturing Method 11] After forming a release layer 13 coated by a 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 . Then, the metal layer 15 is formed. After that, heat treatment in the furnace and hot air treatment are performed by the gravure printing machine 60 installed with two drying furnaces 62, pressure is applied by the connected external pressure device 71, and cooling is performed by the external cooling device 72 . Annealing treatment for baking the dry film of the laminate of 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 heat treatment state of the heating and hot air of the drying furnaces 61 and 62 to a 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 ridged shape having fine irregularities . Then, the adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 that modifies the surface layer of the transfer body 32 is obtained.

[0109] [Manufacturing Method 12] After forming a release layer 13 coated by a 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 ​​​​​​​​​​ It becomes a thermosetting resin layer. Since a plasticizer is added, it becomes a flexible film-forming material. . In the drying furnace 61 of the gravure printing machine 60, the far-infrared heater 67 and hot air treatment are carried out at high temperature for the treatment of the area. Then, the metal layer 15 is formed. Further, in the drying furnace 62 of the gravure printing machine 60, the far-infrared heater 67 and hot air treatment are carried out for the treatment of the high temperature area, and then by performing pressure treatment and cooling treatment, a fine ridged continuous three-dimensional structure layer is formed. After that, the adhesive layer 16 is added. A transfer foil 10 including a transfer laminate 12 for modifying the surface of the transfer body 32 is obtained.

[0110] By setting the temperature control of the first furnace 61 and the second furnace 62 between the low temperature range of 100 to 160 °C and the high temperature range between 140 to 210 °C, in the low temperature range, a flat film structure is formed, and in the high temperature range, a three-dimensional film structure is formed. The film structure can be produced separately for the flat film structure and the three-dimensional structure. The resin-based protective layer 14 is formed by the treatment of the gravure printing machine 60. The treatment by the first drying furnace 61 and the second drying furnace 62, the treatment by the far-infrared heater 67, hot air treatment, pressure treatment, and cooling treatment enable drying, annealing, film modification, and film bonding of the liquid preparation.

[0111] [Manufacturing Method 13] The 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 to 70 μm, a height of 10 to 270 μm, and an arc length of 4 0 to 550 μm.

[0112] The photograph shown in Fig. 8 shows the surface of the transferred transfer laminate 12. The right photograph shown in Fig. 9 is , 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. FIG. 1 The photograph shown in 0 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 gravure-printed on the base film 11 by the dryer 1 type furnace 61 and heated and dried to form a film. Next, the resin-based protective layer 14 containing a plasticizer is dried in the dryer 1 type furnace 61 and heated and dried to form a film. Next, the metal layer 15 is formed using a two-chamber semi-continuous vacuum evaporator via a high-frequency excited plasma activation reactive device to form the metal layer 15. Next, in the dryer 2 type furnace 62 of the gravure printer 60, the release layer 13, the protective layer 14, and the vapor deposition film are formed on the base film 11 and at the same time, annealing treatment is performed in the high-temperature region within 150 to 210 °C 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 dryer 1 type furnace 61 of the gravure printer 60 to complete the three-dimensional film of the transfer laminate 1 2.

[0114] In the formation of the three-dimensional film, the interface between the protective layer 14 and the metal layer 15 has excellent bonding properties with affinity-based interface fixing and forms a film. In the above example, it has a continuous three-dimensional structure with a cross-section of an arc of 20 to 550 μm in a bow shape. The area of the film after the formation of the vapor deposition film and the area after the process of the dryer 2 type furnace 6 2 were measured and compared in a state including the film, and they were the same area. Heat treatment, hot air treatment, pressurization treatment, and cooling of the resin-based protective layer 14 containing a plasticizer and the metal layer 15 combined ​​​After the operation of the process, a three-dimensional film was formed, and the cross-section of the arcuate arc was 20 to 55 0 μm, which represents the magnification of stretching. No cracks, breaks, bulges, etc. were observed in either the protective layer 14 or the metal layer 15 after stretching. There was no change in the luminance after transfer.

[0115] The resin-based protective layer 14 containing a plasticizer is subjected to heating, hot air, pressurization, and cooling treatment by the drying furnaces 61 and 62 of the gravure printing machine 60, resulting in a thermosetting resin film that hardens. The plasticizer in the mesh structure film imparts flexibility to the film quality. Furthermore, by using a plasticizer that migrates and induces within the film within limits, a plurality of plasticizers with flexibility and migration-inducing properties are formulated and added to 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 one to flexibility and interfacial inductivity. The protective layer 14 with hard and tough properties in the film becomes sticky, and the flexibility becomes stretchable. The interfacial inductivity of the plasticizer guides the interfacial part of the protective layer 14, which has an affinity for the metal deposition layer and the grain boundaries of the island-like layer of the metal layer 15. The plasticizer, combined with its flexibility-indicating performance, is required to maintain the heat resistance of the transfer laminate 12. 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-inducing properties, the affinity for the metal layer 15 is promoted, and the fixation at the interface between the protective layer 14 and the metal layer 15 is enhanced by cooling outside the furnace. The number of plasticizers added to the resin-based protective layer 1 4 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 plasticizer -containing resin-based protective layer 14 has heat resistance as a thermosetting resin film and undergoes annealing treatment for dry film bay king, the stress is removed by pressurization, and it also has flexibility due to the plasticizer. The interface-induced plasticizer in the film, together with the flexible plasticizer, leads to the interface of the metal layer 1 5. The heat resistance, flexibility, and stretchability of the protective layer 14 are enhanced from the generation of interface affinity to more intimate fixing due to 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, resulting in a film formation that maintains the adhesion between layers. 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 on migration are selected. Furthermore, the plasticizer maintains heat resistance during transfer. By preventing the lack of affinity with the interface of the metal layer 15, through operations such as heating, hot air, pressurization, and cooling, the metal layer 15 undergoes metal plastic deformation, and due to the migration induction by the plasticizer in the formulation of the protective layer 14 along its metal deposition structure or metal island structure, the affinity is increased, and further, it intervenes in the metal layer 15 and progresses to bonding, and the fixing between layers further progresses. Regarding the defects of the transfer foil 10, there are 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 light

[0117] luminance, poor weather resistance, foil peeling due to poor adhesion, incomplete slipperiness of the foil surface layer, discoloration, attenuation of the metallic effect, and poor film permeability. Among these, regarding cracks, splits, and swelling, the selection of a plasticizer that imparts flexibility to the protective layer 14 and a plasticizer that acts on migration is carried out. Furthermore, the plasticizer maintains heat resistance during transfer. By preventing the lack of affinity with the interface of the metal layer 15, through operations such as heating, hot air, pressurization, and cooling, the metal layer 15 undergoes metal plastic deformation, and due to the migration induction by the plasticizer in the formulation of the protective layer 14 along its metal deposition structure or metal island structure, the affinity is increased, and further, it intervenes in the metal layer 15 and progresses to bonding, and the fixing between layers further progresses. Regarding the defects of the transfer foil 10, there are 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 light luminance, poor weather resistance, foil peeling due to poor adhesion, incomplete slipperiness of the foil surface layer, discoloration, attenuation of the metallic effect, and poor film permeability. Among these, regarding cracks, splits, and swelling, the affinity is increased due to the migration induction by the plasticizer in the formulation of the protective layer 14 along the metal deposition structure or metal island structure of the metal layer 15, and further, it intervenes in the metal layer 15 and progresses to bonding, and the fixing between layers further progresses. Furthermore, it progresses.

[0118] Regarding the defects of the transfer foil 10, there are 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 light luminance, poor weather resistance, foil peeling due to poor adhesion, incomplete slipperiness of the foil surface layer, discoloration, attenuation of the metallic effect, and poor film permeability. Among these, regarding cracks, splits, and swelling, for these, As a phenomenon occurring during transfer, it leads to a drop in brilliance, which is related to the factor of foil peeling over time and results in damage to the aesthetic feeling etc. In the transfer target 32, dimensional changes also occur over time due to humidity, temperature, and climate These effects also cause the transfer laminate 12 to lose its modification properties, get damaged, and experience foil peeling to occur

[0119] Figs. 11 to 14 are photographs of cracks, fractures, and bulges in the transfer laminate 12

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

[0121] In view of the above, in this embodiment, in order to suppress cracks, fractures, bulges, etc. in the transfer foil 10 and improve heat resistance, light resistance, etc., the selection of materials used in the transfer laminate 12, 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 occurring between the transfer laminate 12, the transfer equipment, and the transfer target 32 experiments have been repeated, and the details are listed below ​

[0122] [Experiment 1] As the base film 11, a polyester film with a thickness of 12 μm was used. The base film 11 was formed with a release layer 13 thereon. Specifically, 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), Fisher-Tropsch wax 1.04% by weight (Sadole Co., Ltd.; A859), 0.9% by weight of an acrylic resin (Nippon Catalyst Co., Ltd.; UV-G301) were formulated into a release agent, which was applied and dried by a gravure printing machine 60 to form a release layer 13 with a thickness of 0.5 μm. Using a furnace 61 of a certain type of gravure printing machine 60 , the film was allowed to stay for 20 to 50 seconds in an environment with a heating temperature of 100 to 120 °C to produce a flat film (release layer 13) with a thickness of 0.5 μ m.

[0123] Next, a resin-based protective layer 14 was formed on the release layer 13. After formulation, it was applied and dried by a gravure printing machine 60 to form a resin-based protective layer 14 with a thickness of 1 μm. The resin-based protective layer 14 consisted 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 Catalyst Co., Ltd.; UV-G301) , 11.7% by weight of an acrylic resin (Alfa Chemical Research Co., Ltd.; silicone acrylate silicate UVHA), 1.19% by weight of an acrylic resin (Wilbur-Ellis Co.; Paraloid AT7 40), 1.49% by weight of a melamine resin (Nippon Carbide Co., Ltd.; MS-001), ketone 4.4 wt% of N-based resin (Worley Co., Ltd.; Polytone K-97), 0.08 wt % (BASF; Tinuvin 1600), 0.08 wt% of ultraviolet absorber (BASF; Tinuv in 479), 0.08 wt% of light stabilizer (BASF; Tinuvin 249), 0.0 8 wt% of light blocker (Tokyo Chemical Industry Co., Ltd.; phenyl salicylate), 0.03 wt% of curing agent (Tokyo Chemical Industry Co., Ltd.; p-toluenesulfonic acid), etc., were used to prepare the thermosetting resin-based protective layer 14 as a formulation.

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

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

[0126] Next, the adhesive layer 16 was formed on the metal layer 15. 50.0 wt% of toluene (Idemitsu Kosan Co., Ltd.), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m company), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m company), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m company), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m company), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m company), 37.7 wt% of ethyl acetate (Showa Denko KK), 1.5 wt% of butyl acetate (Standard Oil Co., Ltd.), 0.07 wt% of ethyl silicate (Colcoat Co., Ltd.; ethyl silicate 100), 2.7 wt% of acrylic resin (Mitsubishi Chemical Corporation; Corponeel N2147), 2.7 wt% of ethylene vinyl acetate (Mitsubishi Chemical Corporation; Soanol D2908), 3.0 wt% of ketone resin (Worley Co., Ltd.; Polytone K-97) were used to produce films with thicknesses of 1 μm and 2 μm by a gravure coater. Using a volume of 5.28 m device and a high-frequency induction heating metal melting heat source.3 One type of furnace 61 was used and allowed to stay at a heating temperature of 100 to 120 °C for 20 to 50 seconds to produce flat films (adhesive layer 16) with thicknesses of 1 μm and 2 μ m.

[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 fabricated. Using a hot press transfer machine 51, the occurrence of cracks in the transfer foil 10 was evaluated.

[0128] When the resin-based protective layer 14 was made thermosetting or thermoplastic, confirmation was carried out for the case where 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, the transfer body 32 was a soft vinyl chloride sheet with a thickness of 0. 9 mm, and the occurrence of cracks after transfer was confirmed. The photographs shown in Fig. 11 show the cracks, cracks, and bulges of the transfer foil 10. The photograph shown in Fig. 12 shows the cracks of the transfer foil 10 on the transfer body 32 with unevenness. The photographs shown in Figs. 13 and 14 are enlarged views of the openings of the cracks of the transfer foil 10.

[0129] For each of the thermosetting and thermoplastic transfer laminates 12, using an up-down type transfer foil press 31 or 41, the transfer temperature was 120 °C or 160 °C, the transfer pressure was 5 Kg / cm and the transfer residence time was 0.5 seconds 2 for transfer. In both the thermosetting and thermoplastic resin-based protective layers 14, the plasticizer content was set to 3.0%. As a result, cracks were observed on all the transfer foils 10 It was not observed. The elongation of the soft vinyl chloride sheet was also not 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] In addition, by changing the transfer residence time, the change in the elongation of the object to be transferred 32 and the influence on the transfer foil 10 were set and confirmed as follows. The transfer residence time was divided into three stages of 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 . The vertical and horizontal transfer foil pressing machine 41 using a relief plate 40 (3 mm long × 6.75 mm wide × 2 mm high) was used for 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 preparation 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 8.2% increase. When the crack of the transfer foil 10 was confirmed, no crack was 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 1 0 is described in Table 2. Here, the protective layer 14 was divided into thermosetting and thermoplastic, and moreover, the transfer residence time was divided into 0.5 seconds, 0.75 seconds, and 1.00 seconds .

[0132] In addition, 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 was elongated by 2%, and the opening width was 7 μm. When the transfer residence time was 1.00 seconds, the soft vinyl chloride sheet was elongated by 8.2%, and the opening width was 282 μm. From these results, the transfer conditions of heating, pressing, and time onto the soft vinyl chloride sheet as the transfer body 32 are applied, and the metal layer 15 of the transfer laminate 12 is affected by the tensile stress and compressive stress that cause the soft vinyl chloride sheet to expand and contract during the cycle until the pressure is released and it returns to room temperature. The cohesive failure of the metal layer 15 with weak cohesive force progresses, and the stress of the crack progresses from the break of the metal layer 15 to the interface of the protective layer 14 and the protective layer 14, resulting in the generation of cracks. It was found that the resin-based protective layer 14 generates cracks in both cases of thermosetting and thermoplasticity when the transfer residence time is 0.75 seconds and 1.00 seconds. The results are shown in Table 2. When the protective layer 14 does not contain a plasticizer, both the crack opening width and the elongation ratio become extremely large.

[0133]

Table 2

[0134] [Experiment 3] From the results of the above Experiment 2, it was found that cracks occur when the transfer residence time is 0.75 to 1.00 seconds. To improve this, in order to cope with the expansion and contraction of the transfer body 32, ​​​​​​​​​​​​​​It is necessary to provide means in the transfer foil 10. The object to be transferred 32 has a wide variety of material shapes including flat surfaces, three-dimensional surfaces, hard materials, soft materials, organic materials, inorganic materials, etc. Between the object to be transferred 32 and the transfer laminate 12, various stresses such as external forces and internal forces generated during transfer cause deformation such as strain, elongation, contraction, displacement, torsion, bending, inclination, etc., and it is necessary to cope with these. 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 shear. It is difficult for the transfer laminate 12 to maintain its film properties against the influence of the film having transfer breakage properties, the expansion and contraction of the object to be transferred 32, and the various stresses caused by transfer. Here, while maintaining the breakage and shear resistance of the transfer laminate 12, a state that can withstand cracks, etc., and maintain elasticity was considered. From among the above-mentioned plasticizers, the selection of additive materials was carried out in the formulation of the resin-based protective layer 14 so that the deformation of the transfer laminate 12 caused by the transfer elongation of the flexible vinyl chloride sheet can maintain resistance against the influence on the generation of cracks in the transfer foil 10. As functions obtained when introduced as formulation additives such as the resin-based protective layer 14 and the color-forming resin-based protective layer 14, there are flexibility, stretchability, transparency, miscibility, no inhibition of interlayer adhesion, no whitening phenomenon and interface alteration after component migration, no change with time, no change in heat resistance,

[0135] and no influence on the breakage of the film. For these selections, the transfer foil 10 was manufactured by sequentially laminating each layer on the base film 11. Among the laminations such as the release layer 13, the resin-based protective layer 14, the metal layer 15, and the adhesive layer 16 on the base film 11, the resin-based protective layer 14 and the adhesive layer 16 are provided at the interface of the metal layer 15 with weak cohesion.

[0136] ​ If the extensibility of the resin-based protective layer 14 is improved, deformation of the transfer laminate 12 can be prevented. A thermosetting film was used as a crack inhibitor caused by plastic deformation of the film, and a plasticizer was added to obtain flexibility and extensibility and to prevent a decrease in the softening point and shearing of the film.

[0137] On a base film 11 made of a 12-μm-thick polyester film, 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 (Alpha Kaken Co., Ltd.; UVHA), 1.19% by weight of an acrylic resin (Wilbur-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., Ltd.; Polytone K97), 0.08% by weight of an ultraviolet absorber (BASF Co., Ltd.; Tinuvin 1600), 0.08% by weight of an ultraviolet absorber (BASF Co., Ltd.; Tinuvin 479), 0.08% by weight of a light stabilizer (BASF Co., Ltd.; Tinuvin 249), 0.08% by weight of a light blocker (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 a coating conditioner, a one-kind furnace 61 (volume 5.28 m 3 ) of a gravure printing machine 60 was used, and film formation was carried out by passing and staying in an atmosphere of 150 to 210°C for 20 to 50 seconds. The film thickness was 1 μm. Next, in the same manner as in Experiment 1 above, a metal layer 15 and an adhesive layer 16 were formed, and a transfer foil 10 having a flat film structure was produced therefrom . Next, an up-and-down type transfer foil press 4 1 equipped with a relief plate 40 was used to perform thermal pressure transfer onto a soft vinyl chloride sheet, and the base film 11 was peeled off to confirm the transfer state.

[0140] As evaluation items of the plasticizer, the following functions were determined. 1: Mixability with the conditioner (affinity with other materials during mixing at the time of conditioning) 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 making of the transfer device, soft vinyl chloride sheet transfer material) 4: Flexibility of the transfer laminate 12 (cracks in the foil due to relief plate making of the transfer device, soft vinyl chloride sheet transfer material) 5: Heat resistance of the transfer laminate 12 (relief plate making of the transfer device, temperature 160°C, transfer residence time 0.5 seconds , transfer pressure 5 Kg / cm 2 , transfer material, soft vinyl chloride sheet, attenuation of brilliance) 6: Breakability of the transfer laminate 12 (breakage of the transfer film of the pictorial image during transfer, state of the sheared appearance) 7: Compatibility at both interfaces of the protective layer 14 (affinity at the adjacent layer interfaces, by peeling of the adhesive tape) ) 8: Stretchability of the transfer laminate 12 (in the intaglio plate making 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 substrate) ) 9: Interlayer adhesion at both interfaces of the protective layer 14 (with upper and lower adhesive tapes provided inside the transfer layer, confirmed by the peeling state of the interface in the 180 °C peel test) 10: Migration property of the added plasticizer (the transferred materials on the soft vinyl chloride sheet are put together, a load of 5 00 g is applied, after 48 hours at 160 °C in a thermostatic and humidistatic chamber, returned to room temperature, and peeling is confirmed)

[0141] Table 3 shows the judgment 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 target. (c) Phosphate ester-based is lacking in flexibility, so it may be excluded from the selection target . (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 property. (e) Ethylene olefin-based showed abnormalities in extensibility, stretchability, interlayer adhesion, and migration property, but characteristics of interfacial induction were recognized in migration property. The use of this material should determine the addition amount so as to improve the affinity to the metal layer 15 of the protective layer 14, ​​​​The effects were confirmed. As a result, (d) the toluenesulfonamide type was good in all evaluation items. (e) The ethylene olefin type was selected to reconfirm the interface conductivity. As described above, it is preferable to select (d) the toluenesulfonamide type and (e) the ethylene olefin type.

[0144] [Experiment 4]

[0145] (d) The protective layer 14 added with a plasticizer of the toluenesulfonamide type and (e) the ethylene olefin type was selected. In these two points, in order to confirm the changes 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. The test contents were carried out through the heat resistance test to determine whether the transfer foil 10 would lead to cracks, breaks, swelling, etc. caused by the results of transfer pressure, transparency, heat resistance, stretchability, interlayer adhesion, migration, etc.

[0146] The heat resistance evaluation was carried out as follows. An acrylic binder film with a length of 10 cm × a width of 3 cm × a thickness of 1 μm was printed and coated on a transparent glass with a length of 10 cm × a width of 10 cm × a thickness of 0.5 cm using a silk screen and dried to obtain a resin film as the transfer body 32.

[0147] A transfer foil 10 including a thermosetting protective layer 14 containing a (d) toluenesulfonamide-based plasticizer was produced in the protective layer 14 provided with a release layer 13 on the base film 11. Further, a transfer foil 10 including a protective layer 14 containing an (e) ethylene olefin-based 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. Thus, the transfer machine 51 uses a silicon rubber roller as the heat and pressure application medium, and transfers onto the acrylic resin layer formed on the glass under the conditions of a transfer line pressure of 0.5 Kg / cm , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. 2 , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. Thus, the transfer machine 51 uses a silicon rubber roller as the heat and pressure application medium, and transfers onto the acrylic resin layer formed on the glass under the conditions of a transfer line pressure of 0.5 Kg / cm , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc.

[0149] (d) For the toluenesulfonamide-based plasticizer, no problems such as glitter, adhesion, crack generation, crack generation, or swelling were observed. (e) For the ethylene olefin-based 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. (d) The toluenesulfonamide-based plasticizer remained within the protective layer 14, and (e) the ethylene olefin-based plasticizer showed migration properties in the thermosetting film of the protective layer 14. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc. , a foil feed rate of 2.5 m / sec, and a roller surface temperature of 200°C. After 2 hours from the transfer, 5 samples of each of the above two types of specimens prepared on the glass substrate were placed in a thermostatic chamber. The temperature was raised from room temperature to 380°C over 200 minutes, held for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours from the cooling, the specimens were taken out and the transfer laminate 12 on the specimens was confirmed. The visual results were used to identify and evaluate the effects of the plasticizer added in terms of gloss attenuation due to transparency change, 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, swelling generated in the transfer laminate 12, etc.

[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 transfer was performed with 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 a 15-mm-wide adhesive tape, confirmation was made by a 180-degree peel test. 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. Bubble generation: 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: Problems 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, partial delamination phenomena occurred at both interfaces of the protective layer 1 and 4. The protective layer 14 in which the plasticizer was formulated is a thermosetting film. Without being blocked by the aggregated resin chains in this film, the (e) ethylene olefin-based plasticizer migrated to both interfaces of the release layer 13 and the metal layer 15 and reached there, which was shown. In order to complement maintaining the elasticity of the protective layer 14, maintaining the breakability, increasing the stretchability, maintaining the migration

[0156] inductivity, giving flexibility, and maintaining the interfacial adhesion, etc., 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%, 0.025 wt%, and the formulation was carried out to form the transfer laminate 12, and the transfer foil 10 having a flat film structure was produced.

[0158] As described above, resin processing was performed on the glass substrate, roll transfer was performed, and the substrate was left in a constant temperature bath and then taken out, and the performance was confirmed in the order described above. The results are shown in Table 5. In the table, "△" 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% and, it was found to be effective without change in adhesion. As a transfer inducer of materials and the like, flexibility can be used as an interlayer propagator of the flexibility of the resin-based protective layer 14 together with other plasticizers as a propagation material of flexibility.

[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-off 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. Swelling generation: The specimen was magnified 500 times and visually confirmed.

[0163] [Evaluation results] Heat resistance: There was no change in the brilliance, and all showed good results. Interlayer adhesion: When the addition amount was 0.075 wt%, it showed poor results. When the addition amount was 0.05 wt%, it showed the inclusion of defects. When the addition amount was 0.025 wt%, it showed good results. (e) Ethylene olefin plasticizer, at an addition amount of 0.025 wt%, after the heat resistance test, Regarding the adhesion, crack generation, crack occurrence, and swelling occurrence visually observed, the results showed that it was unrelated to film deterioration and that the resistance could be maintained was confirmed.

[0164] [Experiment 6] Due to the above process, (e) ethylene olefin plasticizer caused a phenomenon of migrating to the interface of the protective layer 1 4 of the thermosetting resin film up to the layer interface in the cured resin film. It was related to the peeling of the interface of the protective layer 14. Furthermore, as a result of attempting to adjust the addition amount, with 0.025 wt% as the upper limit, there was no abnormal occurrence regarding the peeling of the interlayer adhesion, and it became possible to participate in the migration induction in the protective layer 14.

[0165] As plasticizers contained in the protective layer 14, phosphate ester-based, toluenesulfonamide-based, and ethylene olefin plasticizers can be used regarding heat resistance, which was confirmed in Experiment 3.

[0166] As the effect of plasticizer input, by inducing the generation of flexibility in the protective layer 14 and the propagation of flexibility to the interface of the protective layer 14, it is predicted that the affinity of the interface of the protective layer 14 for the bonding property with the metal layer 15 will be increased. Through the heat treatment by the gravure printing machine 60, by performing interface modification of the protective layer 14 with plasticizer input, miscibility, transparency, breakability, compatibility, flexibility, heat resistance, and migration induction are generated in the thermosetting film. The protective layer 14 containing plasticizer ​​​​​The spread of the temperature range reaches the interface in the curable film of the protective layer 14. The thermosetting tough film possessed maintains heat resistance while the resin-based protective layer 14 and the metal layer 15 transform into a flexible film. When this occurs, migration inductivity is a necessary condition for the plasticizer to be included. becomes.

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

[0168] Executed in accordance with the processing on the glass substrate cited in Experiment 4, hot pressure transfer was carried out using a roll-type transfer device, a heat resistance test of staying in a thermostatic bath was carried out, and it was taken out and confirmed. Cracks, breaks, and swelling phenomena were not observed. The results were recorded in Table 8. For the coating film formation using the drying furnace 61 of the gravure printing machine 60, type 1 furnace (d)toluenesulfonamide-based plasticizer and (e)ethylene olefin-based plasticizer were added to the tough thermosetting resin film so that flexibility, heat resistance, and migration inductivity of flexibility were taken into account. The above evaluation results are shown in Table 6.

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

[0170]

Table 6

[0171] [Evaluation Method] A resin coating was applied to the glass substrate. After transfer by the roll transfer method, it was placed in a constant temperature bath and stored at room temperature Then, the temperature was raised from room temperature to 380 °C, held for 5 minutes, and after cooling to room temperature, the resistance was confirmed. Other experiments were carried out in the same manner as in Experiment 2 above. Adhesion at the interface after the heat resistance test: Using an adhesive tape with a width of 15 mm, a 180-degree peel test was performed. Crack generation: The specimen was magnified 500 times and visually inspected. Fracture generation: The specimen was magnified 500 times and visually inspected. Bubble generation: The specimen was magnified 500 times and visually inspected.

[0172] [Evaluation Results] As shown in Table 6, as a result of the heat resistance test, no problems were found with the adhesion at the interface between the protective layer 14 and the release layer 13 or the metal layer 15. No change in quality was observed for the phenomena of cracks, fractures, and bubbles either.

[0173] [Experiment 7] A protective layer 14 was prepared by adding 1% by weight of a benzenesulfonamide plasticizer and 0.025 % by weight of an ethylene olefin 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, a letterpress 40 (vertical 3 mm × horizontal 6.75 mm × height of the convex part 2 mm) was used with an up-down type transfer foil press 41 to perform hot pressure transfer onto a soft vinyl chloride sheet. Transfer temperature 160 °C, transfer pressure 5 Kg / cm 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 soft vinyl chloride sheet was confirmed. The results of the elongation during transfer to the soft vinyl chloride sheet and crack generation are 2 shown in Table 7.

[0174] At a transfer residence time of 0.5 seconds, no elongation of the soft vinyl chloride sheet was confirmed, no opening occurred, and no cracks or fractures were observed. 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 soft vinyl chloride sheet and the occurrence of openings and cracks in the transfer laminate 12, the period from 0.5 seconds to 0.75 seconds of the transfer residence time was set in intervals of 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 with 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 soft 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

[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 during the formulation. It has both heat resistance and flexibility, has good adhesion between the protective layer 14 and the metal layer 15, and the elongation of both layers is observed as in the process of Experiment 7 above and shown in Table 7. At a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride soft sheet is 0.8%, and no crack opening was observed in the transfer foil 10 to which two plasticizers were added. This is the effect of the plasticizer received by the resin-based protective layer 14, and it was found that it can follow the elongation of the transfer body 32. It was found that the flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. As shown in Table 7, at a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride soft sheet is 0.8%, and no crack opening was observed in the transfer foil 10 to which two plasticizers were added. This is the effect of the plasticizer received by the resin-based protective layer 14, and it was found that it can follow the elongation of the transfer body 32. As shown in Table 7, at a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride soft sheet is 0.8%, and no crack opening was observed in the transfer foil 10 to which two plasticizers were added. This is the effect of the plasticizer received by the resin-based protective layer 14, and it was found that it can follow the elongation of the transfer body 32. As shown in Table 7, at a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride soft sheet is 0.8%, and no crack opening was observed in the transfer foil 10 to which two plasticizers were added. This is the effect of the plasticizer received by the resin-based protective layer 14, and it was found that it can follow the elongation of the transfer body 32. As shown in Table 7, at a transfer residence time of 0.58 seconds, the elongation rate of the polyvinyl chloride soft sheet is 0.8%, and no crack opening was observed in the transfer foil 10 to which two plasticizers were added. This is the effect of the plasticizer received by the resin-based protective layer 14, and it was found that it can follow the elongation of the transfer body 32.

[0181] The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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. The flexibility of the protective layer 14 containing the plasticizer weakens the internal stress applied during film formation, and thus can simultaneously weaken film breakage and film shearing with respect to the metal layer 15. During transfer, the elongation occurring in the transfer body 32 and the elongation occurring in the transfer laminate 12 can relieve the cracks, cracks, swelling, etc. of the transfer laminate 12 that appear from the aggregation fracture generated in the metal layer 15. When the transfer body 32 exhibits an elongation 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, cracks, swelling, etc.

[0183] Examples of the base film 11 include polyesters such as polyethylene terephthalate, polypropylene, polycarbonate, vinyl chloride, polystyrene, polyethylene, polyimide, etc. The thickness of the film is selected from 12 to 75 μm. The base film 11 Examples of the base film 11 include polyesters such as polyethylene terephthalate, polypropylene, polycarbonate, vinyl chloride, polystyrene, polyethylene, polyimide, etc. The thickness of the film is selected from 12 to 75 μm. The base film 11 Examples of the base film 11 include polyesters such as polyethylene terephthalate, polypropylene, polycarbonate, vinyl chloride, polystyrene, polyethylene, polyimide, etc. The thickness of the film is selected from 12 to 75 μm. The base film 11 A release layer 13 is provided between the and the protective layer 14. It is a layer made of resins, waxes, etc. For example, polyethylene resins, polypropylene resins, polystyrene resins, vinyl chloride resins, polyester resins, acrylic resins, urethane resins, melamine resins, epoxy resins, fluorine resins, waxes, etc. can be used, and they can be used alone or as a mixture of two 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, plasticizers. The thickness is preferably 1 to 20 μm. The metal layer 15 is made of one or more metals such as Ag, Cu, Sn, In, Al, Ni, Cr, Si, Zn, In2O3, CdO, CdIn2 O4, Cd2SnO4, TiO2, SnO2, ZnO, SiO2, ZrO2, ZnS, MgF2, etc., or alloys using one or more of these metals can also be used. 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, deposition methods such as vacuum evaporation, electron beam evaporation, chemical vapor deposition, and sputtering can be mentioned. The adhesive layer 16 has a function of adhering the transfer body 32 and the transfer laminate 12 (modified laminate). As the adhesive, acrylic resins, chlorinated polypropylene resins, vinyl chloride acetate resins, polyester resins can be mentioned. A mixture of two or more can also be used. The thickness of the adhesive layer 16 is preferably between 1 and 10 μm. The transfer body 32 includes 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 evaporation device. Considering the adhesion between the resin-based protective layer 14 and the metal layer 15, dry plating is selected. Specifically, deposition methods such as vacuum evaporation, electron beam evaporation, chemical vapor deposition, and sputtering can be mentioned. The adhesive layer 16 has a function of adhering the transfer body 32 and the transfer laminate 12 (modified laminate). As the adhesive, acrylic resins, chlorinated polypropylene resins, vinyl chloride acetate resins, polyester resins can be mentioned. A mixture of two or more can also be used. The thickness of the adhesive layer 16 is preferably between 1 and 10 μm. The transfer body 32 includes 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 evaporation device. m. The transfer body 32 includes resins, 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 evaporation device. A two-chamber semi-continuous vacuum evaporation device is used.

[0184] Transfer lamination (modified lamination) 12 A film protective layer 22 may be provided between the base film 11 and the release layer 13. Among the resins and hardeners, melamine resins and sulfonic acid hardeners are used for gravure printing machines 6 In order to ensure the smoothness of the surface of the base film 11 and the uniformity of the peelability, The film is adhered to a base film 11. The thickness is preferably between 0.5 and 5 μm.

[0185] A resin-based protective layer 14 may be provided between the metal layer 15 and the adhesive layer 16. 11, a peeling layer 13, a resin-based protective layer 14, a metal layer 15, a resin-based protective layer 14, and an adhesive layer 16 In this structure, the same protective layer 14 is used for both layers, which further prevents cohesive failure of the metal layer 15. A color-developing resin-based protective layer using a coloring agent is provided between the release layer 13 and the metal layer 15. The resin-based protective layer 14 may be laminated. 15 may also be the transfer stack 12 removed.

[0186] [Experiment 8] The base film 11 is a polyester film having a thickness of 12 μm. A peelable layer 13 was formed thereon. 3 Gravi with The printing machine 60 is heated to 100 to 140 degrees Celsius by the infrared heater 67 and the hot air device 69. The film thickness was 0.5 to 0.8 μm when the residence time was in the range of 20 to 50 seconds. The protective layer 14 was made of a drying furnace 61 (volume 5.28 m 3 ) Gravure stamp Using the printing machine 60, the temperature inside the oven is kept at 150 to 210°C by using the far infrared heater 67 and the hot air device 69. It was made to travel for a residence time of 20 to 50 seconds inside to produce a flat film with a thickness of 1 to 2 μm. The liquid preparation for the protective layer 14 was also a thermosetting resin film as in Experiment 1. As a plasticizer, benzene sulfonamide 1 wt% (Fuji Film Wako Pure Chemical Industries, Ltd.), 0.025 wt% of an ethylene olefin-based resin (Idemitsu Kosan Co., Ltd. Linearene 6) was added. Then, the metal layer 15 was formed. Using a two-chamber semicontinuous vacuum evaporation apparatus and a high-frequency induction heating metal melting heat source, the protective layer 14 was coated with aluminum with a thickness of 40 to 60 nm. Next, the adhesive layer 16 was formed. The formulation was the same as in Experiment 1 was used. Film formation was carried out at a thickness of 1 μm with a residence running time of 20 to 50 seconds at an in-furnace temperature of 80 to 110 °C 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 3 80 °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. The results by visual inspection were carried out in terms of cracks, cracks, swelling, and loss of gloss, and no abnormalities were observed .

[0188] [Experiment 9] A base film of a polyester film with a thickness of 12 μm was used for the base material film 11, and the release layer 13 was formed thereon. The gravure printing machine 60 having a drying furnace 61 (volume 5.28 m 3 ) was used to form a film with a thickness of 0.5 μm to 0.8 within a range of an in-furnace travel residence time of 20 to 50 seconds at 100 to 140 °C by a far-infrared heater 67 and a hot air device 69. The liquid preparation was the same as in Experiment 1 was used. The protective layer 14 was made of a drying furnace 61 (volume 5.28 m 3 ) Gravure stamp Using the printing machine 60, the temperature inside the oven is kept at 150 to 210°C by using the far infrared heater 67 and the hot air device 69. The protective layer 14 was passed through the filter for a residence time of 20 to 50 seconds to prepare a flat film having a thickness of 1 to 2 μm. The solution was a thermosetting resin film, the same as in Experiment 1. Benzene sulfonamide 1 was used as a plasticizer. Weight percent (Fujifilm Wako Pure Chemical Industries, Ltd.), ethylene olefin resin 0.025 weight percent (Idemitsu Kosan Co., Ltd. Linearen 6) was added. Then, a gravimetric oven with a type 2 drying oven 62 was used. Using a printing machine 60, the temperature inside the oven is 100 to 210°C and the residence time inside the oven is 20 to 50 seconds. An annealing process was then performed to bake the necessary dry film. Then, a metal layer 15 was formed. Using a two-chamber semi-continuous vacuum deposition device and a high-frequency induction heating metal melting heat source, The protective layer 14 was coated with aluminum of 1000 nm. Next, the adhesive layer 16 was formed. The temperature inside the drying oven 61 of the gravure printing machine 60 was set to 80 to 110°C. A film with a thickness of 1 μm was formed with a residence time of 20 to 50 seconds.

[0189] Using this flat-film structure transfer foil 10, ten glass test pieces shown in Table 2 were prepared and soldered. The transfer was performed using a transfer machine 51, and the film was then placed in a thermostatic chamber for a heat resistance test. The temperature was raised to room temperature over 200 minutes, then allowed to stand for 5 minutes, and then cooled to room temperature over 150 minutes. After 12 hours at constant temperature, the specimen was taken out and the transfer laminate 12 on the specimen was confirmed. The results were examined for cracks, breaks, swelling, and loss of gloss, and no abnormalities were found. I did.

[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 using a gravure printing machine 60 having a drying furnace 1 type furnace 61 . Then, a metal layer 15 was formed of aluminum. Then, using the drying furnace 2 type furnace 62 of the gravure printing machine 60, with the base material film 11, the release layer 13, the protective layer 14 , and the metal layer 15 formed, under the conditions of a furnace temperature of 150 to 210 °C and a furnace running residence time of 20 to 50 seconds, heating was performed for annealing treatment. Then, the 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 obtained in terms of cracks, breaks, swelling, and gloss attenuation, and no abnormalities were observed . .

[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 using a gravure printing machine 60 having a drying furnace 1 type furnace 61 . Then, a metal layer 15 was formed of aluminum. Then, using the drying furnace 2 type furnace 62 of the gravure printing machine 60, with the base material film 11, the release layer 13, the protective layer 14 , and the metal layer 15 formed, under the conditions of a furnace temperature of 150 to 210 °C and a furnace running residence time of 20 to 50 seconds, heating was performed 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 sent into the furnace by the hot air device 69 . Furthermore, using a furnace external pressure device 71 directly connected to the furnace, the transfer linear pressure was 10 to 50 Kg / cm . While the EPDM roll was being pressed against the metal roll from which the pressure was obtained , it was passed through. Subsequently, the furnace external cooling device 72 was 2 . used Using, the substrate film was passed through the space between the Si roll and the metal roll maintained at 5 to 15 °C under pressure. It was passed through the release layer 13, the protective layer 14, the metal layer 15, and the adhesive layer 16 as well. Then, the 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 conducted according to the above . The visual inspection results were carried out in terms of cracks, breaks, bulges, and gloss attenuation, and no abnormalities were observed .

[0192] [Experiment 12] In the film-forming operation according to Experiment 11, annealing treatment with a hot air temperature of 120 to 140 °C set at a heating temperature of 180 to 210 °C by two types of drying furnaces 62 of the gravure printing machine 60, pressure application, and cooling were carried out, resulting in a continuous three-dimensional structure presenting a ridged and wrinkled shape with irregularities. A heat resistance test was conducted according to the above. The visual inspection results were carried out in terms of cracks, breaks, bulges, and gloss attenuation , and no abnormalities were observed .

[0193] Photographs of the enlarged surface of the transfer laminate 12 with a three-dimensional structure after transfer 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 2 2.30 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 54 2.70 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, pressure application, and cooling processes, resulting in film modification It was formed to achieve bonding between layers, and even when facing the load of film stretching, no defects occurred.

[0195] [Experiment 13] In the film formation operation according to Experiment 11, annealing treatment was carried out by setting the hot air at 80 - 100°C with a heating temperature of 120 - 160°C in the two - type furnace 62 of the drying furnace of the gravure printing machine 60, followed by pressurization and cooling, thereby obtaining a transfer laminate 12 presenting a flat film. 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. Visual results were examined in terms of cracks, fractures, swelling, and loss of gloss, and no abnormalities were observed in either the flat - film structure, three - dimensional structure.

[0196] The evaluation results of cracks, fractures, swelling, and gloss from the heat resistance tests of Experiments 8 - 13 are shown in Table 10.

[0197]

Table 10

[0198] In dealing with cracks, fractures, and swelling of the transfer laminate 12, any manufacturing method in Experiments 8 - 13 can be adopted. In the manufacturing method of Experiment 8, as shown in Table 9, a transfer laminate 12 of a flat film that follows the elongation up to 0.8% of the transfer body 32 is shown. In the manufacturing method of Experiment 12, as described above, the elongation of the transfer laminate 12 of the three - dimensional film shows a length of 40 - 550μm of the cross - section of the arcuate parabola arc. The means to obtain this extensibility, as described above, can be made into flat - film - like and three - dimensional - film - like structures. By the one - type furnace 61 of the drying furnace of the gravure printing machine 6 0 and the two - type furnace 62 of the drying furnace of the gravure printing machine 60, heating and hot air ​​​​​By means of drying the liquid preparation, annealing treatment of the dry film of the protective layer 14, the pressurizing device 71, and the cooling device 72 To achieve hardening, softening, and stress modification of the protective layer 14 and the metal layer 15 through the treatment by By doing so, without losing the metallic luster, the stretchability following property of the flat film and the three-dimensional film transfer laminate 12 can be achieved. According to Experiments 8 to 12, (1) Drying by the single-layer furnace 61 for the release layer 13 and the protective layer 14, annealing drying by the two-layer furnace 62, the metal layer 15, the adhesive layer 16, (2) Drying by the single-layer furnace 61 for the release layer 1 3 and the protective layer 14, the metal layer 15, annealing treatment by the two-layer furnace 62, the adhesive layer 16, or (3) Drying by the single-layer furnace 61 for the release layer 13 and the protective layer 14, the metal layer 15, annealing treatment including hot air treatment by the two-layer furnace 62, pressurizing treatment, cooling treatment, the adhesive layer 16. Up to here, by controlling each treatment, the film can be formed flat. Furthermore, high-temperature drying by the single-layer furnace 61 for the release layer 13 and the protective layer 14, the metal layer 15, high-temperature annealing treatment including hot air treatment by the two-layer furnace 62, pressurizing treatment, cooling treatment, the adhesive layer 16. In 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 material film 11, a two-chamber semi-continuous vacuum evaporation machine was used to form the metal layer 15. Specifically, in the range of a thickness of 20 to 65 nm metal layers 15 of Al, Cr, and Sn were respectively formed. Then, the adhesive layer 16 was formed, and thereby the transfer laminate 12 was produced. Next, using the hot pressure transfer machine 51, on the calendered glossy thick 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 at after transferring the transfer laminate 12, the reflectance of the metal layer 15 on its surface was measured using a spectro-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] On the base material film 11, 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 were formed to produce the transfer laminate 12. Next, using the hot pressure transfer machine 51, on the calendered glossy thick 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 at, after transferring the transfer laminate 12, the reflectance of the metal layer 15 on its surface was measured through the color-forming resin-based protective layer 14 using a spectro-calorimeter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance L of Al was 80.21. According to JISZ8781-4, the spatial measurement was performed. The chromaticity L*a*b* 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 obtained the reflection of the metal layer 15 and was a transparent metallized gold-colored flat film structure.

[0206] [Experiment 16] On the base film 11, a release layer 13, a color-forming resin protection layer 14 containing micronized transparent pigments, an Al metal layer 15 with a thickness of 20 - 65 nm, and a pressure-sensitive and heat-sensitive adhesive layer 16 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 - 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 through the color-forming resin protection layer 14 using a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The spectral reflectance of Al was L = 82.15. The spatial chromaticity L*a*b* according to JISZ8 781-4 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 obtained the reflection of the metal layer 15 and was a transparent metallized gold-colored flat film structure.

[0207] [Experiment 17] On the base film 11, a release layer 13, a color-forming resin protection layer 14 containing general-purpose pigments, a thickness of 20 - 65 nm of an Al metal layer 15, 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 the hot press transfer machine 51, onto the calendared​ On the 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 through the color-forming resin-based protective layer 14 using a spectrophotometer (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). 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). The lightness and chromaticity were measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90) for the spatial chromaticity L*a*b* according to JIS Z8781-4. (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The color-forming resin-based protective layer 14 containing the pigment reduced the reflectance of Al due to the appearance of its hiding property. The spectral reflectance L of Al was 43.99 when containing a blue pigment, 61.28 when containing a pink pigment, 45.84 when containing a red pigment, 81.85 when containing a yellow pigment, and 31.63 when containing a black pigment. was 43.99 when containing a blue pigment, 61.28 when containing a pink pigment, 45.84 when containing a red pigment, 81.85 when containing a yellow pigment, and 31.63 when containing a black pigment. was 43.99 when containing a blue pigment, 61.28 when containing a pink pigment, 45.84 when containing a red pigment, 81.85 when containing a yellow pigment, and 31.63 when containing a black pigment. was 43.99 when containing a blue pigment, 61.28 when containing a pink pigment, 45.84 when containing a red pigment, 81.85 when containing a yellow pigment, and 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 furnaces 62 of the drying furnace of the 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, an adhesive layer 16 was formed thereon to produce a transfer laminate 12. Next, using a hot press transfer machine 51, on the calendered glossy paper 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 furnaces 62 of the drying furnace of the 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, an adhesive layer 16 was formed thereon to produce a transfer laminate 12. Next, using a hot press transfer machine 51, on the calendered glossy paper 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 furnaces 62 of the drying furnace of the 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, an adhesive layer 16 was formed thereon to produce a transfer laminate 12. Next, using a hot press transfer machine 51, on the calendered glossy paper 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 furnaces 62 of the drying furnace of the 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, an adhesive layer 16 was formed thereon to produce a transfer laminate 12. Next, using a hot press transfer machine 51, on the calendered glossy paper 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 furnaces 62 of the drying furnace of the 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, an adhesive layer 16 was formed thereon to produce a transfer laminate 12. 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 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.; S ZS-Σ90). 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). The spectral reflectance L of Al was 75.40. The spatial chromaticity L*a *b* was measured using a color difference meter (Nippon Denshoku Industries Co., Ltd.; SZS-Σ90). The lightness color degree was L = 75.40, a = 3.06, and b = 28.67. The transfer laminate 12 obtains the reflection of the metal layer 15 and has a three-dimensional structure presenting a permeable metallized gold color.

[0209] [Experiment 19] On the base film 11, after forming a release layer 13, a transparent resin-based protective layer 14, and an Al metal layer 15 with a thickness of 20 - 65 nm , two types of furnaces 62 in the drying furnace of the gravure printing machine 60 were used to perform annealing treatment, hot air treatment, pressure treatment, and cooling treatment by annealing to make the laminate up to the metal layer 15 into a three-dimensional film. Further, by forming an adhesive layer 16 thereon, the transfer laminate 12 was fabricated . Next, using a hot press transfer machine 51, the transfer laminate 12 was transferred onto a calendered glossy paper at a transfer temperature of 10 0 - 140 °C, a transfer residence time of 0.5 seconds, and a pressure of 5 Kg / cm . After the transfer laminate 12 was transferred 2 , 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 of Al L was 87.74. 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 = 87. 74, a = -0.17, and b = 0.76. The transfer laminate 12 obtains the reflection of the metal layer 15

[0210] and has a three-dimensional structure presenting a permeable metallized silver color. [Table 14]

[0211] The attenuation of the reflectance of the protective layer 14 was confirmed from the spectral reflectance of the metal layer 15. It was found that the fine pigments had good transparency. In experiment 19, the three-dimensional structure of the film was also produced. It was found that the reflectance of the Al metal layer 15 did not change. In experiment 17, the pigment showed the same color and transparency as the metal-containing dye. In both experiments, the reflection of the Al metal layer 15 was blocked. No attenuation of the spectral reflectance was observed.

[0212] [Experiment 20] The base film 11 is used as a frame support, and the peelable layer 13 is a color-changing resin system using a transparent pigment. A transfer laminate 12 was formed, which was composed of a protective layer 14, an Al metal layer 15, and an adhesive layer 16. The following was set for the experiment: 72.2% by weight of toluene (Idemitsu Kosan Co., Ltd.) was used as the solvent. Company), MIBK25.4% by weight (Mitsubishi Chemical Holdings), Ethylene Glyco 0.03% by weight of Fischer-T Roffic wax 1.07% by weight (Sador; A859), fatty acid ester 0.04 % by weight (NOF Corporation; WEP), acrylic resin 0.9% by weight (Nippon Shokubai Co., Ltd.; U V-G301) were used to mix these. A gravure printing machine was used, and the drying temperature in the oven was 90 to 140°C, residence time in the drying ovens 61 and 62 is 20 to 60 seconds, and thickness is 0.1 to 20 μm. The resin-based protective layer 14 was formed using a pigment as a coloring agent. , toluene 14.6% by weight (Idemitsu Kosan Co., Ltd.), butyl acetate 8.7% by weight (S Standard Petroleum), MEK 17.0% by weight (Idemitsu Kosan Co., Ltd.), MIBK 17.0% by weight (Mitsubishi Chemical Holdings Corporation), 0.004% by weight of ethylene glycol ( Wako Pure Chemical Industries, Ltd., Kyoto), 20.5% by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UV -G301), 1.1% by weight of acrylic resin (Wilbur-Ellis; AT740), mel amine resin 1.3% by weight (Nippon Carbide; MS-001), 4.3% by weight of ketone resin ( Worley; K-95), 0.1% by weight of hardener (Tokyo Chemical Industry Co., Ltd.; p-toluene sulfonic acid), 1.0% by weight of red iron oxide (Mikuni Shikiso Co., Ltd.; 8196M), yellow acid iron oxide 0.05% by weight (Mikuni Shikiso Co., Ltd.; 8197M), 1.0% by weight of red pigment (Du Pont; Sinicasia Red B), 0.95% by weight of yellow pigment (BASF Japan Ltd. ; Paliotol Yellow 1070) were formulated to obtain a preparation liquid. The release layer 13 and the resin-based protective layer 14 were formed into films using a gravure printing machine 60 under the conditions of a temperature of 100 to 180°C in drying ovens 61, 62, a residence time of 20 to 60 seconds, and a thickness of 0.5 to 20 μm. It is more preferable 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 development property, transparency, and reflectivity from the metal layer 15 to exhibit metallic properties. The pigments were sized for fine particle dispersion using a bead mill type pigment disperser KD-5 type 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 in-furnace running residence time was 10 to 40 seconds. The formulation was 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 (Co ​​​​ Lukote 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; D 2908), 3.0% by weight of a ketone resin (Worley Co., Ltd.; K-95) were used.

[0213] Despite using pigments, the coloring of the resin protective layer 14 of the completed transfer foil 10 became highly transparent. A ball paper that was smoothly calendered and surface resin-coated was used for transfer using an up-down type thermal transfer machine 51 to produce a specimen (transferred transfer laminate 12). A xenon arc type lightfastness tester (Suga Test Instruments Co., Ltd.; XT1500) was used and after 800 hours, the specimen was taken out and a spectroscopic color difference meter (Nippon Denshoku Industries Co., Ltd.; S ZS-Σ90) was used to measure the color displacement ΔE. The results of the presence or absence of exposure are shown in Table 15. The transfer laminate 12 having a resin protective layer 14 containing a refined pigment and obtaining a metallic reflection with a transparent gold coloring became excellent in lightfastness.

[0214]

Table 15

[0215] [Experiment 21] In Experiment 20, the transfer laminate 12 using a refined transparent pigment had a metallic layer 15 and thus showed a metallic coloring and had lightfastness. In Experiment 22, further known materials were used to promote the resistance to lightfastness.

[0216] The finely processed, transparent pigment showed colorability, and the metallic layer 15 with a metallizing feeling A supplementary note on the light resistance of the transfer laminate 12 from which reflection can be obtained was imposed. Substrate film 11 On top of this, a release layer 13, a color-forming resin-based protective layer 14, a metal layer 15, and an adhesive layer 16 are formed to form a transfer In laminate 12, the following were added to the release layer 13 and the color-forming resin-based protective layer 14 to attempt to improve light resistance .

[0217] When the color-forming resin-based protective layer 14 is exposed to ultraviolet light, the hydrogen atoms of the polymer are cleaved to form hydroperoxides which causes the polymer to deteriorate. To prevent this, hindered amine-based materials are used. Polymer deterioration occurs as a chain reaction of radical generation due to photodegradation but this is suppressed. An acrylic resin that hardly absorbs ultraviolet light is selected, and at the same time silicon with good light resistance, a silicate-based material with light-shielding properties, and a polymerized acrylic polymer material such as hindered amine are selected as light stabilizers . For the acrylic resin, Halstead Hybrid UV-G301 manufactured by Nippon Shokubai Co., Ltd. in which hindered amine is polymerized, and for the acrylic resin UV H manufactured by Alpha Chemical Co., Ltd. in which silicon, silicate, and hindered amine are polymerized was selected. Also, as a stabilizer against the photodegradation action of ultraviolet light on the resin, Tinuvin 249 manufactured by BASF, a neutral-spec monomeric hindered amine , was selected. As an ultraviolet absorber , a hydroxyphenyltriazine-based material was selected. Specifically, Tinuvin 479 and 1600 were selected by choosing a wavelength range from among the Tinuvin types manufactured by BASF . As a light-shielding agent , iron oxides, titanium oxides, and organic pigments with good light resistance and color-forming properties that were refined to a particle size of 10 to 80 nm were selected. As an inhibitor of light action, phenyl salicylate, which does not transfer ultraviolet light quanta with a blocking effect to the polymer chain , was selected. In the release layer 13, as an ultraviolet light-shielding agent ​​​​ Using titanium oxide, iron oxide, and phenyl salicylate, and as a binder, a hindered amine, an acrylic resin which is a polymer material was selected. The formulation of the release layer 13 is 72.2 parts by weight of toluene (Idemitsu Kosan Co., Ltd.), 25.4 parts by weight of MIBK (Mitsubishi Chemical Holdings) , 0.03 parts by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), Fischer Tro Fic wax 1.07 parts by weight (Sadole Co., Ltd. A859), 0.04 parts by weight of fatty acid ester (NOF Corporation; WEP), 0.91 parts by weight of acrylic resin (Nippon Shokubai Co., Ltd.), a halos hybrid UV-G301 in which a hindered amine is polymerized, 0.05 parts by weight of iron oxide (Mikuni Shikiso Co., Ltd.; 8197M), 0.062 parts by weight of titanium oxide (Ishihara Techno Co., Ltd. ;; TTO-55D), 0.081 parts by weight of phenyl salicylate (Tokyo Chemical Industry Co., Ltd.) were used. The formulation of the color-forming resin-based protective layer 14 is 14.65 parts by weight of toluene (Idemitsu Kosan Co., Ltd.), 8.57 parts by weight of butyl acetate (Standard Oil Co., Ltd.), 17 parts by weight of MEK (Idemitsu Kosan Co., Ltd.) , 17 parts by weight of MIBK (Mitsubishi Chemical Holdings Corporation), 0.0039 parts by weight of ethylene glycol (Wako Pure Chemical Industries, Ltd.), 1.0 8 parts by weight of acrylic resin (Wilbur-Ellis Co.; AT740), 1.37 parts by weight of amino resin (Nippon Carbide Industries Co., Ltd. ; MS-001), 4.32 parts by weight of ketone resin (Worley Co.; K9 5), 20.5 parts by weight of acrylic resin (Nippon Shokubai Co., Ltd.; UV-G301), 11.7 parts by weight of acrylic resin (Alpha Kaken Co., Ltd.; UVHA), 0.078 parts by weight of ultraviolet absorber (BASF; Tinuvin1600), 0.078 parts by weight of ultraviolet absorber (BASF; 5), and the like were used. The formulation of the color-forming resin-based protective layer 14 is 14.65 parts by weight of toluene (Idemitsu Kosan Co., Ltd.), 8.57 parts by weight of butyl acetate (Standard Oil Co., Ltd.), 17 parts by weight of MEK (Idemitsu Kosan Co., Ltd.) 479), 0.157 wt% cerium oxide (Takagi Chemical Co., Ltd.; B10), 0 .157 wt% titanium oxide (Ishihara Techno Co., Ltd.; TTO-55T), 0.049 wt% iron oxide (Mikoshu Shikiso Co., Ltd.; 8197M) , 0.9836 wt% iron oxide (Mikoshu Shikiso Co., Ltd. 8196 M), 0.9836 wt% red pigment (DuPont; Synshaka Red B), yellow pigment 0.934 wt% (BASF; Pario Tol Yellow 1070), phenyl salicylate 0.078 wt% (Tokyo Chemical Industry Co., Ltd.). The particle size of cerium oxide is 10 - 30 n m, 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 the color-forming pigment of 60 - 100 nm leads the permeability and is good as a color-forming effect. For the metal layer 1 5 and the adhesive layer 16, film formation was carried out according to the above. For the release layer 13, the color-forming resin-based protection layer 14 and the adhesive layer 16, a gravure printing machine 60 was used, the drying temperature was 90 - 180 °C, the residence time in the drying furnaces 61, 62 was 20 - 60 seconds, the thickness was 0.1 - 20 μm, and film formation was carried out in one type of drying furnace 61 (volume 5.28 m 3

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

[0219]

Table 16

[0220] As for the color-forming effect of the resin-based protection 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 ​​​It was at the same level as the original at 81.53%. Regarding the change in the spatial chromaticity Lab value after 1400 hours, ΔE was 1.23, and the color rendering was equivalent to the original. The reflectance of the metal layer 15 containing the finely processed, highly transparent color - presenting pigment became high. For the formulation of the release layer 13, an acrylic resin containing a hindered amine, finely processed iron oxide, titanium oxide, and phenyl salicylate, a light - shielding agent, were added. For the formulation of the color - presenting 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 color - presenting materials, and organic pigments with excellent light resistance were selected and disposed, and the improvement of light resistance was required in the continuous layer 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 pigments used in the formulation of the protective layer 14 in Experiment 20 was maintained.

Explanation of Symbols

[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 lamination. The transfer lamination is A release layer formed on the substrate film; a first resin-based protective layer formed on the release layer; an adhesive layer formed on the first resin-based protective layer, The transfer foil, wherein the first resin-based protective layer contains a plasticizer.

2. The transfer foil according to claim 1, The transfer lamination further comprises: A transfer foil comprising a metal layer formed between the first resin-based protective layer and the adhesive layer.

3. The transfer foil according to claim 2, The transfer lamination further comprises: A transfer foil comprising a second resin-based protective layer formed between the metal layer and the adhesive layer.

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

5. The transfer foil according to claim 1, The plasticizer may be chlorinated paraffin, butyl adipate, 2-ethylhexyl adipate, Dioctyl adipate, 2-ethylhexyl azelaate, phthalate esters, phthalic acid Dibutyl, diheptyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate , diisodecyl phthalate, citrate esters, succinic acid and triethylene glycol mono Esters of adipic acid and diethylene glycol monomethyl ether, esters of tricarboxylic acids such as trioctyl trimellitate, 1,3,6-hexyl Ester of trihexatricarboxylic acid with butyl diglycol, tricresyl phosphate, Triphenyl phosphate, tri-2-ethylhexyl phosphate, trixylenyl phosphite phosphate, triethyl phosphate, low molecular weight polyesters, epoxidized soybean oil, epoxy Epoxidized linseed oil, epoxidized octyl stearate, epoxidized fatty butyl, epoxidized flaxseed oil Di-oil fatty acid butyl, trimellitic acid ester, pyromellitic acid ester, sebacic acid ester ester, azelaic ester, maleic ester, benzoic ester, methyl azide butyl oleate, oxyacid ester, dihydric alcohol ester, aliphatic dibasic acid ester Stearyl, triphenyl phosphate, dinonylnaphthalene, acetyl citrate tributary p-Toluenesulfonamide, Toluenesulfonamide, Toluenesulfonethyl Aminobenzenesulfonamide compounds, aminotoluenesulfonamide compounds, N -Butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, dinonyl The group consisting of nalene, acetyl tributyl citrate, and ethylene olefin oligomers A transfer foil comprising one or more selected from the following:

6. The transfer foil according to claim 1, The plasticizer is p-toluenesulfonamide, toluenesulfonamide, toluenesulfonamide, N-ethyl-o-toluenesulfonamide, aminotoluenesulfonamide compounds, N-ethyl-o-toluenesulfonamide A transfer foil comprising one or more selected from the group consisting of sulfonamides.

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

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

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

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

11. The transfer foil according to claim 1, The first resin-based protective layer comprises a color developer.

12. The transfer foil according to claim 11, The color developer comprises a pigment having a particle size of 10 to 120 nm.

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

14. The transfer foil according to claim 12, The first resin-based protective layer comprises an ultraviolet absorbing agent.

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