JPS641115Y2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a transfer sheet capable of forming a transfer layer having excellent physical properties such as chemical resistance and solvent resistance on a transfer target. BACKGROUND ART Traditionally, transfer painting methods have often been used to paint objects that are difficult to print directly. For example, there are many transfer sheets called hot stamps, and they have been used as a simple method for painting on paper, synthetic leather, and plastic molded products, and are effectively used in a wide range of applications. Most of them have a base film such as polyester, a transparent layer made of acrylic resin, rubber resin, vinyl resin, etc., and a pattern layer.
It is a stack of adhesive layers, and the transparent layer functions as a protective layer to protect the pattern layer after transfer. However, since these layers are manufactured using printing ink made by dissolving resin in a solvent, they can be resistant to certain solvents, but they are generally resistant to ester-based solvents and ketone-based solvents. , it had no solvent resistance at all to aromatic solvents. This not only limits its use in places where solvent resistance is required, but also usually involves screen printing letters, marks, etc. on the transfer surface after transfer, but it can cause defects during screen printing. However, there was a need for a transfer sheet with excellent chemical and solvent resistance, as there were drawbacks such as the inability to modify the product. However,
To construct a protective layer with solvent resistance, it is sufficient to use a polymer with a crosslinked structure. Sometimes, the inconvenience that the protective layer becomes difficult to peel off from the base sheet cannot be avoided. As a result of various studies to solve the above-mentioned drawbacks, the inventor of the present invention has developed a protective layer that protects the surface after transfer by using an ultraviolet curing material and a layer that is cured by ultraviolet irradiation, thereby improving solvent resistance, chemical resistance, and It has been found that the peelability from the base sheet is significantly improved. In other words, curing by ultraviolet irradiation is
A three-dimensionally crosslinked cured film is formed, and this cured film is extremely difficult to dissolve in solvents and is generally an insoluble film. In addition, according to the research results of the present inventor, it was found that a cured film cured by irradiation with ultraviolet rays or electron beams has poor adhesion to a base sheet such as a polyester film. The reason for this is that when ultraviolet curable materials and electron beam curable materials rapidly solidify from a liquid to a solid upon irradiation with ultraviolet rays or electron beams, volume shrinkage and distortion occur, which reduces their adhesion to the polyester film. This is thought to be due to the presence of The present inventor focused on the fact that the above-mentioned cured film is an insoluble film and that it has poor adhesion to polyester film, especially the latter point, which is usually regarded as a drawback. By creating a structure in which the transfer layer is protected by the cured film, the solvent resistance of the transfer layer is significantly improved, and the film cured by ultraviolet irradiation has good releasability from the base sheet, which led to the completion of this invention. It is. Therefore, the gist of the present invention is to provide an insoluble transparent protective layer made of an ultraviolet curable material cured by ultraviolet irradiation on one side of a polyester film, provide a pattern layer on the insoluble transparent protective layer, and then apply an adhesive. This is a transfer sheet made up of layers. Next, the present invention will be explained in detail with reference to the drawings. Figure 1 shows a cross-sectional view of the simplest transfer sheet of the present invention, in which 1 is a polyester film as a base sheet, 2 is an insoluble transparent protective layer cured by ultraviolet irradiation, 3 is a pattern layer, and 4 is an adhesive. It is a layer. FIG. 2 is a sectional view of a transfer sheet of the present invention shown in FIG. 1 in which a convex pattern layer 5 is provided on the side of the polyester film 1 on which the transparent protective layer 2 is provided. FIG. 3 is a schematic cross-sectional view of a transfer product obtained by adhering the transfer sheet shown in FIG. 1 to a transfer target 6 via an adhesive layer 4 and peeling off a polyester film 1 from an insoluble transparent protective layer 2. FIG. 4 is a schematic cross-sectional view of a transfer product obtained by adhering the transfer sheet shown in FIG. 2 to the transfer target 6 with an adhesive layer 4 and peeling off the polyester film 1 from the insoluble transparent protective layer 2. . The transfer sheet shown in Figure 1 is made by applying an ultraviolet curable material consisting of an ultraviolet curable prepolymer, a photoinitiator, a reactive diluent, and various additives as necessary to a polyester film 1 by gravure printing, offset printing, or screen printing. After being coated by a printing method such as printing, it is cured by irradiation with ultraviolet rays, and then a pattern layer 3 and an adhesive layer 4 are printed thereon. The UV-curable prepolymer here refers to a prepolymer having ethylenically unsaturated bonds, specifically acrylates such as unsaturated polyester, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate. If necessary, one or more methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate can be used, and the reactive diluent is It plays the role of controlling the viscosity of the ultraviolet curable material as well as the physical properties of the cured film, and specifically refers to low-viscosity products or thiols having ethylenically unsaturated bonds as described below. Namely, styrenic monomers such as styrene and α-methyltyrene; acrylic acids such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; Esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate,
Methacrylic acid esters such as lauryl methacrylate; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic acid 2-(N,N-
dimethylamino)ethyl, methacrylic acid 2-(N,
N-dimethylamino)ethyl, acrylic acid 2-
Substituted amino alcohol esters of unsaturated acids such as (N,N-dibenzylamino)ethyl, (N,N-dimethylamino)methyl methacrylate, and 2-(N,N-diethylamino)propyl acrylate;
Ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate , polyfunctional compounds such as diethylene glycol dimethacrylate; trimethylolpropane trithiocricolate, trimethylolpropane, trithiopropionate,
These include polyfunctional thiols such as pentaerythritol tetrathioglycolate, and one type or two or more types of these can be used as required. As the photoinitiator, substances that generally generate radicals upon irradiation with ultraviolet light, such as benzoin ethers, halogenated acetophenones, benzophenones, and biacetyls, can be used. The insoluble transparent protective layer 2 is obtained by curing the ultraviolet curing material coated on one side of the polyester film 1 using a commercially available ultraviolet curing device, such as Nippon Battery Co., Ltd.'s Ultra Violet Drying System. The transparent protective layer 2 is preferably provided with a thickness of about 0.5 to 20 microns. Next, the pattern layer 3 provided on the insoluble transparent protective layer 2 is made of an ink composition obtained by adding color pigments and various additives to a vehicle in which a resin binder that has good adhesion to the insoluble transparent protective layer 2 is dissolved in a solvent. It can be formed by a gravure printing method, an offset printing method, a screen printing method, etc. Next, acrylic resin, ABS resin,
The adhesive layer 4 is formed by applying a resin-based ink composition such as various hard resins, chlorinated polyethylene, and chlorinated polypropylene by a printing method such as a gravure printing method or a screen printing method. It can be manufactured using Therefore, in the transfer sheet according to the present invention described above, the insoluble transparent protective layer 2 of the polyester film 1 is
The surface on which the transfer layer is to be provided may be made matte so that the surface of the transfer layer becomes matte. Next, in the transfer sheet according to the present invention described above, the insoluble transparent protective layer may be formed by curing an ultraviolet curing material mixed with a dye. Next, the method for manufacturing the transfer sheet shown in FIG. 2 is similar to the method for manufacturing the transfer sheet shown in FIG. 1 above, except that in this case, a convex pattern layer 5 is formed on the polyester film 1. It is something. In this case, the convex pattern layer 5 is made of polyester film 1.
It is necessary to have good adhesion with the insoluble transparent protective layer 2 and to be able to peel it off from the insoluble transparent protective layer 2. Accordingly, it is possible to use an ink composition which is printed and molded using an ink composition to which a water repellent such as silicone and a volatile agent are added. Next, specific embodiments of the present invention will be described. In the following text, "parts" indicate "parts by weight." Example 1 25μ thick polyester film (manufactured by Toray Industries)
30 parts oligoester acrylate (manufactured by Toagosei Co., Ltd., Aronix M8060), an ultraviolet curing material for forming an insoluble protective layer on one side of the
X513A) 65 parts of benzophenone 5 parts was uniformly coated on the entire surface with a gravure solid plate with a printing depth of 40 μm, and while being wound up at a speed of 30 m/min, ultraviolet rays were irradiated with two 2KW GS Hi-Kure lamps manufactured by Nippon Battery Co., Ltd. Next, a wood grain pattern was printed using a halftone gravure plate using a printing ink having the following composition: 25 parts of acrylic resin, 20 parts of pigment, 25 parts of methyl ethyl ketone, and 30 parts of toluene.
Next, the printing surface was uniformly coated with an adhesive layer forming ink having the following composition: 30 parts of acrylic resin, 35 parts of methyl ethyl ketone, and 35 parts of toluene using a gravure solid plate with a plate depth of 60 μm to obtain a transfer sheet A of the present invention. . The above transfer sheet A was brought into close contact with the ABS resin plate, and a pressure of 6.5 was applied using a silicone rubber roller with a surface temperature of 200°C.
Transfer was carried out under conditions of Kg/cm ² and running speed of 15 mm/sec. The pattern of the resulting wood grain pattern transfer layer did not change at all even when it was rubbed 50 times with a Gakushin-type Masatsu tester using a cotton cloth soaked with a solvent of ethyl acetate, toluene, or methyl ethyl ketone. Example 2 25μ thick polyester film (manufactured by Toray Industries)
A convex pattern was printed on one side with an ink containing a polyester resin and an extender pigment, and thereafter, in the same manner as in Example 1, the entire printed surface was coated with an ultraviolet curable material for forming an insoluble transparent protective layer having the following composition, and cured by ultraviolet rays. Ta. Next, a wood grain pattern was printed, and then the entire surface was coated with ink for forming an adhesive layer to obtain a transfer sheet B of the present invention. (Ultraviolet curing material composition) Acrylic urethane resin (XP- manufactured by Nippon Gosei Co., Ltd.)
4200T) 40 parts oligoester acrylate (manufactured by Toagosei Co., Ltd.)
X511A) 50 parts benzophenone 5 parts N,N-tetraethyl-4,4-diaminobenzophenone (Countercure EAB manufactured by Sandoz)
Part 5: Place the above transfer sheet B on the ABS resin plate,
Press with a silicone rubber roller with a surface temperature of 200℃.
Transfer was carried out under conditions of 6.5 kg/cm ² and a running speed of 15 mm/sec. In the obtained transfer layer, no change occurred in the same solvent resistance test as in Example 1. Example 3 25μ thick polyester film (manufactured by Toray Industries)
Example 1 was coated uniformly on one side of the matte surface using a gravure solid plate with a plate depth of 25μ with a matte ink consisting of polyester resin, extender pigment, wax, and solvent. Transfer sheet C was obtained in the same manner as above except that the ultraviolet curing material had the following composition. (Ultraviolet curable material composition) Polyurethane acrylate (Orestar XRA1149 manufactured by Mitsui Toatsu Co., Ltd.) 40 parts Oligoester acrylate (Aronix M8030 manufactured by Toagosei Co., Ltd.) 40 parts Trimethylolpropane triacrylate 15 parts Benzophenone 5 parts Same as in Example 1 The surface of the transferred product obtained by transferring to the ABS resin plate was matte, and no change was observed in the solvent resistance test. Example 4 A convex pattern was printed on one side of a 25 μm thick matte polyester film (manufactured by Diafoil Co., Ltd.) using an ink containing a polyester resin and an extender pigment, and the process was repeated in the same manner as in Example 1 to obtain a transfer sheet D. The transfer sheet D was brought into close contact with the ABS resin plate, and a pressure of 6.5 kg was applied using a silicone rubber roller with a surface temperature of 200°C.
Transfer was performed under the conditions of cm ² and a running speed of 15 mm/sec. The obtained transfer product had a matte surface and an embossed pattern, and no change was observed in the solvent resistance test. Comparative Examples 1 to 3 25μ thick polyester film (manufactured by Toray Industries)
A transparent protective layer was provided by uniformly coating the entire surface with a transparent protective layer forming ink having the following compositions 1 to 3 using a 40μ solid gravure plate. (Ink 1); 20 parts of reduced rubber, 40 parts of toluene, 40 parts of ethyl acetate (Ink 2); 25 parts of acrylic resin, 40 parts of methyl ethyl ketone, 35 parts of ethyl acetate (Ink 3); 25 parts of PVC resin, 40 parts of methyl ethyl ketone Then, in the same manner as in Example 1, a wood grain pattern was printed using a printing ink, and then an adhesive layer was provided using an adhesive layer forming ink, and conventional transfer sheets E and F were used. , I got G. The obtained transfer sheets E, F, and G were transferred to an ABS resin plate in the same manner as in the above example. Using a Gakushin friction tester, the obtained transfer material was subjected to a solvent resistance test by rubbing it 50 times with a cotton cloth soaked in toluene, ethyl acetate, methyl ethyl ketone, and methanol at a load of 1200 ml. The results of the solvent resistance test were as follows. 【table】

△; The pattern is blurred. ○; There is no change in the pattern.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views schematically showing the transfer sheet according to the present invention, and FIGS. 3 and 4 show how to apply the transfer sheet to an object using the transfer sheet shown in FIGS. 1 and 2, respectively. FIG. 3 is a cross-sectional view schematically showing a transferred area. 1... Polyester film, 2... Insoluble transparent protective layer, 3... Pattern layer, 4... Adhesive layer.

Claims (1)

[Claims for Utility Model Registration] (1) On one side of a polyester film, an ultraviolet curable material that has releasability to the film and has high adhesion to the printed pattern layer described below is cured by ultraviolet irradiation. 1. A transfer sheet comprising an insoluble transparent protective layer, a printed pattern layer, and an adhesive layer laminated in this order. (2) The transfer sheet according to claim 1, wherein the base sheet has a convex pattern layer on the side on which the transparent protective layer is laminated. (3) The transfer sheet according to claim 1, wherein the surface of the base sheet on which the transparent protective layer is laminated is matte.