JPS63130762A - Production of transfer sheet having partially vapor deposited metal layer - Google Patents

Abstract

PURPOSE:To permit production of a product having a distinctly contoured beautiful metallic pattern by preliminarily forming a hydrophobic ink layer in a method for forming a vapor deposited metal layer over the entire surface of a printed pattern layer of water soluble ink, then removing said deposited layer together with the former. CONSTITUTION:The printed illustration layer 2 is provided to the desired pattern at need on the surface of a heat resistant substrate 1. A release agent layer 3 is usually provided on the surface prior to such provision. The hydrophobic ink layer 4 of the desired pattern is then formed of the hydrophobic ink consisting of an urethane resin, epoxy resin, etc. Provision of a heat resistant resin layer 5 prior to said formation is more preferable. The water soluble ink layer 6 is provided to the part where the ink layer 4 is not formed. A surfactant coated layer 7 is preferably provided on the surface thereof before said provision. After the vapor deposited metal layer 8 is provided over the entire top surface thereof, the surface is cleaned by a water soluble solvent, by which the water soluble ink is dissolved away and the layer 8 on the layer 6 is accordingly removed. The partially vapor deposited metal layer 9 consisting of the layer 8 remaining on the layer 4 is thus formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a transfer sheet having a partially metallized layer.

[Conventional technology]

2. Description of the Related Art As a transfer sheet used to transfer and form a metallic luster pattern onto a transfer material, a transfer sheet having a partial metal vapor deposition layer formed by forming a transfer metal vapor deposition layer in a desired pattern has conventionally been used. Conventionally, for this type of transfer sheet, a pattern printing layer with a desired pattern is formed using water-soluble ink on a peelable substrate, and then a metal vapor-deposited layer is formed on the entire surface, and then washed with water to print the water-soluble ink along with the water-soluble ink. A manufacturing method is known in which the metal vapor deposited layer on the ink layer is removed and a partial metal vapor deposited layer is formed by removing the metal vapor deposited layer on the part where the water-soluble ink layer is not formed.
f21124).

[Problem that the invention seeks to solve]

However, in the conventional method described above, the outline of the pattern formed with water-soluble ink is unclear due to reasons such as the fact that water-soluble ink is difficult to compatibility with the release substrate, which generally has a hydrophobic surface, and the viscosity of water-soluble ink is low. Then,
As a result, after the water-soluble ink is removed by washing with water, the outline of the pattern formed by the partial metal vapor deposition layer that remains in the areas where the water-soluble ink is not formed becomes unclear, making it impossible to form a beautiful metallic luster pattern. There was a drawback.

c. Means for Solving Problems] In view of the above points, the present inventors conducted intensive research and found that after applying a stamp with hydrophobic ink to the area where the metal vapor deposited layer should remain, the hydrophobic ink layer was By adopting a method of printing and forming a water-soluble ink layer on non-forming areas, the outline of the pattern created by the water-soluble ink layer becomes clear, and as a result, after the metal vapor deposition layer is applied to this entire surface, it is washed with an aqueous solvent and the water-soluble ink layer is printed. The partial metal vapor deposited layer, which is formed by removing the metal vapor deposited layer on the hydrophobic ink layer together with the water-soluble ink and remaining in the area where the water-soluble ink layer is not formed (i.e., the area where the hydrophobic ink layer is formed), also has a clear outline. The present inventors discovered that it was possible to obtain a transfer sheet with a beautiful metallic luster pattern, and completed the present invention.

That is, in the present invention, after providing a pattern printing layer with a desired pattern on the surface of a heat-resistant base material as necessary, printing is performed in the desired pattern with hydrophobic ink, and then printing with water-soluble ink to form the above-mentioned pattern. After forming a water-soluble ink layer on the area where the hydrophobic ink layer is not formed, a metal vapor deposition layer is formed on the entire surface, and then the metal vapor deposition layer on the water-soluble ink layer is washed and removed together with the water-soluble ink using an aqueous solvent. The gist of the present invention is to provide a method for producing a transfer sheet having a partially vapor-deposited metal layer, characterized in that a partially vapor-deposited metal layer is formed remaining on the hydrophobic ink layer.

〔Example〕

Hereinafter, one embodiment of the present invention will be described based on the drawings.

First, as shown in FIG. 1, a pattern printing layer 2 is provided on the surface of a heat-resistant base material 1 in a desired pattern if necessary. However, before forming the pattern printing layer 2, a release agent layer 3 is usually provided. It will be done. As the heat-resistant base material 1, a film or sheet made of resin such as polyethylene terephthalate, nylon, stretched polypropylene, unstretched polypropylene, polyvinyl chloride, polystyrene, vinylon, polycarbonate, ABS, etc. is usually used, and its thickness is 15 mm. ~500μ is preferable. The release agent layer 3 is composed of acrylic resin, urethane resin, cellulose resin, butyral resin, chlorinated rubber, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, etc. It can be formed by applying an ink using a coating method such as gravure coating, roll coating, silk screen coating, etc. and drying it. ff1lJ The delamination layer 3 is preferably formed to have a thickness of about 0.5 to 10 μm. The pattern printing layer 2 can be formed by printing a desired pattern using ordinary printing ink. The pattern printing layer 2 can be provided either in a part corresponding to a position where a partial metal vapor deposition layer is formed or in a part corresponding to a position where a partial metal vapor deposition layer is not formed, but usually corresponds to a position where a partial metal vapor deposition layer is not formed. It is preferable to provide the

Next, a desired pattern is printed with a hydrophobic ink to form a hydrophobic ink layer 4, but it is preferable to provide a heat-resistant resin layer 5 before forming the hydrophobic ink layer 4. Examples of the resin used to form the heat-resistant resin layer 5 include urethane resin, cellulose resin, epoxy resin, modified melamine resin, ultraviolet curable resin,
Examples include electron beam curable resins and butyral resins.

When the heat-resistant resin layer 5 is provided, its thickness is 0.5 to 10
It is preferably about μ. The hydrophobic ink used to form the hydrophobic ink layer preferably has heat resistance, and resins used for such ink include urethane resins, epoxy resins, and vinyl chloride-vinyl acetate copolymer resins. , polyester resins, polyamide resins, butyral resins, acrylic resins, etc., and hydrophobic compounds such as silicone, acrylic acid amide, carbonate, fluorine resins, etc. Examples include those to which jAM is added.

After forming the hydrophobic ink layer 4, a water-soluble ink layer 6 is formed on the portion where the hydrophobic ink layer 4 is not formed, but a surfactant coating layer 7 is formed on the surface where the water-soluble ink layer 6 is formed. If a surfactant is applied to the surface on which the water-soluble ink layer 6 is formed, the boundary between the water-soluble ink layer 6 and the hydrophobic ink layer 4 can have a clear outline. It is sufficient that the surfactant coating layer 7 is formed on the surface on which the water-soluble ink layer 6 is formed, and as shown in FIG. It is possible to adopt a method in which a hydrophobic ink layer 4 is formed in a pattern by applying a surfactant over the entire surface, and then a hydrophobic ink layer 4 is formed in the area where the surfactant layer 7 is not formed. It may be configured such that the surfactant layer is provided only on the portion where the overline water-based ink layer 4 is not formed by printing in the form of a pattern. The above-mentioned surfactants include fatty acid salts, alkyl sulfate ester salts, alkyl hanzene sulfonates, alkylnaphthalene sulfonates, alkyl phosphate ester salts, polyoxyethylene alkyl sulfate ester salts, and anionic surfactants such as sodium alginate. Activator; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether,
Polyoxyethylene fatty acid ester, sorbitan fat 7
Nonionic surfactants such as fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene amines, glycerin fatty acid esters, oxyethylene-oxypropylene broth copolymers; cations such as alkylamine salts, quaternary ammonium salts, etc. system surfactant;
Examples include amphoteric surfactants such as alkyl betaines.

Water-soluble inks include starches such as starch, cationic starch, carboxy starch, dialdehyde starch, polyvinyl alcohol, dextrin, British rubber, carboxymethyl cellulose, methyl cellulose, sodium polyacrylate, alginic acid and its derivatives, water-soluble alkyd resin, polyvinyl ether,
Using ink in which maleic acid copolymer, polyethylene imine, polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, sodium polyphosphate, etc. are dissolved in water, and ink in which silica, precipitated barium, and other extender pigments are added to these are used. Also good. The water-soluble ink layer 6 can be formed by printing water-soluble ink in a pattern on the non-forming surface of the hydrophobic ink layer 4, but it may also be printed on the entire surface from above the hydrophobic ink layer 4. In this case, the water-soluble ink placed on the hydrophobic ink layer 4 is repelled by the hydrophobic ink layer 4 and collects in the portion where the hydrophobic ink layer 4 is not formed. When a water-soluble ink is applied over the entire surface of the hydrophobic ink layer 4 in this way, if the surfactant layer 7 is present on the surface on which the water-soluble ink layer is formed, the water-soluble ink repelled on the hydrophobic ink layer 4 The ink is attracted to the surfactant, and as a result, the water-soluble ink reliably gathers in the area where the water-soluble ink layer is to be formed, forming a good water-soluble ink layer 6.

After forming the water-soluble ink layer 6 as described above, a metal vapor deposition layer 8 is formed on the entire upper surface, as shown in FIG. The metal vapor deposition layer 8 is made of metals such as aluminum and chromium, and oxides and alloys of these metals, and is formed by vacuum vapor deposition, sputtering, ion blasting, and the like.

The metal vapor deposition layer 8 is preferably formed to a thickness of about 100 to 800 layers.

After forming the metal vapor deposited layer 8, the water soluble ink is dissolved and removed by washing with an aqueous solvent, and the metal vapor deposited layer on the water soluble ink layer 6 is also removed as the water soluble ink is dissolved. Thus, as shown in FIG. 3, a partial metal vapor deposited layer 9 consisting of the metal vapor deposited layer remaining on the hydrophobic ink layer 4 is formed. Examples of the aqueous solvent include hot water, methanol, ethanol, dioxane, ethylene glycol,
Examples include water-soluble organic solvents such as glycerin, cellosolve, dimethylformamide, and ethanolamine, and mixed solvents of these water-soluble organic solvents and hot water. Further, an acidic aqueous solution, an alkaline aqueous solution, or a surfactant-containing aqueous solution can also be used. Examples of the surfactant include linear magnesium alkylbenzene sulfonate, sodium alkyl ether sulfate, sodium α-olefin sulfonate, higher alcohol phosphate ester salt, higher alcohol ethylene oxide phosphate ester, and the like.

After forming the partial metal vapor deposition layer 9, an adhesive layer IO is usually provided on the side of the partial metal vapor deposition layer 9 (FIG. 4). The adhesive layer 10 is generally made of a heat-sensitive adhesive, and examples of the heat-sensitive adhesive include those made of acrylic resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated rubber, vinyl chloride resin, polystyrene, etc. . These adhesives are appropriately selected and used with high adhesiveness to the transfer material, but it is preferable to use adhesives with a low melting temperature.

The adhesive N10 is formed by applying the above adhesive by roll coating, gravure coating, silk screen coating, etc.

In the above embodiment, after providing the heat-resistant resin layer 5, the hydrophobic ink layer 4 and the water-soluble ink layer 6 are provided. However, after providing the release layer 3 and the pattern layer 2 on the base material 1, the hydrophobic A water-soluble ink layer 4 and a water-soluble ink layer 6 are provided, and then a metal vapor deposition layer is formed, and then washed with an aqueous solvent to form a partial metal vapor deposition layer 9, and a heat-resistant resin layer 5 and an adhesive layer 10 are formed on the upper surface of the metal vapor deposition layer 9. It is also possible to provide a transfer sheet having a structure as shown in FIG. Alternatively, after providing the heat-resistant resin layer 5, a hydrophobic ink layer 4 and a water-soluble ink layer 6 may be provided to form the partial metal vapor deposition layer 9, and then the heat-resistant resin layer 5 may be further formed on the upper surface thereof. .

The present invention will be explained in more detail below with reference to specific examples.

Example 1 A 25 μm polyester film was used as the base material, and ink made of acrylic resin was applied to one side of the film (@Showa Ink Kogyo Co., Ltd.:
GP 52) was applied at a basis weight of 2 g/m to form a release layer, and then gravure ink (@Showa Ink Industries: G Ink) using an acrylic resin as a vehicle was applied to the alpha vent background. After printing the corresponding pattern, a quaternary ammonium type cationic surfactant (
Made by Kao ■: Cortamine 24P) as methyl ethyl ketone
0.5g diluted 10 times with methanol mixed solvent
It was applied at a basis weight of /A. Next, a hydrophobic gravure ink (manufactured by Showa Ink Kogyo: @Showa Ink Kogyo) was prepared by adding 1.0% of a fluorine-based surfactant (manufactured by Ohara Palladium Chemical ■: Paragard ○-650) to an acrylic polyol-based urethane resin ink.
After printing an alphabet pattern with VMS), print with the hydrophobic ink using polyvinyl alcohol as a vehicle and a water-soluble ink (WAO-100-TA manufactured by Showa Ink Kogyo Co., Ltd.) containing 5% microsilica. Printing was performed on the part where the hydrophobic ink layer was not formed, partially overlapping the formed pattern. Next, an aluminum vapor deposited layer with a thickness of about 400 mm was formed by vacuum deposition, and then immersed in warm water at 50°C containing 1% surfactant for about 1 minute to form on the water-soluble ink and the water-soluble ink layer. The aluminum evaporation layer that had been left on the hydrophobic ink layer was removed to form a partial aluminum evaporation layer consisting of the aluminum evaporation layer remaining on the hydrophobic ink layer. After drying, an adhesive made of vinyl chloride-vinyl acetate copolymer resin was applied to the entire surface of the partially aluminum vapor-deposited layer to prepare a transfer sheet.

When this transfer sheet was used to transfer onto a transfer material, a pattern consisting of alpha vents with clear outlines and a beautiful metallic luster and a colored background was transferred.

Example 2 After forming a release layer and a pattern printing layer on a base material, 2 g/n? of gravure ink made of acrylic polyol-based urethane resin was applied thereon. A transfer sheet was obtained in the same manner as in Example 1, except that a heat-resistant resin layer was formed by coating at a basis weight of . When this transfer sheet was used to transfer onto a transfer material, a pattern consisting of an alphabet with clear outlines and a beautiful metallic luster and a colored background was transferred. This transfer sheet also has excellent heat resistance, reaching temperatures up to 230°C.
Even with roll transfer, the specularity of the deposited area was not impaired.

Example 3 After forming the partial aluminum vapor deposition layer and before forming the adhesive layer, an ink made of acrylic polyol-based urethane resin was applied at a basis weight of 3 g/m to form a heat-resistant resin layer. A transfer sheet was obtained in the same manner as in 2. When this transfer sheet was used to transfer onto a transfer material, a pattern consisting of alpha vents with clear outlines and a beautiful metallic luster and a colored background was transferred. Furthermore, this transfer sheet had excellent heat resistance, and the specularity of the thinly applied portions was not impaired even after roll transfer at 250°C. Further, even in a heat resistance test at 80°C for 13 days, the specularity of the deposited area was not impaired.

〔Effect of the invention〕

As explained above, the method of the present invention adopts a method in which a hydrophobic ink layer is first formed and then a water-soluble ink layer is formed on the part where the hydrophobic ink layer is not formed. As a result, after forming a metal vapor deposited layer on the entire surface, the metal vapor deposited layer on the water soluble ink layer is washed away with an aqueous solvent together with the water soluble ink layer, and a hydrophobic ink layer is formed. The partial metal evaporation layer formed by leaving the upper metal evaporation layer has a clear outline, and there is no risk of the outline of the partial metal evaporation layer becoming unclear as in the conventional method, resulting in a beautiful partial metal evaporation layer. This has the effect that a transfer sheet having the following properties can be manufactured.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, FIGS. 1 to 4 are longitudinal cross-sectional views showing each step of the manufacturing method of the present invention, and FIG. 5 is a longitudinal cross-sectional view showing different aspects of the transfer sheet obtained by the method of the present invention. It is a front view. 1...Heat-resistant base material 2...Picture printing layer 4...Hydrophobic ink layer 6...Water-soluble ink layer 8...Metal deposition layer 9...Partial metal deposition layer Fig. 1 Figure 2 Figure 3

Claims (5)

[Claims] (1) After providing a pattern printing layer with a desired pattern on the surface of the heat-resistant base material as needed, printing the desired pattern with hydrophobic ink, and then printing with water-soluble ink to form the hydrophobic layer. After forming a water-soluble ink layer on the part where the ink layer is not formed, a metal vapor deposition layer is formed on the entire surface, and then the metal vapor deposition layer on the water-soluble ink layer is washed and removed together with the water-soluble ink using an aqueous solvent. A method for producing a transfer sheet having a partial metal vapor deposition layer, which comprises forming a partial metal vapor deposition layer remaining on a hydrophobic ink layer. (2) A method for producing a transfer sheet having a partially metal-deposited layer according to claim 1, wherein a surfactant is coated on at least the water-soluble ink coated surface. (3) A method for producing a transfer sheet having a partially metal-deposited layer according to claim 1 or 2, in which a heat-resistant resin layer is provided prior to the formation of the hydrophobic ink layer. (4) A method for producing a transfer sheet having a partial metal vapor deposition layer according to any one of claims 1 to 3, in which a heat-resistant resin layer is provided after forming the partial metal vapor deposition layer. (5) A method for manufacturing a transfer sheet having a partially metal-deposited layer according to any one of claims 1 to 4, in which the hydrophobic ink has heat resistance.