JPH0469230B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing decorative sheets for decorated paintings, certificates, cards, and the like.

[Conventional technology]

Ordinary paintings, certificates of commendation, cards, etc. are made by applying predetermined patterns, figures, characters, etc. (hereinafter collectively referred to as patterns) on sheets of paper or synthetic resin. Therefore, they cannot withstand long-term use, and for example, in the case of portable cards, they may have creases or
Easy to damage.

Therefore, in order to improve durability, metal sheets with decorations applied are used in some cases. For example, Japanese Utility Model Application No. 61-71478 introduces a business card in which a pattern is written by a recess formed on the surface of a thin metal plate, and the recess is painted. The pattern formed in this way is
Easy to peel off from metal surfaces. Also, when cleaning a dirty surface with an oil-based detergent, part of the paint film dissolves, causing the pattern to bleed. Therefore, Utsukai Showa 61-71478
In the publication, a transparent resin layer is formed on the entire surface of a thin metal plate after a coating film has been formed to protect the coating film.

[Problem to be solved by the invention]

However, by coating the entire surface with a transparent resin layer, the impression created by the metal background is diluted, resulting in a low commercial value. If coating with a transparent resin layer is omitted to emphasize this impression, not only will the pattern become unclear due to elution of the coating film as described above, but also the metal surface will be easily damaged.

Further, in Japanese Utility Model Application Publication No. 61-71478, etching is employed as an example of forming the recessed portions. However, normal etching requires a pre-process of applying a resist to the target surface and exposing the resist to form a resist pattern with a predetermined pattern. This complicates the work and increases the price of the product.

Therefore, the present invention aims to produce a decorative sheet with excellent durability in a simple process by using a ceramic coating provided to color the stainless steel surface and also use it as a resist to prevent scratches. purpose.

[Means to solve the problem]

In order to achieve the object, the decorative sheet manufacturing method of the present invention applies masking with a predetermined pattern to a stainless steel foil or thin plate, and applies ceramic coating to the surface of the foil or thin plate that is not covered with the masking. The method is characterized in that the masking is removed, and then an oxide film is formed on the metal surface of the foil or thin plate in an acid bath and colored. It is also contemplated by the present invention to etch the unmasked stainless steel foil or sheet, and to etch and then color it by forming an oxide film in an acid bath.

Note that the decorative sheet referred to here includes various types of sheets such as paintings, certificates of commendation, cards, calendars, and business cards.

[Effect]

In the present invention, the foil has a thickness of 200 μm or less,
The thin plate has a thickness of more than 200 μm. After applying a masking with a predetermined pattern to the surface of such a stainless steel foil or thin plate, ceramic coating is applied to form a pattern consisting of a ceramic layer on the surface of the foil or thin plate not covered by the masking.

This ceramic layer is formed by a method such as ion plating, plasma CVD, or sputtering. Further, the layer thickness is preferably 500 Å or more in order to prevent scratches and provide corrosion resistance during pickling bath treatment and etching treatment.

This type of ceramic layer is formed in close contact with the surface of the underlying foil or thin plate, so this treatment makes use of the texture unique to stainless steel and provides a colored surface with various tones unique to ceramics. It will be done. Ceramics used include those with color tones depending on the material color, such as TiN (gold), ZrN (gold), TiC (black), or NbO _x ,
_CrOx , _SiOx , _Al2O3 , _NiOx , _C0x , _{M0Ox ,}
There are some that have color tones due to interference colors such as _WOX . The latter can be achieved by adjusting the layer thickness.
It can produce various color tones such as blue, gold, red, and green.

Furthermore, the surface of the foil or thin plate to be coated with ceramics may be made glossy by bright annealing, buffing, or the like. When such a glossy surface is coated, the surface of the formed ceramic layer also becomes glossy.

The masking is then removed and, in claim 1, the foil or thin plate is immersed in an acidic bath, such as a mixed aqueous solution of sulfuric acid and chromic acid. By this acid bath treatment, an oxide film is formed on the surface of the foil or thin plate on which the ceramic layer is not formed. At this time, since the ceramic is not oxidized, no oxide film is formed on the ceramic layer. On the other hand, in areas where there is no ceramic layer, depending on the thickness of the oxide film,
Coloring is done in various tones using interference colors. This color tone adjustment is performed by changing the processing time. As the processing time increases, the color tone progresses from translucent gray to blue, gold, magenta, and green. This coloring tone is gradual, and it is also possible to take intermediate colors.

Since the formed oxide film is a film formed by oxidizing the surface of stainless steel, it has sufficient adhesion to the base. Next, electrolysis is performed in a mixed aqueous solution of phosphoric acid and chromic acid using stainless steel as a cathode. Through this treatment, the oxide film becomes a surface that has excellent wear resistance and is resistant to scratches and the like. Therefore, it is possible to obtain a colored surface in various tones with excellent abrasion resistance that takes advantage of the impression of the texture peculiar to stainless steel.

In this way, stainless steel foil or thin plate
A decorative sheet in which a colored surface by ceramic coating and a colored surface by an oxide film are formed, and a pattern is formed by combining various tones by setting the type of ceramic, the conditions for ceramic coating, and the conditions for forming the oxide film, respectively. is obtained. Each colored surface has its own unique color tone that creates a contrast, making use of the impression of the texture unique to stainless steel.
It has excellent rust resistance and abrasion resistance without peeling.

Next, in claim 2, the stainless steel foil or thin plate from which the masking has been removed is etched. Etching solutions include hydrochloric acid, ferric chloride,
A liquid that dissolves the surface of stainless steel, such as nitric fluoric acid, can be used, and the liquid is selected depending on the type of stainless steel used and the required properties of the etched surface.

A pattern consisting of a ceramic layer is formed on the surface of the stainless steel foil or thin plate, and this ceramic layer has a
Low reactivity to etching solutions. For this purpose, when a foil or thin plate coated with ceramics is brought into contact with an etching solution, only the exposed stainless steel surface is first etched, so by stopping the process before etching progresses, the ceramic coating Only the parts that are not etched are etched to create a satin finish. The unevenness of this satin-like surface creates a deep impression. Furthermore, due to the rust resistance of the stainless steel base material, rust does not occur over a long period of time. In this way, a decorative sheet with a strong contrast is obtained in which the colored surface of the ceramic coating and the satin-like surface are combined.

Next, claim 3. In this method, the unmasked stainless steel foil or sheet is etched and then colored by forming an oxide film in an acid bath. The colored surface obtained at this time takes advantage of the matte texture of the background and exhibits dark blue, gold, red, green, etc. tones. In this way, a decorative sheet with a stronger contrast can be obtained, in which the colored surface formed by the ceramic coating is combined with the dark colored colored surface formed on the satin-like surface.

[Example] A shiny SUS304 stainless steel foil with a thickness of 100 μm was cut into a piece of 450 mm in length and 370 mm in width to prepare a specimen. This specimen was covered with a heat-resistant mask with a predetermined pattern, and a thickness of 2000 Å was formed by ion plating.
After forming the TiN ceramic layer, the mask was removed. Next, an etching solution having a composition of a 43% aqueous solution of ferric chloride and a temperature of 50° C. was sprayed onto the specimen. As a result of this treatment, the portion where the ceramic layer was formed was not etched, and only the stainless steel surface that was not covered with the ceramic layer was etched in a matte finish.

Next, sulfuric acid 500g/, chromic anhydride 250g/
By immersing the specimen in a mixed aqueous solution of phosphoric acid and chromic acid, an oxide film is formed on the surface of the etched stainless steel, producing a blue color due to interference color, and the specimen is further immersed in a mixed aqueous solution of phosphoric acid and chromic acid as a cathode. Electrolysis was performed to harden the oxide film. With this treatment, no oxide film was formed on the part where the ceramic layer was formed, and the initial surface was maintained.

The decorative sheet thus obtained had a contrast between the shiny gold color of TiN and the satin-like dark blue color. Each colored portion did not peel or fade and had excellent rust resistance and abrasion resistance.

By adjusting the processing time in the oxide film formation process, the matte area can be colored dark gold, dark red, or
It was colored in various tones such as dark green. Further, when coloring was carried out under the same conditions except that the etching was omitted, the obtained decorative sheet was colored in a bright tone due to the oxide film forming treatment.

Furthermore, a resist pattern with a predetermined pattern was formed on the same specimen, and this resist pattern was used as a mask to coat TiC as a ceramic layer by ion plating. After removing the resist, etching was performed under the same conditions. The obtained decorative sheet had excellent durability, with a contrast between the glossy black color of TiC and the satin-like stainless steel surface.

〔Effect of the invention〕

As explained above, in the present invention, since the ceramic layer formed on the surface of the stainless steel foil or stainless steel plate also serves as a resist, the process can be simplified. In addition, on stainless steel surfaces on which no ceramic layer is formed, an interference color film is formed in an acid bath, or a matte skin is formed in etching, resulting in a surface condition that gives a deep impression. . and,
These surfaces contrast with the ceramic-coated colored surface, resulting in a highly durable decorative sheet.

Claims (1)

[Scope of Claims] 1. A stainless steel foil or thin plate is masked with a predetermined pattern, a ceramic coating is applied to the surface of the foil or thin plate that is not covered with the masking, the masking is removed, and then the A method for producing a decorative sheet, which comprises forming an oxide film on the metal surface of a foil or thin plate in an acidic bath to color the metal surface. 2 Masking a stainless steel foil or thin plate with a predetermined pattern, applying ceramic coating to the surface of the foil or thin plate that is not covered by the masking, and removing the masking,
A method for producing a decorative sheet, which comprises etching the foil or thin plate. 3 Masking a stainless steel foil or thin plate with a predetermined pattern, applying ceramic coating to the surface of the foil or thin plate that is not covered with the masking, and etching the foil or thin plate after removing the masking. 2. A method for producing a decorative sheet, which is then colored by forming an oxide film on the metal surface of the foil or thin plate in an acidic bath.