JP2920610B2 - Method and apparatus for forming patina film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a patina film capable of forming a patina film on a surface of a substrate made of copper or a copper alloy in a short time.

[0002]

2. Description of the Related Art Shinto shrines and temples often use copper roofs. Over a long period of time, these copper houses have formed patina due to the effects of oxygen, water vapor, carbon dioxide, sulfur compounds, and salts in the atmosphere. To go. However, since the formation of patina requires several years to about 20 years, in recent years many methods for artificially forming patina have been proposed, and artificial patina plates using these surface treatment techniques actively. Has been implemented.

A number of methods proposed for forming artificial patina are roughly classified as follows. A chemical conversion treatment method in which the surface of a substrate is brought into contact with a chemical solution to form patina (Japanese Patent Publication No. 57-51468). A method in which a base material is subjected to a chemical conversion treatment, and a coating material is further coated thereon (Japanese Patent Application Laid-Open No. 55-8491). A method of immersing in a chemical solution and performing electrolytic treatment (Japanese Patent Publication No. 555-1)
No. 2117). A method in which copper or copper alloy powder is adhered to a substrate having a roughened surface with an adhesive, and a green-blue coloring liquid is applied (Japanese Patent Publication No. Sho 57).
-52425). A method of coating with a paint containing a green-blue forming substance (JP-A-5
5-139467).

[0004]

The method for producing an artificial green bronze plate by the above-mentioned methods has a problem that industrial productivity is poor for the following reasons. It takes a long time to produce a product by a natural drying process after the chemical conversion treatment or a repeated process of the chemical conversion treatment and drying. There are many steps such as a natural drying step after the chemical conversion treatment, or a long time until commercialization due to a repeated step of the chemical conversion treatment and drying, and a coating step of a paint for preventing peeling of the patina film. The management of the electrolyte is difficult and a large capital investment is required. There are many steps for forming an artificial patina, such as a copper or copper alloy powder bonding step, a patina coloring liquid applying step, and a drying step, and it takes a long time to commercialize. There are many steps including a green-blue formed product manufacturing step, a pigment manufacturing step, and a painting step, and each step is a single step. Therefore, there has been a need for a method for easily forming an artificial patina in a short time.

[0005]

In order to achieve the above object,
As a result of repeated studies through numerous tests, it was found that to form a patina film in a short period of time, `` After applying a patina color developing solution to the surface of a copper or copper alloy base material, forcibly reacting by brushing And immediately add water to the surface of the reacted copper and copper alloy, and immediately forcibly oxidize with an oxidizing gas without leaving a time. "

The present invention has been completed based on the above findings, and includes a step of applying a green-blue coloring liquid to a surface of a substrate made of copper or a copper alloy, a step of brushing, a step of adding moisture, and Provided are a method for forming a patina film, wherein a step of supplying an oxidizing gas is sequentially and continuously performed, and a forming apparatus for performing the method.

The green-blue coloring liquid used in the present invention is not particularly limited as long as it is a liquid that generates basic copper chloride, basic copper carbonate and basic copper sulfate having a green-blue composition. Ammonium salts, hydrochloric acid, caustic soda, sulfides, sulfates, nitrates, acetates, carbonates, bicarbonates, solutions containing alum and the like and combinations thereof are known. An aqueous solution obtained by adding an alkali metal chloride and / or an alkaline earth metal chloride to nitric acid and ammonium sulfate, an aqueous solution obtained by adding cupric chloride, and copper sulfate added to an alkali metal chloride and / or an alkaline earth metal chloride An aqueous solution can be used. In the step of applying the green-blue coloring liquid, any known method or mechanism such as a method using a spray, a method using a droplet, a method using a brush or a roller may be used. The brushing material used in the brushing step may be any material as long as it is corrosion-resistant, and any method and mechanism may be adopted as long as the brushing material is rubbed on the surface of the base material. In this step, the green-blue color developing solution comes into contact with the substrate surface by brushing, and the reaction is promoted in a very active state. In the step of adding water, any known method,
Although a mechanism may be adopted, a necessary amount, that is, a small amount of water is added by using water vapor generated by heating (or boiling water), water vapor generated by ultrasonic waves, or fine water droplets formed by spraying. A method and mechanism for forming a humidified atmosphere and allowing the substrate to pass through this atmosphere are economically preferable. In the method using an oxidizing gas, an oxidizing gas atmosphere such as an ozone gas is formed, and a method and a mechanism in which the base material passes through this atmosphere are economically preferable.

In the present invention, immediately after the patina-coloring liquid is applied to the surface of the copper and copper alloy, if the brushing is performed immediately, the patina-coloring liquid and the substrate surface come into contact with each other to react, and a large amount of copper ions are generated. The substrate surface becomes very active. Immediately after adding the required amount of water to the surface of copper and copper alloy under such properties, and immediately thereafter, forcibly oxidizing it with an oxidizing gas without leaving time, cuprous oxide and copper oxide are generated in a short time. A patina crystal is formed. In this state, the surface of the base material is wet and deep green because of the presence of moisture. However, when the surface of the base material starts drying due to the heat of the oxidation reaction generated at that time, a bright green-blue color is presented.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described based on an embodiment shown in the drawings. On a long plate material (base material) 1 made of copper or a copper alloy, a patina-coloring liquid containing chloride as a main component is applied in a patina-coloring liquid applying mechanism (step) 2. The green-blue coloring liquid application mechanism (step) 2 has a structure in which a liquid is dropped from a chemical liquid tank 2a to a brush 2c via a chemical liquid pump 2b, and is uniformly applied to the surface of the plate material 1.

Next, after the surface of the plate 1 is brushed by the brushing mechanism (step) 3, it is immediately transferred to the humidifying mechanism (step) 4. In the brushing step 3, the brush 3a has a structure in which nylon fibers are planted on a resin disk, the tip of the nylon fibers is brought into contact with the surface of the plate member 1, and the brush is rotated and brushed by the drive motor 3b.
In the figure, reference numeral 3c denotes a waste liquid tank.

The plate material transferred to the humidifying mechanism (step) 4 is
After moisture is added to the surface of the plate 1 through the humidification tank 4b filled with the steam generated by the steam generator 4a, it is immediately transferred to the oxidizing gas supply mechanism (step) 5. still,
The steam generator 4a applied ultrasonic humidification, and the steam generation rate was 1200 cc / hour. In the figure, 4
d is a waste liquid tank.

The plate 1 transferred to the oxidizing gas supply mechanism (step) 5 passes through an oxidizing tank 5c which is filled with gas generated by an oxidizing gas generator 5a for generating ozone via an injection pipe 5b. . In this oxidation tank 5c, cuprous oxide and copper oxide are generated in a short time, and green-blue crystals are formed.
When the surface of the plate material 1 starts drying due to the heat of the oxidation reaction generated at that time, a bright green-blue color is presented. In the figure, 5e
Is an oxidizing gas detoxifying device, and 5f is an exhaust fan.

The transfer of the plate 1 between each mechanism (process) is as follows.
The belt conveyors 2d, 4c, and 5d are continuous, and the total conveyor length is 20 m. Green-blue coloring liquid application mechanism (process)
The formation of patina was confirmed in a short time of 8 minutes after inserting the plate material 1 into 2.

The amount of waste liquid collected in the waste liquid tanks 3c and 4d was extremely small.

[0015]

As described above, conventionally, it took a long time to form patina, but according to the method for forming a patina film of the present invention, patina can be formed in a short time, and industrial productivity is improved. , It is also economical.

Further, the forming apparatus of the present invention does not require special mechanical equipment and the like, so that it is highly practical.

[Brief description of the drawings]

FIG. 1 is a side view schematically showing one embodiment of an apparatus for forming a patina film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Plate material 2 Green-blue color liquid application mechanism 2a Chemical liquid tank 2b Chemical liquid pump 2c Brush 2d Green-blue color liquid application conveyor 3 Brushing mechanism 3a Brush 3b Drive motor 3c Waste liquid tank 4 Humidification mechanism 4a Steam generator 4b Humidification tank 4c Humidification conveyor 4d Waste water Oxidizing gas supply mechanism 5a Oxidizing gas generator 5b Injection pipe 5c Oxidation tank 5d Oxidizing conveyor 5e Oxidizing gas detoxifying device 5f Exhaust fan

Continuation of the front page (56) References JP-A-62-253775 (JP, A) JP-A-62-253774 (JP, A) JP-A-4-193958 (JP, A) JP-A-3-236480 (JP, A) , A) JP-A-4-325689 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C23C 22/00-22/86

Claims (2)

(57) [Claims] 1. A step of applying a green-blue coloring liquid, a step of brushing, a step of adding moisture, and a step of supplying an oxidizing gas to a surface of a substrate made of copper or a copper alloy are sequentially and sequentially performed. A method for forming a patina film, comprising: 2. A mechanism for applying a green-blue coloring liquid, a mechanism for performing brushing, a mechanism for forming a humidified atmosphere, and an oxidizing gas atmosphere on a path of a traveling mechanism for continuously traveling a substrate made of copper or a copper alloy. An apparatus for forming a patina film, wherein a mechanism for forming a green color is faced in this order.