JPS593551B2 - Treatment agent for metal coating surfaces - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment agent for a metal coating surface that darkens the copper metal coating surface of a sculpture and further develops green rust thereon.

Among traditional sculptures, metal castings have been widely admired and loved by the public.

Many of these pieces are made of copper, bronze, or iron, and as they age, these surfaces become dark brown, discolored, and even develop a green rust-like rust, giving them the deep-floored aesthetic that is unique to castings. , and in addition to this, there are many things that provide bone-like value. 5
However, these castings are manufactured through complicated processes such as V) melting, pouring, breaking the mold, and finishing, and cannot be easily manufactured by ordinary people.

Therefore, if metal sculptures such as those described above can be manufactured easily, even people with 70 degrees of artistic desire can satisfy their artistic desire. Previously, the inventor created various sculptures using synthetic clay, and by directly applying colored paint to the sculptures, he was able to obtain sculptures with a beautiful finish similar to that of pottery. suspended in organic resin liquid 1
By applying 5 types of coatings, a product with no deterioration was obtained that looked exactly like a copper cast sculpture. However, although the sculpture made as described above has the beauty of a metal-like copper color, it lacks the unique beauty of aged metal casting, so the copper-colored surface of the sculpture made as described above becomes dark brown. It is clear that if green rust can be appropriately generated on the color, it is possible to exhibit a natural and deep appearance similar to that of aged metal castings.

However, in this case, applying dark brown paint or the like to the surface of the sculpture produced as described above does not give the aged, natural, yet deep appearance of the metal casting.

Therefore, there has been a desire for a treatment agent that would enable the above-mentioned sculptures to be obtained only by surface treatment of the surfaces of the sculptures. The present invention focuses on and solves the above-mentioned problems, and provides a treatment agent for metal coating surfaces that darkens the copper metal coating surface of sculptures and causes green rust to occur thereon. The purpose is to.

That is, in order to darken and green rust the surface of the copper metal coating on the sculpture of the present invention, an aqueous solution prepared by combining ammonium carbonate and ammonium chloride in an aqueous alkali sulfide solution and a water-soluble organic solvent is used. characterized by something.

Next, embodiments based on the present invention will be described.

As described above, in the present invention, a copper metal coating surface (hereinafter referred to as a copper coating surface) obtained by applying metal powder such as copper powder suspended in an organic resin liquid to the surface of a sculpture made of synthetic clay. )
By applying the treatment agent according to the present invention to the surface, the surface was dark browned, and a green cast was formed on the surface, which was exactly the same as an aged bronze sculpture. Furthermore, unlike natural clay or china clay, the synthetic clay used in the above process is characterized in that the resulting sculpture has a large tensile stress and compressive force.

Produced appropriately in this way? Metal powder suspended in a resin liquid is applied to the surface of the carved sculpture as described above, and the metal powder used is copper, brass, gun metal powder, etc., and all of them contain 70% or more of copper. }V, when treated with the treatment agent based on the present invention, the treatment agent turns dark brown and turns green, although there are differences in the duration of action. Mainly used in this example? The copper coating surface using copper powder will be explained.

Furthermore, in the present invention, as the resin liquid used as the copper coating agent, although various emulsions are commercially available, an emulsion containing polyacrylic acid ester as a main component was used.

This polyacrylic acid engineered steel emulsion is compatible with synthetic clay and copper powder, and can closely adhere to each other.
Therefore, it is the most excellent coating agent for real sculptures. Also, the mixing ratio of the emulsion liquid and copper powder is preferably 10:1 to 4 by weight. If it is less than 10:1, the dark brown degree of the treatment liquid will be too weak, and if it is more than 10:4, it will be difficult to apply the coating agent smoothly on the surface of the sculpture.

Next, the present treatment agent for the copper coating surface is an aqueous solution containing alkali sulfide, ammonium carbonate, ammonium chloride, and a highly soluble organic solvent. ammonium carbonate and ammonium chloride contribute to the formation of green rust, and the water-soluble organic solvent swells the resin content in the copper coating surface to facilitate contact between the copper metal surface and the coarse components of the treatment solution. The property of this treatment agent is that it contributes to promoting the treatment reaction. Furthermore, the characteristics of each component of the processing agent will be explained. First, the alkali sulfides include potassium sulfide (K2S:) and soda sulfide (Na2S).
and ammonium sulfide [(NH4)2S].

Both K2S and Na2s are hygroscopic and are often commercially available in granular or plate-like crushed form, while (NH4)2S is sold as an aqueous solution. In addition, it is desirable to display the purity of alkali sulfide in terms of sulfur equivalent* due to the water content. especially(
There is no other way to display NH4)2S like this.

Note *Seiji Takagi (Experiments and Calculations of Quantitative Analysis) Revised Edition Volume 27
Page 7 Published by Kyoritsu Shuppan Co., Ltd.In addition, the concentrations of Na2s and K2S mentioned above can be freely adjusted in their aqueous solutions, but in the case of (NH4)2S, it is difficult to achieve a concentration of 4% or more in terms of sulfur. The color changes from anhydrous to yellow, and the odor gradually becomes more intense, making it difficult to use regularly.

Also, in general, an aqueous alkali sulfide solution dissociates into hydrogen sulfide ions, which are oxidized in the air. It is said that the concentration of hydrosulfide ions will gradually decrease. In particular, the aqueous solution of (NH4)2S shows a steep decreasing tendency. Also, in terms of sulfur, the same concentration of Na2S, . The degree of dark browning on the surface of the copper coating differs between each solution treatment agent, which is an aqueous solution of K2S} and (NH4)2S. For example, compared to the dark brown degree of Na'2s, K2S exhibits a reddish dark brown degree, and in the case of (NH4)2S, the dark brown degree is weaker and becomes dark grayish brown. This seems to be an effect of the degree of dissociation of hydrosulfide ions in each aqueous alkali sulfide solution. Next, the treatment agent of the present invention is characterized by co-dissolving ammonium carbonate} and ammonium chloride, which will be explained.

First, ammon carbonate has the effect of suppressing the decrease in effectiveness of the (NH4)2S aqueous solution and at the same time suppressing the bad odor of ammonium sulfide.

For example, an aqueous solution of (NH4)2S having a sulfur equivalent concentration of 2% gradually turns yellow over 20 to 30 days in summer, and the dissociation of hydrosulfide ions deteriorates. However, when 2% ammonium carbonate was added to this, it could remain colorless for 50 to 60 days. This also has the same effect on suppressing decomposition and deterioration of the alkali sulfide aqueous solution when ammonium carbonate and ammonium chloride are added to the alkali sulfide aqueous solution described later.

When copper powder was suspended in water and ammonium carbonate was added to it, the liquid gradually took on the blue-indigo color characteristic of ammoniacal copper. However, even if ammonium chloride (described later) is added instead of ammonium carbonate and left for 2 to 3 days, the color does not turn blue. ．． This is thought to be due to promoting copper ionization on the surface of the copper powder (by mixing ammonium carbonate into the treatment solution). Furthermore, in the case of using only ammonium chloride (described below) without ammonium carbonate in the treatment agent of the present application, it takes more than 20 hours to treat the copper coating surface and cause green rust, but when ammonium carbonate is co-dissolved, it takes 30 hours or more. Green rust can develop within ~5 hours. It is clear from the properties of these ammonium carbonates that it greatly contributes to the green rusting of the copper coating surface. The reason why ammonium carbonate is mixed into the treatment agent of the present invention is because of the above-mentioned properties. In addition, the amount of ammonium carbonate added in the treatment solution is 1 to 1.
3% is desirable. Next, the effect of ammonium chloride will be explained.

When ammonium chloride is added to an aqueous solution of potassium sulfide or sodium sulfide, it reacts as shown in the following equation. Although an aqueous solution of Na2s or K2S exhibits strong alkalinity, the alkalinity can be gradually weakened by adding ammonium chloride to a neutralized state.

When the alkalinity is weakened in this way, erosion of brushes and brushes using the treatment liquid is alleviated. N
When H4CI is added, Na2S is added to the alkali sulfide aqueous solution.
Since (or K2S) and (NH4)2S are co-dissolved, the dark brownness of the copper coating surface can also be changed. Furthermore, the mixing of ammonium chloride can cause dark browning and trailing edge rust on the surface of the dicopper coating.

However, as mentioned above, co-dissolution of ammonium carbonate significantly promotes green rust. Based on the above properties, is ammonium chloride mixed with this treatment agent? For this reason, the amount of V1 ammonium chloride added is desirably 3 to 6% of the treating agent. If it is less than 1%, the green rust effect is too weak, and if it is more than 10%, the degree of darkness changes, but the green rust effect does not change.

For the above reasons, it is thought that an aqueous solution containing alkali sulfide as a main component and a mixture of ammonium carbonate and ammonium chloride is sufficient as a treatment agent, but this alone is not sufficient as a treatment agent. That is, the copper coating paint was applied to the sculpture for 30 minutes.
If treated with the above-mentioned treatment agent until the coated surface dries after ~50 minutes, dark browning can be achieved, but as the coated surface gradually dries after 1 hour, the treatment effect becomes almost negligible. This is because the polyacrylic acid polystyrene emulsion in the copper coating film used progresses to harden, making it difficult for the processing agent to infiltrate into the coating film. Therefore, in order to increase the treatment effect of this treatment agent, it is necessary to swell the polyacrylate resin film of the copper coating to allow the treatment solution to penetrate and come into contact with the copper powder surface within the film. . For this purpose, the present invention is characterized in that a water-soluble organic solvent is mixed into the processing agent. The above water-soluble organic solvents include dioxane, propylene glycol,
Cellosolve (monoalkyl form), Cellosolve and ethanolamine. These have a high boiling point, are easily water soluble, have a high flash point, and are particularly characterized by the ability to dissolve general organic resins. By mixing the above-mentioned water-soluble organic solvent with this treatment agent, the resin in the copper coating film is swollen, and the treatment solution permeates into the film and comes into direct contact with the copper powder surface to remove the copper. The grain surface turns dark brown and eventually develops green rust.

Furthermore, since these water-soluble organic solvents have a high boiling point, a processing agent mixed with them is less likely to evaporate during processing and drying, and exhibits a secondary effect of sustaining the processing reaction. In addition, the amount of these water-soluble organic solvents added is 0.5 to 0.5 to the volume of the treated aqueous solution.
15% volume is desirable. In other words, if the additive volume is less than 0.5 (!), the above-mentioned solvent effect will be weak, and if it is more than 15%, the solvent will remain on the painted surface and warp and peel off the copper coating, which is not fun, and furthermore, the cost will increase accordingly. It gets expensive. From the above, the treatment agent for producing dark brown color and green rust on the copper coating surface of sculptures based on the present invention has alwari sulfide as its main component.
It is an aqueous solution containing ammonium carbonate and ammonium chloride as subcomponents and a water-soluble organic solvent co-dissolved therein.

By dipping a brush or brush into this treatment agent and applying it on the copper coating surface of the sculpture at room temperature, the coating surface turns dark brown, and by leaving it for a while, the green rust will be completely removed. It looked almost the same as a bronze metal sculpture with a patina of color. That is, the treatment agent based on the present invention darkens the copper coating surface of the sculpture, and ? Moreover, it is possible to give the appearance exactly the same as a patina-colored metal sculpture that has developed green rust and has aged in a short period of time, and can be easily used by the general public, and is worthy enough to stimulate the desire for craft production. be.

Next, examples based on the present invention will be shown.

Example 1 A mixture of 8 parts by weight of polyacrylic acid engineering still emulsion (commercially available) and 2 parts by weight of copper powder (100 mesh) is applied to the surface of a sculpture made of synthetic clay.

30 minutes after application, a post-treatment agent containing 5 tons of Na2S5H2O, 2 tons of ammonium carbonate, and 3.2 tons of ammonium chloride dissolved in water was applied to the copper coating surface. After several minutes, the color darkened and gradually turned to dark brown-gray V1. After several hours, edge rust gradually appeared from the concave surface. Example 2 After forming a copper coating on a sculpture obtained by the same treatment as in Example 1 1
After 0 hours, the copper coating surface was treated with 5t of Na2S5H2O and 1t$ of ammonium carbonate? 5 tons of ammonium chloride and 20 cc of propylene glycol as a water-soluble organic solvent were mixed with 100 cc of water.
When it was coated with a treatment agent mixed with C, it easily turned dark brown and gray, and after a few hours, green rust gradually formed, and when it was left to stand for a day, green rust formed on the entire coating surface.

When I gently wiped this off with a piece of paper, I was able to obtain something that was exactly the same as an old bronze carved proboscis. In this case, dioxane, cellosolve, and ethanolamine were used as a water-soluble organic solvent in place of propylene glycol, but almost the same dark brownish gray color and green rust were obtained. Example 3 After drying, the painted surface of a sculpture treated in the same manner as in Example 1 was treated with K2S2f. as a post-treatment agent for 10 hours. (NH4)2C031v
SNH4CI2.8t} and propylene glycol 10
A mixture of CC and 100 cc of water gradually turned dark reddish brown after coating, and green rust appeared on the entire surface after 20 hours.

When this was gently wiped off with a piece of paper, a bronze sculpture with an old, pale appearance similar to that of Example 2 was obtained. As described above, the treatment agent based on the present invention darkens the copper coating surface of sculptures made of synthetic clay and causes green rust, and the resulting sculptures exhibit a completely aged and aged appearance. The processing agent, its manufacturing method, and its usage are extremely simple, and even ordinary people can easily imitate aged sculptures, stimulate their artistic desire, and contribute to the art world.

Claims (1)

[Scope of Claims] 1. Ammonium carbonate and ammonium chloride for dark browning and green rusting the surface of a copper coating formed by coating the surface of a sculpture with a coating containing copper or copper alloy powder mixed with a polyacrylate emulsion. A treatment agent for metal coating surfaces, characterized in that it is an aqueous solution in which a water-soluble organic solvent is further co-dissolved in an aqueous alkali sulfide solution containing dissolved alkali sulfide. 2. The treatment agent for metal coating surfaces according to claim 1, wherein the water-soluble organic solvent is dioxane, propylene glycol, cellosolve, ethanolamine, or a mixture thereof.