JPS60180914A - Manufacture of patina-like substance - Google Patents

Abstract

PURPOSE:To manufacture a patina-like substance at a low cost in a short time by mixing copper powder with an aqueous soln. of the ammonium salt of a solid org. acid, adding ammonium carbonate powder to the mixture, and mixing and stirring them in the air. CONSTITUTION:Copper powder is mixed with an aqueous soln. or dispersion of the ammonium salt of an org. acid which is solid at ordinary temp. such as stearic acid or resin acid to prepare a uniform wet powdery mixture. Powder of ammonium carbonate or hydrogencarbonate is added to the mixture, and they are stirred by slow cutting and turning so that gas permeability can be maintained. A mild exothermic reaction accompanied by the generation of gaseous ammonia takes place, and the formation of patina proceeds. Thus, a stable powdery patina-like substance with low toxicity is obtd. in <=about 24hr without requiring drying by heating.

Description

[Detailed description of the invention] The present invention relates to a method for producing a patina-like material.

Patina is a general term for green rust that occurs on copper metal, and mainly refers to (1) the basic cupric acetate Cu(Cl-111COO)1-CuO- produced when acetic acid vapor acts on copper or copper alloys;
AH20; (2) Basic cupric carbonate C that is formed on the surface when copper is exposed to an atmosphere containing moisture and carbon dioxide for a long time.
uCO3・Cu(OH)s; and (3) basic copper sulfate Cu804・3cu(OH)1 produced by the oxidation of the reaction product with hydrogen nitride or sulfur dioxide slightly present in the air.
It is roughly divided into three types. These patina substances require a considerable amount of time not only when they are produced naturally but also when they are produced artificially.

During research on antifouling coatings containing copper or copper compounds as antifouling active ingredients, the inventor found that when copper comes into contact with water, especially seawater, a patina-like substance is produced that is superior to copper, copper oxide, and cuprous oxide. Focusing on the fact that it is stable in fresh water and mountain water, and its toxicity is much lower than that of steel oxide and cuprous oxide, we have developed a method for producing such a low-toxicity, stable patina-like substance in a short period of time and in a completely artificial manner. As a result of various studies aimed at developing a method for mass-production at low cost, we finally established a method for mass-producing a verdigris-like substance using copper powder as a raw material.

Therefore, the present invention involves adding and mixing an aqueous solution or dispersion of an ammonium salt of an organic acid that is solid at room temperature to copper powder, and then adding all of ammonium carbonate or ammonium bicarbonate powder to the resulting wet powder mixture. The present invention provides a method for producing a verdigris-like substance, which is characterized by stirring and mixing in the presence of a green-blue material.

In the present invention, an organic acid that is solid at room temperature is dissolved or dispersed in water in the form of an ammonium salt, instead of a highly corrosive low-molecular-weight liquid acid such as acetic acid, which is conventionally used in the production of patina. The primary feature is that it can be used in any situation. A wide range of organic acids that are solid at room temperature can be used; however, from a practical standpoint, fatty acids or resin acids,
It is typically preferable to use stearic acid or pine resin (0 gin, the main component being abietic acid).

For convenience, the case where pine resin is used will be explained below.
Kofl'l! ) Ammonia water (e.g. Ko!~J, r%
(Concentration) to form an ammonium salt, diluted with approximately twice the same amount of water as nf, and added to the total copper powder at a ratio of approximately 0.2 to /j parts by weight of pine resin per ioo part by weight. Mix. After a uniform wet powder is obtained, about 20 to 100 parts by weight of ammonium carbonate or ammonium bicarbonate powder is added, and the whole is stirred by slowly cutting back and forth to maintain air permeability at all times, generating ammonia gas. A mild exothermic reaction occurs and the patina progresses. Thus, a homogeneous powdery patina-like material can be obtained, usually within day and night, without the need for a heat drying step. The ammonium carbonate or ammonium bicarbonate powder may be added all at once, or may be added in appropriate portions.

According to the present invention, as described above, an organic acid that is solid at room temperature,
In particular, by using fatty acids or resin acids and using ammonia, which is highly reactive toward copper, as a neutralizing agent, i.e., a saponifying agent, it is possible to uniformly disperse the solid acid in water, and the copper Uniform and easy progress of the complexation reaction of the powder with solid ammonium acid and the subsequent basic carbonation reaction with ammonium carbonate or ammonium bicarbonate is achieved. In this reaction, it is important to continue to mix slowly but uniformly throughout the reaction to avoid excessive accumulation of reaction heat and to ensure sufficient aeration conditions. When the temperature rises, the decomposition of ammonium carbonate or ammonium bicarbonate into CO3 and NH3 becomes excessive, which is lost to the atmosphere without participating in the patina reaction, resulting in the formation of coarse black particles, especially within the mixture.

However, it is necessary to uniformly mix and aerate the mixture so that the internal temperature does not reach 10°C or higher. Therefore, the method of the present invention can be summarized as follows: (11 copper powder, (2) solid organic acid, (
3) In order to carry out the mutual reaction between carbon dioxide and (4) water uniformly and rapidly, (2) and (4) are ammonium salt aqueous solutions or dispersions, and (3) is solid ammonium carbonate or bicarbonate. It is characterized in that it can be mixed with (1) in the form of ammonium powder to form a wet powder that is easy to handle during the reaction, thereby generally requiring no additional drying step in a short period of time, such as just one day and night. The desired green growth-like substance can be obtained in the form of a homogeneous dry powder. Furthermore, since the patina substance obtained by the present invention is not a pure inorganic patina but a patina containing organic matter, it has the characteristics of having good affinity with the glaucoma substance and having a small ratio.

The patina-like material obtained according to the invention can be used for any patina application. For example, it can be used in the form of a suitable mortar, paint, etc. for coating roof tiles, roof panels, and other building materials. It can also be mixed into a container for manufacturing plastic plates and other plastic landforms for molding. In particular, the patina-like substance obtained by the present invention has been found to be effective as an antifouling active ingredient in surface antifouling and anticorrosion coating compositions such as antifouling paints and antifouling cements.

In particular, if it is intended to use the patina substance as an antifouling active ingredient in antifouling cements, preferably antifouling polymer cements, the reaction according to the invention can be carried out using sand, for example silica sand No. 1 to No. 7, especially silica sand No. 6. By conducting the reaction under mixed conditions, aeration during the reaction becomes better, facilitating the reaction, and the product is convenient for blending into the cement base material. This method constitutes a preferred embodiment of the present invention. In this case, the preferred mixing ratios of the reaction components are OO to aOOl parts of sand per 100 parts by weight of copper powder, 0 to 7 parts by weight of rosin O, and 0 to 3 parts by weight of ammonium carbonate or ammonium bicarbonate. It is about the same level as Kenbabe.

On the other hand, in the production of a patina-like substance used as an antifouling active ingredient for antifouling paints, in order to keep the amount of unreacted copper powder as low as possible, it is necessary to produce a 77 to 100 ml per ioo part by weight of copper powder. Parts by weight, ammonium carbonate or ammonium bicarbonate 70 to io
It is preferable to use an irises section. The patina-like material obtained by the method of the present invention compositionally contains a solid organic acid, so it has a much greater affinity with paint vehicles than suboxide steel or metallic copper, and has a smaller true specific gravity, so it can be used as a paint vehicle. Since the dispersibility is good and the amount of sedimentation is very small, the concentration of the antifouling active ingredient in the vehicle can be maintained at a high concentration of about 30 to jθ%.

As mentioned above, the patina-like substance obtained by the present invention has surface antifouling,
As a corrosion-preventive coating, it can be used in the form of a cement paint composition depending on the object to which it is applied;
It also has the advantage that it is more stable than cuprous oxide and copper metal, and can achieve the desired antifouling effect over a long period of time without swelling, peeling, or falling off.

The surface antifouling and anticorrosion coating composition containing the verdigris-like substance obtained by the present invention as an antifouling active ingredient is useful for preventing corrosion and adhesion of aquatic organisms on the surface of any steel or concrete object.
It can be widely used for antifouling fishing nets, ropes, etc. related to fisheries, and for preventing decay of wooden houses and other wood.

Next, examples of the production method of the present invention and usage examples (reference examples) of the resulting patina-like substances will be shown, but the present invention is not limited thereto, of course.

Example 1 Ammonium rosin acid (coj% ammonia water I water, 1 water, gin powder added little by little to copper powder iKf, mixed and finally coop@ 9 viscous transparent liquid) 100 scratches! (Rosin content 0./Kf) Josui 200 inertia! Add 0.7 kft of ammonium bicarbonate powder to the wet copper powder obtained by diluting it with water and uniformly spraying the diluted liquid and mixing well. When the mixture is mixed slowly and continuously, ammonia gas is generated. The rosin oxidation, hydroxylation, and carbonation reactions of the metal steel progress simultaneously, and a homogeneous verdigris-like powder is obtained in about 2 hours.

Example.

Copper powders i and z~ are evenly mixed with No. 6 silica sand and 7~, and mixed with ammonium rosinate (approximately 1 liter of ammonia water).
Add rosin powder (a viscous transparent liquid) little by little and mix (rosin content Joy) into water J
Ammonium bicarbonate powder O, T is added to the wet powder mixture obtained by evenly spreading the liquid diluted with
Add Kf'1. When mixed slowly while turning the whole thing to maintain air permeability, simultaneous reactions such as rosin oxidation, hydroxylation, and carbonation of metallic copper occur with mild heat generation and generation of ammonia gas, and complexation progresses. , about 2
6. Homogeneous verdigris-like dry powder after drying time. You can get ri~.

Reference Example 1 Prepare 10 concrete plates with a surface of Q, rim, /, IB. On the other hand, Portland cement i, o Kg k mix well, J
8RM) Matsukusuno e- (SBR latex, contains same type of g!chi) 0. Add j aid and stir, add water o, i, 2
Add Kf and adjust the viscosity to a slurry obtained by applying it to one side of two concrete plates using a mortar spray gun.

On the other hand, for comparison, copper powder, 24! %, portland cement i, o ~, Tomatsukunoya 10, j Kf, water 0, /
2~t - Slurry obtained by mixing and stirring ■ and 2 kg of No. 6 silica sand containing no copper, 1.0 Kf1 of Portland cement/e Q, j first, water 0
．． Slurry obtained by mixing /Kfk ◎ [Apply each to one side of a concrete board using a mortar spray gun. Furthermore, for comparison, a commercially available ship bottom paint containing organic tin and cuprous oxide, 0t, was similarly applied to one side of the two concrete plates mentioned above.

These concrete plates were installed in the final sedimentation pond of the Seto Inland Sea Sewage Purification Center and in the Seto Inland Sea Port of the Onishimachi Shipyard, and were maintained and observed for 2μ months, and the results are shown in the wmi table.

Table 1 Sewage Purification Final Sedimentation Tank Middle Port Seawater Reference Example 2 Antifouling paint prepared by mixing the verdigris-like powder substance obtained in Example 1 with alkyd resin paint at a ratio of 25 parts to 100 parts of vehicle excluding solvent. A and, for comparison, vehicle 100 in which metallic copper powder was used as a substitute for the patina-like powder material and the solvent was removed.
Antifouling paint B added to alkyd resin paint at a ratio of 25 parts per part and commercially available organic tin and cuprous oxide-containing ship bottom paint C
were applied to both sides of a 50 ctn x 50 Iyn x 3 inch iron plate, and the plates were hung from a pier on the Goi coast of Tokyo Bay and kept in seawater for 24 months. The observation results are shown in Table 2.

Table 2 Reference Example 3 The verdigris-like powder material obtained in Example 1 was added to an alkyd resin paint (10 parts of polyisobutylene (8 stone polybutene HV55) was previously mixed with 100 parts of this paint) in a solvent. 25W per 100 parts of vehicle excluding
For comparison, the antifouling paint was mixed at a ratio of 1.5% and a vehicle of 10.0% for the above-mentioned patina-like powder substance) was mixed with gold-plated copper powder.
Antifouling paint E added to the same polyisobutylene-blended alkyd resin paint as above at a ratio of 25 parts per 0 parts and commercially available organic tin and cuprous oxide-blended bottom paint F (same as antifouling paint C of Reference Example 2). A 30cm x 50I:rn cut piece of a polyester fishing net for culturing yellowtail was dipped in each of these paints, pulled up and dried, then lowered into the sea from a pier on the Goi coast and held for 12 months. The antifouling effect was observed. The results are shown in Table 3.

Claims (1)

[Claims] Adding and mixing an aqueous solution or dispersion file of an isoformic ammonium salt of an organic acid to copper powder at room temperature, adding ammonium carbonate or ammonium bicarbonate powder to the resulting wet powder mixture, and stirring and mixing in the presence of air. A method for producing a verdigris-like substance characterized by: