KR100411724B1 - Water soluble black coloring agent, the method of manufacturing the same, and volts and nuts coated with the same - Google Patents

Abstract

The present invention relates to a method for preparing a water-soluble black colorant which is environmentally friendly and improves productivity and economy, and a water-soluble black colorant prepared thereby, and a bolt and nut coated with such a colorant and coated with rust-preventive oil. And the first process of preparing an aqueous colorant solution mixed with a carbon black pigment powder and a liquid surfactant, and the surfactants I (nonionic activator) and Ⅱ (anionic activator) of soap components in the mixed aqueous colorant solution. And a third step of adding a second step of making a solution in which the pigment is well dispersed, and a third step of adding and diluting the antifoaming agent and water to the dispersed solution, and mixing and stirring the same. A water-soluble black colorant prepared by the present invention, and a bolt and nut coated with such a water-soluble black colorant and coated with rust-preventive oil .

Description

Water soluble black coloring agent, the method of manufacturing the same, and volts and nuts coated with the same}

The present invention is a water-soluble black colorant coated on the metal surface after heat treatment, environmentally friendly, pollution-free, productivity and economical efficiency, excellent corrosion resistance, long-term storage during application and easy removal of the coating film and its manufacture The present invention relates to a method of preparing a water-based colorant solution mixed with water, carbon black pigment powder, and a liquid surfactant, and a soap-based surfactant I in the mixed aqueous colorant solution. A second step of adding a nonionic activator) and II (anionic activator) to form a solution in which the pigment is well dispersed, and a third step of adding and diluting the antifoaming agent and water to the dispersed solution, and mixing and stirring the same. A method for producing a water-soluble black colorant and a water-soluble black colorant prepared by the method and the water-soluble black colorant are coated and Relates to applied bolts and nuts.

In recent years, the term coating has been used in a wide range of thicknesses ranging from 1 to 2 mm lining to thin coatings of 100 μm or less, and in the Gumi region, the term coating is used. In addition, metals are used in the same meaning as metal finishing, and coating, plasma spraying, plating, and hardfacing are all surface coatings. In terms of engineering, coating materials, coating materials, coating technology and coating properties are important. Accordingly, the coating of metals is classified based on the components to be coated. First, the method using chemical change, second, the case of attaching the same metal or the other metal, the third case of adhering the mixture, and the fourth, each combination It can be divided into four categories such as coating. As such, there are many types of coating methods for coating metals and various coating techniques, and the most important thing in coatings is the use of coating materials, printing inks, adhesives, etc., which are widely used as coating materials. A lot of research and development is being done. That is, it aims to give various functions by using the interaction of the multi-component system based on the bulk property of the coating material. To this end, it is necessary to have various physical properties as a coating material. Recently, the use of various physical properties of such coating materials has been extended to thin film coating of medicine, electronics industry, cassette tape, and VTR tape as well as industrial fields.

On the other hand, among the various methods of coating, an environmentally friendly and low pollution problem water-based coating is usually made by the transition from the liquid (Sol) to the solid (Gel) state, so that the coating film is formed and the performance required along with the formation process of the coating film. Methods and techniques for the composition of various components are required in order to function. However, these techniques are also subject to trial and error. As a result, the role of the coating film is to use the functions of the coated material together with protection from the environment such as corrosion, deterioration and corrosive contaminants. The invention of the environmentally friendly, productive and economical coating material is important.

Most of the colorants of quenched and tempered metals, which are widely used in Korea and abroad, have to go through a separate rust prevention process for corrosion resistance and long-term storage, or use only soft water or tap water. A treatment process is added in which the coating must be removed separately. An example of such a colorant is Blacker 9696, a water-soluble black salt resin coating agent recently developed in Japan. This material is manufactured by adding solid ultra-fine carbon based on a special binder, and using the tempering heat of 300-500 ° C possessed in heat treatment of metal parts such as bolts. It is in close contact with the surface of the to form a black salt resin film. Although this coating film has a property of rapidly drying, it has been reported to be a uniform and glossy hard film by applying antirust oil thereafter, but there are many difficulties such as managing the black salt solution and maintaining the coating temperature, and also post-treatment such as plating. Although the coating material is called water-soluble when it is required, it is difficult to remove it because it is a resin coating, which is very disadvantageous in terms of environmental protection, productivity and economy.

Therefore, an object of the present invention is to produce such a water-soluble black colorant which is environmentally friendly and improves productivity and economical efficiency.

More specifically, the object of the present invention is to invent a water-soluble colorant. First, when the post-treatment such as plating is required, the coating material of the conventionally developed colorants is water-soluble, but it is removed because it is a resin film attached with a binder. It is difficult to provide a water-soluble colorant that can be easily removed, and secondly, environmentally friendly colorants for preventing and blocking living sewage due to colorants removed during the removal of conventional colorants and protecting and preserving sewage. Third, to provide a colorant maximized economical by reducing the production cost by replacing the tap water and soft water limited water with hard water, and fourth, develop a quenched and tempered metal body It is directly deposited and dried on the prepared black colorant solution to form a coating film. It is to provide a colorant which is excellent in corrosion resistance and can be stored for a long time during application. Fifth, since the removal of the coating film is easy to provide a colorant that can reduce the process of removing the film during the metal surface plating treatment.

Other objects and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

1 is a front view showing the shape and size of the bolt material for coating with a water-soluble black colorant of the present invention.

Figure 2 is a graph showing the particle size analysis results for the pigment particles of the aqueous colorant solution of the present invention.

Figure 3 is a perspective view showing the cross-sectional structure and coating film form of 51B20 bolt material coated with the aqueous colorant solution of the present invention.

Figure 4. A representative graph of qualitative analysis of the coating film of the bolt material with FT-IR infrared spectroscopy.

Figure 5 is a comparison showing the salt spray test results for the bolt material of the present invention and the bolt of the comparative example.

Hereinafter, a method for preparing a water-soluble black colorant which is environmentally friendly and improves productivity and economy according to the present invention, and a bolt and nut coated with the water-soluble black colorant and the colorant prepared by the method will be described in detail.

The water-soluble colorant according to the present invention comprises the first step of making an aqueous colorant solution mixed with water, carbon black pigment powder and a liquid surfactant, and the surfactant I (non-soap) in the mixed aqueous colorant solution. And a third step of adding a ionic activator) and II (anionic activator) to form a solution in which the pigment is well dispersed, and a third step of adding and diluting and mixing and stirring the antifoaming agent and water to the dispersed solution. It is manufactured by the method for producing a water-soluble black colorant.

The above process will be described in more detail below.

The first step is a step of mixing water, carbon black, and a liquid surfactant. Ethylene glycol is a solvent similar to a vehicle solution, which normally gives dispersion and dielectric properties of the pigment and fixes the pigment to the printing surface when ink is manufactured. In particular, glycols are dihydric alcohols, which are well mixed with water, so that the carbon black pigment used in the present invention dissolves poorly solubility in water, thereby facilitating mixing, and is a stable liquid with low reactivity even at room temperature and atmospheric pressure. Somewhat dissolve | dissolves in solvents, such as acetone and acetone, is also revealed and the dispersion | distribution of the pigment in the 2nd process following that is performed well.

The second process is polyoxyalkylene alkylphenylether, RC ₁₄ H ₁₂ O (CH ₂ CH ₂ O), which is a nonionic surfactant I that facilitates the penetration of the mixed colorant as well as the emulsifying and dispersing agent. _n H] and RCOONa, a surfactant II that is an anionic activator, are mixed with a water-soluble oil and fat having a carbon number of _{10 to 18} carbon atoms. The anionic activator has a polar portion of -COONa, which ionizes in water, and most of its molecules become anions, which can emulsify the pigment particles mixed with the aqueous colorant well in water. Can serve as an auxiliary for nonionic surfactants. This hydrocarbon group R portion is a lipophilic (hydrophobic) group, and the -COONa portion is a hydrophilic polar group. That is, when mixed with water, the hydrophilic portion is arranged toward the water side and the lipophilic portion is arranged toward the air side, so that the surface tension of the water during the addition may be reduced. Therefore, since the surfactant II has an appropriate hydrophobic part together with the hydrophilic part, the surfactant is smoothed and the mixing of the colorant is smoothed.

The third step is a process in which the antifoaming agent, which is an emulsion concentrate of the Siloxane system, and water are added to the well-dispersed solution of the pigment, and then mixed and stirred for 3 hours or more. Anti-foam agent or Frothkiller is needed to suppress the foam. Its liquid penetrates into the liquid with foam and the liquid membrane of the foam is thinned, so that the invading part is thinned and the foam is destroyed. It suppresses the molecules of and forms an adsorption membrane, which damages the foam and destroys the foam in the liquid containing the foam. Therefore, a substance having low volatility, which does not dissolve in each other and which is easy to expand to the liquid level should be added to the liquid containing the sachet. For this purpose, the foam generated to mix and stir various chemicals in the preparation of the black colorant solution is removed, and it is a non-ionic antifoaming agent and also serves to reduce the surface tension. Polydimethyl siloxane emulsions belonging to the emulsion were mixed. The viscosity of the antifoamer was moderate and the density was 1.0 g * cm at 25 degreeC. The water used in the preparation of the antifoam solution was 50% or more, polydimethylsiloxane was 50% or less, and the additive was 10% or less.

Water (H ₂ O) for preparing a water-soluble black colorant solution was used as it is, hard water collected from the basement, and water is added according to the mixing amount of the aqueous colorant and surfactants I and II in order to maintain proper concentration and dilution.

The pH value of the black colorant solution prepared through the first, second, and third processes was about 6.6, surface tension at room temperature was about 36 dyne / cm, and contact angle was about 44 °, and the viscosity was about 1.5 poise (at room temperature). dyne sec / cm 2).

The average height roughness (Ra) and the maximum height (R _max ) of the surface roughness after coating with the colorant according to the present invention were 2.5 μm and 16.2 μm, respectively, indicating that the coated surface had a thin film thickness and excellent surface smoothness. .

The colorant according to the present invention can be used for various applications, and is particularly used for coating bolts and nuts. FIG. 1 is a front view showing a representative shape and size of an AISI 51B20 bolt material as an example of a bolt material for coating with a water-soluble black colorant of the present invention. to be. In addition to these bolts, the coating of the colorant of the present invention may be applied to various bolts and nuts.

Hereinafter, the configuration and working effects of the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples are only intended to specifically illustrate the present invention, it is obvious to those skilled in the art that the scope of the present invention is not limited. Therefore, simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

(Example)

Table 1 below shows the mixing order and the mixing amount table of the water-soluble black coloring agent according to an embodiment of the present invention. In the first step, 20 l of water, 5 kg of carbon black (carbon black), which is a synthetic pigment powder, and 5 kg of ethylene glycol (Ethyleneglycol, HOCH ₂ OH), which is a liquid surfactant, are mixed. Next, in the second step, 20 kg of polyoxyalkylene alkylphenylether (RC ₁₄ H ₁₂ O (CH ₂ CH ₂ O) _n H] which is a nonionic surfactant I and RCOONa which is a surfactant II carbon atoms are mixed with C ₁₀ ~C ₁₈ range in aqueous retentate 20㎏. Thereafter, 0.3 kg of an antifoaming agent, an emulsion concentrate of a Siloxane system, and 30 l of water are added and diluted in a third step, and the mixture is stirred and stirred for 3 hours or more. This is shown in Table 1 below.

Mixed order Mixture Amount One water 20ℓ 2 Water-based coloring agent (carbon black, ethylene glycol 5kg each) 10 kg 3 Surfactant I 20 kg 4 Surfactant II 20 kg 5 Antifoam 0.3kg 6 water 30ℓ

Experimental Example 1 Improvement of Coating Film

Figure 2 is a graph showing the particle size analysis results for the pigment particles of the aqueous colorant solution of the present invention. 2 shows the particle size analysis results of the pigment particles dispersed in the aqueous colorant solution, which is the most important element in the black colorant. It is a result measured by a laser particle size analyzer, the average particle size of 180nm shows a fine and uniform particle size distribution.

Figure 3 is a cross-sectional structure and coating film form of the 51B20 bolt material coated with a water-soluble black colorant of the present invention in a magnified image taken by a scanning electron microscope. In FIG. 3, the thickness of the entire coating film is about 6 µm, but the lower coating layer firmly fixed to the base is about 2 µm, and the upper coating layer of about 4 µm is bounded by the lower coating layer. It is highly likely to be disbonded during various treatments after coating with a colorant. In addition, the colorant coating film of the present invention serves as a thin iron oxide film having a boundary between the firmly adhered lower layer layer of about 2 μm and the base material, which is not a metallurgical bond, and has a weaker adhesion than a general coating or plating layer. It is estimated. Therefore, it is considered that the coating layer which has adhesion and can provide corrosion resistance to the base material is a lower coating layer firmly fixed to the surface of the bolt material having a thickness of about 2 μm.

Figure 4 is a representative graph of qualitative analysis of the coating film of the bolt material by FT-IR infrared spectroscopy. This method uses the interaction of the coating material with infrared radiation to study the molecular structure. From the analysis results, the absorption peak of the surfactant used to disperse the pigment particles in the colorant solution is 1200-1000 cm ^-1 . It can be seen that many appear mainly in the area. In addition, the effect of the C = O group in the vicinity of 1700 cm ^-1 indicates that the colorant has a certain degree of polar group, which effectively binds to the surface of the bolt material and removes the film for post-treatment such as plating after coating. In addition, it can be seen that it also has a factor that can be easily removed. In addition, these results were found to be almost similar in various coating films according to the concentration of the colorant solution or the liquid temperature. Thus, even when the water-soluble black colorant of the present invention is working at a high temperature of the metal material compared to the existing product is produced in part peeled off or coated with a hard coating, there is no peeling phenomenon of the film by a conveyor or the like during drying. In addition, the coating film is water-soluble, like N's product in Korea, so it is easy to pickling during plating process. The water-soluble black colorant of the present invention is effective in coloring extremely small precision mechanical parts because the coating film on the metal surface is thinly coated, and the coating film is also good.

Experimental Example 2 Corrosion Resistance Improvement

The method of forming a high resistance film on the metal surface of the present invention to reduce the corrosion current is described by applying to the coating film of the present invention. Since the coating film becomes a resistor for ion permeation, the resistance of the film is increased, thereby preventing the movement of ions and reducing the corrosion current. In other words, the metal base is formed as a barrier against corrosion and the ion diffusion of the film by the pigment and surfactant components contained in the colorant. Therefore, the coating coated on the metal body prevents the transport or movement of the electric charges necessary for the electrochemical corrosion reaction, thereby increasing the corrosion resistance than without the coating.

FIG. 5 is a comparative view showing the results of a test of saline spraying with a normal 5% saline solution, which is a common method for estimating the corrosion resistance of a coating coated on a metal body. FIG. According to the salt spray test of KSD 9502, the salt solution concentration is 5 ± 0.1%, pH 6.5∼7.2, spray chamber temperature 35 ± 1 ℃, and the spray pressure of salt solution is 1.0 ± 0.1kgf /. Bolting material (A) and coated bolting material (B) after the heat treatment to a constant cm, and bolting material (C) coated only with rustproof oil after heat treatment and bolting material coated with rustproof oil after coating As a result of performing a test for a predetermined time (45 hours after 24 hours salt spray) for (D), the degree of rust resistance was compared, as shown in FIG. It was found that the time when blue was detected was short as 1 hour, but the coated B showed a large difference in corrosion resistance at 8 hours. However, as in the case of D, the application of the rust-preventive oil was confirmed that no rust was observed even when exposed to the salt spray for 24 hours and exposed to the atmosphere for 45 hours, but in the case of C, a very small amount of application was recognized only in the screw part.

Particularly, in the case of A and B of FIG. 5, a significant difference is shown in the degree of rusting when the salt is sprayed for 24 hours and exposed for 45 hours. In the case of A, extreme frontal corrosion occurs and in B, the degree is much smaller. Able to know. Of course, when applying rust preventive oil, as in the case of C or D, the difference in the test time is not clear.However, in the case of a long time test, the application of rust preventive oil after coating is far superior to the case where only rust preventive oil is applied without coating. It is assumed. Therefore, it is excellent in corrosion resistance even without the application of rust preventive oil and can be stored for a long time during application, thereby maximizing the productivity and economic effect.

The method for preparing a water-soluble black colorant of the present invention can produce a colorant with uniform particles and a good coating on a metal surface, and can also use hard water, thereby reducing costs, and the water-soluble black colorant according to the present invention is water-soluble. It is easy to remove and does not cause any waste disposal problems, thus preventing environmental pollution. In addition, the bolt and nut coated with the water-soluble black colorant according to the present invention is excellent in corrosion resistance even without the application of rust-proof oil and can be stored for a long time when the coating, the strength of the coating does not peel off during the post-treatment.

Claims (9)

In the method for producing a water-soluble black colorant, A first step of making an aqueous colorant solution mixed with water, a carbon black pigment powder, and a liquid surfactant; A second step of adding a soap-based surfactant I (nonionic activator) and II (anionic activator) to the mixed aqueous colorant solution to form a well-dispersed solution, And a third step of diluting by adding an antifoaming agent and water to the dispersed solution and mixing and stirring the same. Method for producing a water-soluble black colorant. The method for producing a water-soluble black colorant according to claim 1, wherein 5 kg of carbon black pigment powder, 5 kg of surfactant, and 20 L of water are mixed in the first step. The method for producing a water-soluble black colorant according to claim 2, wherein the liquid surfactant is ethylene glycol. The method for producing a water-soluble black colorant according to claim 1, wherein the nonionic surfactant I and the anionic surfactant II of the soap component of the second step are each added 20 kg. The nonionic surfactant I of the soap component of the second step is polyoxyalkylenes alkylphenylether, and the anionic surfactant II has 10 to 18 carbon atoms of the hydrocarbon group R. It is RCOONa which is between dogs, The manufacturing method of the water-soluble black coloring agent. The method for producing a water-soluble black colorant according to claim 1, wherein the third step is diluted by adding 30 L of water to 0.3 kg of the antifoaming agent and mixing the mixture for at least 3 hours. 7. The method of claim 6, wherein said antifoaming agent is a polydimethylsiloxane emulsion made of at least 50% water, at most 50% polydimethylsiloxane and at most 10% additives. Water-soluble black colorant prepared by the method of any one of claims 1 to 7. A bolt and nut coated with a water-soluble black colorant prepared by the method of any one of claims 1 to 7, and coated with rust preventive oil.