RU2849779C2 - Method for producing anti-fouling self-polishing enamel with low metal ion content - Google Patents

Abstract

FIELD: means of protection against fouling by marine organisms on underwater parts of ships.

SUBSTANCE: anti-fouling self-polishing enamel is obtained in three stages. In the first stage, a pigment paste is prepared by mixing a biocide (copper oxychloride), red iron oxide pigment, talc, zinc oxide, copper zinc acrylate, Traifix 150 and methoxypropanol in a mixer. The resulting mixture is dispersed in a bead mill for 1 hour to a grind size of 70-80 microns. In the second stage, a film-forming base is prepared by mixing copper zinc acrylate, 50% rosin in xylene, chlorinated paraffin and orthoxylene in a mixer for at least 1 hour. In the third stage, combine the resulting pigment paste, film-forming base and Benton 38 thickener, and mix for at least 1 hour.

EFFECT: reduction in copper content and increased anti-fouling properties of the enamel when using more environmentally friendly biocides.

2 tbl, 5 ex

Description

The invention relates to a self-polishing antifouling agent for underwater parts of ships and vessels. The material is more environmentally friendly than similar materials with low metal ion content and is characterized by the use of eco-friendly biocides.

The modern range of antifouling paints and varnishes includes enamels that differ in binder type, effectiveness, service life, and durability. Environmental performance is currently paramount, due to the presence of biocidal additives in antifouling coatings, which are released into the environment and affect the vital functions of marine organisms. Based on their protective mechanism, paints and varnishes currently in use can be divided into contact-type materials, soluble materials, and self-polishing paints and varnishes.

The protective mechanism of traditional contact enamels is based on biocide leaching, roughly proportional to its content in the paint film. Increasing the biocide content in the film increases the coating's effectiveness, but also increases the rate of biocide consumption. Therefore, service life extension is not linearly related to the amount of biocide. Furthermore, a gradual increase in the thickness of the leached layer leads to a decrease in the rate of biocide leaching from the remaining coating mass. At a leached layer thickness of approximately 50-70 µm, the leaching rate decreases to a level at which fouling becomes possible. Thus, the biocide remaining in the film no longer provides protection against fouling. Therefore, it is clear that simply increasing the thickness of a traditional coating does not increase its service life.

Traditional antifouling paints and varnishes are currently produced primarily on vinyl and chlorinated rubber bases. They use cuprous oxide as a biocide. The service life of such coatings does not exceed 2-2.5 years. These enamels are recommended for vessels operating in northern and temperate latitudes. Solvent-based antifouling paints are typically rosin-based and use copper compounds as biocides.

A known method for producing an antifouling paint (enamel) includes a film-forming base, a copper-containing biocide, a solvent, wherein the film-forming base contains perchlorovinyl resin mixed with rosin and (or) pentaphthalic varnish, the biocide is a spent copper-chromium-barium catalyst for the hydrogenation of synthetic fatty acids into higher fatty alcohols, and the solvent is a mixture of solvent naphtha and butyl acetate in a ratio of 1: 4 with the following ratio of components, wt. %: film-forming base - 14.4-21.7; spent copper-chromium-barium catalyst - 6.0-39.0; solvent - the rest. Antifouling paint HV-5295 is prepared in the usual way in a ball mill. First, the spent copper-chromium-barium catalyst (CBC) is melted with rosin at 160-185°C for 2 hours. The resulting alloy is broken into pieces and loaded into a ball mill. Additives and a portion of the solvent are added. The mixture is ground for 16-25 hours, after which the PSKh-LS resin is added with the remaining solvent. The solution is mixed in a ball mill until homogeneous to obtain a paint of the appropriate dispersion (RU 2115680, 20.07.1998).

However, enamel has an insufficient coating service life, a high rate of copper oxide leaching and high consumption, as well as low coating elasticity.

The closest to the proposed method is the method for obtaining antifouling enamel, characterized by the fact that first benzenesulfonic acid, cyclohexanone, a mixture of salicylic acid and salicylic acid anilide and acetone in a ratio of respectively between themselves by weight. %: 0.9-0.3: 3.2-2.6: 2.1-1.5: 10.6-9.0 are mixed at a temperature of 18-22 ° C for at least 1 hour, then a copper-containing biocide, cuprous oxide, is added and the mixture is impregnated for 25-40 minutes, the resulting mass is treated with a 50-60% solution of rosin in solvent at a temperature of 18-25 ° C, and then combined with the remaining rosin, an epoxy ester varnish film former, a vinyl chloride-vinyl acetate copolymer, epoxy diane resin, a plasticizer, dibutyl phthalate, and a pigment, zinc oxide, after which the mixture is dispersed to a grinding degree of 50-70 μm with the following ratio of components, wt. %: rosin - 11.9-13.0; vinyl chloride-vinyl acetate copolymer - 2.4-3.7; epoxy diane resin - 0.48-1.9; epoxy ester varnish - 4.0-5.0; biocide - cuprous oxide - 45.0-50.0; dibutyl phthalate - 3.0-4.0; zinc oxide - 1.2-1.7; salicylic acid - 1.6-2.0; salicylic acid anilide - 1.5-2.1; benzenesulfonic acid - 0.3-0.9; organic solvents - the rest (RU 2394864, 20.07.2010). However, this option contains a large amount of cuprous oxide, benzenesulfonic acid, which can have a negative impact on marine flora and fauna.

The technical result of the proposed invention consists in obtaining an antifouling self-polishing enamel with a reduced content of copper ions and the use of more environmentally friendly biocides.

The technical result is achieved in that the production of antifouling self-polishing enamel consists in the fact that at the first stage a pigment paste is prepared by mixing in a mixer a biocide - cuprous oxide, red iron oxide pigment, talc, zinc oxide, Trifix 150 and methoxypropanol at a weight ratio of them, respectively, to each other: 40.0-43.0: 5.0-9.0: 4.0-6.0: 2.0-4.0: 5.0-7.0: 0.9-2.0: 2.0-5.5, then the resulting mixture is dispersed in a bead mill for 1 hour to a grinding index of 70-80 μm, at the second stage a film-forming base is prepared for this in a mixer for at least 1 hour mixing the remaining part of copper zincarylate, 50% gum rosin in xylene, chloroparaffin and orthoxylene in a weight ratio of 8.0-10.0:14.0-18.0:1.0-3.0:3.0-7.0, respectively, at the third stage the obtained pigment paste and film former are combined, thickener Benton 38 is added in a ratio of wt. %: 0.1-0.5 and mixed for at least 1 hour in the following ratio of components, wt. %:

Copper oxide 40.0-43.0 Copper zinc acrylate 13.0-17.0 Talc 4.0-6.0 Red iron oxide pigment 5.0-9.0 Zinc oxide 2.0-4.0 Chloroparaffin 1.0-3.0 Gum rosin 50% in xylene 14.0-18.0 Methoxypropanol 2.0-5.5 Thickener Benton 38 0.1-0.5 Trifix 150 0.9-2.0 Orthoxylene rest

The method is implemented as follows.

Enamel is prepared in three stages.

At the first stage, a pigment paste is prepared: for this purpose, the biocide - cuprous oxide, red iron oxide pigment, talc, zinc oxide, biocide - copper zinc acrylate, dispersant Trifix 15, methoxypropanol are mixed in a mixer in the ratio of wt. %: 40.0-43.0: 5.0-9.0: 4.0-6.0: 2.0-4.0: 5.0-7.0: 0.9-2.0: 2.0: 2.0-5.5. Then, dispersion is carried out in a bead mill for 1 hour until the grinding index is 70-80 μm.

At the second stage, a film-forming agent is prepared: for this purpose, the remaining portion of copper zincarylate, 50% gum rosin in xylene, chloroparaffin, and orthoxylene are mixed in a mixer for at least 1 hour in the following weight ratio: 8.0-10.0:14.0-18.0:1.0-3.0:3.0-7.0.

In the third stage, the resulting pigment paste and film former are combined, and Benton 38 thickener is added in a ratio of 0.1-0.5% by weight, followed by mixing for at least 1 hour. If necessary, orthoxylene is added to achieve the desired viscosity. The resulting enamel is then filtered and packaged.

In this case, the antifouling self-polishing enamel contains the following ratio of components, wt. %:

Copper oxide 40.0-43.0 Copper zinc acrylate 13.0-17.0 Talc 4.0-6.0 Red iron oxide pigment (YUKOP) 5.0-9.0 Zinc oxide 2.0-4.0 Chloroparaffin 1.0-3.0 Gum rosin 50% in xylene 14.0-18.0 Methoxypropanol 2.0-5.5 Thickener Benton 38 0.1-0.5 Trifix 150 0.9-2.0 Orthoxylene rest

The stated antifouling self-polishing enamel is thixotropic, but requires thorough mixing before use. The enamel is applied with a brush, roller, spatula, or specialized equipment. The enamel is applied in two coats with intermediate drying. The primer and anticorrosive coating is designed to create antifouling systems, such as primers: VL-023, EP-0263S, EP-0325, EP-0199, and anticorrosive enamels: EP-46U, HS-436, HV-453.

The specific component contents of the five antifouling enamel compositions are given in Table 1.

Example 1 (for composition No. 1). For 100 kg of enamel, the following are loaded into the mixer at the first stage to prepare the pigment paste: 43 kg of biocide - cuprous oxide, 9 kg of red iron oxide pigment, 4 kg of talc, 2 kg of zinc oxide, 7 kg of biocide - copper zinc acrylate, 0.9 kg of Trifix 150, 2 kg of methoxypropanol and mixed. Then, dispersion is carried out in a bead mill for 1 hour to a grinding value of 70-80 µm. In the second stage, a film-forming agent is prepared: for this, the remaining part of 10 kg of copper zinc acrylate, 18 kg of 50% gum rosin in xylene, 1 kg of chloroparaffin and 3 kg of orthoxylene are loaded into the mixer and mixed for at least 1 hour. In the third stage, the resulting pigment paste and film former are combined, an additional 0.1 kg of Benton 38 thickener is added, and the mixture is mixed again for at least 1 hour. If necessary, orthoxylene is added to achieve the desired viscosity. The resulting enamel is then filtered and packaged. The performance characteristics of this antifouling self-polishing enamel composition are presented in Table 2.

Example 2 (for composition No. 2). For 100 kg of enamel, the following are loaded into the mixer at the first stage to prepare the pigment paste: 42.5 kg of biocide - cuprous oxide, 8 kg of red iron oxide pigment, 4.5 kg of talc, 2.5 kg of zinc oxide, 7 kg of biocide - copper zinc acrylate, 1.3 kg of Trifix 150, 2.5 kg of methoxypropanol and mixed. Then, dispersion is carried out in a bead mill for 1 hour to a grinding value of 70-80 µm. In the second stage, a film-forming agent is prepared: for this, the remaining part of 9 kg of copper zinc acrylate, 17 kg of 50% gum rosin in xylene, 1.5 kg of chlorinated paraffin and 4 kg of orthoxylene are loaded into the mixer and mixed for at least 1 hour. In the third stage, the resulting pigment paste and film former are combined, an additional 0.2 kg of Benton 38 thickener is added, and the mixture is mixed again for at least 1 hour. If necessary, orthoxylene is added to achieve the desired viscosity. The resulting enamel is then filtered and packaged. The performance characteristics of this antifouling self-polishing enamel composition are presented in Table 2.

Example 3 (for composition No. 3). For 100 kg of enamel, the following are loaded into the mixer at the first stage to prepare the pigment paste: 42.2 kg of cuprous oxide biocide, 7 kg of red iron oxide pigment, 5 kg of talc, 3 kg of zinc oxide, 6 kg of copper zinc acrylate biocide, 1.5 kg of Trifix 150, 3 kg of methoxypropanol and mixed. Then, dispersion is carried out in a bead mill for 1 hour to a grinding value of 70-80 µm. In the second stage, a film-forming agent is prepared: for this, the remaining part (9 kg of copper zinc acrylate), 16 kg of 50% gum rosin in xylene, 2 kg of chloroparaffin and 5 kg of orthoxylene are loaded into the mixer and mixed for at least 1 hour. In the third stage, combine the resulting pigment paste and film former, add an additional 0.3 kg of Benton 38 thickener, and mix again for at least 1 hour. If necessary, add orthoxylene to achieve the desired process viscosity.

The resulting enamel is then filtered and packaged. The performance characteristics of this antifouling self-polishing enamel composition are presented in Table 2.

Example 4 (for composition No. 4). For 100 kg of enamel, the following are loaded into the mixer at the first stage to prepare the pigment paste: 41.8 kg of biocide - cuprous oxide, 6 kg of red iron oxide pigment, 5.5 kg of talc, 3.5 kg of zinc oxide, 6 kg of biocide - copper zinc acrylate, 1.8 kg of Trifix 150, 3.5 kg of methoxypropanol and mixed. Then, dispersion is carried out in a bead mill for 1 hour to a grinding value of 70-80 µm. In the second stage, a film-forming agent is prepared: for this, the remaining part of 8 kg of copper zinc acrylate, 15 kg of 50% gum rosin in xylene, 2.5 kg of chlorinated paraffin and 6 kg of orthoxylene are loaded into the mixer and mixed for at least 1 hour. In the third stage, the resulting pigment paste and film former are combined, 0.4 kg of Benton 38 thickener is added, and the mixture is mixed again for at least 1 hour. If necessary, orthoxylene is added to achieve the desired viscosity. The resulting enamel is then filtered and packaged. The performance characteristics of this antifouling self-polishing enamel composition are presented in Table 2.

Example 5 (for composition No. 5). For 100 kg of enamel, the following are loaded into the mixer at the first stage to prepare the pigment paste: 40 kg of cuprous oxide biocide, 5 kg of red iron oxide pigment, 6 kg of talc, 4 kg of zinc oxide, 5 kg of copper zinc acrylate biocide, 2 kg of Trifix 150, 5.5 kg of methoxypropanol and mixed. Then, dispersion is carried out in a bead mill for 1 hour to a grinding value of 70-80 µm. In the second stage, a film-forming agent is prepared: for this, the remaining part (8 kg of copper zinc arylate), 14 kg of 50% gum rosin in xylene, 3 kg of chloroparaffin and 7 kg of orthoxylene are loaded into the mixer and mixed for at least 1 hour. In the third stage, the resulting pigment paste and film former are combined, an additional 0.5 kg of Benton 38 thickener is added, and the mixture is mixed again for at least 1 hour. If necessary, orthoxylene is added to achieve the desired viscosity. The resulting enamel is then filtered and packaged. The performance characteristics of this antifouling self-polishing enamel composition are presented in Table 2.

Table 1. Quantitative characteristics of the five studied compositions of the claimed antifouling self-polishing enamel and the closest analogue according to patent RU 2394864.

Table 2. Technological indicators of the declared antifouling self-polishing enamel and its closest analogue according to patent RU 2394864.

As can be seen from Table 2, the coating based on the proposed antifouling self-polishing enamel (example 2) exceeds the prototype in terms of service life in the tropics and has a greater thickness in the coating system, which has a positive effect on the anti-corrosion properties.

Also, the antifouling self-polishing enamel according to example 2 has a large maximum thickness of a non-flowing wet layer from a vertical surface, which is very important when applying enamel to the surface of a vessel or ship.

The main advantage of this enamel is that it contains less copper oxide than the prototype, while offering better antifouling properties and milder eco-friendly biocides that have a minimal negative impact on the environment.

Claims (2)

A method for producing an antifouling self-polishing enamel, which consists in the fact that at the first stage a pigment paste is prepared by mixing in a mixer a biocide - cuprous oxide, red iron oxide pigment, talc, zinc oxide, copper zinc acrylate, Trifix 150 and methoxypropanol in a mass ratio of respectively: 40.0-43.0: 5.0-9.0: 4.0-6.0: 2.0-4.0: 5.0-7.0: 0.9-2.0: 2.0-5.5, then the resulting mixture is dispersed in a bead mill for 1 hour to a grinding index of 70-80 μm, at the second stage a film-forming base is prepared, for this purpose in a mixer for at least 1 hour mixing the remaining part of copper zinc acrylate, 50% gum rosin in xylene, chlorinated paraffin and orthoxylene in a weight ratio of 8.0-10.0:14.0-18.0:1.0-3.0:3.0-7.0, respectively, at the third stage the obtained pigment paste and film former are combined, thickener Benton 38 is added and mixed for at least 1 hour in the following ratio of components, wt.%: Copper oxide 40.0-43.0 Copper zinc acrylate 13.0-17.0 Talc 4.0-6.0 Red iron oxide pigment 5.0-9.0 Zinc oxide 2.0-4.0 Chloroparaffin 1.0-3.0 Gum rosin 50% in xylene 14.0-18.0 Methoxypropanol 2.0-5.5 Thickener Benton 38 0.1-0.5 Trifix 150 0.9-2.0 Orthoxylene rest