KR101254723B1 - Environmental-friendly antifouling paint composition comprising zinc undecylenate - Google Patents

Abstract

The present invention relates to an environmentally friendly antifouling agent and an antifouling coating composition, and more particularly, to an antifouling agent comprising zinc undecylenate as an antifouling agent and an antifouling coating composition using the same, and an antifouling agent and an antifouling coating composition according to the present invention. Since it does not use any marine pollutants such as organotin and nitrous oxide, it does not harm the marine environment and human body at all, and shows excellent antifouling effect on marine attached organisms and can be used for fishing nets, ships and marine structures.

Description

Environmentally friendly antifouling paint composition comprising zinc undecylenate}

The present invention relates to an antifouling agent and an antifouling coating composition, and more particularly, to a novel environmentally friendly antifouling agent including zinc undecylenate and an antifouling coating composition using the same.

Many sea creatures inhabit the sea such as reefs, shellfishes, moss, diatoms, oysters, pearls, sponges, seashells, beatings, shellfish, and sea urchins. Parasitic attachment to nets can cause damage to deposits. In particular, when marine life is attached to the bottom of the ship, the hull surface is roughened and needs to be repaired frequently. When the hull surface is roughened by 0.01 mm, the fuel consumption increases by 0.3 to 1.0%, resulting in increased fuel economy. Especially in the case of large ships, fuel costs account for about 50% of the ship's operating costs, so the attached organisms on the bottom of the ship are very serious problems.

In order to prevent contamination of the dry matter by the marine organisms, an antifouling coating composition in which rosin, a plasticizer and an antifouling agent is mixed with a vinyl chloride resin or a vinyl resin is conventionally used, but this type of antifouling coating composition is used as an antifouling agent. , Mercury, organotin compounds and the like have a problem of contaminating the marine environment.

In addition, zinc acrylate resin which can be hydrolyzed by sea water is gradually hydrolyzed at the contact point of the zinc, and the carboxyl groups at the leaving site form a salt, so that the polymer is solvated or swelled and released from the surface. The new surface layer protrudes and is currently the most used resin. However, by using a high concentration of toxic copper oxide and other organic compounds as an antifouling agent in order to improve the antifouling effect, there is a problem of marine accumulation of heavy metals and toxicity to non-specific marine life. Therefore, there is an urgent need for the development of new antifouling agents and antifouling paint compositions having excellent antifouling performance in terms of marine life and marine environmental protection.

Accordingly, the present inventors have studied to solve the above problems, and as a result, have found that the antifouling effect of zinc undecylenate is excellent, thereby completing the present invention by developing an antifouling agent including the same. Accordingly, it is an object of the present invention to provide a novel environmentally friendly antifouling agent exhibiting excellent antifouling effect against various marine attachment organisms without any harm to the marine environment and human body.

In addition, another object of the present invention is to provide an antifouling coating composition which does not contain marine pollutants such as organotin, nitrous oxide compound, etc., as an antifouling coating for marine use in fishing nets, ships, marine structures, and the like.

The present invention relates to an environmentally friendly antifouling agent comprising zinc undecylenate represented by the following Chemical Formula 1 as an active ingredient.

[Formula 1]

In addition, the present invention relates to an antifouling coating composition comprising a resin, a solvent, a pigment, and an antifouling agent, wherein the antifouling agent is zinc undecylenate.

The antifouling agent and the antifouling coating composition according to the present invention do not use any marine pollutants such as organic tin, nitrous oxide, and toxic organic antifouling agents, which are conventionally used, and are naturally friendly and can exhibit excellent antifouling power.

That is, there is no harm to the marine environment and the human body, and due to the characteristics that show excellent antifouling effect on marine attached organisms, it can be utilized as an excellent antifouling paint on fishing nets, ships, and marine structures.

The present invention is characterized by an environmentally friendly antifouling agent comprising zinc undecylenate as an active ingredient. In addition, the present invention is an antifouling coating composition composed of a resin, a solvent, a pigment, and an antifouling agent, wherein the antifouling agent is another feature of an antifouling coating composition, characterized in that zinc undecylenate.

Hereinafter, the present invention will be described in more detail.

The present invention is characterized by an environmentally friendly antifouling agent comprising zinc undecylenate as an active ingredient.

Zinc undecylenate antifouling agent of the formula (1) according to the present invention is a very stable material at room temperature, and has a property of dissolving only a very small amount in a non-polar solvent. It also exhibits chemical and physically stable characteristics when used with hydrolyzable resins such as zinc acrylate resins.

[Formula 1]

The zinc undecylenate forms a complex salt with an enzyme containing zinc by photolysis of seawater or ionization by seawater, thereby inhibiting the activity of the enzyme and thereby inhibiting the growth of marine adherents. . Undecylenate also acts to prevent adhesion by accessing the cell membranes of bacteria and marine organisms, causing membrane structure disturbance and destruction. That is, it exhibits strong antibacterial effects on marine bacteria, which are attached organisms, and does not harm animal marine life and the human body. Therefore, when zinc undecylenate is used as an antifouling agent, it may be environmentally friendly and may exhibit excellent antifouling efficacy.

In addition, the present invention is an antifouling coating composition composed of a resin, a solvent, a pigment, and an antifouling agent, wherein the antifouling agent is another feature of an antifouling coating composition, characterized in that zinc undecylenate. When zinc undecylenate, an antifouling agent according to the present invention, is used in the form of an antifouling coating composition together with a resin, it is possible to effectively block the attachment step of marine adherent organisms, thereby realizing excellent antifouling efficacy.

Zinc undecylenate of the present invention has a feature that can block the marine attachment organism from the early stage by showing a strong antifouling effect as described above. In the antifouling paint composition, the zinc undecylenate is preferably included in the range of 5 to 10% by weight, and when used at less than 5% by weight, has a disadvantage in that antifouling efficacy is reduced, and used in excess of 10% by weight. In this case, the coating state becomes unstable, and there is a problem in that the production cost is increased and economic efficiency is lowered.

As the resin used in the antifouling coating composition according to the present invention, any resin used in a conventional antifouling coating composition may be used without limitation. Examples of the resin that can be used in the antifouling paint of the present invention include vinyl resins such as vinyl acetate resin and vinyl chloride resin, urethane resins, chlorinated rubber resins, phthalic acid resins, alkyd resins, epoxy resins, phenolic resins, melanin resins, and acrylic resins. , Natural resins such as fluororesins, silicone resins, metal acrylate resins, or rosin, may be used alone or in combination of two or more kinds thereof.In addition to such synthetic or natural resins, various water-soluble resins or fat-soluble resins may be used in combination. It may be. More preferably, zinc acrylate resin is used among the metal acrylate resins.

In the case of the zinc acrylate resin, it is hydrolyzed in seawater to collapse the coating film and form a new type of coating film. However, due to the hydrolysis rate and instability of various marine environments, the antifouling action is not smooth. Therefore, in order to compensate for this, high concentrations of copper oxide and organic antifouling agents were used together as antifouling agents, but they were affected by non-target organisms. There was a problem that eventually adversely affects human and marine ecosystems. However, when using the zinc undecylenate almost no toxicity according to the present invention as an antifouling agent can solve the existing pollution problem, as well as exhibit an excellent antifouling effect by blocking the intermediate step of the attachment mechanism.

The amount of the resin is preferably used in 10 to 20% by weight in the whole antifouling paint composition, if the amount is less than 10% by weight there is a problem that the adhesion and durability of the antifouling paint is lowered, exceeding 20% by weight If used, problems with storage are encountered.

As the solvent used in the antifouling coating composition of the present invention, various solvents known in the art can be used without limitation, and for example, hydrocarbon-based and ketone-based solvents such as xylene, methyl ethyl ketone, methyl isobutyl ketone, etc. may be used alone. Or it can mix and use 2 or more types. The amount of the solvent is preferably used in an amount of 30 to 40% by weight based on the total antifouling paint composition. If the amount of the solvent is less than 30% by weight, a problem arises in that the viscosity becomes excessively high. There is a fear that the adhesion and antifouling property to

As the pigment used in the antifouling coating composition of the present invention, various pigments known in the art can be used without limitation, and for example, non-toxic azo pigments as well as inorganic pigments of light metals such as iron oxide, titanium oxide, zinc oxide, and talc. Etc. can be used in various ways, and these can be used individually or in mixture. The pigment is preferably used 40 to 50% by weight based on the total composition of the paint, if the amount of the pigment is less than 40% by weight, there is a problem of discoloration of the paint, if it exceeds 50% by weight is a problem that the durability is lowered have.

In addition, the antifouling coating composition according to the present invention can be used including various known additives. As the additive, an additive such as polyamide wax, bentonite, clay, polyethylene wax, or the like may be added and used for the purpose of preventing sedimentation of paint and improving durability. The additive is preferably used in 0.001% to 7% by weight of the total composition. When using more than 7% by weight, there is a problem in that paint drying difficulty, rapid rise in viscosity and durability are lowered.

The antifouling coating composition of the present invention can be produced through a conventional paint production method. For example, after dissolving the resin in a solvent, the pigment and antifouling agent is added, dispersed and pulverized in a sand mill (ball mill) or a ball mill (ball mill), etc., and then by adding an additive and stirring in a paint-only stirrer Paint can be completed.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

< Experimental Example  1> On antifouling agent  According Antibacterial  Efficacy experiment

Zinc pyrithione, copper pyrithione, copper pyrithione, Zineb and Ziram and Bonn are the most used organic antifouling agents in the existing antifouling paint industry to verify the antifouling efficacy of antifouling agents. Zinc undecylenate, an antifouling agent represented by Chemical Formula 1, was used, and 1 mg (10 ppm) to 0.001 mg (0.01 ppm) of an antifouling agent was dissolved in 100 ml of methanol, respectively. After application, antibacterial experiments were performed using the most active bacteria ( Streptomyces sp.) In the marine environment, and the results are shown in Table 1 below.

Antibacterial  Efficacy test results ( Streptomyces SP ) Antifouling substances 10ppm 1 ppm 0.1 ppm 0.01 ppm Zinc Undecylenate
(Zinc undecylenate) 2.0cm 2.1 cm 1.5 cm 1.4 cm Zinc pyrithione
(Zinc pyrithione) 1.6 cm 1.0 cm 0.6 cm 0.3cm Capperityon
(Copper pyrithione) 1.8 cm 1.2 cm 0.3cm 0.2cm Genev
(Zineb) 1.3 cm 0.5cm 0.4cm 0.4cm Ground
(Ziram) 1.1 cm 0.7 cm 0.5cm 0.5cm Control group 0 0 0 0

As can be seen in Table 1, at 10 ppm, zinc undecylenate showed the best antibacterial activity of 2 cm and the lowest antibacterial activity of the ground as 1.1 cm. In addition, zinc undecylenate showed 1.4 cm at 0.01 ppm, which was much better than other antifouling agents. As a result, the use of zinc undecylenate showed the strongest antibacterial effect, and when used as antifouling agent, it is expected to be able to block marine attachment organisms from the early stage.

< Experimental Example  2> On antifouling agent  Oyster Larval Survival Test

Zinc pyrithione, copper pyrithione, zinc pyrithione, Zineb, Ziram, organic antifouling agents most used in the existing antifouling paint industry to verify the antifouling efficacy of the antifouling agent of the present invention. ) And an antifouling agent represented by Formula 1 of the present invention, zinc undecylenate, was added to oyster larvae at different concentrations and subjected to a survival test after 24 hours, and the results are shown in Table 2 below.

Oyster Larval Survival Experiment Antifouling substances Zinc Undecylenate
(Zinc undecylenate) density 2.5 ppm 5 ppm 10 ppm 20 ppm Survival rate
Of control 120% 100% 62% 0% Zinc pyrithione
(Zinc pyrithione) density 0.005 ppm 0.001 ppm 0.025 ppm 0.05 ppm Survival rate
Of control 143% 138% 120% 90% Capperityon
(Copper pyrithione) density 0.01 ppm 0.05 ppm 0.1 ppm 0.15 ppm Survival rate
Of control 113% 58.10 0% 0% Genev
(Zineb) density 0.5 ppm 1 ppm 2 ppm 4 ppm Survival rate
Of control 151% 131% 78% 57% Ground
(Ziram) density 0.05 ppm 0.1 ppm 0.25 ppm 0.5 ppm Survival rate
Of control 144% 131% 118% 90%

As can be seen in Table 2, in the case of zinc pyrithione, the survival rate was high at low concentrations such as 0.005 ppm to 0.025 ppm, but the survival rate fell from 0.05 ppm to 100% or less (90%), and 0.05 ppm in the case of capperity ion. The survival rate was only 58.10%, and the survival rate was almost half.In the case of Genev, the survival rate was 131% at 1 ppm, which is a relatively high concentration, but the survival rate dropped sharply to 78% after 2 ppm. In case of Giram, the survival rate also dropped from 0.5 ppm to less than 100%. On the other hand, zinc undecylenate shows 120% survival rate at 2.5 ppm and 100% survival rate at high concentration of 5 ppm, so that even when used at high concentration, the impact on marine environment (marine animal) is minimal. Could know.

As described through the above experimental examples, the zinc undecylenate of the present invention exhibits strong antifouling effect on marine adherent organisms and has a small effect on animal marine organisms, which is environmentally friendly, and can achieve excellent antifouling performance.

< Example  1 to 6 and Comparative example  1 to 5> Antifouling paint  Preparation of the composition

The zinc acrylate resin was completely dissolved in xylene and methyl isobutyl ketone, and then iron oxide, zinc oxide, talc, and zinc undecylenate, an antifouling agent, were added in the following compositions, which were then sand milled. The mixture was dispersed and ground with a high-speed stirrer and stirred at 1,500 rpm for 60 minutes. After the addition of polyamide as an additive to complete the antifouling paint having a composition as shown in Table 3.

Paint composition Content (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Suzy Zinc acrylate 10 13 15 17 10 10 8 10 10 10 10 Antifouling agent Zinc Undecylenate 5 5 5 5 7 9 5 0 2 4 11 Pigment Iron oxide 15 14 13 12 14 14 16 17 16 15 13 Zinc oxide 15 14 13 12 14 14 16 17 16 14 13 Talc 14 13 13 12 14 12 14 15 15 14 12 solvent xylene 25 25 25 25 25 25 25 25 25 25 25 Methyl isobutyl ketone 15 15 15 15 15 15 15 15 15 15 15 additive Polyamide One One One One One One One One One One One sum 100 100 100 100 100 100 100 100 100 100 100

< Experimental Example  3> Antifouling paint  Measurement of durability of the composition

In order to measure the durability of the antifouling coating composition, the weight percent of zinc acrylate resin was measured in Examples 1 (10% by weight), Example 2 (13% by weight), Example 3 (15% by weight), respectively. An antifouling coating composition was prepared by adjusting Example 4 (17 wt%) and Comparative Example 1 (8 wt%).

In order to measure the durability of the antifouling coating composition (spray caterpillar test method), spray coating is applied to one zinc steel sheet having a width × length × thickness of 300 × 300 × 3.2 mm according to ASTM 3170, and then the humidity film is 250 microns. After drying, the prescribed sand was sprayed to measure the strength of the coating film, the weight of the peeled paint was measured to calculate the weight reduction rate, and the results are shown in Table 4 below.

Weight loss of coating division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Weight loss rate 20% 18% 16% 14% 60%

As shown in Table 4, when using the zinc acrylate resin in the antifouling coating composition at 10 to 17% by weight as in the case of Examples 1 to 4, the weight reduction rate of the coating film was low, but the zinc acrylate resin as in Comparative Example 1 When less than 10% by weight (8% by weight) is used, the weight reduction rate is high, resulting in low durability.

< Experimental Example  4> Antifouling paint  Of the composition Antifouling  Effect experiment

In order to confirm the optimum concentration of zinc undecylenate, an antifouling agent in the antifouling coating composition, the concentrations were respectively measured in Examples 1 (5% by weight), Example 5 (7% by weight), Example 6 (9% by weight), and Comparative Examples. 2 (0% by weight), Comparative Example 3 (2% by weight), Comparative Example 4 (4% by weight) and Comparative Example 5 (11% by weight) were adjusted to prepare an antifouling coating composition.

After coating the prepared antifouling coating composition in the same manner as in Experimental Example 3, was immersed in an immersion test site of Mizo-myeon, Sacheon-si, Gyeongnam at 1 m depth to observe the antifouling state 6 months later, the results are shown in Table 5 below. . Marine adhesion area within 50,000 m ² of effective area excluding 20 mm side of coated steel plate was calculated by rounding off within 5% of the same arithmetic mean of three steel plates.

Antifouling effect  Test result division Pollution Area (%) Coating state Seaweed Slime Barnacle Example 1 3 5 none stability Example 5 3 10 none stability Example 6 3 8 none stability Comparative Example 2 20 40 40 stability Comparative Example 3 20 20 60 stability Comparative Example 4 10 40 30 stability Comparative Example 5 3 5 none Instability

In the case of the attachment mechanism, the organic material is first adhered to the vessel in the seawater, and bacteria are formed accordingly, and then, microalgae, macroalgae, banache and shellfish are sequentially attached. As can be seen in Table 5, when preparing the antifouling coating composition using the zinc undecylenate according to the present invention, it can be seen that marine attached organisms such as seaweed, slime and batacles are significantly reduced, and also a stable coating state It can be seen that it can be maintained.

Claims (13)

In the antifouling paint composition consisting of a resin, a solvent, a pigment and an antifouling agent, the resin is a zinc acrylate resin, and the antifouling agent is an environmentally friendly product characterized in that it is zinc undecylenate represented by the following Chemical Formula 1. An antifouling coating composition, wherein the content of the resin is 10 to 20% by weight, the antifouling paint composition is characterized in that 5 to 10% by weight.
[Formula 1]

delete The antifouling coating composition according to claim 1, further comprising an additive.
delete The antifouling coating composition according to claim 1 or 3, wherein the solvent content is 30 to 40% by weight.
The antifouling coating composition according to claim 1 or 3, wherein the pigment content is 40 to 50% by weight.
delete The antifouling coating composition according to claim 3, wherein the content of the additive is 0.001 to 7 wt%.
delete delete The antifouling coating composition according to claim 1 or 3, wherein the solvent is one or a mixture of two or more selected from the group consisting of xylene, methyl ethyl ketone and methyl isobutyl ketone.
The antifouling coating composition according to claim 1 or 3, wherein the pigment is one or a mixture of two or more selected from the group consisting of iron oxide, titanium oxide, zinc oxide and talc.
The antifouling coating composition according to claim 3, wherein the additive is polyamide wax, bentonite, clay or polyethylene wax.