KR20160017805A - Antifouling agent and antifouling paint composition comprising alizarin - Google Patents

Abstract

The present invention relates to an eco-friendly antifoulant and an antifouling paint composition and, more specifically, to an antifoulant containing alizarin which is represented by chemical formula 1 as an active ingredient, and to an antifouling paint composition using the same. According to the present invention, the antifouling paint composition does not contain toxic materials such as organic tin and cuprous oxide which were used in the past. The antifouling paint composition also does not contain marine pollutants such as heavy metals, thereby exhibiting superior antifouling effects against marine adherent-staged organisms while seldom affecting the marine ecosystem and the human body. Thus, the composition can be applied as an antifouling system used in maritime structures, vessels, fishing nets, and seawater pipes.

Description

[0001] The present invention relates to an antifouling agent and an antifouling paint composition comprising alizarin,

The present invention relates to an antifouling agent and an antifouling paint composition, and more particularly, to a new antifouling agent containing alizarin and having a small effect on the marine environment and human body and having an excellent antifouling effect, and an antifouling paint composition using the same .

In the seawater, a large number of marine creatures such as large algae and microalgae, mussels, slime, oysters, sea urchins, sponges, and endocytic organisms are attached to the stones. In addition, man - made artificial marine facilities, ships, Many fish and other living things are attached to fishing nets and marine structures of fish farms. The adherence of these organisms causes various economic and industrial damages to humans.

Among them, when attached to an offshore structure, an increase in the mass of the structure itself and a synergistic effect due to chemical action occur, thereby shortening the lifetime of the structure and inducing the shape change. Therefore, various attempts have been made to prevent the attachment of living organisms for economic reasons due to periodic structural replacement.

In order to prevent corrosion and contamination of underwater structures by marine organisms, an antifouling coating composition comprising rosin or a vinyl chloride resin, a plasticizer and an antifouling agent is conventionally used as the vinyl resin. However, , Copper, organotin, and organotin compounds contaminate the marine environment from toxicity and heavy metal content.

The use of metal acrylate resin capable of hydrolysis by seawater in order to reduce pollution of the marine environment and to construct an efficient anti-fouling system allows the metal to slowly hydrolyze off at the seawater contact site, A system in which a new surface layer is developed due to swelling or water absorption of the polymer as a result of the formation of a salt is used. However, in addition to chemical endeavors for the above-mentioned antifouling effect, it is possible to improve the efficacy by using high concentration of ash antioxidant and other organic compounds, which are highly toxic, together with an antifouling agent, but the side effects on non-target marine organisms and the accumulation of heavy metals There is a problem that it is causing.

A conventional antifouling agent is Korean Patent Publication No. 10-0592438 for an antifouling paint composition containing no copper oxide and organotin. The antifouling paint composition described in the above patent publication is a composition comprising a polymerizable unsaturated monomer obtained by reacting a metal (meth) acrylate, a metal di (meth) acrylate, a compound having an inorganic metal compound and a carboxyl group, and a (meth) 2-n-octyl-4-isothiazolin-3-one and a metal pyrithione compound obtained by copolymerizing an unsaturated monomer in the radical. However, the prior art described in the patent publication can not fundamentally solve the marine pollution problem. This is because the primary purpose is to provide an antifouling paint which can be used at a constant speed regardless of the coating area and maintain excellent antifouling performance for a long period of time.

In WO 2007-74765, a structural unit derived from (A) a structural unit derived from an unsaturated carboxylic acid monomer (a1) and another unsaturated compound monomer (a2) copolymerizable with the unsaturated carboxylic acid monomer (a1) (B) a polyvalent metal compound capable of reacting with a carboxyl group of the carboxyl group-containing copolymer (A), (C) a polyvalent metal compound capable of reacting with a carboxyl group-containing copolymer Based antifouling paint composition has been proposed. This antifouling paint composition has excellent antifouling properties, has excellent uniformity of coating film consumption, excellent long-term antifouling performance of the coating film, or low impact on the human body. There was a problem that it was impossible to secure all of the environment-friendliness.

The surface coating composition containing a fatty acid methacrylate as a binder is described in U.S. Patent No. 5,202,378, but is not related to an environmentally friendly antifouling agent exhibiting excellent antifouling effect.

Therefore, there is a demand for international development of novel antifouling and antifouling coating compositions having excellent antifouling performance in terms of marine environment protection and marine life.

In order to solve the above-mentioned problems, the present inventors made efforts to search for and research materials, and discovered that alizarin contains excellent performance in antifouling effect, and developed antifouling agent containing the antifouling agent.

Accordingly, it is an object of the present invention to provide a novel environmentally friendly antifouling agent exhibiting excellent antifouling effect on various marine adherence organisms and having little influence on the marine environment and the human body.

It is still another object of the present invention to provide an antifouling paint composition which does not contain marine pollutants such as organic tin and a copper oxyhydroxide compound and exhibits an excellent antifouling effect on seawater antifouling paints such as fishing nets, ships and underwater structures.

According to an embodiment of the present invention,

(Alizarin) represented by the following general formula (1) as an active ingredient.

[Chemical Formula 1]

An antifouling paint composition according to another embodiment of the present invention is an antifouling paint composition comprising a resin, a solvent, a pigment and an antifouling agent,

(Alizarin) represented by the following general formula (1) as an active ingredient as the antifouling agent.

[Chemical Formula 1]

The content of the resin, the solvent, the pigment and the antifouling agent is 10 to 30% by weight, 20 to 40% by weight, 20 to 30% by weight and 2 to 8% by weight, respectively.

The resin is preferably selected from the group consisting of urethane resin, urethane resin, chlorinated rubber resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melanin resin, acrylic resin, fluorine resin, silicone resin, metal acrylate resin and rosin And at least one selected.

The solvent is characterized by being at least one selected from xylene, methyl ethyl ketone and methyl isobutyl ketone.

The pigment is characterized in that it is at least one selected from iron oxide, silica, zinc oxide and talc.

Wherein the additive is polyamide wax, bentonite, clay or polyethylene wax, and the content thereof is 0.7 to 8% by weight.

Since the antifouling agent and antifouling paint composition according to the present invention have a relatively low proportion of marine pollutants unlike the conventional organotin, copper halide, copper and toxic organic antifouling agents, Friendly and less impact on the marine environment.

As described above, the antifouling agent and antifouling agent composition of the present invention is characterized in that it has an antifouling effect on environment-friendly but marine-adhered creatures by using a low toxic substance having little influence on the human body and the marine environment as an effective ingredient exhibiting an antifouling effect It can be used as an antifouling paint suitable for fishing nets, ships and offshore structures.

The present invention relates to an antifouling agent containing alizarin represented by the following general formula (1) as an active ingredient. The present invention relates to an antifouling coating composition comprising a resin, a pigment, a solvent and an antifouling agent, And an antifouling paint composition comprising alizarin as an antifouling agent.

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

Alizarin represented by the following formula (1) according to the present invention is an aromatic organic compound and has a property of dissolving in an organic solvent. Therefore, it can be usefully used in the production of paints. In particular, a coating composition suitable for the purpose of the present invention can be constituted when it is used together with a vinyl chloride resin, a vinyl resin, a polyurea resin or the like to exhibit more physical and chemical stability.

[Chemical Formula 1]

The Alizarin ingredient of the formula 1 can be extracted from the roots of Western blossoms, and thus it can be used environmentally friendly since it has little effect on the chemical environment chemically. In addition, it is known that it is possible to use water as an insoluble pigment by solidifying the water-soluble macromolecule pigment by treating the madder plant with alum, thereby helping to form a stable coating film of the paint acting in the seawater. In conclusion, alizarin is an environmentally friendly antifouling agent that can hardly remain in the marine environment and can exhibit excellent antifouling effects on marine algae.

Further, as a suitable application example of the present invention, in the antifouling paint composition comprising a resin, a solvent, a pigment and an antifouling agent, the antifouling agent is further characterized by an antifouling paint composition using alizarin.

Alizarin, which is an antifouling agent according to the present invention, can effectively block the adhering step of an adhered organism when used in the form of an antifouling paint composition together with a resin and the like, thereby exhibiting an excellent antifouling effect.

As the resin used in the antifouling paint composition according to the present invention, any resin used in the basic antifouling paint composition can be used without limitation. Usable examples of the resin that can be contained in the antifouling paint of the present invention include chlorinated rubber resins, phthalic acid resins, alkyd resins or vinyl resins such as vinyl chloride resins and vinyl acetate resins, urethane resins, epoxy resins, phenol resins, melamine resins, A synthetic resin such as an acrylic resin, a fluororesin, a silicone resin, a metal acrylate resin, or a natural resin such as rosin may be used alone or in combination of two or more. In addition to such a synthetic or natural resin, various water- It is possible. In order to more suitably use the object of the present invention, it is preferable to use a urethane resin in the resin.

The zinc acrylate resin is hydrolyzed in the seawater to break down the coating film and form a new type of coating film, which is advantageous in that it can detach adherent organisms. However, since the hydrolysis rate is low and the antifouling effect due to instability of various marine environments is not easy, In order to compensate, high concentrations of ash antioxidant and organic antifouling agent were used together as an antifouling agent. However, these components have the problem of adversely affecting non-target creatures and ultimately damaging human and marine ecosystems. However, when the antifouling agent containing the low-toxicity Alizarin according to the present invention is mixed with the urethane resin, it is possible to reduce the existing contamination problem, to prevent the intermediate step of the attachment mechanism and to provide excellent stability to the marine environment Therefore, it is possible to exhibit a relatively excellent antifouling effect on environmentally friendly basis.

When the amount of the resin used is less than 10% by weight, the adhesion and durability of the antifouling coating are lowered. When the amount of the resin is more than 30% by weight, the storage stability of the antifouling paint composition is lowered. And preferably 10 to 30% by weight.

As the solvent used in the antifouling paint composition of the present invention, various solvents known in this technical field can be used without limitation. For example, hydrocarbon-based and ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and xylene may be used alone or in combination of two or more. The appropriate amount of the solvent may be 20 When the amount of the antifouling coating composition is less than 40 wt.%, The viscosity of the coating composition is lowered. Therefore, the adhesion to the coating film and the antifouling property may be reduced. .

Examples of the pigments used in the antifouling paint composition of the present invention include inorganic pigments such as iron oxide, silica, zinc oxide, and talc, as well as non-toxic azo pigments. Various pigments known in the art can be used without limitation, Or one or more of them may be used in combination. The pigment is preferably used in an amount of 20 to 30% by weight with respect to the total composition of the paint. If the amount of the pigment is less than 20% by weight, there is a problem of discoloration of the paint. If the amount is more than 30% by weight, .

In addition, the antifouling paint composition according to the present invention includes additives such as polyamide wax, bentonite, clay, polyethylene wax, and the like in order to prevent sedimentation of paints and improve durability. Can be added. When the additive is used in an amount of more than 1% by weight, it is difficult to dry the paint, and when the additive is used, it is preferable to use 0.7% by weight to 1% by weight of the whole composition because of a problem of a sharp increase in viscosity and a decrease in durability.

The antifouling paint composition of the present invention can be produced by a conventional method for producing a paint. For example, after a resin is dissolved in a solvent, a pigment and an antifouling agent are added thereto, and the mixture is dispersed and pulverized with a ball mill or a sand mill. Then, an additive is added and stirred in a paint- The paint can be completed.

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

Experimental Example 1: Antibacterial activity (antifouling activity)

In order to verify the antifouling effect of alizarin represented by the above formula (1), zinc pyrithione, copper pyrithione, which is an organic antifouling agent most commonly used as an antifouling paint, and copper pyrithione, After dissolving Alizarin in each ethanol, dry it by concentration on the paper disk as shown in the following table, and then spray the Marine bacteria which acts as primary attachment organisms in the seawater. A paper disk coated on the smoothed LB medium is placed and cultured for 24 hours under 25 conditions. After 24 hours, the restraint that occurred in the periphery of the paper disk placed at each concentration was measured, and the results are shown in Table 1 below.

Results of antibacterial efficacy experiments Antifouling material 10,000ppm 5,000 ppm 1,000ppm 500ppm Formula 1 Alizarin
(Alizarin) 2.8 cm 2cm 1.5cm 1.1cm Zinc pyrithione
(zinc pyrithione) 3.9cm 3.5cm 2.1cm 1.5cm Capper pyrithione
(copper pyrithione) 3.1cm 3cm 2.3cm 1.2cm Control group 0cm 0cm 0cm 0cm

As can be seen from Table 1, the results of the antibacterial experiment using marine bacteria revealed that Alizarin was used in combination with zinc pyrithione and copper pyrithione, which are currently used as commercial antifouling agents, , It is confirmed that it has an effect of blocking bacteria as a primary attachment organism when it is used as an antifouling agent because it has an excellent effect as compared with a control group which is not treated with anything.

≪ Experimental Example 2: Microbial growth inhibition (antifouling effect)

In order to verify the antifouling effect of Alizarin, zinc pyrithione, copper pyrithione, and Alizarin, which are the most commonly used antifouling paints, (1, 2, 4, 8, 16, 32 /) and coated on each well of a well plate. After a certain amount of microalgae is cultured on the coated well plate, the absorbance is measured after 3 days. The results are shown in Table 2 below.

density
(Μl / cm 2) One 2 4 8 16 32 Antifouling agent Formula 1
(Alizarin) 0.044 0.042 0.048 0.041 0.032 0.021 Zinc pyrithione
(zinc pyrithione) 0.056 0.055 0.052 0.049 0.033 0.029 Capper pyrithione
(copper pyrithione) 0.049 0.042 0.059 0.043 0.038 0.024 Control group 0.18

As can be seen from the above Table 2, the microscopic algae absorbance of zinc pyrithione and capper pyrithione was high at all the concentrations of 1 to 32 μl / cm 2, but the alizarin of formula (1) showed a comparatively low absorbance. As a result, it can be confirmed that the compound of formula (1) is superior in antifouling activity to the conventional commercial antifouling agent. In addition, the activity of Alizarin (1) is lowered at a high concentration, so that the higher the concentration of Alizarin, the higher the antifouling activity.

<Experimental Example 3: Inhibition of Parasitosis (Antifouling Effect) Verification Test>

In order to verify the antifouling effect of alizarin, zinc pyrithione, copper pyrithione, and alizarin represented by the above formula (1), which are the most frequently used organic antifouling agents in the conventional antifouling paints industry, ) Was applied on a slide glass at each concentration (5, 50 mg / ml), dried, and incubated with a certain amount of parasitic solution. After 3 days, the rate of confluency was measured and the results are shown in Table 3 below.

density 50 mg / ml 5 mg / ml Antifouling agent Formula 1
(Alizarin) 15% 20% Zinc pyrithione
(zinc pyrithione) 20% 30% Capper pyrithione
(copper pyrithione) 25% 35% Control group 100%

As shown in Table 3, the most commonly used organic antifouling agents, zinc pyrithione and capper pyrithione, have a confluency rate of 20 to 35%, and the compounding ratio of Formula 1 is 15 to 20%. When the zinc pyrithione and cappyrithione were compared with Alizarin (Formula 1), a high rate of hybridization was obtained. In the control group without any treatment, 100% confluency was observed. This shows that the antifouling effect of Alizarin antifungal agent of Formula 1 above is greater than that of conventional antifouling agent.

As shown in Experimental Examples 1 to 3, Alizarin of the present invention exhibited a high activity inhibitory effect on bacteria when compared with conventional commercial antifouling agents, and it was found that the microorganisms, which are vegetable marine organisms, It was confirmed that it exhibits excellent antifouling efficacy against the antifouling agent.

&Lt; Examples 1 to 4 and Comparative Examples 1 to 4: Preparation of antifouling paint composition >

After completely dissolving the urethane resin in xylene and methyl isobutyl ketone, a pigment such as iron oxide, silica, talc, zinc pyrithione, copper pyrithione, (Alizarin) were prepared in the form of the compositions shown in Table 4 below, dispersed and pulverized in a sand mill, and then stirred at 1,500 rpm for 60 minutes using a high-speed stirrer. Then, polyamide as an additive was added to prepare an antifouling paint having the composition shown in Table 4 below.

Paint composition Content (% by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Suzy Urethane resin 30 30 30 30 30 30 30 0 alizarin Formula 1 2 4 6 8 0 0 0 0 Commercial antifouling agent Zinc pyrithione 0 0 0 0 6 0 0 0 Capper pyrithione 0 0 0 0 0 6 0 0 Pigment Iron oxide 16 15 14 13 14 14 16 0 Silica 10 9 8 7 8 8 11 0 Talc One One One One One One 2 0 solvent Xylene 25 25 25 25 25 25 25 0 Methyl isobutyl ketone 15 15 15 15 15 15 15 0 additive Polyamide One One One One One One One 0 sum 100 100 100 100 100 100 100 0

Experimental Example 4: Inhibition of activity of antifouling paint against parasitism (antifouling activity)

An antifouling paint is prepared with the composition shown in Table 4, and a certain amount of parasitic spore is cultured on a slide glass coated with each paint to make the antifouling. After 3 days, the adhesion rate was measured and the adhesion inhibition efficacy test was performed. The results are shown in Table 5 below.

Paint composition Adhesion rate Example 1 38% Example 2 31% Example 3 25% Example 4 22% Comparative Example 1 29% Comparative Example 2 35% Comparative Example 3 50% Comparative Example 4 100%

As shown in Table 5, the adhesion ratios of 22 to 38% were shown in Examples 1 to 4, which are antifouling paints prepared in the composition of Table 4, and Comparative Examples 1 and 2, which use commercial antifouling agents, %, And Comparative Example 3 using only a paint containing no antifouling agent exhibited an adhesion rate of 50%. Comparative Example 4 in which nothing was treated showed an adhesion rate of 100%. This shows that the antifouling effect of Alizarin antifoulant of formula (1) is higher than that of conventional antifouling agent.

&Lt; Experimental Example 5: Antifouling effect test of antifouling paint on actual sea area >

In order to confirm the effective concentration of the antifouling effect in the case of using the alizarin antifouling agent of the above formula (1) in the antifouling paint composition, the used concentration was adjusted to 2 to 8 wt% in each of Examples and Comparative Examples to obtain an antifouling paint composition Was subjected to an antifouling performance test on the composition shown in Table 4 above.

Each of the paints according to Table 5 was made to have a humidity of 250 microns by using brush coating method on the PVC (10 cm 10 cm) panel of Table 4 above. The painted panel was immersed in the same depth of 1 ~ 1.5 m in the immersion test site on the coast of Mizoe - myeon, Syeon - nam, Gyeongsangnam - do, and the antifouling condition was confirmed after 3 months. The antifouling effect was checked using ASTM 3623. The results are shown in Table 6 below.

3 month anti-fungal efficacy test result division Mounting area (%) Coat state Seaweed Biofilm Invertebrate Example 1 5 38 7 stability Example 2 5 29 6 stability Example 3 3 15 4 stability Example 4 2 14 5 stability Comparative Example 1 6 16 6 stability Comparative Example 2 8 15 7 stability Comparative Example 3 14 45 9 stability Comparative Example 4 20 65 15 -

In the case of the attachment mechanism, it is reported that organic matter is first adhered to a ship or a structure in seawater and then bacteria are formed, and then microalgae, large algae, barnacles and shellfish are attached. As can be seen from Table 6, the adhesion tendency in Comparative Examples 1 and 2 in which the coating materials of Examples 1 to 4 and the commercial antifouling agent containing Alizarin antifouling agent of Formula 1 were added showed the tendency that algae, However, it was found that Example 1 was much stronger in antifouling effect than Comparative Example 1 in comparison with Examples using Comparative Example 1 containing the commercial antifouling agent and Formula 1 through the adhesion ratio of invertebrates as a standard of the antifouling effect And it was confirmed that a stable coating film state was maintained at the concentration.

Claims (8)

An antifouling agent characterized by containing alizarin represented by the following formula (1) as an effective component.
[Chemical Formula 1]

1. An antifouling paint composition comprising a resin, a solvent, a pigment and an antifouling agent,
Wherein the antifouling agent comprises alizarin represented by the following formula (1) as an active ingredient.
[Chemical Formula 1]

3. The method of claim 2,
Wherein the content of the resin, the solvent, the pigment and the antifouling agent is 10 to 30% by weight, 20 to 40% by weight, 20 to 30% by weight and 2 to 8% by weight, respectively. The method according to claim 2 or 3,
The resin is preferably selected from the group consisting of urethane resin, urethane resin, chlorinated rubber resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melanin resin, acrylic resin, fluorine resin, silicone resin, metal acrylate resin and rosin Wherein the antifouling coating composition is at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The method according to claim 2 or 3,
Wherein the solvent is at least one selected from xylene, methyl ethyl ketone and methyl isobutyl ketone. The method according to claim 2 or 3,
Wherein the pigment is at least one selected from iron oxide, silica, zinc oxide and talc. The method according to claim 2 or 3,
The antifouling paint composition of claim 1, further comprising an additive. 8. The method of claim 7,
Wherein the additive is polyamide wax, bentonite, clay or polyethylene wax and the content thereof is 0.7 to 8% by weight.