KR20160014854A - Antifouling agent and antifouling paint composition comprising thymol - Google Patents

Abstract

The present invention relates to an eco-friendly antifoulant and an antifouling paint composition. More specifically, the present invention relates to an antifoulant containing, as an active ingredient, thymol which is represented by chemical formula 1, and to an antifouling paint composition using the same. According to the present invention, the antifouling paint composition does not contain marine pollutants such as organic tin and cuprous oxide and thus exhibits superior antifouling effects against marine adherent organisms while seldom affecting the marine ecosystem and the human body. Thus, the composition can be applied as an antifouling system used in fishing nets, vessels, and maritime structures.

Description

[0001] Antifouling agents and antifouling paint compositions comprising thymol [0002]

The present invention relates to an antifouling agent and an antifouling paint composition, and more particularly, to a novel antifouling agent having excellent antifouling performance including thymol and having little influence on the marine environment and human body, and an antifouling paint composition using the antifouling agent .

Many marine organisms such as large algae and microalgae, mussels, slime, oysters, sea urchins, sponges, and pericarctic animals living in the seawater are attached. For the convenience of man, artificial marine facilities, ships, harbors, farms Fisheries, marine structures, etc., and many other living organisms are attached to the fish.

Among them, corrosion of marine structures is caused by the adherence of living organisms, resulting in an increase in the mass of the marine structure, thereby shortening the life of the structure and inducing the shape change. Therefore, since the structure must be replaced periodically, various efforts have been made to prevent the attachment of living things for economic reasons.

In order to prevent corrosion and contamination of underwater structures by marine organisms, antifouling coating compositions comprising rosin, plasticizer and antifouling agent mixed with vinyl chloride resin or vinyl resin have been used. However, this type of antifouling coating composition is used as an antifouling agent Organic tin, copper, mercury, organotin compounds, etc., contaminate the marine environment due to the inclusion of heavy metals.

In order to reduce such pollution and to construct an efficient anti-fouling system, metal acrylate resin which can be hydrolyzed by seawater is used to cause the metal to be slowly hydrolyzed off at the seawater contact site, Thereby causing a new surface layer to protrude as the polymer is swollen or swollen from the surface. However, in addition to the chemical endeavors for the above-mentioned antifouling effect, the use of a high concentration of toxic copper oxide and other organic compounds as an antifouling agent in order to improve the efficacy can prevent the accumulation of heavy metals and adverse effects on non-target marine life .

As a conventional antifouling agent, Korean Patent Publication No. 10-0592438 discloses 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 di (meth) acrylate, a metal (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 above patent publication has a primary purpose in providing an antifouling paint which can be used at a constant rate regardless of the painting site and can maintain excellent antifouling performance for a long period of time. The problem of marine pollution caused by the antifouling paint It was something that could not be solved fundamentally.

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.

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

Therefore, development of a novel antifouling agent and antifouling paint composition having excellent antifouling performance in view of protecting marine life and marine environment is urgently required.

Accordingly, the present inventors have made efforts to solve the above-mentioned problems, and discovered that thiomoleic acid has excellent 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 which exhibits an excellent antifouling effect on various marine adherent organisms, while having little influence on the marine environment and the human body.

Another object of the present invention is to provide an antifouling paint composition exhibiting an excellent antifouling effect as an antifouling paint for sea water such as a fishing net, a ship, an underwater structure, and the like without containing marine pollutants such as organotin,

In order to accomplish the above object, an embodiment of the present invention is characterized by including thymol represented by the following formula (1) as an active ingredient.

[Chemical Formula 1]

Another embodiment of the present invention is an antifouling paint composition comprising a resin, a solvent, a pigment and an antifouling agent, wherein the antifouling agent comprises thymol represented by the following formula (1) as an active ingredient.

[Chemical Formula 1]

The present invention is characterized by further comprising an additive.

The content of the resin is 10 to 30% by weight and the resin is at least one selected from the group consisting of vinyl acetate resin, vinyl chloride resin, urethane resin, chlorinated rubber resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melamine resin, A resin, a silicone resin, a metal acrylate resin and a rosin.

The content of the solvent is 20 to 40% by weight, and the solvent is any one selected from the group consisting of xylene, methyl ethyl ketone and methyl isobutyl ketone.

The content of the pigment is 20 to 30% by weight, and the pigment is any one selected from the group consisting of iron oxide, silica, zinc oxide, and talc.

The content of the antifouling agent is 2 to 8% by weight.

The content of the additive is 0.7 to 1% by weight, and the additive is polyamide wax, bentonite, clay or polyethylene wax.

Since the antifouling and antifouling paint compositions according to the present invention contain a relatively low proportion of marine pollutants such as organotin, copper oxide, copper and toxic organic antifouling agents, which are conventionally used, It exhibits excellent antifouling efficacy while showing little effect.

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 thymol represented by the above-mentioned formula (1) as an effective component. 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 thymol as the antifouling agent.

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

Thymol represented by the following formula (1) according to the present invention has a property of dissolving only a very small amount in a non-polar solvent and is a very stable material in seawater.

In particular, when used together with a vinyl chloride resin, a vinyl resin, a polyurea resin or the like, it exhibits more physical and chemical stability, and thus a coating composition suitable for the purpose of the present invention can be constituted.

[Chemical Formula 1]

Thymol of the above formula 1 has a strong sulfation property and is known to have antimicrobial activity such as penicillin and thus has an effect of lowering the adhesion inhibiting effect and activity against the bacteria that are primary attachment bacteria in seawater . In addition, since thymol is a substance that can be extracted from plants, it has little chemical impact on the marine environment and can be used environmentally. In conclusion, thiom is an antifouling agent that does not remain in the marine environment for half an hour within 24 hours.

Further, as a preferred 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 thymol.

The thymol, which is an antifouling agent according to the present invention, can effectively block the adhering step of marine organisms when used together with a resin or the like in the form of an antifouling paint composition, thereby exhibiting an excellent antifouling effect.

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

In the case of zinc acrylate resin, it is hydrolyzed in seawater and the coating film is collapsed and a new type of coating film is formed. However, the zinc acrylate resin is hydrolyzed at a low rate and the antifouling action is not easy due to instability of various marine environments. To cope with this problem, conventionally, high concentration of zinc oxide and organic antifouling agent were used together as an antifouling agent. However, these components have a problem of affecting non-target creatures, which adversely affect human and marine ecosystems. However, when the low-toxicity antifouling agent of the present invention is mixed with the urethane resin, the conventional contamination problem can be reduced, and the stability against the marine environment is excellent, and the intermediate step of the attachment mechanism It is possible to exhibit a relatively excellent antifouling effect on environmentally friendly.

The amount of the resin used in the preparation of the paint is preferably 10 to 30% by weight in the entire antifouling coating composition, and if the amount is less than 10% by weight, the adhesion and durability of the antifouling paint deteriorate. There is a problem of storage stability.

As the solvent used in the antifouling paint composition of the present invention, various solvents well known in the art can be used without limitation, and examples thereof include hydrocarbons such as xylene, methyl ethyl ketone, methyl isobutyl ketone, Based solvent may be used alone or in combination of two or more. The amount of the solvent used is preferably 20 to 40 wt% based on the total antifouling paint composition. If the amount of the solvent is less than 20 wt%, the viscosity of the antifouling paint composition is excessively high. If the amount of the solvent is more than 40 wt% The adhesion and the antifouling property to the coating film may be reduced.

As the pigment used in the antifouling paint composition of the present invention, various pigments known in this technical field can be used without limitation. For example, inorganic pigments such as iron oxide, silica, zinc oxide and talc, as well as inorganic pigments such as nontoxic azo pigments And the like, and they can be used singly or in a mixture of one or more. The pigment is preferably used in an amount of 20 to 30 wt% based on the total composition of the paint. If the amount of the pigment is less than 20 wt%, there is a problem of discoloration of the paint. If the amount of the pigment is more than 30 wt% There is a problem.

In addition, the antifouling paint composition according to the present invention may contain various kinds of additives known to include additives. As the additive, additives such as polyamide wax, bentonite, clay, polyethylene wax and the like may be added for the purpose of preventing sedimentation of the paint and improving durability. The additive is preferably used in an amount of 0.7 wt% to 1 wt% in the whole composition. When it exceeds 1% by weight, there is a problem that it is difficult to dry the paint when used, and the viscosity is rapidly increased and the durability is lowered.

The antifouling paint composition of the present invention can be produced by a conventional method for producing a paint. For example, after the resin is dissolved in a solvent, a pigment and an antifouling agent are added and dispersed and pulverized with a ball mill or a sand mill, and then an additive is added to the resin, 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 activity of thymol represented by the above formula (1), zinc pyrithione, copper pyrithione, which is the most frequently used organic antifouling agent in the conventional antifouling paint industry, and copper pyrithione, Thymol were dissolved in ethanol, respectively, and treated with paper disks according to the concentration as shown in the following table, followed by incubation for 7 hours in LB medium, 25% by using Marine bacteria, The clean zone, which is the active inhibition of the disk, was measured, and the results are shown in the following Table 1.

Results of antibacterial efficacy experiments Antifouling material 10000 ppm 5000ppm 1000ppm 500ppm 1-thymol
(Thymol) 2cm 3.3cm 2cm 1cm Zinc pyrithione
(zinc pyrithione) 4cm 3cm 2cm 1.5cm Capper pyrithione
(copper pyrithione) 2cm 3cm 1cm 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 Thymol was used as a commercially available antifouling agent such as zinc pyrithione and copper pyrithione , It is confirmed that it has an effect of blocking bacteria as an early attachment organism when it is used as an antifouling agent because it has better efficacy than a control group which is not treated with anything.

Experimental Example 2: Inhibition of growth of microalgae (antifouling effect)

In order to verify the antifouling effect of thymol, zinc pyrithione, copper pyrithione and thymol represented by the above formula (1), which are the organic antifouling agents most commonly used in the conventional antifouling paints industry, And a certain amount of microalgae were cultured. After 3 days, the absorbance was measured. The results are shown in Table 2 below.

density
(Μl / cm 2) One 2 4 8 16 32 Antifouling agent Formula 1
(thymol) 0.042 0.043 0.058 0.048 0.037 0.027 Zinc pyrithione
(zinc pyrithione) 0.059 0.057 0.057 0.051 0.036 0.034 Capper pyrithione
(copper pyrithione) 0.050 0.052 0.069 0.053 0.048 0.035 Control group 0.15

As can be seen from the above Table 2, the activity of microalgae was high at all concentrations of 1 to 32 μl / cm 2 for zinc pyrithione and capper pyrithione, but all of the thymol of Chemical Formula 1 showed low activity. This shows that the antifouling effect of the compound of formula (1) is superior to that of the conventional commercial antifouling agent. However, the activity of thymol of the formula (1) is lowered at a high concentration, indicating that the higher the concentration of thymol, the higher the antifouling activity.

Experimental Example 3: Inhibition of parasitism (antifouling activity)

In order to verify the antifouling effect of thymol, zinc pyrithione, copper pyrithione and thymol represented by the above formula (1), which are the organic antifouling agents most commonly used in the conventional antifouling paints industry, The resulting solution was applied to a slide glass, incubated with a certain amount of Paraspora solution, and cultured. After 3 days, the result of the multiplication rate was shown in Table 3 below.

density 50 mg / ml 5 mg / ml Antifouling agent Formula 1
(thymol) 20% 30% Zinc pyrithione
(zinc pyrithione) 30% 40% Capper pyrithione
(copper pyrithione) 35% 45% Control group 100%

As shown in Table 3, the compounding ratio of the compound of Formula 1 was 20 to 30%, and the compounding ratio of zinc pyrithione and capper pyrithione, which are the most commonly used organic antifouling agents, was 30 to 45% Compared with thymol, it showed a high hybridization rate. In the control group without any treatment, 100% confluency was observed. This shows that the antimicrobial effect of the antimicrobial agent of the above formula (1) is higher than that of the conventional antifouling agent.

As shown in Experimental Examples 1 to 3, the thymol of the present invention exhibits an activity inhibiting effect against bacteria as compared with conventional commercial antifouling agents, and exhibits an excellent antifouling effect against vegetable marine organisms It was confirmed that it was useful as an antifouling agent.

≪ 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, Of thioimide were prepared in the form of the compositions shown in Table 4 below, dispersed and pulverized using 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 Thymol 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)

Antifouling paints were prepared with the above composition, and a certain amount of Parasitic spore was cultured on a slide glass coated with each paint, and the experiment for inhibiting the multiplication rate was performed after 3 days. The results are shown in Table 5 below.

Paint composition Adhesion rate Example 1 40% Example 2 35% Example 3 27% Example 4 25% Comparative Example 1 30% Comparative Example 2 35% Comparative Example 3 55% Comparative Example 4 100%

As shown in Table 5, in each of the antifouling paint compositions, adhesion rates of 25 to 40% were shown in Examples 1 to 4, Comparative Examples 1 and 2 using commercial antifouling agents showed adhesion rates of 30 to 35% , And Comparative Example 3 using only a paint containing no antifouling agent exhibited an adhesion rate of 55%. In Comparative Example 4, in which nothing was treated, the adhesion rate was 100%. This shows that the antifouling effect of the antimicrobial agent of the above formula (1) is higher than that of the conventional antifouling agent.

≪ 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 thymol antifouling agent of the above formula (1) in the antifouling paint composition, the antifouling paint composition was prepared by controlling the concentrations used at 2 to 8 wt% The composition of Table 4 was subjected to an antifouling performance test.

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 4 38 8 stability Example 2 4 30 6 stability Example 3 2 15 3 stability Example 4 3 13 4 stability Comparative Example 1 5 15 5 stability Comparative Example 2 7 15 8 stability Comparative Example 3 16 47 7 stability Comparative Example 4 18 69 13 -

In the case of the attachment mechanism, it is reported that organic matter is firstly adhered to a ship in seawater and then bacteria are formed, and then microalgae, large algae, barnacles and shellfish are attached. As shown in Table 6, in Examples 1 to 4 using the thymol antifouling agent of Formula 1 and Comparative Examples 1 and 2 in which the antifouling agent was added, the tendency of adhesion was observed in seaweeds, biofilms and invertebrates, Comparing Example 1, in which the commercial antifouling agent was included, with Example 1 using the adherence rate of the invertebrate as a standard of efficacy, Example 1 was much stronger in antifouling effect than Comparative Example 1, and It was confirmed that a stable coating film state was maintained at the corresponding concentration.

Claims (8)

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

An antifouling paint composition comprising a resin, a solvent, a pigment and an antifouling agent, wherein the antifouling agent comprises thymol represented by the following formula (1) as an effective component.
[Chemical Formula 1]

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