KR101263261B1 - Antifoul agent and antifouling paint composition comprising hexadecyl methacylate - 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 including hexadecyl methacylate and an antifouling coating composition using the same, and marine pollution such as organic tin and copper nitrous oxide. Since no materials are used at all, there is no harm to the marine environment and the human body, and it shows excellent antifouling effect on marine attached organisms, which can be used as antifouling systems for fishing nets, ships, and marine structures.

Description

 Antifouling agent and antifouling paint composition comprising hexadecyl methacrylate {Antifoul agent and antifouling paint composition comprising hexadecyl methacylate}

The present invention relates to an antifouling agent and an antifouling coating composition, and more particularly, to a novel eco-friendly antifouling agent containing hexadecyl methacrylate as an active ingredient and an antifouling coating composition using the same.

Among marine aquatic organisms, there are inhabitants of affixed species that attach to aquatic objects and survive, and these are known to have 600 plants and 1300 animals. However, when attached creatures are attached to ships, fishing nets, and offshore structures, they increase their weight and water resistance, which can damage them. For example, when attached to a ship, the maximum speed is reduced by 25%. It is said that the amount of fuel used is increased by about 30%, and for this economic point of view, various measures are taken to prevent the attachment of organisms.

Organic tin and heavy metal antifouling agents were used to inhibit the adhesion of these marine organisms. However, these antifouling agents are toxic. Thus, toxic antifouling agents eluted in seawater inhibit fertilization and cell division of marine organisms. It causes serious problems such as malformation, malformation, and imposex.

Metal acrylate resin that can be hydrolyzed by seawater is used to reduce such contamination and to effectively prevent fouling. The metal is slowly hydrolyzed at the seawater contact point, and the carboxyl group at the leaving site forms a salt. As the polymer is solvated or swelled off the surface, a new surface layer protrudes and is currently the most commonly used resin. However, despite the chemical efforts for the antifouling effect, the use of high concentrations of toxic copper oxide and herbicides together to enhance the efficacy, resulting in marine accumulation of heavy metals and adverse effects on non-target marine life have.

In addition, as examples of antifouling agents using methacrylates, Korean Patent Registration Nos. 100518 and 100519 have proposed techniques for using methacrylate-based radical polymerizable monomers in antifouling paints. However, while describing the use of radical polymerizable antifouling monomers, metal polyvalent radical polymerizable monomers, metal monovalent radical polymerizable monomers, and the like, acrylates, methacrylates, vinyls, maleimides and the like are described as radical polymerizable monomers. As the radically polymerizable antifouling monomer, maleimide, rosinimide, phthalimide, hexahydrophthalimide, 2-α-thiohomomaleimide, 2-α-thiohomophthalimide , 2-α-thio homohexahydrophthalimide, isothiazolones, pyrazoles, rhodanines, and imidazoles are used, but the composition of the components is hardly regarded as an environmentally friendly antifouling agent, and its antifouling performance is also poor.

In addition, Korean Patent Laid-Open Publication No. 2004-71245 discloses an antifouling coating composition substantially free of cuprous oxide and organotin, wherein the polymerizable unsaturated monomer (a1) containing metal and the radical polymerization property containing no metal are contained. A metal-containing copolymer obtained by copolymerizing an unsaturated monomer (a2), containing (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and (C) metal pyrithione compound In WO 2007-74765, a structure derived from (A) a structural unit derived from an unsaturated carboxylic acid monomer (a1) and another unsaturated compound monomer (a2) copolymerizable with this unsaturated carboxylic acid monomer (a1) is proposed. A carboxyl group-containing copolymer having a unit and having a weight average molecular weight of 1,000 to 6,000 measured by GPC, (B) a polyvalent metal compound capable of reacting with a carboxyl group of the carboxyl group-containing copolymer (A), and (C) an antifouling agent High solids An antifouling coating composition has been proposed. Although the antifouling coating composition has excellent antifouling properties, it is described as having excellent uniform consumption performance of the coating film, and excellent long-term antifouling performance of the coating film or less human impact, but it has antifouling performance and environmental friendliness. There was a problem that can not be secured.

In addition, US Patent No. 5,202,378 describes a surface coating composition containing a fatty acid methacrylate as a binder, but is not related to an environmentally friendly antifouling agent.

Therefore, there is an urgent need for development of new antifouling agents and antifouling paint compositions that are environmentally friendly and have 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, hexadecyl methacrylate (Hexadecyl methacrylate) was found to have an excellent antifouling effect to complete the present invention by developing antifouling agents 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 environmentally friendly antifouling coating composition which does not contain marine pollutants such as organotin and nitrous oxide compounds as marine antifouling paints for fishing nets, ships, and marine structures.

In order to solve the above problems, the present invention provides an environmentally friendly antifouling agent using hexadecyl methacrylate (Hexadecyl methacrylate) represented by the following formula (1) as an active ingredient.

[Formula 1]

The present invention also provides an antifouling coating composition comprising hexadecyl methacrylate represented by Formula 1 as an antifouling agent component.

The active ingredient exhibiting an antifouling effect in the antifouling agent and antifouling paint composition according to the present invention is a non-toxic substance and is eco-friendly and has the same antifouling power as an existing antifouling agent without using any toxic heavy metal substances such as organotin and copper oxide. Can be represented.

In addition, it is a non-toxic substance that is harmless to the marine environment and the human body, and because of the excellent antifouling effect on marine attached organisms, it can be utilized as an excellent antifouling coating composition for fishing nets, ships and marine structures.

The present invention relates to an environmentally friendly antifouling agent having hexadecyl methacrylate represented by Formula 1 as an antifouling active ingredient, and in the present invention, to an antifouling coating composition comprising a resin, a solvent, a pigment, and an antifouling agent. The present invention includes application to antifouling systems such as antifouling paint compositions using hexadecyl acrylate as the antifouling agent.

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

Hexadecyl acrylate of the following Chemical Formula 1 according to the present invention is very stable in seawater, and has a property of dissolving only a very small amount in a hydrophilic solvent. Particularly, various coating resins and the like may be chemically and physically stable in terms of stabilization of the coating material to prepare the coating composition.

[Formula 1]

Hexadecyl methacrylate of Chemical Formula 1 is a radical ion dissolved in photodegradation or soluble in seawater, combined with a strong metal group, to lower the adhesion inhibitory effect and activity on adherent organisms, and has a hydrophobic long chain chemical structure. Since it has an effect of inhibiting growth of antifouling organisms by disturbing or destroying the membrane structure by approaching the cell membrane, it can be preferably used as an antifouling agent. In addition, this component remains stable in the van der Waals bonding state when combined with the paint, and has a property of naturally falling off even when marine organisms are physically attached due to the hydrophobicity slowly eluting from the surface. . In particular, the hexadecyl methacrylate is used as an optical brightening agent in cosmetics, so it is proved to be harmless to the human body, and thus, it is environmentally friendly, and when used in the ocean, it may exhibit excellent antifouling efficacy.

In addition, in the antifouling coating composition comprising a resin, a solvent, a pigment, and an antifouling agent, an antifouling coating composition using hexadecyl methacrylate of the formula (I) as the antifouling agent component is used. It is another feature. The hexadecyl methacrylate, an antifouling active ingredient according to the present invention, when used in the form of an antifouling coating composition together with a resin, can effectively block the attachment step of marine adherent organisms and can exhibit excellent antifouling efficacy.

As such, hexadecyl methacrylate, an antifouling effective ingredient according to the present invention, has a strong antifouling effect as described above, and thus, marine attachment organisms can be blocked from an early stage, and the hexadecyl methacrylate is antifouling. When used in the coating composition is preferably included in the range of 1 to 10% by weight, more preferably 5 to 10% by weight. When used in less than 1% by weight has a disadvantage in that the antifouling effect is poor, when used in excess of 10% by weight is unstable coating state, there is a problem that the production cost is increased to decrease the economic efficiency.

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 acrylics. Natural resins such as resins, fluororesins, silicone resins, metal acrylate resins or rosin can be used singly or in combination of two or more kinds.In addition to these synthetic or natural resins, various water-soluble resins or fat-soluble resins can be used together. Can also be used. More preferably, zinc acrylate resin is used among the metal acrylate resins.

In the case of zinc acrylate resin, the coating film collapses due to hydrolysis in seawater, and a new type of coating film is formed, so that the adherent organism can be separated. However, zinc acrylate resins have not been smoothly stained due to hydrolysis rate and instability of various marine environments. Therefore, high concentrations of copper oxide and organic antifouling agents were used together as antifouling agents. There was a problem that it could affect (non-target) organisms and eventually adversely affect human and marine ecosystems. However, when the antifouling agent containing the non-toxic hexadecyl methacrylate according to the present invention is excellent in the marine environment and can solve the existing pollution problem, as well as blocking the intermediate step of the attachment mechanism. Excellent antifouling effect can be achieved without adverse environmental impact.

The amount of the resin used in preparing the paint is preferably used in an amount of 10 to 20% by weight in the entire antifouling paint composition. If the amount is less than 10% by weight, there is a problem in that adhesion and durability of the antifouling paint are deteriorated. When used in excess of the storage problem occurs.

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. It can be used or mixed two or more kinds. 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, for example, inorganic pigments of light metals such as iron oxide, titanium oxide, zinc oxide, talc, as well as non-toxic azo-based. Pigments and the like can be used in various ways, and these can be used alone or in combination of one or more. 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 at 0.7% by weight to 1% by weight in the total composition. When using more than 1% by weight, there is a difficulty in drying the paint, and there is a problem in that a sudden increase 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: Antibacterial (antifouling effect) experiment of hexadecyl methacrylate

Zinc pyrithione, copper pyrithione, an organic antifouling agent most used in the existing antifouling paint industry, and the chemical formula 1 to verify antifouling efficacy as an antifouling agent against hexadecyl methacrylate. Hexadecyl methacrylate, which is a antifouling agent, is dissolved in methanol, and then applied to paper discs according to the concentrations as shown in Table 1 below. Then, M1 medium and 25 ° C. conditions are used using marine bacteria, the most active marine bacteria in the marine environment. (Buerer et al., 1966. Antibiotic susceptibility testing by a standardized single disc method) was performed for 7 hours, and the results are shown in Table 1 below.

Antibacterial  Efficacy Experiment Results Antifouling substances 10ppm 1 ppm 0.1 ppm 0.01 ppm Hexadecyl methacrylate 2.3mm 1.4mm 0.4mm 0.2mm Capperityon
(copper pyrithione) 3.2mm 2.1mm 0.9mm 0.6mm Zinc pyrithione
(zinc pyrithione) 3.5mm 2.2 mm 1mm 0.5mm Control group 0 mm 0 mm 0 mm 0 mm

As can be seen in Table 1, when analyzing the antibacterial test results using marine bacteria, hexadecyl methacrylate (Hexadecyl methacrylate) is the main antifouling agent of the current copper pyrithion (Copper pyrithion) and zinc pyrithione (Zinc) Pyrithione) showed a similar or better antifouling effect than when used, it was confirmed that there is an effect to block the early adherent organisms when used as an antifouling agent.

Experimental Example 2: Eco-Friendly Experiments on Green Spores

In order to verify the eco-friendliness as well as the antifouling effect as a antifouling agent against hexadecyl methacrylate, copper pyritione, zinc pyrithione and hexa, which are the most used organic antifouling agents in the antifouling paint industry The decyl methacrylate was added to each concentration of a certain amount of green spores, and after 24 hours, a survival test was performed. The results are shown in Table 2 below.

Lap adhesion test Antifouling substances density 1 ppm 5 ppm 10 ppm 15 ppm Hexadecyl methacrylate Survival rate
Of control 75% 71% 43% 30% Capperityon
(Copper pyrithione) Survival rate
Of control 45% 26% 9% 0% Zinc pyrithione
(Zinc pyrithione) Survival rate
Of control 40% 25% 11% 0% Control group Survival rate
Of control 100%

As can be seen in Table 2, in the case of hexadecyl methacrylate, the antifouling efficacy was lowered by less than 50% at 5-10 ppm compared to commercial antifouling products, and zinc pyrithione and copper pyrithione were 1-5 ppm. Although the adhesion rate was lowered to less than 50% in hexadecyl methacrylate, it inhibited the adhesion of algae spores hydrophobicly instead of directly affecting the seaweed, which is a test organism, compared to other commercial antifouling agents. Prove that it is an environmentally friendly material that is not coated.

As seen through Experimental Examples 1 to 2, the hexadecyl methacrylate of the present invention exhibited strong antifouling effect against marine adherent organisms, and confirmed that the ecological adverse effects on animal marine organisms appeared to be small. Hexadecyl methacrylate was found to be environmentally friendly and exhibit excellent antifouling performance compared to conventional antifouling agents.

Examples 1 to 5 and Comparative Examples 1 to 3: Preparation of an antifouling paint composition

After dissolving the zinc acrylate resin completely in xylene and methyl isobutyl ketone, hexadecyl methacrylate (Hexadecyl methacrylate) or a commercial antifouling agent of Formula 1, which are pigments iron oxide, zinc oxide, talc, and antifouling agent, are respectively shown in the following table. It was added in the same composition as 3, which was dispersed and crushed in a sand mill and then stirred at a high speed stirrer at 1,500 rpm for 60 minutes. After the addition of the polyamide additive was prepared an antifouling paint of the composition shown in Table 3, respectively.

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

Experimental Example 3: Durability Test of Antifouling Coating Composition

In order to measure the durability of the antifouling coating composition, the weight% of the zinc acrylate resin and the antifouling agent were prepared as in Examples 1 to 5 and Comparative Examples 1 to 2, respectively. The resin is fixed at 10% by weight of the composition, and the hexadecyl methacrylate of Formula 1, which is an antifouling agent in Examples 1 to 5, is 1%, 3%, 5%, 7%, and 9%, respectively. In the case of the antifouling agent, the durability test was carried out for the compositions of the above Examples and Comparative Examples, in which the antifouling coating composition was prepared at 5%.

As a method for measuring the durability of the antifouling coating composition, a spray caterpillar test method was applied according to ASTM 3170 to spray a coating of one type of zinc steel sheet having a width × length × 300 × 300 × 3.2 mm, and then completely dried the moisture film to be 250 microns. After 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 loss rate and the results are shown in Table 4 below.

Weight loss rate of coating film (% by weight) division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Weight loss rate 19% 17% 13% 13% 13% 20% 20% 18%

As shown in Table 4, in the antifouling paint composition, in the case of Examples 1-5 to which the hexadecyl acrylate of Chemical Formula 1 was added, the coating film hardness result showed a weight loss rate of 13-19 wt%, but Comparative Example 1 to 2 was added to the commercial antifouling agents copper pyrithione and zinc pyrithione showed a 20% weight loss rate, Comparative Example 3 without any antifouling component showed a 18% weight loss. This shows that the antifouling paint composition to which the hexadecyl acrylate of Formula 1 is added is more durable than the conventional antifouling agent.

Experimental Example 4: Antifouling effect experiment of the antifouling paint composition

In order to confirm the optimal concentration of hexadecyl methacrylate as an antifouling agent in the antifouling coating composition, the concentrations of the compounds were used in Examples 1 (1% by weight), Example 2 (3% by weight), Example 3 (5% by weight), Antifouling paint by adjusting to Example 4 (7% by weight), Example 5 (9% by weight), Comparative Example 1 (5% by weight), Comparative Example 2 (5% by weight), Comparative Example 3 (0% by weight) The antifouling performance test was performed on the composition of Table 3, which prepared the composition.

The paint of Table 3 was sprayed on a PVC (10cm × 10cm) panel to make each paint according to Table 3 to 250 micron of a humidity film. The painted panels were immersed at the same depth of 1-1.5 m in the immersion test site of Mizo-myeon, Sacheon-si, Gyeongnam, and confirmed the staining state after 6 months. The antifouling efficacy was measured using ASTM 3623. The results are shown in Table 5 below.

6 months Antifouling effect  Test result division Mounting area (%) Coating state Seaweed Biofilm Invertebrates Example 1 5 35 10 stability Example 2 5 40 7 stability Example 3 5 31 5 stability Example 4 5 37 9 stability Example 5 5 39 7 stability Comparative Example 1 5 41 11 stability Comparative Example 2 5 40 15 stability Comparative Example 3 10 20 70 stability

In the case of the attachment mechanism, the organic material is first adhered to the vessel in the sea water, and then bacteria are formed according to it, and then microalgae, macroalgae, banache and shellfish are sequentially attached. As can be seen in Table 5, the adhesion tendency of the coating composition of Examples 1-5 using the hexadecyl methacrylate of Formula 1 and the commercial antifouling agent was added in Comparative Examples 1-2, which is used for algae, biofilm and invertebrates. Although the adherence rate of the invertebrates, which are attached to the antifouling efficacy standards, is compared with Comparative Examples 1 to 2 containing commercial antifouling agents and Examples using Formula 1, Examples 1 to 5 are compared to fertilizers 1 to 2 The antifouling effect was found to be significantly strong, and it was confirmed that the coating film was maintained at a stable concentration.

Claims (13)

An antifouling agent comprising hexadecyl methacrylate represented by Formula 1 as an active ingredient.
[Formula 1]

An antifouling coating composition comprising a resin, a solvent, a pigment, and an antifouling agent, wherein the antifouling agent comprises a hexadecyl methacrylate represented by the following Chemical Formula 1 (Hexadecyl methacrylate).
[Formula 1]

The antifouling coating composition according to claim 2, further comprising an additive.
The antifouling coating composition according to claim 2 or 3, wherein the resin has a content of 10 to 20 wt%.
The antifouling coating composition according to claim 2 or 3, wherein the content of the solvent is 30 to 40% by weight.
The antifouling coating composition according to claim 2 or 3, wherein the pigment content is 40 to 50% by weight.
The antifouling coating composition according to claim 2 or 3, wherein the content of the antifouling agent is 1 to 10% by weight.
The antifouling coating composition according to claim 3, wherein the content of the additive is 0.7 to 1% by weight.
The resin according to claim 2 or 3, wherein the resin is a vinyl acetate resin, a vinyl chloride resin, or the like, 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, Antifouling coating composition, characterized in that one or two or more selected from the group consisting of silicone resins, metal acrylate resins and rosin.
The antifouling coating composition according to claim 9, wherein the metal acrylate resin is a zinc acrylate resin.
The antifouling coating composition according to claim 2 or 3, wherein the solvent is one kind or a mixture of two or more kinds selected from the group consisting of xylene, methyl ethyl ketone and methyl isobutyl ketone.
The antifouling coating composition according to claim 2 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 or 8, wherein the additive is polyamide wax, bentonite, clay or polyethylene wax.