KR102737125B1 - Antifouling composition immobilized with marine life-derived active material and manufacturing method therof - Google Patents

Abstract

The present invention relates to an antifouling composition and a method for producing the same. More specifically, the present invention can provide an antifouling composition and a method for producing the same, which can exhibit excellent antifouling performance while preventing environmental pollution and the emission of hazardous substances through the introduction of a wax or the like having a marine organism-derived active substance fixed therein.

Description

{Antifouling composition immobilized with marine life-derived active material and manufacturing method therof}

The present invention relates to an antifouling composition having a marine organism-derived active substance fixed therein and a method for producing the same. More specifically, the present invention relates to an antifouling composition having a marine organism-derived active substance fixed therein and capable of preventing environmental pollution and emission of hazardous substances while exhibiting excellent antifouling performance, and a method for producing the same.

As ships and offshore structures float on the sea or are in contact with the sea 24 hours a day, there is an increasing number of cases where problems arise due to contact with numerous marine life.

For example, various aquatic organisms such as slime, algae, and barnacles can stick to the hull, increasing frictional resistance and thus reducing operational efficiency.

In addition, there are many cases where numerous marine organisms such as clams, razor clams, mosses, diatoms, oysters, pearl oysters, sponges, conches, whelks, green seaweeds, and sea squirts attach to and parasitize on underwater facilities, ships, lifeboats, port facilities, aquaculture nets, and fishing nets, causing damage to the objects attached to them.

To solve these problems, an organotin antifouling agent called tributyl tin has been used by mixing it with paints, coating agents, or polymer resins. However, it was discovered that tributyl tin has a negative impact on the marine environment. As a result, the Marine Environment Protection Committee banned the use of tributyl tin starting January 1, 2003, and implemented regulations requiring that tributyl tin be completely removed from ships starting in 2008.

Accordingly, tin-free antifouling agents are currently being used to replace tributyltin. As non-tin-based antifouling agents, examples thereof include copper oxide and zinc, as disclosed in Korean Patent Publication No. 2001-0099049. However, tin-based antifouling agents have insufficient antifouling effects on seaweed, and copper oxide antifouling agents in particular have a relatively wide antifouling effect on marine organisms, but have a short half-life and can accumulate in the seabed, causing adverse effects on the environment.

Accordingly, interest in eco-friendly antifouling compositions that have excellent antifouling effects on marine organisms and microorganisms while having no environmental and sanitary problems is increasing.

For example, prior art document 1 discloses an eco-friendly antifouling agent containing a diketopiperazine compound that has the effect of preventing spore attachment and spore germination and can prevent environmental pollution by toxic chemical products.

As another example, prior art document 2 discloses 6-formyl-3,4-dihydro-2,8-dimethyl-2-(3',6'-dienyl-8'-hydroxy-4'-methylnonane)-2H-1-benzopyran isolated from Saragassum confusum, which is harmless to the environment, has an antifouling effect on a wide range of target organisms, and has the advantage of being extractable from nature, thus having a low production cost.

As another example, prior art document 3 discloses an antifouling agent including a cyclodextrin complex combined with hexadecenoic acid, which does not use any marine pollutants such as organotin and cuprous oxide and thus is not harmful to the marine environment or the human body, while exhibiting excellent antifouling effects, and an antifouling paint composition using the same.

As another example, prior art document 4 provides a stain-repellent fabric with excellent water-repellent and oil-repellent properties and a method for manufacturing the same without containing perfluorinated chemicals (PFCs). The stain-repellent fabric has excellent stain-repellent properties even after wear, and thus can be applied to seats for transportation vehicles.

As another example, prior art document 5 provides an antifouling agent containing Giffinisterone B, an environmentally friendly ingredient isolated from Leucothrix mucor, an adherent filamentous bacterium, which has spore attachment-prevention and germination-inhibiting effects and can prevent environmental pollution caused by chemical products.

As another example, prior art document 6 provides an eco-friendly antifouling agent containing at least one selected from methyl palmitate, methyl stearate, and methyl linoleate. The antifouling agent of the invention has antifouling properties for a wide range of target organisms, is inexpensive to manufacture because it is extracted from a natural product, and has the characteristics of effectively preventing pollution of the marine environment caused by the use of toxic antifouling agents such as TBT.

As another example, prior art document 7 provides an environmentally friendly antifouling agent containing a substance extracted from mustard leaves, a natural substance. The environmentally friendly antifouling agent according to the invention contains allyl isothiocyanate, which is an extract of mustard leaves, and thus is harmless to the environment, has antifouling properties for a wide range of target organisms, and has the characteristics of effectively preventing pollution of the marine environment caused by the use of toxic antifouling agents such as TBT.

As another example, prior document 8 relates to an environmentally friendly antifouling agent containing a substance extracted from lemon, a natural substance, and is characterized by containing one or more selected from 1-octanol, methyl caporate, and ethyl heptanoate. According to prior document 8, an antifouling agent that is harmless to the environment, has antifouling properties for a wide range of target organisms, and is inexpensive to manufacture because it is extracted from a natural substance can be obtained, thereby effectively preventing pollution of the marine environment caused by the use of toxic antifouling agents such as TBT.

{Prior Document 1} Republic of Korea Patent No. 101344075 {Prior Document 2} Republic of Korea Patent No. 100621357 {Prior Document 3} Republic of Korea Patent No. 101365715 {Prior Document 4} Republic of Korea Patent No. 102178195 {Prior Document 5} Republic of Korea Publication Patent No. 1020130112269 {Prior Document 6} Republic of Korea Patent No. 100594347 {Prior Document 7} Republic of Korea Publication Patent No. 1020060017992 {Prior Document 8} Republic of Korea Patent No. 100659536

The purpose of the present invention is to provide an antifouling composition which is harmless to the marine environment and human body, exhibits an excellent antifouling effect against various marine organisms, and has excellent antibacterial properties and durability, and a method for producing the same.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

One aspect of the present application relates to an antifouling composition.

The antifouling composition of the present application may include, for example, a polymer resin; a wax on which an active substance is fixed, and/or an active agent. The wax on which the active substance is fixed may, for example, include an active substance in an amount ranging from 10 to 50 parts by weight per 100 parts by weight of the reactive wax.

The above reactive wax may contain, for example, 5 to 50 parts by weight of acryloyl isocyanate per 100 parts by weight of polyolefin wax.

The above active substance may be, for example, an active substance derived from marine organisms.

The above marine organism-derived active substances include, for example, 6-bromindole-3-carbaldhyde, 3-methyl-N-(2-phenylethyl) butanamide, cyclo-D-phenylalanyl-L-proline, dihydroquinolin-2(1H)-one, pyolipic acid, phenazine-1-carboxylic acid, 6-bromindole-3-carbaldhyde, resorcyclic acid lactone, di(1H-indol-3-yl)methane. methane], (5Z)-4-bromo-5-(bromomethylene)-3-butyl-2(5H)-furanone, galactoglycerolipid, sesquiterpenoid (-)-gleenol, sn-3-O-(geranylgeranyl)glycerol, cystophloroketals A-E meroditerpenoid, 1-O-octadecenoylglycerol, It may be at least one selected from the group consisting of sn-3-Ο-(geranylgeranyl)glycerol, diterpene, 6-octadecenoic acid, dimethylsulphopropionate, and proline.

In the antifouling composition of the present application, the polymer resin may be, for example, at least one selected from the group consisting of polyolefin or ethylene copolymer.

In the antifouling composition of the present application, the active agent may include, for example, a metal nitrate.

The above-mentioned active agent may have an average particle diameter of, for example, 10 to 80 nm.

The antifouling composition of the present application may, for example, contain a wax having an active material fixed therein in an amount of 11 to 15 parts by weight per 100 parts by weight of the polymer resin.

The antifouling composition of the present application may, for example, contain an active agent in a range of 0.05 to 2.5 parts by weight per 100 parts by weight of the polymer resin.

The antifouling composition of the present application may further comprise, for example, an additive.

Another aspect of the present application relates to a method for preparing an antifouling composition.

The method for preparing the antifouling composition of the present application may include, for example, a step of immobilizing an active material in a reactive wax.

The step of immobilizing the active material in the reactive wax may include, for example, a step of mixing the reactive wax, the active material and/or the reaction catalyst to form a mixture; and/or a step of soaking the mixture.

The step of soaking the above mixture can be performed at a temperature of, for example, 50°C to 120°C.

The method for producing the antifouling composition of the present application may additionally include, for example, a step of extracting an active substance from a marine organism.

The step of extracting an active substance from the above marine organism may include, for example, a step of extracting bacteria or fungi from the marine organism; a step of culturing the extracted bacteria or fungi to prepare a culture solution; and/or a step of extracting an active substance from the culture solution.

The present invention provides an antifouling composition which is harmless to the marine environment and human body, exhibits an excellent antifouling effect against various marine attached organisms, and has excellent antibacterial properties and durability, and a method for producing the same.

It should be understood that the effects of the present invention are not limited to the above effects, but include all effects that can be inferred from the composition of the invention described in the description or claims of the present invention.

Among the properties mentioned in this specification, properties whose results are affected by the measurement temperature and/or measurement pressure are the results measured at room temperature and/or normal pressure, unless specifically stated otherwise.

The term room temperature means a natural temperature that is neither heated nor cooled, and means, for example, a temperature within the range of 10°C to 30°C, or about 23°C or about 25°C. In addition, the unit of temperature in this specification is ℃ unless specifically specified otherwise.

The term atmospheric pressure is the natural pressure that has not been pressurized or depressurized, and usually means about 1 atmosphere of pressure, which is the level of atmospheric pressure.

In the case of properties in which the measured humidity affects the results in this specification, unless otherwise specifically specified, the properties are properties measured at natural humidity that is not specifically controlled at the above-mentioned room temperature and/or pressure.

One aspect of the present application relates to an antifouling composition.

The present application may relate to an antifouling composition comprising, for example, a polymer resin; a wax having an active substance fixed thereon; and/or an active agent. In the present specification, the wax having an active substance fixed thereon may be, for example, an active substance and a reactive wax forming a bond by, for example, a covalent bond, an electrical interaction of ions, and/or a Van der Waals force, and preferably, a bond by a Van der Waals force.

The antifouling composition of the present application comprises a wax in which an active substance is fixed, and by appropriately combining a polymer resin and/or an active agent, etc., it does not dissolve in seawater even when exposed to seawater for a long period of time, or even if it does dissolve, the amount of dissolved substance is very small, so that it can have excellent antifouling and antibacterial properties for a long period of time.

The wax on which the active substance is fixed can, for example, contain the active substance in a range of 10 to 50 parts by weight per 100 parts by weight of the reactive wax. In other examples, the wax on which the active substance is fixed can contain 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, or 19 parts by weight or more of the active substance, or 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less of the active substance, per 100 parts by weight of the reactive wax.

The above reactive wax may include, for example, a polyolefin wax. Examples of the polyolefin wax include, but are not limited to, polyethylene wax or polypropylene wax.

The above reactive wax may further include, for example, an acryloyl isocyanate. As the acryloyl isocyanate, acryloyl isocyanate, methacryloyloxyethyl isocyanate, or 2-acryloyloxyethyl isocyanate may be exemplified, and one or more types may be introduced.

The reactive wax of the present application may contain, for example, 5 to 50 parts by weight of acryloyl isocyanate per 100 parts by weight of the polyolefin wax. In other examples, the reactive wax of the present application may contain 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, or 14 parts by weight or more, or 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less, of acryloyl isocyanate per 100 parts by weight of the polyolefin wax.

The reactive wax of the present application may further include, for example, a reaction solvent. Examples of the reaction solvent include chlorobenzene, toluene, xylene, benzene, or ethylbenzene. The reaction solvent may be included in an amount of, for example, 100 to 5,000 parts by weight relative to 100 parts by weight of the polyolefin wax. The reactive wax of the present application may, for example, contain 200 parts by weight or more, 300 parts by weight or more, 400 parts by weight or more, 500 parts by weight or more, 600 parts by weight or more, 700 parts by weight or more, 800 parts by weight or more, or 900 parts by weight or more, or contain 4500 parts by weight or less, 4000 parts by weight or less, 3500 parts by weight or less, 3000 parts by weight or less, 2500 parts by weight or less, 2000 parts by weight or less, or 1500 parts by weight or less of the reaction solvent, based on 100 parts by weight of the polyolefin wax.

The reactive wax of the present application may also further include, for example, an initiator. As the initiator, a grafting polymerization agent, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide or 2,2-azobis-isobutyronitrile may be exemplified, and one or more kinds may be used. The initiator may be included, for example, in an amount of 0.01 to 1 part by weight relative to 100 parts by weight of the polyolefin wax. In other examples, the initiator may be included in an amount of 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.15 parts by weight or more, or 0.9 parts by weight or less, 0.8 parts by weight or less, 0.7 parts by weight or less, 0.6 parts by weight or less, 0.5 parts by weight or less, 0.4 parts by weight or less, or 0.3 parts by weight or less, relative to 100 parts by weight of the polyolefin wax. The reactive wax of the present application may have excellent polymerization reactivity by including the initiator within the above range.

In the present application, the active substance may be, for example, an active substance derived from marine organisms. In the present specification, the active substance derived from marine organisms may refer to a substance extracted by growing Acinetobacter sp. bacteria, Letendraea helminthicola fungi, Scopulariopsis sp. fungi, Pseudomonas sp. bacteria, etc., in an agar culture medium, for example, extracted from marine organisms such as brown algae, sponges, corals, snails, and sea squirts.

The above marine organism-derived active substances include, for example, 6-bromindole-3-carbaldhyde, 3-methyl-N-(2-phenylethyl) butanamide, cyclo-D-phenylalanyl-L-proline, dihydroquinolin-2(1H)-one, pyolipic acid, phenazine-1-carboxylic acid, 6-bromindole-3-carbaldhyde, resorcyclic acid lactone, di(1H-indol-3-yl)methane. methane], (5Z)-4-bromo-5-(bromomethylene)-3-butyl-2(5H)-furanone, galactoglycerolipid, sesquiterpenoid (-)-gleenol, sn-3-O-(geranylgeranyl)glycerol, cystophloroketals A-E meroditerpenoid, 1-O-octadecenoylglycerol, It may be at least one selected from the group consisting of sn-3-Ο-(geranylgeranyl)glycerol, diterpene, 6-octadecenoic acid, dimethylsulphopropionate, and proline.

As described above, the present application provides an antifouling composition that exhibits excellent antifouling effects against various marine organisms while being harmless to the marine environment and human body by introducing an active substance derived from marine organisms, and has excellent antibacterial properties and durability.

The wax on which the above active material is fixed may further include, for example, a reaction catalyst. As the reaction catalyst, at least one selected from the group consisting of tin compounds such as tetramethylstannoxy dioleate, tetramethylstannoxy dilaurate, dibutyltin dilaurate, dimethyltin dipalmetate, dimethyltin dilaurate, and dimethyltin bis(2-neodecanoate) may be exemplified.

In the present application, the wax on which the active substance is immobilized may contain, for example, a reaction catalyst in a range of 0.1 to 5 parts by weight per 100 parts by weight of the reactive wax. In the present application, the wax on which the active substance is immobilized may, in other examples, contain 0.11 parts by weight or more, 0.12 parts by weight or more, 0.13 parts by weight or more, 0.14 parts by weight or more, 0.15 parts by weight or more, 0.16 parts by weight or more, 0.17 parts by weight or more, 0.18 parts by weight or more, or 0.19 parts by weight or more, or 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, 3 parts by weight or less, 2.5 parts by weight or less, 2 parts by weight or less, 1.5 parts by weight or less, 1 part by weight or less, or 0.5 parts by weight or less of the reaction catalyst per 100 parts by weight of the reactive wax.

In the present application, the polymer resin may be at least one selected from the group consisting of, for example, polyolefins such as polyethylene and polypropylene; ethylene copolymers such as an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-butyl methacrylate copolymer. The above polyolefin may be, for example, a high density polyolefin, a medium density polyolefin, a linear low density polyolefin, or a low density polyolefin.

In the present application, the active agent may include, for example, a metal nitrate. The metal nitrate may be, for example, at least one selected from the group consisting of titanium nitrate, silver nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, and copper nitrate.

In the present application, the active agent may additionally include, for example, a surfactant. Examples of the surfactant include starch, polyethylene glycol, or polyvinyl alcohol.

The active agent of the present application may, for example, contain the surfactant in a range of 1 to 20 parts by weight relative to 100 parts by weight of the metal nitrate. In another example, the active agent of the present application may contain the surfactant in an amount of 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, or 12 parts by weight or more, or 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, or 13 parts by weight or less, relative to 100 parts by weight of the metal nitrate. The active agent of the present application may have excellent dispersibility and may enable control of impurities by containing the surfactant in the above range.

In the present application, the active agent may further include, for example, ion-exchange water. The active agent of the present application may include, for example, 1000 to 5000 parts by weight of ion-exchange water with respect to 100 parts by weight of the metal nitrate. In another example, the active agent of the present application may include 1200 parts by weight or more, 1400 parts by weight or more, 1600 parts by weight or more, 1800 parts by weight or more, 2000 parts by weight or more, 2200 parts by weight or more, or 2400 parts by weight or more of ion-exchange water with respect to 100 parts by weight of the metal nitrate, or 4500 parts by weight or less, 4000 parts by weight or less, 3500 parts by weight or less, or 3000 parts by weight or less.

The active agent of the present application can have a desired average particle size, etc. while being economical by controlling the composition and/or weight ratio, etc. as described above.

The above active agent can have an average particle size of, for example, 10 to 80 nm. The average particle size can be measured by a scanning electron microscope. The average particle size of the above active agent can be, in other examples, 11 nm or more, 12 nm or more, 13 nm or more, 14 nm or more, 15 nm or more, 16 nm or more, 17 nm or more, 18 nm or more, or 19 nm or more, or 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, or 30 nm or less.

The antifouling composition of the present application may, for example, contain the wax on which the active material is fixed in an amount of 5 to 30 parts by weight per 100 parts by weight of the polymer resin. In another example, the antifouling composition of the present application may contain the wax on which the active material is fixed in an amount of 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, or 11 parts by weight or more, or 28 parts by weight or less, 26 parts by weight or less, 24 parts by weight or less, 22 parts by weight or less, 20 parts by weight or less, 18 parts by weight or less, 16 parts by weight or less, or 14 parts by weight or less, per 100 parts by weight of the polymer resin.

The antifouling composition of the present application may, for example, contain the active agent in a range of 0.05 to 2.5 parts by weight per 100 parts by weight of the polymer resin. In another example, the antifouling composition of the present application may contain 0.1 part by weight or more, 0.15 part by weight or more, 0.2 part by weight or more, 0.25 part by weight or more, 0.3 part by weight or more, 0.35 part by weight or more, 0.4 part by weight or more, 0.45 part by weight or more, 0.5 part by weight or more, 0.55 part by weight or more, 0.6 part by weight or more, 0.65 part by weight or more, 0.7 part by weight or more, 0.75 part by weight or more, 0.8 part by weight or more, 0.85 part by weight or more, 0.9 part by weight or more, or 0.95 part by weight or more, or 2 parts by weight or less or 1.5 parts by weight or less, per 100 parts by weight of the polymer resin.

The antifouling composition of the present application may further comprise, for example, an additive. Examples of the additive include a pH regulator, an ultraviolet-blocking pigment, an antioxidant, an amine light stabilizer, and/or a stabilizer selected from a benzophenone compound.

Examples of the pH regulator include, but are not limited to, sodium hydroxide, ammonia, or trisodium citrate. The pH regulator may be included, for example, in an amount of 0.0001 to 0.1 part by weight relative to 100 parts by weight of the polymer resin.

Examples of the above UV-blocking pigment include carbon black, graphite, iron oxide, titanium dioxide, tungsten oxide, or cerium oxide, and one or more types may be used. The above UV-blocking pigment may be included in an amount of, for example, 0.7 to 1.2 parts by weight relative to 100 parts by weight of the polymer resin.

The antioxidants mentioned above include 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, Examples thereof include 3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, and one or more thereof may be selected and used. The above antioxidant may be included, for example, in an amount ranging from 0.65 to 1.05 parts by weight per 100 parts by weight of the polymer resin.

The above amine light stabilizer may be N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, or Hindered amine light stabilizers such as bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate can be exemplified, and one or more types can be selected and used. The amine light stabilizer can be included in an amount of, for example, 0.3 to 0.7 parts by weight relative to 100 parts by weight of the polymer resin.

Examples of the stabilizer include benzophenone compounds such as 2-hydroxy-4-(octyloxy)benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, or benzophenone, and one or more of these may be selected and used. The above stabilizer may be included, for example, in an amount of 0.3 to 0.7 parts by weight relative to 100 parts by weight of the polymer resin. By including the stabilizer in the above range, the antifouling composition of the present application can have excellent long-term photostability while controlling the phenomenon of the stabilizer being transferred to the surface of the antifouling composition.

Another aspect of the present application relates to a method for producing an antifouling composition. The content of the antifouling composition described above can be equally applied to the method for producing an antifouling composition of the present application.

The method for preparing the antifouling composition of the present application may include, for example, a step of fixing an active material to a reactive wax. The step of fixing the active material to the reactive wax may include, for example, a step of mixing a reactive wax, an active material, and/or a reaction catalyst to form a mixture; and/or a step of soaking the mixture.

In the method for producing the antifouling composition of the present application, the step of soaking the mixture can be performed at a temperature of, for example, 50°C to 120°C. The step of soaking the mixture can be performed at a temperature of, for example, 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, or 75°C or higher, or at a temperature of, for example, 115°C or lower, 110°C or lower, 105°C or higher, 100°C or lower, 95°C or lower, 90°C or lower, or 85°C or lower. The step of soaking the mixture can be performed for, for example, 10 minutes to 60 minutes. The step of soaking the mixture can be performed for, for example, 15 minutes or higher, 20 minutes or higher, or 25 minutes or higher, or for 55 minutes or lower, 50 minutes or lower, 45 minutes or lower, 40 minutes or lower, or 35 minutes or lower.

In the method for producing the antifouling composition of the present application, the step of forming a mixture by mixing a reactive wax, an active substance and/or a reaction catalyst may be performed by sequentially administering the reactive wax, the active substance and/or the reaction catalyst or by administering them in any order.

The method for producing the antifouling composition of the present application may further include, for example, a step of extracting an active substance from a marine organism. The step of extracting the active substance from the marine organism may include, for example, a step of extracting bacteria or fungi from the marine organism; a step of culturing the extracted bacteria or fungi to prepare a culture solution; and/or a step of extracting the active substance from the culture solution. The step of extracting the active substance from the culture solution may include, for example, a step of adding an organic solvent such as hexane, toluene, diethyl ether, dichloromethane or ethyl acetate to the culture solution. The step of extracting the active substance from the culture solution may be performed, for example, by a liquid-liquid extraction method.

The method for preparing the antifouling composition of the present application may additionally include a step of preparing a reactive wax.

The step of preparing the above reactive wax may be performed, for example, under inert conditions. The inert conditions may mean, for example, forming an inert gas atmosphere by purging with an inert gas such as nitrogen, argon or helium of 99% or more, or in other examples, 99.5% or more, 99.7% or more or 99.9% or more.

The step of preparing the above reactive wax may include, for example, a step of mixing and stirring a polyolefin wax and a reaction solvent. The stirring may be performed at, for example, a speed of 100 to 2000 RPM. In other examples, the stirring may be performed at a speed of 200 RPM or more, 300 RPM or more, 400 RPM or more, 500 RPM or more, 600 RPM or more, or 700 RPM or more, or at a speed of 1900 RPM or less, 1800 RPM or less, 1700 RPM or less, 1600 RPM or less, 1500 RPM or less, 1400 RPM or less, 1300 RPM or less, 1200 RPM or less, 1100 RPM or less, 1000 RPM or less, or 900 RPM or less. The stirring may be performed at a temperature in the range of, for example, 100° C. to 160° C. The above stirring may be performed at a temperature of, in other examples, 102°C or higher, 104°C or higher, 106°C or higher, 108°C or higher, 110°C or higher, 112°C or higher, 114°C or higher, 116°C or higher, or 118°C or higher, or at a temperature of 190°C or lower, 180°C or lower, 170°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, or 130°C or lower.

The step of preparing the above reactive wax may include, for example, a step of adding an acryloyl isocyanate and/or an initiator and reacting. The step of adding an acryloyl isocyanate and/or an initiator and reacting may be performed, for example, at a temperature equal to the stirring temperature for 2 to 8 hours.

The step of preparing the reactive wax may further include, for example, a step of adding methanol or ethanol; a step of drying; and/or a step of pelletizing. The methanol or ethanol may be added in an amount of 10 to 50 parts by weight relative to 100 parts by weight of the polyolefin wax. The drying step may be performed, for example, at a temperature in a range of 40° C. to 90° C. for 15 to 30 hours.

The method for preparing the antifouling composition of the present application may include, for example, a step of preparing an active agent. The step of preparing the active agent may include, for example, a step of mixing ion-exchange water, a metal nitrate, and/or a surfactant to form a mixture; a step of stirring the mixture; a step of drying and/or a step of calcining. The step of stirring the mixture may be performed two or more times, for example, under different conditions. In one example, the step of stirring the mixture may include a step of stirring the mixture at a speed of 300 to 700 RPM (first stirring); and a step of adding a solution dropwise to the mixture and stirring at a speed of 800 to 1200 RPM (second stirring). The second stirring may be performed at, for example, a temperature within a range of 70° C. to 120° C., and may be performed for a time within a range of 150 to 300 minutes. The solution may be formed by dissolving ammonia in ion-exchange water. In the step of manufacturing the active agent of the present application, the drying step can be performed, for example, at a temperature in the range of 60°C to 100°C for 16 to 30 hours. In the step of manufacturing the active agent of the present application, the calcining step can be performed, for example, at a temperature in the range of 400°C to 1000°C for 2 to 8 hours, and in another example, can be performed at a temperature in the range of 500°C to 700°C for 3 to 5 hours.

The method for producing the antifouling composition of the present application may further include, for example, a step of mixing and pelletizing a polymer resin, a wax having an active material fixed therein, an active auxiliary agent and/or an additive. The step of mixing and pelletizing the polymer resin, a wax having an active material fixed therein, an active auxiliary agent and/or an additive may be performed, for example, at a temperature of 80° C. to 300° C. for 20 to 40 minutes.

The present invention will be specifically described based on the following examples, but the scope of the present invention is not limited thereto.

Example 1

Preparation of reactive wax

10,000 g of xylene and 1,000 g of polyethylene wax were added to a nitrogen-purged reactor, stirred at a speed of 800 RPM, the reactor temperature was raised to 120 °C, and stirred until the polyethylene wax was completely melted. 150 g of acryloyl isocyanate and 2 g of dicumyl peroxide were added to the reactor, and the reaction was performed for 4 hours. The reaction was terminated by cooling the reactor to room temperature. 2,000 g of methanol was added thereto, and the precipitated reactant was filtered, washed, dried in an oven at 60 °C for 24 hours, and pelletized to prepare a reactive wax.

Extraction and separation of active substances from marine organisms

Acinetobacter sp. extracted from brown algae was grown in 100 mL Zobell marine agar culture medium at 30 °C for 24 hours, inoculated into a 50 L incubator, and cultured for 20 days. The culture medium was centrifuged to remove solids, followed by repeated liquid-liquid extraction with ethyl acetate, and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent was evaporated on a rotary evaporator, and the residue was purified by chromatography to produce 6-bromindol-3-carbalhydride active substance.

Preparation of wax with fixed active substance

10,000 g of the above-mentioned manufactured reactive wax, 2,000 g of the above-mentioned manufactured active substance, and 20 g of dibutyl tin dilaurate were sequentially added to a Henschel mixer, and then soaked at a temperature of 80° C. for 30 minutes to produce a wax with the active substance fixed therein.

Preparation of active ingredients

10,000 g of ion-exchange water, 400 g of silver nitrate, and 50 g of polyethylene glycol were added to a reactor and dissolved while stirring at a speed of 500 RPM. 200 g of a solution prepared by dissolving 8.5 parts by weight of ammonia per 100 parts by weight of ion-exchange water was added dropwise over 30 minutes, the reactor temperature was raised to 95 °C, stirred at a speed of 1,000 RPM for 240 minutes, and then cooled to room temperature. The cooled mixture was filtered and washed, dried in an oven at 80 °C for 24 hours, and then calcined in a heating furnace maintained at 600 °C for 4 hours to prepare an active agent having an average particle size of 20 nm.

Preparation of polymer complex composition with immobilized active substance

In a kneader mixer, 100,000 g of high-density polyethylene, 12,000 g of the wax having the active substance fixed therein, 1,000 g of the active auxiliary agent prepared above, 800 g of carbon black, 850 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 500 g of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 500 g of 2-hydroxy-4-(octyloxy)benzophenone were sequentially added, melted and mixed at a temperature of 120°C for 30 minutes, and the resulting lump dough was transferred to a twin-screw extruder to manufacture composition pellets having a size of 2 to 4 mm through extrusion molding, and then dried in an oven at 80°C and subjected to a particle size screening process. A polymer complex composition with an active substance immobilized therein was prepared.

Example 2

Preparation of reactive wax

10,000 g of xylene and 1,000 g of polypropylene wax were added to a nitrogen-purged reactor, stirred at a speed of 800 RPM, the reactor temperature was raised to 120 °C, and stirred until the polypropylene wax was completely melted. 150 g of methacryloyloxyethyl isocyanate and 2 g of di-tert-butyl peroxide were added to the reactor, and the reaction was performed for 4 hours. The reaction was terminated by cooling the reactor to room temperature. 2,000 g of methanol was added thereto, and the precipitated reactant was filtered, washed, dried in an oven at 60 °C for 24 hours, and pelletized to prepare a reactive wax.

Extraction and separation of active substances from marine organisms

Letendraea helminthicola, a fungus extracted from a sponge, was grown on 100 mL of Conidia IDFP agar culture medium at 28°C for 24 hours , inoculated into a 50 L incubator, and cultured for 20 days. The culture medium was centrifuged to remove solids, followed by repeated liquid-liquid extraction with ethyl acetate. The organic phase was collected and dried over anhydrous sodium sulfate. The solvent was evaporated on a rotary evaporator, and the residue was purified by chromatography to produce 3-methyl-N-(2-phenylethyl) butanamide, an active ingredient.

Preparation of wax with fixed active substance

10,000 g of the above-mentioned manufactured reactive wax, 2,000 g of the above-mentioned manufactured active substance, and 20 g of dibutyl tin dilaurate were sequentially added to a Henschel mixer, and then soaked at a temperature of 80° C. for 30 minutes to produce a wax in which the active substance was fixed.

Preparation of active ingredients

10,000 g of ion-exchange water, 400 g of silver nitrate, and 50 g of polyethylene glycol were added to a reactor and stirred at a speed of 500 RPM to dissolve the mixture. 200 g of a solution prepared by dissolving 8.5 parts by weight of ammonia per 100 parts by weight of ion-exchange water was added dropwise over 30 minutes, the reactor temperature was raised to 95 °C, stirred at a speed of 1,000 RPM for 240 minutes, and then cooled to room temperature. The cooled mixture was filtered and washed, dried in an oven at 80 °C for 24 hours, and then calcined in a heating furnace maintained at 600 °C for 4 hours to prepare an active agent having an average particle size of 20 nm.

Preparation of polymer complex composition with immobilized active substance

In a kneader mixer, 100,000 g of polypropylene , 12,000 g of the wax having the active substance fixed therein, 1,000 g of the active auxiliary agent prepared above, 800 g of carbon black, 850 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 500 g of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 500 g of 2-hydroxy-4-(octyloxy)benzophenone were sequentially added and melted at a temperature of 180°C for 30 minutes. The resulting lump dough was transferred to a twin-screw extruder to produce composition pellets of 2 to 4 mm in size through extrusion molding, and then dried in an oven at 80°C and subjected to a particle size screening process to obtain the active substance. A fixed polymer complex composition was prepared.

Example 3

Preparation of reactive wax

10,000 g of xylene and 1,000 g of polyethylene wax are added to a nitrogen-purged reactor, stirred at a speed of 800 RPM, the reactor temperature is raised to 120 °C, and stirred until the polyethylene wax is completely melted. 150 g of methacryloyloxyethyl isocyanate and 2 g of dicumyl peroxide are added to the reactor, the reaction is performed for 4 hours, and the reaction is terminated by cooling the reactor to room temperature. 2,000 g of methanol is added thereto, and the precipitated reactant is filtered, washed, dried in an oven at 60 °C for 24 hours, and pelletized to produce a reactive wax.

Extraction and separation of active substances from marine organisms

The fungus Scopulariopsis sp. extracted from coral was grown in 100 mL of Conidia adieffhi agar culture medium at 28°C for 24 hours, inoculated into a 50 L incubator, and cultured for 20 days. The culture medium was centrifuged to remove solids, followed by repeated liquid-liquid extraction with ethyl acetate, and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent was evaporated on a rotary evaporator, and the residue was purified by chromatography to produce dihydroquinolin-2(1H)-one active ingredient .

Preparation of wax with fixed active substance

10,000 g of the above-mentioned manufactured reactive wax, 2,000 g of the above-mentioned manufactured active substance, and 20 g of dibutyl tin dilaurate were sequentially added to a Henschel mixer, and then soaked at a temperature of 80° C. for 30 minutes to produce a wax with the active substance fixed therein.

Preparation of active ingredients

10,000 g of ion-exchange water, 400 g of silver nitrate, and 50 g of polyethylene glycol were added to a reactor and dissolved while stirring at a speed of 500 RPM. 200 g of a solution prepared by dissolving 8.5 parts by weight of ammonia per 100 parts by weight of ion-exchange water was added dropwise over 30 minutes, the reactor temperature was increased to 95 °C, stirred at a speed of 1,000 RPM for 240 minutes, and then cooled to room temperature. The cooled mixture was filtered and washed, dried in an oven at 80 °C for 24 hours, and then calcined in a heating furnace maintained at 600 °C for 4 hours to prepare an active agent having an average particle size of 20 nm.

Preparation of polymer complex composition with immobilized active substance

In a kneader mixer, 100,000 g of ethylene-vinylacetate copolymer , 12,000 g of wax having the active material fixed therein, 1,000 g of the active auxiliary agent prepared above, 800 g of carbon black, 850 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 500 g of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 500 g of 2-hydroxy-4-(octyloxy)benzophenone were sequentially added, melted and mixed at a temperature of 100°C for 30 minutes, and the resulting lump dough was transferred to a twin-screw extruder to produce composition pellets having a size of 2 to 4 mm through extrusion molding, and then dried in an oven at 80°C. A polymer complex composition with an active substance immobilized therein was manufactured through a particle size selection process.

Example 4

A polymer complex composition with an active substance immobilized therein was manufactured in the same manner as in Example 1, except that the active substance extraction and separation steps of Example 1 were performed as follows.

Extraction and separation of active substances from marine organisms

Pseudomonas sp. bacteria extracted from snails were grown in 100 mL Zobel Marine agar culture medium at 30°C for 24 hours , inoculated into a 50 L incubator, and cultured for 20 days. The culture medium was centrifuged to remove solids, then liquid-liquid extracted with ethyl acetate was repeated, and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent was evaporated in a rotary evaporator, and the residue was repeatedly fractionated using a chromatography device to produce the active ingredient phenazine-1-carboxylic acid .

Example 5

A polymer complex composition with an active substance immobilized therein was manufactured in the same manner as in Example 1, except that the active substance extraction and separation steps of Example 1 were performed as follows.

Extraction and separation of active substances from marine organisms

Acinetobacter sp. bacteria extracted from the genus Acinetobacter were grown in 100 mL Zobel Marine agar culture medium at 30°C for 24 hours , inoculated into a 50 L incubator, and cultured for 20 days. The culture medium was centrifuged to remove solids, and liquid-liquid extraction was repeated with ethyl acetate. The organic phase was collected and dried over anhydrous sodium sulfate. The solvent was evaporated on a rotary evaporator, and the residue was repeatedly fractionated using chromatography equipment to obtain 6-bromindol-3-carbalhydride. The active substance was manufactured .

Example 6

In the manufacturing step of the polymer complex composition of Example 5, a polymer complex composition having an active substance immobilized therein was manufactured in the same manner as in Example 5, except that an ethylene-ethyl acrylate copolymer was used instead of high-density polyethylene.

Example 7

In the manufacturing step of the polymer complex composition of Example 5, a polymer complex composition having an active material immobilized therein was manufactured in the same manner as in Example 5, except that an ethylene-acrylic acid copolymer was used instead of high-density polyethylene.

Example 8

In the step of manufacturing the active ingredient in Example 1, a polymer complex composition with an active ingredient immobilized therein was manufactured in the same manner as in Example 1, except that magnesium nitrate was used instead of silver nitrate.

Example 9

In the step of manufacturing the active agent of Example 1, a polymer complex composition having an active substance immobilized therein was manufactured in the same manner as in Example 1, except that titanium nitrate was used instead of silver nitrate.

Example 10

In the step of manufacturing the active agent of Example 1, a polymer complex composition having an active substance immobilized therein was manufactured in the same manner as in Example 1, except that aluminum nitrate was used instead of silver nitrate.

Comparative Example 1

Preparation of active ingredients

An active ingredient was prepared in the same manner as in Example 1.

Preparation of polymer composite compositions

100,000 g of high-density polyethylene, 1,000 g of the above-mentioned manufactured active agent, 800 g of carbon black, 850 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 500 g of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 500 g of 2-hydroxy-4-(octyloxy)benzophenone were sequentially added to a kneader mixer and melt-mixed at a temperature of 120°C for 30 minutes. The resulting lump dough was transferred to a twin-screw extruder to produce composition pellets of 2-4 mm in size through extrusion molding, followed by drying in an oven at 80°C and going through a particle size screening process to produce a polymer composite composition.

Comparative Example 2

A polymer complex composition was prepared in the same manner as in Example 1, except that no active agent was introduced.

Comparative Example 3

A polymer complex composition was prepared in the same manner as in Example 1, except that 100,000 g of high-density polyethylene, 10,000 g of polyethylene wax, 2,000 g of the active substance, 800 g of carbon black, 850 g of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 500 g of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 500 g of 2-hydroxy-4-(octyloxy)benzophenone were sequentially added to a kneader mixer without the step of preparing a wax on which the active substance is fixed.

The polymer complex composition thus manufactured was hot-pressed to produce sheets at a temperature of 100 to 180°C, and the seawater release rate, antibacterial properties, antifouling properties, and discoloration were evaluated.

The seawater release rate (%) was derived using Equation 1 below.

[Formula 1]

Seawater release rate (%) = (Initial mass of sheet - Mass of sheet left in seawater) × 100 / (Initial mass of sheet)

In the above equation 1, the initial mass of the sheet means the mass before the manufactured 10 cm x 10 cm sheet is placed in seawater, and the mass of the sheet left in seawater means the mass after the manufactured 10 cm x 10 cm sheet is immersed in seawater and left at a temperature of 80°C for 14 days.

Antibacterial properties were tested against Escherichia coli and Staphylococcus aureus using the manufactured sheet (5 cm x 5 cm) according to the standards of KS M ISO 22196.

[Antibacterial Evaluation Criteria]

Excellent: Bacteria reduction rate of 90% or more

Good: Bacterial reduction rate less than 90%, more than 80%

Normal: Bacterial reduction rate less than 80%, more than 50%

None: Less than 50% bacterial reduction

The evaluation of water resistance and discoloration was conducted by qualitatively evaluating the condition of the sheet after leaving the manufactured sheet in seawater for 60 days at room temperature.

[Anti-fouling evaluation criteria]

Excellent: The degree of contamination of the sheet after exposure to seawater is less than 10% of the total sheet area.

Normal: After being exposed to seawater, the contamination level of the sheet is more than 10% and less than 30% of the total sheet area.

Bad: The degree of contamination of the sheet after exposure to seawater exceeds 30% of the total sheet area.

[Discoloration Evaluation Criteria]

Present: Color change upon visual observation

None: No color change observed with the naked eye

division Example 1 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Seawater discharge rate (%) 0.1 0.1 0.1 0.3 0.2 0.8 Antibacterial (E. coli, Staphylococcus aureus) excellence excellence excellence doesn't exist commonly Good Anti-fouling (anti-marine organism adhesion) excellence excellence excellence Bad Bad commonly discoloration doesn't exist doesn't exist doesn't exist doesn't exist doesn't exist doesn't exist

Claims (15)

Polymer resin; containing wax with fixed active material and active agent,
The wax in which the above active substance is fixed contains the active substance in the range of 10 to 50 parts by weight per 100 parts by weight of the reactive wax,
The above reactive wax is a polyolefin wax containing acryloyl isocyanate,
The above active substance is an active substance derived from marine organisms,
The above active agent is an antifouling composition containing a metal nitrate.
In claim 1, an antifouling composition comprising an acryloyl isocyanate in an amount of 5 to 50 parts by weight per 100 parts by weight of polyolefin wax.
delete In claim 1, the marine organism-derived active substance is 6-bromindole-3-carbaldhyde, 3-methyl-N-(2-phenylethyl) butanamide, cyclo-D-phenylalanyl-L-proline, dihydroquinolin-2(1H)-one, pyolipic acid, phenazine-1-carboxylic acid, 6-bromindole-3-carbaldhyde, resorcyclic acid lactone, di(1H-indol-3-yl) methane, (5Z)-4-bromo-5-(bromomethylene)-3-butyl-2(5H)-furanone, galactoglycerolipid, sesquiterpenoid(-)-gleenol, sn-3-O-(geranylgeranyl)glycerol, cystophloroketals AE, meroditerpenoid, 1-O-octadecenoylglycerol, An antifouling composition comprising at least one selected from the group consisting of sn-3-Ο-(geranylgeranyl)glycerol, diterpene, 6-octadecenoic acid, dimethylsulphopropionate, and proline.
In claim 1, an antifouling composition wherein the polymer resin is at least one selected from the group consisting of polyolefin or ethylene copolymer.
delete In the first paragraph, the antifouling composition has an average particle size of 10 to 80 nm.
An antifouling composition comprising, in claim 1, 11 to 15 parts by weight of a wax having an active material fixed therein, per 100 parts by weight of a polymer resin.
An antifouling composition comprising an active agent in an amount of 0.05 to 2.5 parts by weight per 100 parts by weight of a polymer resin in claim 1.
An antifouling composition according to claim 1, further comprising an additive.
A method for producing an anti-fouling composition according to Article 1,
A method for preparing an antifouling composition comprising the step of fixing an active substance to a reactive wax.
In claim 11, a method for producing an antifouling composition, wherein the step of fixing the active material to the reactive wax comprises the steps of: forming a mixture by mixing the reactive wax, the active material, and the reaction catalyst; and soaking the mixture.
A method for producing an antifouling composition, wherein in claim 12, the step of soaking the mixture is performed at a temperature of 50°C to 120°C.
A method for producing an antifouling composition, further comprising a step of extracting an active substance from marine organisms in claim 11.
In claim 14, a method for producing an antifouling composition, wherein the step of extracting an active substance from a marine organism comprises: a step of extracting bacteria or fungi from the marine organism; a step of culturing the extracted bacteria or fungi to produce a culture solution; and a step of extracting an active substance from the culture solution.