JP2007277431A - Organism antifouling agent, antifouling treatment method and antifouling treated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new antifouling agent against organisms, which takes the environment into account, is safe to marine products for foods and has an excellent antifouling effect. <P>SOLUTION: The organism antifouling agent comprises an organism antifouling polymer fine particle and a coating film-forming material. The polymer fine particle contains at least one kind of a group selected from the group consisting of a hydrophilic group (a), an amphoteric group (b) and an organism repellent group (c). The organism repellent group (c) is at least one kind selected from the group consisting of an amino group, an quaternary ammonium group, a pyridine group, a pyridinium group, a phenolic hydroxy group and a polyethylene glycol group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a biological antifouling agent, an antifouling treatment method, and an antifouling treatment article, and more particularly, an aquatic biofouling antifouling agent using polymer fine particles having aquatic biofouling resistance and a substrate using the same. The present invention relates to an antifouling treatment method and an antifouling treatment article.

  In marine navigating ships, etc., creatures that live in seawater during navigation adhere to or are fixed to the bottom and side surfaces of the ship that are submerged in seawater. The abrasion resistance between these attached organisms and seawater causes a decrease in the navigation speed of the ship, increases the consumption of fuel, increases the frequency of repairs, and causes a lot of economic damage. Has brought. Also, in marine fish farms, marine organisms adhere to the segregated nets in the same way, preventing the inflow of fresh seawater due to the decrease in the openings of the nets, which is detrimental to the growth of farmed fish.

  There are a large number of organisms that inhabit seawater and adhere to hulls and structures in the sea. Aquatic animals include barnacles, bryozoans, selbras, and frogs. In particular, barnacles and seaweeds can be mentioned.

  In order to prevent adhesion of these aquatic organisms, a paint containing a tin compound or a copper compound has been conventionally used as a ship bottom antifouling paint. However, those tin compounds and copper compounds are dissolved in seawater, causing environmental pollution and pollution to fish, shellfish, seaweeds, etc. It has become a big social problem.

  The present invention has been made in view of the above circumstances, and the physiological and physical effects of aquatic organisms found by examining the mechanism of the aquatic organisms' establishment, growth, and shedding on the bottom of a ship, nets, etc. By using non-eluting organic material that does not elute into seawater as an antifouling ingredient, it is a new water tank that is environmentally friendly, safe for edible marine products and has an excellent antifouling effect. It is an object of the present invention to provide a biological antifouling agent, a method for antifouling treatment of a substrate using the same, and an antifouling treatment article.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that polymer fine particles are safe organic substances and may fall off as particles when immersed in seawater for a long time. It was found that it is not a material that elutes into water, does not pollute the environment, and is safe for marine resources. By giving antifouling property to these polymer fine particles and allowing the fine particles to be present at a high density on the surface of the coating film containing the fine particles, the coating film reduces the adhesion of aquatic organisms and adheres. By inhibiting the growth of aquatic organisms, the aquatic organisms peel off from the surface of the substrate over time, and due to the weight of the attached aquatic organisms, the physical action such as the force of seawater flow is finally combined. Discovered the phenomenon that aquatic organisms fall off from the base material, and completed the present invention.

That is, the configuration of the present invention is as follows.
1. A biofouling agent comprising biofouling-resistant polymer fine particles and a film-forming material.
2. 2. The biofouling antifouling according to 1, wherein the polymer fine particles have at least one group selected from the group consisting of a hydrophilic group (a), an amphoteric group (b) and a biorepellent group (c). Agent.
3. The hydrophilic group (a) is at least one selected from the group consisting of an anionic group, a cationic group, a nonionic group and an anionic / nonionic amphoteric group, a cationic / nonionic amphoteric group, and an anionic / cationic amphoteric group. The biological antifouling agent according to 2 above.

4). 3. The biological antifouling agent according to 2 above, wherein the amphoteric group (b) is at least one selected from the group consisting of an anionic / nonionic amphoteric group, a cationic / nonionic amphoteric group and an anionic / cationic amphoteric group.
5). The biological repellent group (c) is at least selected from the group consisting of an aliphatic, alicyclic or aromatic amino group, quaternary ammonium group, pyridine group, pyridinium group, phenolic hydroxyl group and polyethylene glycol group. The biological antifouling agent according to 2 above, which is one type.
6). 6. The biological antifouling agent according to any one of 2 to 5, wherein the polymer fine particles are a mixture of polymer fine particles having different groups.
7). The biological antifouling agent according to any one of 1 to 6, wherein the mass ratio of the polymer fine particles (A) to the coating film forming material (B) is A: B = 95: 5 to 5:95.
8). A biological antifouling treatment method for a substrate, comprising applying the biological antifouling agent according to any one of 1 to 6 above to a substrate, impregnating or kneading the substrate.
9. A biological antifouling treatment article which has been subjected to a biological antifouling treatment by the treatment method according to 8.

  Tin compounds and copper compounds that have been used in conventional antifouling paints act to aquatic organisms by leaching their ions gradually, and aquatic organisms avoid or prevent adhesion to aquatic organisms. It had a function to drop off. On the other hand, the aquatic biofouling agent of the present invention uses polymer fine particles, particularly polymer fine particles having a biological repellent function, as the biofouling agent. These are safe organic substances that, when immersed in seawater for a long period of time, may fall off as particles, but are not materials that elute in water, are not polluting to the environment, are safe, In addition, edible marine products such as fish, shellfish and seaweed are not contaminated and are safe and hygienic.

  Although the biological antifouling agent of the present invention does not necessarily use soluble heavy metal ions, the mechanism that provides the antifouling effect is not necessarily completely elucidated, but the mechanism is a base material such as the bottom of aquatic organisms. Physiological and physical effects such as growth, growth and shedding are considered to be involved. In a coating film formed using a coating material containing polymer fine particles, the presence of the fine particles exposed on the surface thereof reduces the aquatic organism's settlement on the coating film, and the attached aquatic organism cells The growth of the fish was inhibited or killed, and the attached aquatic organisms tended to peel off from the substrate surface. As a result, even if other aquatic organisms adhere to the destroyed aquatic organisms, the attached and accumulated aquatic organisms are also based on their own weight and physical actions such as the force of seawater flow. It is considered to fall out of the material.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
As polymer fine particles used in the present invention, fine particles of all polymer systems such as known addition polymer systems, condensation polymer systems, and thermosetting polymer systems can be used. Addition polymer systems include vinyl, diene, and (meth) acrylic systems, condensation polymerization systems include ester, amide, and urethane systems, and thermosetting polymer systems include melamine-formaldehyde and phenol-formaldehyde. Polymer fine particles such as epoxy-based, epoxy-amine-based, and isocyanate-alcohol-based.

  The polymer fine particles have at least one group selected from the group consisting of a hydrophilic group (a), an amphoteric group (b) and a biorepellent group (c) on the surface thereof. It makes it difficult for aquatic organisms to adhere to the coating film surface. Hereinafter, polymer fine particles having a group selected from the hydrophilic group (a), the zwitterionic group (b) or the biorepellent group (c), a synthesis method thereof, and a production method of a mixture thereof will be described.

(A) By modifying the surface of the fine particles with a hydrophilic group, particularly a polymer chain having a hydrophilic group, a sol film or a gel film (hereinafter simply referred to as a water film or a water film) on the coating film surface comprising the paint containing the fine particles. Polymeric fine particles that may be collectively referred to as “water film.”) And prevent adhesion of aquatic organisms.
As the polymer fine particles, polymer fine particles whose surface is modified with a water film-forming hydrophilic group or a water film-forming polymer chain can be used. Examples of the hydrophilic group include an anionic group, a cationic group, a nonionic group, an anionic / cationic group, an anionic / nonionic group, and a cationic / nonionic group. Examples of anionic groups include sulfone groups, carboxyl groups, sulfate ester groups, and phosphate ester groups. Examples of cationic groups include primary, secondary, tertiary amino groups, quaternary ammonium groups, pyridine groups, and pyridinium. Examples of the nonionic group include a hydroxyl group, an amide group, and a polyethylene glycol group. The polymer chain having these hydrophilic groups is a monomer (co) polymer chain having the above-mentioned hydrophilic groups in the molecule.

  The polymer fine particles can be synthesized by a known method. The monomer used for the synthesis of the polymer fine particles can be a normal monomer or a macromonomer. As the polymerization medium, an organic solvent, a water-organic solvent mixed solvent and water are selected. As the polymerization method of the addition polymer, any known polymerization method suitable for the shape of the polymer fine particles, for example, solution polymerization, emulsion polymerization, suspension polymerization, and soap-free polymerization can be used. As the copolymer, random, block and graft copolymers can be used. As the polymer fine particles, single fine particles or core / shell fine particles can be used. A typical synthesis method is described below.

(A) A method of adding a hydrophilic group to polymer fine particles by mixing and copolymerizing a monomer having a hydrophilic group or a macromonomer with a raw material monomer when synthesizing polymer fine particles.
(Ii) When synthesizing polymer fine particles, a monomer or macromonomer having a group that can be easily changed to the hydrophilic group is mixed and copolymerized, and then easily changed to the hydrophilic group. A method of changing the resulting group to a hydrophilic group.
(A3) A method of copolymerizing a monomer having a reactive group in advance with a raw material monomer and then reacting with a reactive compound having a hydrophilic group in the synthesis of polymer fine particles.
(4) When synthesizing polymer fine particles, polymer fine particles that become cores are synthesized in advance, and a monomer having a hydrophilic group that can become a shell or a group that can be changed to a hydrophilic group is added to the surface of the fine particles. A method of impregnating, polymerizing, and performing the same as the above (ii) if necessary.

  Examples of the monomer having a hydrophilic group include styrene sulfonic acid and vinyl sulfonic acid; (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, half esters and half amides of these dicarboxylic acids; (Meth) acrylic acid ethyl sulfate ester; 2- (meth) acryloylethyl acid phosphate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trimethylammoniumethyl (meth) acrylate hydrochloride, 3-trimethylammonium ( 2-hydroxy) -propyl (meth) acrylate hydrochloride; vinylpyridine, vinylpyridinium hydrochloride and the like.

  Examples of amphoteric monomers include sulfoethylaminoethyl methacrylate, phosphocholine ethyl methacrylate, carbooxymethylaminoethyl methacrylate; maleic acid monodimethylaminoethyl ester-monocarboxylic acid, itaconic acid monodimethylaminoethyl ester-mono Carboxylic acid; Examples thereof include hydroxyethyl esters, glyceryl esters, polyethylene glycol esters, methoxypolyethylene glycol esters of monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, and itaconic acid.

  Polymer fine particles having a macromonomer graft copolymer chain having many hydrophilic groups and a polymer chain having a hydrophilic group bonded with a polyalkylene oxide chain (2 to 3 carbon atoms) as a spacer, Since such hydrophilic polymer chains can be eluted or diffused in seawater, it is easy to form a sol layer or gel layer containing water on the surface of the coating film, and the thickness of the water film is increased, which is effective for antifouling properties. It is.

  Examples of the group that can be easily changed to the hydrophilic group described in (i) above include an acid anhydride group and a lower alkyl ester group. Examples of the monomer include maleic anhydride, itaconic anhydride, ( And (meth) methyl acrylate.

  Examples of the reactive group of the reactive compound having a hydrophilic group described in (a) and the reactive group of the reactive monomer include an acid anhydride group, an acid halogenide group, a lower alkyl ester group, and an epoxy group. An isocyanate group, a methylol group, a methoxymethyl group, a halogenomethyl group, and the like; a hydroxyl group, an amino group, a carboxyl group, and the like. Examples of monomers having such reactive groups include maleic anhydride, itaconic anhydride, (meth) acrylic acid chloride, methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, and allyl. Glycidyl ether, (meth) acrylic acid ethyl isocyanate, isopropenyl phenylene methyl isocyanate, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, chloromethyl styrene, etc .; vinyl acetate (saponified to vinyl alcohol), hydroxyl alkyl ( C2-C6) (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid, maleic acid, itaconic acid and the like.

  Examples of the reactive compound having a hydrophilic group to be reacted with polymer fine particles having a reactive group include, for example, monochloroacetic acid, monochlorovaleric acid, glycolic acid, hydroxypropionic acid, thioglycolic acid, ε-caprolactone, and various amino acids. , Hydroxyethyl sulfuric acid, acidic sodium sulfite, sulfuric acid, sulfur trioxide, phosphoric acid, diethylamine, triethylamine, dimethylethanolamine, diethylethanolamine, N, N-diethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N-diethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopentane, aniline, 4-amino-N, N-diethylaniline and the like can be mentioned.

  Copolymerization of the monomer having the above group with a conventionally known hydrophobic monomer is also a preferable method for producing polymerizable fine particles. Examples of the hydrophobic monomer include styrene, ethylene, propylene, butadiene, isoprene, aliphatic (C1 to C30), aromatic (C6 to C15), and alicyclic (C6 to C15) of (meth) acrylic acid. ) Hydrocarbon esters and the like. Examples of the polyfunctional monomer that brings a cross-linking bond to the polymer fine particles include divinylbenzene, alkylene (C2-C4) glycol di (meth) acrylate, poly (C2-C30) alkylene (C2-C4) glycol. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, methylenebisacrylamide and the like can be mentioned.

(B) Polymer fine particles which modify the same or different polymer fine particles with a zwitterionic group, thereby imparting zwitterionic properties to the coating film, thereby preventing aquatic organisms from adhering to the coating film.
As a result of the immersion test in seawater, the coating containing zwitterionic fine particles showed a tendency to reduce the growth of aquatic organisms, and the growth of attached aquatic organisms was hindered. A tendency to peel off was observed. Many of the groups having a cell destruction function are positively charged amino groups. On the other hand, aquatic organisms are negatively charged. For this reason, by using fine particles having amino groups introduced, the coating film is positively charged, and there is a possibility that aquatic organisms are attracted to the positively charged coating film, while negative charge is applied to the coating film. By introducing it appropriately, the suction force can be eliminated, or a coating film having a repulsive force against aquatic organisms can be obtained.

  In addition, the presence of an anionic group and a cationic group at a very close distance in the coating film in contact with seawater allows both ionic groups to affect each other, and the anionic group and cation in the coating film There is a possibility that the sex group may frequently bind and dissociate with soluble ions such as sodium ions and chlorine ions in seawater, or the surface of the coating film may become a high ion concentration environment. As a result, the cells of the attached aquatic organisms are destroyed, and the attached aquatic organisms are killed and detached from the substrate surface.

  The polymer fine particles having the zwitterionic group include anionic groups such as sulfoethylamino group, phosphoethylamino group, phosphocholine hydrochloride, carboxymethylamino group, carboxyethylamino group, carboxymethylpyridinium group, and cationic groups. Polymer fine particles having a group can be used, and the amphoteric monomer having both an anionic group and a cationic group can be used for the production of the fine particles. Alternatively, the polychloromethylstyrene in the alternating polymer of poly (maleic acid-chloromethylstyrene) is bonded to water by forming an ion complex with the carboxylic acid of the adjacent maleic acid unit by attaching an amino bond or a pyridinium bond to the polychloromethylstyrene. Insoluble polymer fine particles can be prepared.

  Examples of the method for imparting amphoteric properties to the polymer fine particles include the same methods as described in (a) above. Furthermore, the coating film contains amphoteric properties by using polymer fine particles composed of two or more kinds of polymer mixtures having different ionic properties, and using a mixture of polymer fine particles each having different ionic groups. Can be made.

(C) Polymer fine particles capable of preventing the attachment of aquatic organisms by introducing biorepellent groups into the polymer fine particles, thereby providing a biorepellent effect on aquatic organisms on the surface of the coating film containing the fine particles.
The polymer fine particles having repellent groups are present in the coating film, particularly exposed on the coating surface, so that the cells of the attached aquatic organisms are destroyed and the growth is inhibited, and it peels off from the substrate surface. .

  Examples of biological repellent groups bonded to the polymer fine particles include amino groups, ammonium groups, pyridine groups, pyridinium groups, phenol groups, and polyethylene glycol groups. Specifically, for example, n-decylamino group, n-dodecylamino group, aliphatic amino group such as n-hexadecylamino group, alicyclic amino group, N, N-dimethyl-n-octylammonium group, N , N-dimethyl-n-decylammonium group, N, N-dimethyl-n-dodecylammonium group, N, N-dimethyl-n-hexadecylammonium group, aromatic amino group such as aniline group, anisidine group, etc. Ammonium group, 4-octylaniline group, 4-nonylaniline group, aliphatic hydrocarbon group-substituted aromatic amino group such as 4-dodecylaniline group, their ammonium group, pyridine group, pyridinium group, 4-octylpyridine group , 4-nonylpyridine group, 4-dodecylpyridine group and other aliphatic hydrocarbon-substituted pyridine groups, and their pyridi Umumoto, and the like phenol group, cresol group, a phenolic hydroxyl group and polyethylene glycol group, such as aminophenol group. These biorepellent groups are preferably linked to the polymer fine particles via a linking group in order not to separate and elute the group in seawater. Examples of the method for imparting biorepellency to the polymer fine particles include the same methods as described in (a) above.

(D) Polymer fine particles that combine the above-described functions and prevent adhesion of aquatic organisms.
The same polymer fine particles modified with two or more functional groups among the hydrophilic group (a), amphoteric group (b) and biorepellent group (c), or a polymer modified with one functional group By using a mixture of fine particles, it is possible to obtain an aquatic organism antifouling agent having a combined antifouling function.

  When the aquatic organism antifouling agent is used as an antifouling paint, it is preferable that the polymer fine particles in the formed coating film are always exposed to the coating film surface. For example, as a preferable method, there are a method in which polymer fine particles are added at a high concentration in the paint, a method in which the particle size of the polymer fine particles is relatively large, and the like. Furthermore, as the coating film forming material of the paint, the polymer fine particles in the coating film can be sequentially exposed to the surface by using a self-polishing (polishing) type film forming material that gradually dissolves from the surface. it can.

  Examples of the coating film forming material include synthetic rubber resins, acrylic resins, vinyl resins, chlorinated rubber resins, epoxy resins, silicone resins, fluorine resins, and their copolymer systems and mixed systems. Materials.

  In the aquatic biofouling agent described above, the blending mass ratio of the polymer fine particles (A) and the coating film forming material (B) is A: B = 95: 5 to 5:95, and the polymer fine particles are coated on the coating film. In the case of exposing the surface at a high density, the above A: B = 80: 20 to 30:70 is preferable.

  By applying and impregnating the biological antifouling agent of the present invention to the base material, or kneading and internally adding to the base material, the base material is biologically antifouling treated to obtain an aquatic biofouling antifouling treatment article. The aquatic organism antifouling agent of the present invention is used in the same applications as conventional antifouling paints, for example, for painting the bottom and side of a ship that is submerged in the seawater of marine navigating vessels, and also in marine fish farms. Can be used in a wide range of applications such as nets.

  Furthermore, as another embodiment, a synthetic resin is used as a building or member immersed in the sea, or a synthetic fiber is used as a fish net or an isolation net. The surface of these articles is coated with the biofouling agent of the present invention or the substrate is impregnated, and the biofouling agent is contained in these synthetic resin products and synthetic fiber products. The method of attaching is also an excellent method. It is also preferable to use a biobacterial antifouling agent masterbatch that is compatible with these substrates and a biofouling agent dispersion that is compatible with the substrate spinning solution. Examples of the synthetic resin include known resins such as polypropylene resin, polyethylene resin, polyvinyl chloride resin, synthetic rubber, polystyrene resin, ABS resin, nylon resin, polyester resin, and polycarbonate resin. Examples of the synthetic fiber include known fibers such as polypropylene fiber, polyethylene fiber, polyacrylonitrile fiber, nylon fiber, and polyester fiber.

  In addition, the antifouling agent of the present invention is suitable for biological stains such as fungi in washing places, washing places, sinks, washrooms, bathrooms, etc. in buildings and houses, or in houses, hospitals, public It can also be used as an antibacterial antifouling paint for air cleaner fins and fillers in facilities.

  Next, the present invention will be described more specifically with reference to examples. In the text, “part” or “%” is based on mass.

[Synthesis Example 1]
(1) A polymerization reactor equipped with a water bath as a heating device, a stirrer, a monomer dropping device, a reagent charging port, a backflow cooler, and a nitrogen gas blowing port was prepared. In this polymerization vessel, 100 parts of water, 342.5 parts of ethanol and 6 parts of polyacrylic acid (average molecular weight: 250,000) as a dispersion stabilizer were charged and stirred to dissolve the polyacrylic acid. Next, 45 parts of styrene (St) and 0.75 part of azobisisobutyronitrile (AIBN) were mixed and added as monomers, and the mixture was stirred at 70 ° C. for 8 hours under a nitrogen gas stream to perform suspension polymerization. The particle size of the obtained polymer was about 1 μm as measured by the dynamic light scattering method. Further, a mixed liquid of 25 parts of chloromethylstyrene (CMS), 12.5 parts of divinylbenzene (DVB) and 0.56 parts of AIBN was added to this suspension polymerization liquid, stirred, and then at 70 ° C. for 8 hours under a nitrogen gas stream. Polymerization was performed to obtain core-shell type crosslinked fine polymer particles having a reactive chloromethyl group on the surface. Using a centrifuge, polymer fine particles were separated from the polymerization reaction mixture and washed. The obtained crosslinked polymer fine particles were redispersed in a xylene / n-butanol mixed solvent (75:25) (solid content: 21.6%). The polymerization reaction and synthesis reaction in each of the following synthesis examples were also performed using the same apparatus.

(2) 107.2 parts of a 50% xylene / n-butanol mixed solvent (75:25) solution of diglycidyl ether (epoxy equivalent: 268) of polyethylene glycol (PEG) (average polymerization degree: about 9) was charged. Thereto, 41.2 parts of a 50% xylene / n-butanol mixed solvent (75:25) solution of octylaniline was added dropwise at 85 to 90 ° C. over 3 hours, and the mixture was further stirred at 90 to 115 ° C. for 4 hours. Next, 15.0 parts of a 50% methyl isobutyl ketone (MIBK) solution of diethylamine (DEA) was added dropwise at 50 ° C. over 3 hours, and the mixture was further stirred at 50 to 55 ° C. for 5 hours to cause the reaction to be tertiary aminated. did. A mixture solution of a PEG derivative mainly composed of PEG having one end having an octylaniline group and a 3-diethylamino (2-hydroxy) propyl group bonded to the other end was obtained (solid content: 51.8%). The progress of the reaction at each stage was confirmed by infrared spectrum.

(3) A reaction vessel was charged with 250 parts of a dispersion of core-shell type crosslinked polymer fine particles having a chloromethyl group obtained in (1) above, and then 3-diethylamino (2-hydroxy) obtained in (2) above. 27.0 parts of a xylene / n-butanol mixed solvent (75:25) solution containing 13.5 parts of a PEG derivative in which a propyl group and a 3-octylphenylamino (2-hydroxy) propyl group are bonded to each other at 70 ° C. For 3 hours and at 80 ° C. for 5 hours. After the reaction, the reaction solution was poured into 300 parts of ethanol, and polymer fine particles were separated by filtration and washed with ethanol. Unreacted PEG derivatives were separated by filtration, and a crosslinked polymer fine particle paste modified partly with octylaniline via a PEG chain, partly contributing to bonding between particles was obtained. Hereinafter, it is referred to as “repellent fine particles-1”.

[Synthesis Example 2]
(1) In the same manner as in Synthesis Example 1 (2), 59.6 parts of a 10% xylene / n-butanol mixed solvent solution of diglycidyl ether (epoxy equivalent: 551) of PEG (approximately average polymerization degree: 22) was added. Prepared. Thereto, 5 parts of octylaniline was added dropwise at 85 to 90 ° C. over 3 hours, and further stirred at 90 to 115 ° C. for 4 hours. Next, 2.3 parts of chloroacetic acid was charged and reacted at 50 ° C. Subsequently, 2.67 parts of methyl chloroacetate was added to the reaction solution, reacted at 50 ° C. for 8 hours, adjusted to pH 8-9 with sodium hydroxide, and distilled under reduced pressure to remove methyl chloroacetate. Subsequently, 1.8 parts of DEA was added dropwise at 50 ° C. over 3 hours, and the mixture was further stirred at 50 to 55 ° C. for 5 hours to cause a tertiary amination. A PEG mixed derivative solution containing PEG having one end as a carboxylated octylaniline group and a 3-diethylamino (2-hydroxy) propyl group bonded to the other end as a main component was obtained. Progress of the reaction at each stage was confirmed by infrared spectrum and GPC.

(2) The reaction vessel was charged with 250 parts of a dispersion of core-shell type crosslinked polymer fine particles having a chloromethyl group obtained in Synthesis Example 1 (1), and then 3 obtained in Synthesis Example 2 (1). -27.0 parts of a xylene / n-butanol mixed solvent solution containing 13.5 parts of a PEG derivative in which a diethylamino (2-hydroxy) propyl group and a 3-octylphenylamino (2-hydroxy) propyl group are bonded, and 70 The reaction was carried out at 3 ° C. for 3 hours and at 80 ° C. for 5 hours. After the reaction, the reaction solution was poured into 300 parts of ethanol, and polymer fine particles were separated by filtration and washed with ethanol. A crosslinked polymer fine particle paste modified with octylaniline via a PEG chain was obtained. Hereinafter, it is referred to as “repellent fine particles-2”.

[Synthesis Example 3]
(1) In the same manner as in Synthesis Example 1 (2), 11.2 parts of diglycidyl ether (epoxy equivalent: 551) of PEG (average degree of polymerization: about 22) and 15.2 of 3-ethylamino-4-methylphenol And 7.5 parts of DEA are reacted in order to bind one end to a 3- (hydroxytolyl (ethyl) amino)-(2-hydroxy) propyl group and the other end to a 3-diethylamino (2-hydroxy) propyl group A PEG derivative containing as a main component was obtained. Next, 0.07 part of hydroquinone was added, 30.6 parts of 50% MEK solution of CMS was added dropwise at 50 ° C. over 1 hour, and the mixture was further stirred at 50 to 55 ° C. for 2 hours to cause a reaction. After neutralizing hydrochloric acid with an aqueous sodium hydroxide solution, MEK was distilled off under reduced pressure to obtain a styrene monomer having a 3-ethylamino-4-methylphenol group bonded thereto using PEG as a spacer.

(2) 80 parts of St, 10 parts of styrene monomer to which 3-ethylamino-4-methylphenol group is bonded using PEG obtained in (1) above as a spacer, 10 parts of DVB and 2,2′-azobis (2-amidino Propane) hydrochloride 0.2 part was mixed. 400 parts of deionized water was added to the polymerization reactor. Nitrogen gas was introduced to raise the temperature, the above monomer mixture was dropped, and a polymerization reaction was carried out at 65 to 70 ° C. for 8 hours. Hereinafter, it is referred to as “repellent fine particles-3”.

[Synthesis Example 4]
(1) A reactor was charged with 110.2 parts of a 50% xylene / n-butanol mixed solvent solution of diglycidyl ether of PEG (epoxy equivalent: 551) used in Synthesis Example 2 (1), and 50% xylene of trimethylethylenediamine. 20.4 parts of / n-butanol mixed solvent solution was added dropwise at 50 ° C. over 3 hours, and the mixture was further stirred at 50 to 55 ° C. for 5 hours to cause a reaction to obtain a PEG solution having a trimethylethylenediamine group bonded thereto. The progress of the reaction was confirmed by infrared spectrum.

(2) Charge 250 parts of a dispersion of core-shell type crosslinked polymer fine particles having a chloromethyl group obtained in Synthesis Example 1 (1) into a reaction vessel, and then bond the trimethylethylenediamine group obtained in (1) above 27.0 parts of the MIBK solution of PEG was added and reacted in the same manner as in Synthesis Example 1 (3). After the reaction, polymer fine particles were separated by filtration and washed. Crosslinked polymer fine particles whose surface was modified with a tertiary aminated PEG chain were obtained. Hereinafter, it is referred to as “cationic fine particle-1”.

[Synthesis Examples 5-6]
(1) In the same manner as in the reaction of diglycidyl ether of PEG and DEA in Synthesis Example 2 (1), glycidyl compounds described in Table 1 below were used, and each equivalent DEA was reacted. Furthermore, an equivalent amount of CMS was reacted and neutralized with sodium hydroxide to obtain a styrene monomer derivative to which an alkyl PEG chain or a phenyl PEG chain was bonded via a tertiary amino group.

(2) In the same manner as in the polymerization reaction of Synthesis Example 2 (2), styrene, DVB, and a monomer having styrylmethyl (diethyl) amino groups bonded to both ends of PEG shown in Table 1 were copolymerized, respectively. A crosslinked polymer fine particle paste surface-modified with a derivative chain was obtained.

[Synthesis Example 7]
(1) A reactor was charged with 214.4 parts of a 50% propylene glycol monomethyl acetate solution of PEG diglycidyl ether (epoxy equivalent: 268) used in Synthesis Example 1 (2). 38.6 parts of DEA in 50% propylene glycol monomethyl acetate was added dropwise at 50 ° C. over 3 hours, and the mixture was further stirred at 50 to 55 ° C. for 5 hours to react with 3- (diethylamino) 2- (hydroxy) propyl. A PEG solution with attached groups was obtained. The progress of the reaction was confirmed by infrared spectrum. Subsequently, 88.9 parts of isophorone diisocyanate 50% MIBK solution was added dropwise at 50 ° C. over 1 hour and further stirred at 50 to 55 ° C. for 2 hours to react with a hydroxyl group to obtain an isocyanate derivative. Next, 209.5 parts of a propylene glycol monomethyl acetate solution containing 104.8 parts of lysolecithin having a hydroxyl group (glycerol hydrogenated soybean oil fatty acid monoester-phosphatidylcholine) is added dropwise at 50 ° C. for 2 hours, and further stirred for 4 hours. Then, a tertiary amine to which a PEG chain having a phosphatidylcholine group was bonded was obtained.

(2) The reaction vessel was charged with 250 parts of the core-shell type crosslinked polymer fine particle dispersion having the chloromethyl group obtained in Synthesis Example 1 (1), and the phosphatidylcholine group obtained in (1) was obtained. The particle surface was modified by adding 57.8 parts of a 50% solution of a tertiary amine having a PEG chain attached thereto and reacting at 130 ° C. for 8 hours. After the reaction, the reaction solution was put into 600 parts of ethanol, and polymer fine particles were separated by filtration, washed with ethanol, and a crosslinked polymer fine particle paste whose surface was modified with phosphocholine was obtained. Hereinafter, it is referred to as “Zwitterionic fine particle-1”.

[Synthesis Example 8]
500 parts of deionized water, 10 parts of 4-vinylpyridine, 1 part of DVB and 0.2 part of 2,2′-azobis (2-amidinopropane) hydrochloride were charged, and nitrogen gas was introduced to raise the temperature. The polymerization reaction was carried out at 65 to 70 ° C. for 8 hours. The particle size of the polymer fine particles in the polymerization solution was 350 nm as measured by a dynamic light scattering method. Hereinafter, it is referred to as “cationic fine particle-2”.

[Synthesis Example 9]
To the 4-vinylpyridine crosslinked polymer fine particle dispersion obtained in Synthesis Example 8, 10 parts of monochloroacetic acid was added and reacted at 25 ° C. for 24 hours and at 50 ° C. for 8 hours. Filtration, sufficient water washing with deionized water, drying and pulverization gave a copolymer having a pyridine group and a carboxyl group. Hereinafter, it is referred to as “Zwitterionic fine particle-2”.

[Synthesis Example 10]
250 parts of the core-shell type crosslinked polymer fine particle dispersion having a chloromethyl group obtained in Synthesis Example 1 (1) was charged, 12.3 parts of N, N-dimethylaniline was added, and the mixture was reacted at 130 ° C. for 8 hours. Polymer fine particles whose surface was modified with dimethylaniline were obtained. After the reaction, the reaction solution was poured into 300 parts of ethanol, and polymer fine particles were separated by filtration and washed with ethanol. A crosslinked polymer fine particle paste surface-modified with a phenyldimethylammonium group was obtained. Hereinafter, it is referred to as “repellent fine particles-6”.

[Synthesis Example 11]
In the same manner as the surface modification reaction of the crosslinked polymer fine particles in Synthesis Example 3, 20.3 parts of octylaniline was reacted instead of N, N-dimethylaniline. After the reaction, the reaction solution was poured into ethanol, and the polymer fine particles were separated by filtration, washed, and a crosslinked polymer fine particle paste surface-modified with a basic compound was obtained. Hereinafter, it is referred to as “repellent fine particles-7”.

[Synthesis Example 12]
In a polymerization vessel, 47 parts of acrylic acid, 8.11 parts of DVB and 5.51 parts of maleic acid-modified styrene-ethylene / butylene-styrene block copolymer (styrene content: 30%, average molecular weight 200,000) were added to methylcyclohexane / Dissolve in 550 parts of a mixed solvent of MEK / toluene (5: 3: 2) and add 0.6 part of t-butyl-peroxy-2-ethylhexanate to this to cause radical polymerization by non-aqueous emulsion polymerization. Then, carboxylic acid group-containing crosslinked polymer fine particles were obtained. Hereinafter, it is referred to as “anionic fine particle-1”. The average particle diameter of the anionic fine particles-1 was about 200 nm as measured by a dynamic light scattering method.

[Synthesis Example 13]
In a container equipped with a stirrer, 93 parts of CMS, 50 parts of maleic anhydride and 3 parts of AIBN were added to 74 parts of butyl acetate and dissolved to prepare a monomer solution containing a polymerization initiator. Separately, a polymerization reaction apparatus is prepared, 100 parts of butyl acetate is charged into the reaction vessel, nitrogen gas is introduced and stirred, and the temperature is raised to 70 ° C. 80 parts of the monomer solution described above was added and reacted for 30 minutes, and then the remaining monomer solution was added dropwise over 2 hours, and the polymerization reaction was carried out for 10 hours. 50 parts of the polymer solution obtained above and 30 parts of butyl acetate were charged, stirred and heated. When 15.12 parts of N, N-dimethyloctylamine was added dropwise at 80 ° C., a finely dispersed state was obtained, and the reaction was carried out at a temperature of 120 to 140 ° C. for 8 hours. Next, 8.94 parts of n-butanol was added dropwise to conduct an esterification reaction. When the reaction was allowed to proceed for 8 hours, it was in a precipitated state. The reaction solution was cooled, filtered, thoroughly washed with methanol, and dried. A copolymer having a quaternized octylammonium group and a carboxyl group was obtained. Hereinafter, it is referred to as “Zwitterionic polymer-1”.

[Synthesis Example 14]
(1) In the same manner as in Synthesis Example 5 (1), 268.0 parts of a 50% methyl ethyl ketone (MEK) solution of diglycidyl ether of PEG used in Synthesis Example 1 (2) was charged, and 73.2 parts of a DEA 50% MEK solution Was added dropwise at 50 ° C. over 3 hours, and the mixture was further stirred at 50 to 55 ° C. for 5 hours for reaction to obtain PEG having a diethylamino group bonded thereto. Next, 0.07 part of hydroquinone was added, and 152.6 parts of a 50% MEK solution of CMS was added dropwise at 50 ° C. over 1 hour, and the mixture was further stirred at 50 to 55 ° C. for 2 hours for reaction. After neutralizing hydrochloric acid with an aqueous sodium hydroxide solution, MEK was distilled off under reduced pressure to obtain a monomer in which N-styrylmethyl (N, N-diethyl) amino groups were bonded to both ends of PEG.

(2) St 80 parts, 10 parts of monomer having N-styrylmethyl (N, N-diethyl) amino group bonded to both ends of the PEG obtained in (1) above, 10 parts of DVB and 2,2′-azobis (2 -Amidinopropane) hydrochloride 0.2 part was mixed. 400 parts of deionized water was added to the polymerization apparatus, and the monomer mixture was dropped therein and mixed. Nitrogen gas was introduced to raise the temperature, and a polymerization reaction was carried out at 65 to 70 ° C. for 8 hours. Hereinafter, it is referred to as “cationic fine particle-3”.

[Comparative Example 1]
A polymerization vessel is charged with 150 parts of a xylene / n-butanol mixed solvent (7/3) and heated to 90 ° C. Next, a monomer mixture of 50 parts of MMA, 35 parts of butyl methacrylate (BMA), 15 parts of HEMA, and 1.5 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 2 hours. The mixture was reacted for a time to obtain a xylene solution of MMA-BMA-HEMA copolymer (solid content: 40%). Hereinafter, it is referred to as “comparative acrylic resin”.

[Example 1]
After mixing the repellent fine particles-1 obtained in Synthesis Example 1 with a xylene / n-butanol solution of the following fixing acrylic resin at a solid content mass ratio of 65/35 and adjusting the solid content to 25% with butyl acetate. The repellent fine particles-1 were dispersed with an ultrasonic wave to prepare a paint. Borders were created around the top, bottom, left, and right and center of the test steel sheet that had been subjected to rust prevention treatment, and an epoxy-based primer was applied in a width of about 1 cm to create a protection and a boundary. The above mixture was thickly applied to the lower half and dried at room temperature for 10 days. The coating film was approximately 110 to 130 g / m ² . The upper half was coated with a comparative acrylic resin as shown in Comparative Example 2 below.

The fixing acrylic resin used above was synthesized as follows. Using the polymerization apparatus used in Synthesis Example 1, 114 parts of xylene and 38 parts of n-butanol are charged in a polymerization vessel and heated to 90 ° C. Next, a mixed solution of 35 parts of MMA, 35 parts of BMA, 15 parts of acrylic acid, 15 parts of 2-hydroxyethyl methacrylate (HEMA) and 1.5 parts of t-butylperoxy-2-ethylhexanoate was dropped over 2 hours. And obtained by reacting under a nitrogen gas stream for 6 hours (solid content: 40%). In addition, the above test steel plate is about 150 g / m ² after drying a tar epoxy base coat on a medium-sized double-sided sand plast steel plate (width × length × thickness: 70 × 150 × 1 mm) manufactured by Test Panel. It was applied and air-dried to prepare.

[Comparative Example 2]
The resin solution obtained in Comparative Example 1 for comparison of antifouling performance was applied to the upper half of each of the coated plates prepared in Example 1 and dried at room temperature for 10 days. The thickness of the coating film was approximately 110 to 130 g / m ² . Similarly, in the following examples, the coating was divided into upper and lower portions and compared.

[Examples 2 to 15]
A coated plate was prepared according to the coating preparation method and the coating method described in Example 1 according to the formulation of solids in Table 2. The thickness of the film thickness was approximately 110 to 130 g / m ² .

[Example 16]
(1) The test method and the seawater immersion test of the steel plate for the test were conducted in an environment with a high nutrient content because the fish feed was administered in a place adjacent to the young fish breeding ground in the inner bay where the seawater flow was relatively small. The water temperature was about 25 to 28 ° C., and the COD concentration was 4 to 10 mg / L. The COD concentration is said to be 1 to 2 mg / L in the Seto Inland Sea where the seawater is relatively clean, and 3 to 5 mg / L where the color of the water looks green to yellow, such as in a harbor. The coated steel plates for test prepared in Examples 1 to 15 and Comparative Example 2 were suspended up and down fixed on a polyvinyl chloride frame. The PVC frame was immersed at a depth of 1 to 2 m from the sea surface. The test steel plate was raised every week for 4 weeks, and the state of adhesion of barnacles in the upper and lower halves of the test steel plate was observed to evaluate the change in the state. The evaluation results are shown in Table 3 below.

(2) Results of state observation and evaluation ○: Has a function as a non-eluting antifouling paint.
(Triangle | delta): Although it is non-eluting property, the function as an antifouling paint is a little inadequate.
X: Although it is non-eluting, it does not have a function as an antifouling paint.

[Comparative Example 3]
Polishing type coated plates using cuprous oxide were prepared in the same manner as in the Examples, and were immersed in seawater in the same manner to evaluate antifouling properties. Barnacles hardly adhered and showed very excellent antifouling property, but the barnacles also adhered to the part where the epoxy base coat was applied at the top, bottom, left, and right of the test steel plate and the central boundary. It wasn't. This indicates that the adjacent environment including the part where the antifouling paint is not applied is also affected by the elution of cuprous oxide. On the other hand, the coated materials of Examples 1 to 15 show that the part coated with the epoxy base coat has remarkably many barnacles and is firmly adhered, and the used biorepellent is not eluted. ing. This indicates that the various polymers used in the examples have a low environmental load.

  The biological repellent effect of tin compounds and copper compounds in conventional antifouling paints is that the metal ions gradually elute and act on aquatic organisms, and the aquatic organisms repel and avoid adhesion or even die It is an action to drop off. On the other hand, the aquatic biofouling agent of the present invention uses polymer fine particles, particularly polymer fine particles imparted with a biological repellent function, as a biofouling agent. This polymer fine particle is a safe organic substance, and when it is immersed in seawater for a long period of time, it may fall off as a particle depending on the choice of coating film forming material, but it is not a material that elutes in water, On the other hand, it is safe and hygienic because it does not pollute and is safe, and it does not pollute fishery products such as fish, shellfish and seaweed.

The aquatic organism antifouling agent of the present invention is used in the same applications as conventional antifouling paints, for example, for painting the bottom and side of a ship that is submerged in the seawater of marine navigating vessels, and also in marine fish farms. It can also be used for nets. For synthetic resin moldings such as buildings and parts immersed in the sea, and synthetic fibers such as fish nets and isolation nets, it is compatible with master antibacterial batches and base material spinning solutions that are compatible with base resin In addition, a treatment method of internally adding into a synthetic resin product or a synthetic fiber product using a biological antifouling agent dispersion is also performed. Also used for biological dirt such as mold generated around water in buildings and houses, or as an antibacterial coating material for air cleaner fins and fillers in houses, hospitals, public facilities, etc. it can.

Claims (9)

  A biofouling agent comprising biofouling-resistant polymer fine particles and a film-forming material.   The bioprotection according to claim 1, wherein the polymer fine particles have at least one group selected from the group consisting of a hydrophilic group (a), an amphoteric group (b) and a biorepellent group (c). Soiling agent.   The hydrophilic group (a) is at least one selected from the group consisting of an anionic group, a cationic group, a nonionic group and an anionic / nonionic amphoteric group, a cationic / nonionic amphoteric group, and an anionic / cationic amphoteric group. The biological antifouling agent according to claim 2.   The biological antifouling agent according to claim 2, wherein the amphoteric group (b) is at least one selected from the group consisting of an anionic / nonionic amphoteric group, a cationic / nonionic amphoteric group and an anionic / cationic amphoteric group.   The biological repellent group (c) is at least selected from the group consisting of an aliphatic, alicyclic or aromatic amino group, quaternary ammonium group, pyridine group, pyridinium group, phenolic hydroxyl group and polyethylene glycol group. The biofouling agent according to claim 2, which is one type.   The biofouling agent according to any one of claims 2 to 5, wherein the polymer fine particles are a mixture of polymer fine particles having different groups.   The biofouling antifouling according to any one of claims 1 to 6, wherein a mass ratio of the polymer fine particles (A) to the coating film forming material (B) is A: B = 95: 5 to 5:95. Agent.   A biological antifouling treatment method for a base material, comprising applying the biological antifouling agent according to any one of claims 1 to 6 to the base material, impregnating or kneading the base material. A biological antifouling treatment article which has been subjected to a biological antifouling treatment by the treatment method according to claim 8.