KR101047642B1 - Biological antifouling agent, antifouling paint, antifouling method and antifouling article - Google Patents

Abstract

The present invention is a biological antifouling agent, an antifouling paint, an antifouling treatment method and an antifouling article which are made of polymer particles having a biofouling agent. According to the present invention, a novel antifouling particle (biological antifouling agent), which is safe for the environment and edible aquatic products, and has an excellent antifouling effect, an antifouling paint using the same, an antifouling treatment method for a substrate, and an antifouling article can do.

Description

Biofouling agents, antifouling paints, antifouling methods and antifouling articles {ANTI-BIOFOULING AGENT, ANTI-FOULING COATING, ANTI-FOULING TREATMENT METHOD, AND ANTI-FOULINGLY TREATED MATERIAL}

The present invention relates to biological antifouling agents, antifouling paints, antifouling treatment methods and antifouling articles, more specifically polymer particles having aquatic biofouling properties (preventing adhesion of aquatic organisms) (hereinafter simply referred to as 'antifouling particles'). And an antifouling paint using the same, an antifouling treatment method of a substrate, and an antifouling article.

In marine navigational vessels, creatures that live in seawater during navigation are attached to the bottom or the side of the ship immersed in seawater. The abrasion resistance of these attached organisms and seawater decreases the ship's navigation speed, increases fuel consumption, and increases the frequency of repairs such as the bottom of the ship, resulting in huge economic losses. have. In addition, in marine fish farms, marine organisms are similarly attached to the sequestering network used therein, preventing the inflow of fresh seawater due to the reduction of the net openings, and causing harm to the growth of farmed fish.

There are a large number of creatures that reproduce in seawater and attach to hulls and structures in the sea, and aquatic animals include barnacles, moss, selbra, and sea squirts, and plants include seaweeds. Barnacles and algae are typical examples.

In order to prevent these aquatic organisms from adhering, a coating material containing a tin compound or a copper compound has been conventionally used as a bottom antifouling paint. However, these tin compounds and copper compounds elute from the coating into seawater, pollute environmental pollution, fish, shellfish, seaweed, etc., and spread the pollution to people who eat seafood, which impairs their health. Has been.

[Problem to Solve Invention]

This invention is made | formed in view of the said situation. The present inventors examined the mechanisms of engraftment, growth, and dropping out of the bottom of the aquatic organisms, fishnets, and the like. The present inventors have focused on using the physiological and physical actions of the aquatic organisms discovered by the above studies and using non-release organic materials which do not elute in seawater as antifouling components. An object of the present invention is to provide a novel biological antifouling agent which is safe for the environment and edible marine products, and has an excellent antifouling effect, an antifouling paint, a method of antifouling treatment of a substrate, and an antifouling article using the same.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the polymer particle is a safe organic substance, and when the coating film containing this particle is immersed in seawater for a long time, the material eluting in water may fall out as a particle. Therefore, it has been found that it does not pollute the environment and is also safe for aquatic resources. MEANS TO SOLVE THE PROBLEM The present inventors made these particle | grains antifouling, and by making the said particle | grains densely exist on the surface of the coating film containing the said antifouling particle, the said coating film reduces the growth of aquatic organisms, and also grows the aquatic organisms which adhered. By inhibiting, the aquatic organisms are separated from the substrate surface over time, and also by the weight of the attached aquatic organisms, and also physical action such as the force of the flow of seawater, Discovered a phenomenon in which aquatic organisms fell off the substrate, and came to complete the present invention.

That is, the present invention provides a biofouling agent, comprising polymer particles having a biofouling group.

In the present invention, at least one biofouling group selected from a hydrophilic group (a), anionic and cationic both ionic groups (hereinafter sometimes referred to simply as 'both ionic groups') (b) and biorepellent groups (c) One kind; It is preferable that the said hydrophilic group (a) is at least 1 sort (s) chosen from anionic group, cationic group, nonionic group, anionic and nonionic amphoteric group, cationic and nonionic amphoteric group, and anionic and cationic amphoteric group.

In the present invention, the zwitterionic group (b) is a combination of an anionic group and a cationic group selected from anionic groups, anionic and nonionic amphoteric groups, cationic groups, cationic and nonionic amphoteric groups and anionic and cationic amphoteric groups. To be; It is preferable that the said biorepellent group (c) is at least 1 sort (s) chosen from an aliphatic, alicyclic, or aromatic amino group, a quaternary ammonium group, a pyridine group, a pyridinium group, a phenolic hydroxyl group, and a polyethyleneglycol group, and also the said antifouling property The particles may be a mixture of polymer particles having other antifouling groups.

Moreover, this invention provides the antifouling paint characterized by mix | blending a coating film forming material with the polymer particle (antifouling particle) of the said this invention. About the said antifouling paint, it is preferable that the compounding mass ratio of antifouling particle (A) and coating film forming material (B) is A: B = 95: 5-5: 95.

The present invention also provides a biofouling treatment method for a substrate, wherein the biological antifouling agent or antifouling paint of the present invention is applied to the substrate, impregnated, or kneaded into the substrate; And it provides a biological antifouling treatment article characterized in that the biological antifouling treatment by the treatment method.

[Effects of the Invention]

The tin compounds and copper compounds used in conventional antifouling paints have a function of causing their ions to slowly elute in seawater, acting on aquatic organisms, preventing the aquatic organisms from adhering to the bottom of the aquatic organisms, or even killing and dropping them. Had On the other hand, the aquatic biofouling agent (antifouling particle) of this invention consists of an antifouling polymer particle which has a biological repelling function especially. Such antifouling particles, when immersed in seawater for a long time in a coating film, are not materials eluted into the water even though they may fall out as particles. Therefore, they do not contaminate the environment and are safe and edible for fish, shellfish, seaweed, etc. It does not contaminate seafood, so it is safe and hygienic.

Although the antifouling particles of the present invention do not have soluble heavy metal ions, the mechanism having the antifouling effect is not necessarily fully explained. However, the mechanism is considered to be related to physiological and physical actions such as engraftment, growth, and dropping of the bottom of the aquatic organisms. In a coating film formed by using a paint containing antifouling particles, by exposing and presenting the antifouling particles on its surface, the formation of aquatic organisms on the coating film is reduced, and the growth of cells of attached aquatic organisms is inhibited. The aquatic organisms attached to or killed off were detached from the substrate surface. As a result, even if other aquatic creatures adhere to the destroyed aquatic creatures, the newly attached and deposited aquatic creatures are removed from the substrate by their own weight and also by physical action such as the force of the flow of seawater. do.

BEST MODE FOR CARRYING OUT THE INVENTION [

Best Mode for Carrying Out the Invention The present invention will be described in more detail with reference to the best mode for carrying out the invention.

As the polymer of the antifouling particles of the present invention, all polymers such as known addition polymers, condensation polymers and thermosetting polymers can be used. As addition polymer, vinyl type, diene type, (meth) acrylic type, etc. are condensation polymer, ester type, amide type, urethane type, etc. are thermosetting polymers, such as melamine-formaldehyde type, phenol-formaldehyde type, and epoxy-amine type And polymers such as isocyanate alcohols.

The antifouling particle of this invention has at least 1 sort (s) of group chosen from the hydrophilic group (a), zwitterionic group (b), and biorepellent group (c) on the surface. When a coating film is formed from the coating material containing the said antifouling particle, aquatic organisms become difficult to adhere to the surface of the coating film containing the said antifouling particle. The antifouling particles having a group selected from the above-mentioned hydrophilic group (a), zwitterionic group (b) or biorepellent group (c), the synthesis method thereof, and the manufacturing method of these mixtures are mentioned.

(A) The antifouling particle whose surface was modified by the polymer chain which has a hydrophilic group or a hydrophilic group.

This antifouling particle is formed with a water film or a hydrosol film or a gel film (hereinafter, simply referred to simply as an "water film") on the surface of a coating film made of a coating material containing the antifouling particle. Can block the attachment of a creature.

The hydrophilic group of the antifouling particles may be at least one selected from anionic groups, cationic groups, nonionic groups, anionic and nonionic amphoteric groups, cationic and nonionic amphoteric groups, and anionic and cationic amphoteric groups.

As said anionic group, a sulfone group, a carboxyl group, a sulfate ester group, a phosphate ester group, etc. are mentioned. As said cationic group, a primary, secondary, tertiary amino group, quaternary ammonium group, a pyridine group, a pyridinium group, etc. are mentioned. As said nonionic group, a hydroxyl group, an amide group, a polyethyleneglycol group, etc. are mentioned. Polymers having these hydrophilic groups are (co) polymers composed of monomers having the above hydrophilic group in a molecule.

Said antifouling particle | grains can be synthesize | combined according to a well-known method. As a monomer used for the synthesis | combination of antifouling particle | grains, a macromonomer can also be used besides a normal monomer. The polymerization medium is selected from an organic solvent, a water-organic solvent mixed solvent or water. As a polymerization method of an addition polymer, all the well-known polymerization methods suitable for the form of antifouling particle | grains, for example, solution polymerization, emulsion polymerization, suspension polymerization, and soap-free polymerization, can all be used. The copolymer may be any of random, block and graft copolymers. As antifouling particle | grains, single particle | grains, a core (core), and shell (shell) type particle | grains may be sufficient. Below, the typical synthesis | combining method of the said antifouling particle is demonstrated.

(A1) A method in which a monomer having a hydrophilic group or a macromonomer having a hydrophilic group is copolymerized with a monomer that is a main raw material to give a hydrophilic group to an antifouling particle.

(A2) A method of copolymerizing a monomer or macromonomer having a group which can be easily changed into a hydrophilic group to a monomer which is a main raw material, and then changing a group that can be easily changed into a hydrophilic group to a hydrophilic group.

(A 3) A method of copolymerizing a monomer having a reactor in advance with a monomer which is a main raw material, and then reacting the reactor with a reactive compound having a hydrophilic group.

(A4) Synthesizes particles which become cores in advance, and subsequently impregnates the surface of the particles with a monomer having a hydrophilic group or a group which can be changed into a hydrophilic group to be a shell, and polymerizes as necessary in the above (A). How to.

As a monomer which has the said hydrophilic group, For example, styrene sulfonic acid, vinyl sulfonic acid, etc .; (Meth) acrylic acid, maleic acid, fmaric acid, itaconic acid, half esters of these dicarboxylic acids and half amides; (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.

As a monomer which has an amphoteric ionic group, sulfoethylamino ethyl methacrylate, phosphocholine ethyl methacrylate, carbooxymethyl amino ethyl methacrylate, etc .; Maleic acid monodimethylaminoethyl ester, itaconic acid monodimethylaminoethyl ester; Hydroxyethyl ester, glyceryl ester, polyethyleneglycol ester, methoxy polyethyleneglycol ester, etc. of monomer which have carboxyl groups, such as (meth) acrylic acid, maleic acid, and itaconic acid, are mentioned.

Graft copolymer chains of macromonomers having a large number of hydrophilic groups, and antifouling particles having a polymer chain having a hydrophilic group bonded to each other using a polyalkylene oxide chain (carbon number 2 to 3) as a spacer, only such hydrophilic polymer chains are eluted in seawater. Since it is possible to form a sol layer and a gel layer, which are hydrated on the surface of the coating film, the thickness of the water film becomes thick and excellent in antifouling properties.

Examples of the group that can be easily changed to the hydrophilic group described in the above (A) are acid anhydride groups, lower alkyl ester groups and the like, and examples of the monomers include maleic anhydride, itaconic anhydride and methyl (meth) acrylate. Can be.

As a reactor of the reactive compound which has a hydrophilic group as described in said (A), and a reactor which a reactive monomer has, an acid anhydride group, an acid halogenide group, a lower alkyl ester group, an epoxy group, an isocyanate group, a methirol group, for example. Methoxymethyl group, halogenomethyl group and the like; A hydroxyl group, an amino group, a carboxyl group, etc. are mentioned. As a monomer which has these reactors, for example, maleic anhydride, itaconic anhydride, (meth) acrylic acid chloride, methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, and allyl glycidyl ether Ethyl isocyanate (meth) acrylate, isopropenyl phenylene methyl isocyanate, methrol (meth) acrylamide, methoxymethyl (meth) acrylamide, chloromethyl styrene, etc .; vinyl acetate (blackened to vinyl alcohol), A siloxane alkyl (C2-C6) (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid, maleic acid, itaconic acid, etc. are mentioned.

Moreover, as a reactive compound which has the said hydrophilic group, For example, monoacetic acid, a monochromic acetic acid, glycolic acid, hydroxypropionic acid, thioglycolic acid, (epsilon) -caprolactone, various amino acids, hydroxyethyl sulfuric acid, acidic sulfuric acid Soda, 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.

The method of copolymerizing the hydrophilic monomer which has the said group, and a conventionally well-known hydrophobic monomer is a preferable method at the time of manufacturing antifouling particle. Examples of the hydrophobic monomers include styrene, ethylene, propylene, butadiene, isoprene, aliphatic (C1-C30), aromatic (C6-C15) and alicyclic (C6-C15) hydrocarbon esters of (meth) acrylic acid. Can be.

Moreover, as a polyfunctional monomer which brings about a crosslinking to antifouling particle | grains, For example, divinylbenzene, alkylene (C2-C4) glycol di (meth) acrylate, poly (C2-C30) alkylene (C2-C4). ) Glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimetholpropane tri (meth) acrylate, methylenebisacrylamide, and the like.

(B) antifouling particles wherein same or different polymer particles are modified with zwitterionic groups.

By forming a coating film using this antifouling particle, both ionicity is provided to the coating film surface, and aquatic organisms are prevented from adhering to a coating film.

The coating film containing both ionic antifouling particles showed a tendency to decrease the abundance of aquatic organisms on the coating film, as a result of immersion experiment in the seawater. In addition, the growth of attached aquatic organisms was inhibited, and a tendency to peel off from the substrate surface was observed. Many of the groups having the function of destroying the cells of aquatic organisms are amino groups that are positively charged. On the other hand, aquatic creatures are in charge of wealth. For this reason, by using the antifouling particle | grains which introduce | transduced an amino group as a antifouling agent component of a coating material, the coating film may be positively charged and aquatic organisms may be attracted to the positively charged coating film, On the other hand, a coating film By introducing antifouling particles having a negative charge into the film, the above-mentioned attraction force is lost, or a coating film having a repulsive force against aquatic organisms can be obtained.

In addition, by containing antifouling particles having both ionic groups in the coating film, anionic and cationic groups can be present in a very close distance in the coating film in contact with seawater. By bringing these two ionic groups into close proximity, both ionic groups influence each other, causing frequent coupling with soluble ions such as sodium ions and chlorine ions in seawater and exchange of ion dissociation, or high coating film surfaces. There exists a possibility of becoming an ion concentration environment, and the cells of the aquatic organisms which adhered by these influences are destroyed, and the aquatic organisms which adhered are killed and peeled from a base surface.

Examples of the antifouling particles having both ionic groups include polymer particles having an anionic group and a cationic group, such as sulfoethylamino group, phosphoethylamino group, phosphocholine hydrochloric acid, carboxymethylamino group, carboxyethylamino group and carboxymethylpyridinium group. Can be mentioned. In preparation of this antifouling particle | grain, the zwitterionic monomer which has said anionic group and cationic group together can be used. Or antifouling particles that do not dissolve in water by forming an ionic complex with carboxylic acid of an adjacent maleic acid unit by amino bonding or pyridinium bonding to polychloromethylstyrene in an alternating polymer of poly (maleic acid-chloromethylstyrene). Can be prepared.

As a method of imparting both ionic properties to the antifouling particles, the same method as the method described in the above (A) may be mentioned. In addition, both ionicity can be contained in a coating film by using the mixture of 2 or more types of antifouling particle | grains which have different ionicity, and using the mixture of antifouling particle | grains which respectively have a different ionic group.

(C) antifouling particles incorporating biologically repellent groups;

By introducing a biorepellent group into the polymer particles, biorepellance to aquatic organisms can be imparted to the surface of the coating film including the particles, thereby preventing adhesion of aquatic organisms.

When polymer particles having repellent groups are present in the coating film, in particular, by exposure to the surface of the coating film, the cells of the attached aquatic organisms are destroyed, causing the inhibition of the growth of the aquatic organisms on the coating film. Peel off from substrate surface.

Examples of the biorepellent group to be bonded to the polymer particles include an amino group, an ammonium group, a pyridine group, a pyridinium group, a phenol group or a polyethylene glycol group.

Specifically, for example, aliphatic amino groups such as n-decylamino group, n-dodecylamino group, n-hexadecylamino group, alicyclic amino group, N, N-dimethyl-n-octyl ammonium group, N, N-dimethyl- Aromatic amino groups, such as an aniline group and an anisidine group, such as n-decyl ammonium group, N, N- dimethyl- n-dodecyl ammonium group, N, N-dimethyl- n-hexadecyl ammonium group, their ammonium group, 4-octyl aniline group, 4 Aliphatic hydrocarbon group-substituted aromatic amino groups such as nonylaniline groups and 4-dodecylaniline groups, and their ammonium groups, pyridine groups, pyridinium groups, 4-octylpyridine groups, 4-nonylpyridine groups, and 4-dodecylpyridine groups And phenolic hydroxyl groups such as aliphatic hydrocarbon group-substituted pyridine groups, their pyridinium groups, phenol groups, cresol groups and aminophenol groups, and polyethylene glycol groups.

Even if the polymer particles having these biorepelling groups are contained in the coating film, the groups are preferably not eluted in seawater. Therefore, it is preferable that the biorepelling group is connected to the polymer particles through the linking group. As a method of providing biorepellency to a polymer particle, the method similar to the method demonstrated by said (a) is mentioned.

(D) The antifouling particle which combined each function of said (A)-(C).

By forming a coating film as an antifouling component using a mixture of antifouling particles modified with at least two groups of the hydrophilic group (a), zwitterionic group (b), and biorepellant group (c) or a mixture of antifouling particles modified with a single function group It can be used as aquatic antifouling film with complex antifouling function.

Although the average particle diameter (measurement method: dynamic light-diffusion method) of the antifouling particle | grains of the present invention mentioned above cannot be determined uniformly by the target aquatic organisms etc. according to the use of an antifouling paint, or a use condition, generally 0.05- It is 50 micrometers, Preferably it is 0.1-10 micrometers. If the average particle diameter is less than 0.05 µm, the antifouling particles may be buried in the coating film, making it difficult to be exposed to the surface of the coating film, resulting in inconvenience in that the characteristics as the antifouling agent are difficult to be exhibited. On the other hand, when the average particle diameter exceeds 50 µm, when the physical properties such as the strength of the coating film decrease, or the unevenness of the coating film becomes large, flow water resistance is evidenced, or when discomfort occurs in terms of dropping of the particles. There is.

When using the said antifouling particle of this invention as a component of an antifouling paint, it is preferable that the antifouling particle in the coating film formed from an antifouling paint is always in the state which exposes to a coating film surface. For example, as a preferable method, the antifouling particle | grains are added to high concentration in antifouling paint, the method of making the particle diameter of antifouling particle | grains comparatively large, etc. are mentioned. Moreover, as a coating film formation material of a coating material, the antifouling particle in a coating film can be exposed to a surface one by one by using the self-polishing (polishing) type | mold coating film formation material which melt | dissolves from a surface gradually.

As said coating film forming material, materials, such as a synthetic rubber resin, acrylic resin, vinyl resin, a chlorinated rubber resin, an epoxy resin, a silicone resin, a fluororesin, those copolymerization system, a mixed system, etc. are mentioned, for example.

The antifouling paint of the present invention is obtained by blending the coating film forming material (B) with the antifouling particles (A). The compounding mass ratio of the antifouling particle (A) and the coating film forming material (B) of the present invention is A: B = 95: 5 to 5:95, and when the antifouling particle is exposed to the coating film surface at a high density, the A: B = 80: 20-30: 70 are preferable.

The antifouling particles or antifouling paint of the present invention can be applied to an substrate, impregnated, or kneaded (internally incorporated) into the substrate, whereby the substrate is subjected to biological antifouling treatment to obtain aquatic biological antifouling articles. The antifouling paints of the present invention can be used in the same applications as conventional antifouling paints, for example, for the coating of the bottom of the ship or the side of the ship submerged in seawater of a marine navigation vessel, and for a wide range of uses in marine fish farms and sequestration networks. Can be.

In addition to the bottom of the boat, the isolation net, and the like, synthetic fibers are used as the synthetic resin molded article, the fishing net, the isolation net, and the like as the dried material or member to be immersed in the sea. Not only the method of coating or impregnating the surface with the antifouling paint of the present invention for these articles, but also the method of incorporating the antifouling particles of the present invention in these synthetic resin products or synthetic fiber products are excellent methods.

In the case where the antifouling particles of the present invention are embedded in a base such as the synthetic resin, it is preferable to use a master batch of antifouling particles. In addition, when internally adding to synthetic fiber, it is preferable to use the dispersion liquid of antifouling particle suitable for a spinning liquid.

As said synthetic resin, well-known resin, such as a polypropylene resin, a polyethylene resin, a polyvinyl chloride resin, a synthetic rubber, a polystyrene resin, an ABS resin, a nylon resin, a polyester resin, a polycarbonate resin, is mentioned. As synthetic fiber, well-known fiber, such as a polypropylene fiber, a polyethylene fiber, a polyacrylonitrile fiber, a nylon fiber, a polyester fiber, is mentioned.

In addition, the antifouling paint of the present invention is for biological contamination such as mold in a place where water such as a laundry, a kitchen, a sink, a washroom, a bath in a building or a house is used, or a house, a hospital, a public It can also be used as a fin of an air cleaner such as a facility or an antifouling paint of a filler.

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely. On the other hand, in the sentence, "part" or "%" is based on mass.

Synthesis Example of Antifouling Particle

Synthesis Example 1

(1) A polymerization reactor equipped with a water path, a stirrer, a monomer dropping device, a reagent inlet, a countercurrent cooler, and a nitrogen gas inlet as a heating device was prepared. 100 parts of water, 342.5 parts of ethanol, and 6 parts of polyacrylic acid (average molecular weight: 250,000) were put into this polymerization apparatus, and it stirred and dissolved polyacrylic acid.

Next, 45 parts of styrene (St) and 0.75 parts of azobisisobutyronitrile (AIBN) were mixed and added, stirred at 70 ° C. for 8 hours under a nitrogen gas stream, and suspension polymerization was performed. The particle diameter of the obtained polymer was about 1 micrometer as measured by the dynamic light scattering method.

Subsequently, a mixture of 25 parts of chloromethylstyrene (CMS), 12.5 parts of divinylbenzene (DVB) and 0.56 parts of AIBN was added to the suspension polymerization solution, and stirred, and then polymerized at 70 ° C. under a nitrogen gas stream for 8 hours. Core-shell-type crosslinked polymer particles having a chloromethyl group reactive thereto were obtained. The centrifuge was used to filter and clean the polymer particles from the polymerization reaction mixture. The obtained crosslinked polymer particles were redispersed in xylene / n-butanol mixed solvent (75:25) (solid content: 21.6%). The polymerization reaction and synthesis reaction in each following synthesis examples were also performed using the same apparatus as the above.

(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 degree of polymerization: about 9) was added. 41.2 parts of a 50% xylene / n-butanol mixed solvent (75:25) solution of octylaniline was added dropwise thereto at 85 to 90 ° C for 3 hours, and then stirred at 90 to 115 ° C for 4 hours.

Subsequently, 15.0 parts of 50% methyl isobutyl ketone (MIBK) solutions of diethylamine (DEA) were added dropwise at 50 ° C for 3 hours, and then stirred at 50 to 55 ° C for 5 hours to carry out tertiary amination. A mixture solution of PEG derivatives containing PEG as the main component of which one end is an octylaniline group and a 3-diethylamino (2-hydroxy) propyl group is bonded to the other end was obtained (solid content: 51.8%). The progress of the reaction in each step was confirmed by infrared spectrum.

(3) 250 parts of dispersion liquids of core-shell crosslinked polymer particles having a crawled methyl group obtained in the above (1) were added to the reaction vessel, and then the 3-diethylamino (2-hydroxy) propyl group and 3- obtained in the above (2) were used. 27.0 parts of a xylene / n-butanol mixed solvent (75:25) solution containing 13.5 parts of a PEG derivative having an octylphenylamino (2-hydroxy) propyl group bonded thereto were added, and reacted at 70 ° C for 3 hours and 80 ° C for 5 hours.

After the reaction, the reaction solution was poured into 300 parts of ethanol, the polymer particles were filtered off, and washed with ethanol. Unreacted PEG derivatives were filtered off, partly contributing to the bonding between polymer particles, and partly crosslinked polymer particle pastes modified with octylaniline with a PEG chain therebetween. This is hereinafter referred to as 'repellent antifouling particle-1'.

Synthetic 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 degree of polymerization: 22) was added thereto. . Thereto, 5 parts of octyl aniline was dripped at 85-90 degreeC for 3 hours, and it stirred at 90-115 degreeC then for 4 hours. Subsequently, 2.3 parts of chloroacetic acid was added and reacted at 50 degreeC.

Subsequently, after adding 2.67 parts of methyl chloroacetate to this reaction solution and reacting at 50 degreeC for 8 hours, pH was adjusted to 8-9 with sodium hydroxide, and distillation under reduced pressure removed the methyl chloroacetate. Subsequently, 1.8 part of DEA was dripped at 3 degreeC at 50 degreeC, Then, it stirred at 50-55 degreeC for 5 hours, reacted, and tertiary aminated. A PEG mixed derivative solution containing PEG as the main component, wherein one end was a carboxylated octylaniline group and a 3-diethylamino (2-hydroxy) propyl group was bound to the other end was obtained. The progress of the reaction of each step was confirmed by infrared spectrum and GPC.

(2) 250 parts of the dispersion of the core-shell crosslinked polymer particles having the chloromethyl group obtained in Synthesis Example 1 (1) were added to the reaction vessel, followed by the carboxylated octylaniline group obtained in Synthesis Example 2 (1). 27.0 parts of xylene / n-butanol mixed solvent solution including 13.5 parts of PEG derivatives bonded with 3-diethylamino (2-hydroxy) propyl group were added and reacted at 70 ° C for 3 hours and 80 ° C for 5 hours.

After the reaction, the reaction solution was poured into 300 parts of ethanol, and the polymer particles were filtered off and washed with ethanol. A crosslinked polymer particle paste modified with octylaniline with a PEG chain therebetween was obtained. This is hereinafter referred to as 'repellent antifouling particle-2'.

Synthesis Example 3

(1) 15.2 parts of 3-ethylamino-4-methylphenol in 110.2 parts of diglycidyl ether (epoxy equivalent: 551) of PEG (average degree of polymerization: about 22) in the same manner as in Synthesis example 1 (2); 7.5 parts of DEA were reacted one by one in order to form a PEG having a single end of 3- (hydroxytrile (ethyl) amino)-(2-hydroxy) propyl group and the other end of 3-diethylamino (2-hydroxy) propyl group bound to PEG. A PEG derivative was obtained.

Then, 0.07 part of hydroquinone was added, 30.6 parts of 50% MEK solutions of CMS were dripped at 50 degreeC for 1 hour, and then it stirred at 50-55 degreeC for 2 hours, and made it react. After neutralizing hydrochloric acid with an aqueous sodium hydroxide solution, MEK was removed by distillation under reduced pressure, and a styrene monomer having 3-ethylamino-4-methylphenol group bonded to PEG as a spacer was obtained.

(2) St. 80 parts, 10 parts of styrene-based monomers to which 3-ethylamino-4-methylphenol group is bonded as a spacer obtained from PEG in (1), 10 parts of DVB, and 2,2'-azobis (2-amidino) 0.2 parts of propane) hydrochloride were mixed. 400 parts of deionized water was put into the polymerization reaction apparatus. Nitrogen gas was introduce | transduced, the temperature was raised, the said monomer liquid mixture was dripped, and the polymerization reaction was performed at 65-70 degreeC for 8 hours. This is hereinafter referred to as 'repellent antifouling particle-3'.

Synthesis Example 4

(1) To the reaction apparatus, 110.2 parts of 50% xylene / n-butanol mixed solvent solution of PEG diglycidyl ether (epoxy equivalent: 551) used in Synthesis Example 2 (1) was added, and 50% xylene of trimethylethylenediamine was added. 20.4 parts of / n-butanol mixed solvent solutions were dripped at 50 degreeC for 3 hours, and it stirred for 5 hours at 50-55 degreeC then, it was made to react, and the PEG solution which trimethylethylenediamine group couple | bonded was obtained. The progress of the reaction was confirmed by infrared spectrum.

(2) 250 parts of dispersion liquids of core-shell crosslinked polymer particles having a chloromethyl group obtained in Synthesis Example 1 (1) were added to a reaction vessel, and then 27.0 parts of a MIBK solution of PEG bonded with the trimethylethylenediamine group obtained in (1) above were added. The reaction was carried out in the same manner as in Synthesis example 1 (3). After the reaction, the polymer particles were filtered and washed. The crosslinked polymer particles surface-modified with a tertiary aminated PEG chain were obtained. This is hereinafter referred to as 'cationic antifouling particle-1'.

Synthesis Examples 5 to 6

(1) Synthesis In the same manner as the reaction of diglycidyl ether of PEG and DEA of Example 2 (1), the glycidyl compounds shown in Table 1 below were used, and an equivalent amount of DEA was reacted. Furthermore, an equivalent amount of CMS was reacted, neutralized with sodium hydroxide, and a styrene monomer derivative having an alkyl PEG chain or a phenyl PEG chain bonded through a tertiary amino group was obtained.

(2) Synthesis In the same manner as in the polymerization reaction of Synthesis Example 2 (2), the monomers in which styrylmethyl (diethyl) amino groups were bonded to both ends of styrene, DVB and PEG in Table 1 were copolymerized, respectively, and PEG derivative chains. The crosslinked polymer particle paste obtained by surface modification was obtained.

TABLE 1

Synthetic Example Reacted with DEA
Glycidyl compounds Reaction products with DEA Name of antifouling particle 5 PEG (n: 15) monolauryl ether monoglycidyl ether
(Epoxy equivalent: 971) PEG monolauryl ether with styryl (diethyl) aminomethyl group bonded (M: 1200) Repellent Antifouling Particles-4 6 Monophenyl ether monoglycidyl ether of PEG (n: 15)
(Epoxy equivalent: 400) PEG monophenyl ether with styryl (diethyl) aminomethyl group (M: 600) Repellent Antifouling Particles-5

n represents the approximate average degree of polymerization of ethylene oxide of the PEG chain.

M represents the approximate average molecular weight of the reaction product.

Synthesis Example 7

(1) 214.4 parts of 50% propylene glycol monomethyl acetate solution of PEG diglycidyl ether (epoxy equivalent: 268) used in Synthesis Example 1 (2) was added to the reaction apparatus. 58.6 parts of DEA's 50% propylene glycol monomethyl acetate solution was added dropwise at 50 ° C. for 3 hours, and then stirred at 50 to 55 ° C. for 5 hours to react, whereby a 3- (diethylamino) 2- (hydroxy) propyl group was bound. A PEG solution was obtained.

The progress of the reaction was confirmed by infrared spectrum. Subsequently, 88.9 parts of isophorone diisocyanate 50% MIBK solution were dripped at 50 degreeC for 1 hour, and then it stirred at 50-55 degreeC for 2 hours, and it reacted by hydroxyl group, and obtained the isocyanate derivative.

Subsequently, 209.5 parts of propylene glycol monomethyl acetate solution containing 104.8 parts of risorecithin (glycerol hydrogenated soybean oil fatty acid monoester-phosphatidylcholine) which has a hydroxyl group were dripped at 50 degreeC for 2 hours, and it stirred for 4 hours, and made it react, and then phosphate The tertiary amine which the PEG chain which has thidylcholine group couple | bonded was obtained.

(2) 250 parts of a core-shell crosslinked polymer particle dispersion having a chloromethyl group obtained in Synthesis Example 1 (1) was added to a reaction vessel, and a 50% solution of a tertiary amine bound by a PEG chain having a phosphatidylcholine group obtained in the above (1). 57.8 parts were added and reacted at 130 ° C. for 8 hours to modify the polymer particle surface.

After the reaction, the reaction solution was poured into 600 parts of ethanol, the polymer particles were filtered off, washed with ethanol, and a crosslinked polymer particle paste surface-modified with phosphocholine was obtained. This is hereinafter referred to as 'both ionic antifouling particle-1'.

Synthesis Example 8

500 parts of deionized water, 10 parts of 4-vinylpyridine, 1 part of DVB, and 0.2 parts of 2,2'-azobis (2-amidinopropane) hydrochloride were added, and nitrogen gas was introduce | transduced and the temperature was raised. The polymerization reaction was carried out at 65 to 70 ° C for 8 hours. The particle diameter of the polymer particles in the polymerization solution was 350 nm as measured by the dynamic light scattering method. This is hereinafter referred to as 'cationic antifouling particle-2'.

Synthesis Example 9

10 parts of monochrome acetic acid was added to the 4-vinylpyridine crosslinked polymer particle dispersion liquid obtained in the synthesis example 8, and it was made to react at 25 degreeC for 24 hours and 50 degreeC for 8 hours. The mixture was filtered, thoroughly washed with deionized water, dried and pulverized to obtain copolymer particles having a pyridine group and a carboxyl group. This is hereinafter referred to as 'both ionic antifouling particles-2'.

Synthesis Example 10

250 parts of core-shell cross-linked polymer particle dispersions having a crawl methyl group obtained in Synthesis Example 1 (1) were added, 12.3 parts of N, N-dimethylaniline was added, and the reaction was carried out at 130 ° C. for 8 hours to modify the surface with dimethylaniline. Polymer particles were obtained. After the reaction, the reaction solution was poured into 300 parts of ethanol, and the polymer particles were filtered off and washed with ethanol. The crosslinked polymer particle paste surface-modified with the phenyldimethylammonium group was obtained. This is hereinafter referred to as 'repellent antifouling particle-6'.

Synthesis Example 11

In the same manner as the surface modification reaction of the crosslinked polymer particles of Synthesis Example 10, 20.3 parts of octylaniline were reacted in place of N, N-dimethylaniline. After the reaction, the reaction solution was poured into ethanol, the polymer particles were filtered off, washed, and a crosslinked polymer particle paste obtained by surface modification with an alkaline compound was obtained. This is hereinafter referred to as 'repellent antifouling particle-7'.

Synthesis Example 12

47 parts of acrylic acid, DVB 8.11 parts, and maleic acid-modified styrene-ethylene / butylene-styrene block copolymer (styrene content: 30%, average molecular weight 200,000) were added to the polymerization vessel in methylcyclohexane / MEK / toluene (5: It melt | dissolved in 550 parts of mixed solvents of 3: 2), 0.6 part t-butyl- peroxy-2-ethylhexanate was added to it, and the radical polymerization by nonaqueous emulsion polymerization was performed, and the carboxylic acid group containing crosslinked polymer particle was obtained. . This is hereinafter referred to as 'anionic antifouling particle-1'. The average particle diameter of this anionic antifouling particle | grain 1 was measured by the dynamic light scattering method, and was about 200 nm.

Synthesis Example 13

To a container with a stirrer, 93 parts of CMS, 50 parts of maleic anhydride and 3 parts of AIBN were added and dissolved in 74 parts of butyl acetate to prepare a monomer solution containing a polymerization initiator. Separately, a polymerization reaction apparatus is prepared, 100 parts of butyl acetate are put into a reaction vessel, nitrogen gas is introduced and stirred, and the temperature is raised to 70 ° C. 80 parts of said monomer solutions were added to this, and after making it react for 30 minutes, the remaining monomer solution was dripped over 2 hours, and the polymerization reaction was performed for 10 hours as it was.

50 parts of the polymer solutions obtained above and 30 parts of butyl acetate were put, and it stirred and raised the temperature. When 15.12 parts of N, N- dimethyloctylamine was dripped at 80 degreeC, it will become a microdispersion state and made it react for 8 hours by making temperature 120-140 degreeC. Next, 8.94 parts of n-butanol was dripped, and esterification was performed. When the reaction proceeded for 8 hours, it became a precipitated state. The reaction solution was cooled, filtered, washed sufficiently with methanol and then dried. Copolymer particles having a quaternized octyl ammonium group and a carboxyl group were obtained. This is hereinafter referred to as 'both ionic antifouling particles-3'.

Synthesis Example 14

(1) In the same manner as in Synthesis Example 5 (1), 268.0 parts of a diglycidyl ether 50% methylethylketone (MEK) solution of PEG used in Synthesis Example 1 (2) was added thereto, and a DEA 50% MEK solution 73.2 The part was dripped at 50 degreeC for 3 hours, and then it stirred at 50-55 degreeC for 5 hours, it was made to react, and PEG which the diethylamino group couple | bonded was obtained.

Then, 0.07 part of hydroquinone was added, 152.6 parts of 50% MEK solutions of CMS were dripped at 50 degreeC in 1 hour, and then it stirred at 50-55 degreeC for 2 hours, and made it react. After neutralizing hydrochloric acid with an aqueous sodium hydroxide solution, MEK was distilled off under reduced pressure to obtain a monomer having N-steel methyl (N, N-diethyl) amino groups bonded to both ends of the PEG.

(2) 80 parts of St, 10 parts of monomers having N-steel methyl (N, N-diethyl) amino group bonded to both ends of PEG obtained in (1), 10 parts of DVB and 2,2'-azobis (2 0.2 parts of amidinopropane) hydrochloride was mixed. 400 parts of deionized water was put into the polymerization apparatus, the said monomer liquid mixture was dripped there, and it mixed. Nitrogen gas was introduce | transduced, the temperature was raised, and the polymerization reaction was performed at 65-70 degreeC for 8 hours. This is hereinafter referred to as 'cationic antifouling particle-3'.

Comparative Example 1

150 parts of xylene / n-butanol mixed solvents (7/3) are put into a polymerization vessel, and it heats to 90 degreeC. Subsequently, 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, followed by a nitrogen gas stream. It reacted for 6 hours and obtained the xylene solution of MMA-BMA-HEMA copolymer (solid content: 40%). Hereinafter, this is referred to as 'comparative acrylic resin'.

<Example of application to antifouling paint>

[Application Example 1]

The repellent antifouling particles-1 obtained in Synthesis Example 1 were mixed at 65/35 in a xylene / n-butanol solution of the following fixing acrylic resin and a solid content mass ratio, and adjusted to a solid content of 25% with butyl acetate, and then repellent. Antifouling particle-1 was disperse | distributed by the ultrasonic wave, and the coating material was prepared. The upper and lower sides of the test steel plate subjected to the antirust treatment were made up, down, left, and center around each other, and an epoxy-based paint was applied in a width of about 1 cm, respectively, to create a protection and boundary. The mixture was thickly applied to the lower half of the mixture, and dried at room temperature for 10 days. The coating film was about 110-130 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 synthesize | combined as follows. 114 parts of xylenes and 38 parts of n-butanol are put into a polymerization container using the polymerization apparatus used in the synthesis example 1, and it heats at 90 degreeC. Then a mixture 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 added over 2 hours. It dripped and reacted for 6 hours under nitrogen gas airflow (solid content: 40%). In addition, the said test steel plate is about 150 g / m <2> after drying the tarepoxy base paint on the double-sided sand blast steel plate (width X length X thickness: 70 * 150 * 1mm) of test panel company products. Was applied, and dried by wind to prepare.

Comparative Example 2

The resin solution obtained in the comparative example 1 for comparison of antifouling performance was apply | coated to the divided upper half part on each plate prepared in the application example 1, and it dried at room temperature for 10 days. The thickness of the coating film was about 110-130 g / m <2>. In the following application example, it divided similarly to the top and bottom, and compared.

[Application Examples 2 to 15]

The coating plate was prepared according to the preparation method and coating method of the coating material which were demonstrated by the application example 1 by the compounding prescription in solid content of Table 2. The thickness of the film thickness was almost 110-130 g / m <2>.

TABLE 2-1

(The solid content mass ratio is shown.)

Antifouling particles
Synthesis Example
Application Example 2 3 4 5 6 7 8 Repellent Antifouling Particles-2 2 65 - - - - - - Repellent Antifouling Particles-3 3 - 65 - - - - - Repellent Antifouling Particles-4 5 - - 65 - - - - Zwitterionic Antifouling Particles-1 7 - - - 65 - - - Zwitterionic Antifouling Particles-2 9 - - - - 65 - - Zwitterionic Antifouling Particles-3 13 - - - - - 65 - Repellent Antifouling Particles-5 6 - - - - - - 65 Adhesive Acrylic Resin - 35 35 35 35 35 35 35

Table 2-2

(The solid content mass ratio is shown.)

Antifouling particles
Synthesis Example
Application Example 9 10 11 12 13 14 15 Zwitterionic Antifouling Particles-2 9 - - - - - - 50 Repellent Antifouling Particles-6 10 65 - - - - - - Repellent Antifouling Particles-7 11 - 65 - - - - - Anionic Antifouling Particle-1 12 - - 32.5 29 32.5 50 - Cationic Antifouling Particle-1 4 - - 32.5 - - - - Cationic Antifouling Particles-2 8 - - - 36 - - - Cationic Antifouling Particles-3 14 - - - - 32.5 15 - Adhesive Acrylic Resin - 35 35 35 35 35 35 50

[Application Example 16]

(1) The test method and the seawater immersion test of the test steel plate were carried out in a nutrient-rich environment in which there was a feeding of fish at a place adjacent to the growing place of young fish, which has relatively little sea currents. The water temperature was about 25 to 28 ° C. and the COD concentration was 4 to 10 mg / L. Regarding the COD concentration, it is said that 1 to 2 mg / L in a relatively quiet water of a narrow strait inland sea, and 3 to 5 mg / L where the color of water, such as the inside of a port, appears from green to yellow.

The coated test steel sheets prepared in Application Examples 1 to 15 and Comparative Example 2 were fixed up and down in a frame made of polyvinyl chloride. The vinyl chloride resin mold was immersed at a depth of 1 to 2 m from the sea surface. The test steel plate was lifted every one week over four weeks, and the attachment state of the arthropods of the upper half and lower half of the test steel plate was observed, and the change of state was evaluated. The evaluation results are shown in Table 3 below.

(2) Results and evaluation of state observation

A: It has a function as a non-release antifouling paint.

B: Although it is non-release, the function as an antifouling paint is slightly insufficient.

C: Although it is non-producing, it does not have a function as an antifouling paint.

[Table 3]

Painted steel sheet Result of state observation evaluation Application Example 1




It was recognized that the attachment of barnacles was significantly slower. A Application Example 2 A Application Example 3 A Application Example 4 A Application Example 5 A Application Example 6 A Application Example 7 A Application Example 8 A Application Example 9 A Application Example 12 A Application Example 13 A Application Example 14 A Application Example 15 A Application Example 10 Barnacles grew in 1 to 2 weeks, but clams were removed from the plate from 3 weeks and reattachment of barnacles was not recognized. B Application Example 11 B Comparative Example 2 Barnacle attachment proceeded with time and did not drop off due to firm attachment to the plate. C

Comparative Example 3

In the same manner as in the application example, a polishing-type coated plate using cuprous oxide was prepared. Similarly, seawater immersion was performed, and antifouling properties were evaluated. Barnacles were hardly attached and exhibited very excellent antifouling properties, but barnacles were also not adhered to the parts coated with the epoxy-based undercoat paint around the top, bottom, left, and right sides of the test steel sheet. This indicates that the adjacent environment including the portion where the antifouling paint is not coated is also affected by the dissolution of cuprous oxide. On the other hand, the coating material of the said application examples 1-15 shows that there are remarkably many arthropods in the part which apply | coated the epoxy base coating material, and also adhered firmly, and the biological repellent used was not eluted. Accordingly, the antifouling particles used in the application examples show that the load on the environment is small.

According to the present invention, it is possible to provide a novel antifouling particle (biological antifouling agent), an antifouling paint using the same, an antifouling treatment method of a substrate, and an antifouling article, which are safe for the environment and edible seafood.

Claims (10)

It consists of 0.1 ~ 50㎛ polymer particles having biofouling groups for aquatic animals or plants that reproduce in seawater and attach to hulls or structures in the sea. The biofouling group is at least one selected from a hydrophilic group (a), both anionic and cationic ionic groups (b) and biorepellent groups (c), When the said biofouling group is a hydrophilic group (a), the said polymer particle has the hydrophilic polymer chain which the said hydrophilic group (a) couple | bonded with a polyalkylene oxide (C2-C3) as a spacer, When the said biofouling group is both ionic groups (b), the said polymer particle is a thing in which the same polymer particle was modified by both an anionic group and a cationic group, or the said polymer particle was received by an anionic group. A mixture of a polymer and a polymer modified with cationic groups, In the case where the biofouling group is a biorepellent group (c), the polymer particles have a polymer chain in which the biorepellent group (c) is bonded with a polyalkylene oxide (carbon number 2 to 3) as a spacer. Antifouling agent. The biofouling agent according to claim 1, wherein the polyalkylene oxide is polyethylene glycol. The biological antifouling according to claim 1, wherein the hydrophilic group (a) is at least one selected from anionic groups, cationic groups, nonionic groups, anionic and nonionic amphoteric groups, cationic and nonionic amphoteric groups, and anionic and cationic amphoteric groups. My. The anionic and cationic both ionic groups (b) are anions selected from anionic groups, anionic and nonionic amphoteric groups, cationic groups, cationic and nonionic amphoteric groups, and anionic and cationic amphoteric groups. Biofouling agent which is a combination of genital and cationic groups. The organism according to claim 1, wherein the biorepellent group (c) is at least one member selected from aliphatic, alicyclic or aromatic amino groups, quaternary ammonium groups, pyridine groups, pyridinium groups, phenolic hydroxyl groups and polyethylene glycol groups. Antifouling agent. The biofouling agent according to claim 1, wherein the polymer particles are a mixture of polymer particles having different antifouling groups. The antifouling paint formed by mix | blending a coating film forming material with the polymer particle of Claim 1. The antifouling paint according to claim 7, wherein a blending mass ratio of the polymer particles (A) and the coating film forming material (B) is A: B = 95: 5 to 5:95. The antifouling agent described in claim 1 or the antifouling paint described in claim 7 is applied to the substrate, impregnated, or kneaded with the substrate. Biofouling treatment method. A biofouling treatment article is subjected to biofouling treatment by the treatment method according to claim 9.