JP2005034770A - Antifouling coat to which water creatures do not adhere, antifouling object using the same, and antifouling paint for obtaining the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling coat, in which a preventing action to an adhesion of water creatures is not reduced even if it is used for a long time. <P>SOLUTION: The antifouling coat to which no water creature adheres is formed by forming the coat on a substrate, ships, subaquatic structures, seawater introduction pipes, fish-nets, or undersea cables with the antifouling paint containing an antifouling agent and an organic solvent in a polymer hydrogel composed of a three-dimentional crosslinking material of a vinyl polymer containing not less than 50 mol% of a hydrophilic monomer, and thereafter by being immersed under water. The antifouling object is one using this anifouling coat. The antifouling paint to which no water creature adheres contains an antifouling agent, an organic solvent, a crosslinking agent, and a vinyl polymer in which the hydrophilic monomer is contained in an amount of not less than 50 mol%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antifouling coating to which aquatic organisms do not adhere, an antifouling object having the coating on the surface, and an antifouling coating that forms the antifouling coating.

  Various aquatic organisms adhere to artifacts that exist in the sea and lakes. The attachment of aquatic organisms causes various problems. For example, in the case of a ship, shells, seaweeds, and the like adhere to a portion that is in contact with water, thereby increasing the resistance to water and causing a situation that significantly impedes the traveling of the ship. Also, in places where seawater is used such as thermal power plants, seawater introduction pipes that introduce seawater are found in the sea, where shellfish, hydrozoa and other coelenterates, polychaetes, seaweeds, mollusks, etc. If the marine organisms adhere, there will be a large fluctuation in the amount of water taken in the seawater, and sometimes it may not be possible to take in the water. In addition, the offshore structure not only harms aesthetics due to the attachment of aquatic organisms, but may also cause deterioration of the structure itself.

  Therefore, many techniques for preventing such aquatic organisms from adhering to artifacts have been proposed. For example, as a ship bottom paint for painting on the bottom of a ship or the like, many proposals have been proposed, such as Japanese Unexamined Patent Publication No. 2002-3776 (Patent Document 1) and Japanese Unexamined Patent Publication No. 2000-248207 (Patent Document 2). These known ship bottom paints have a property (self-polishing property) that the formed coating film self-decomposes by hydrolysis and decomposes itself even if aquatic organisms adhere to the paint. However, not only the disadvantage that seawater contamination is caused by the hydrolyzed coating film, but also it was impossible to seek antifouling over a long period of 2 years or more due to the decrease of the coating film due to hydrolysis.

In addition to the above self-polishing type coating, as shown in Japanese Patent Laid-Open No. 2002-348536 (Patent Document 3) and Japanese Patent Laid-Open No. 2002-80778 (Patent Document 4), it is harmful to have a highly water-repellent surface. Proposals have been made for methods such as suppressing the attachment of marine organisms. Since these methods are not hydrolyzed, they do not cause seawater contamination. However, the water repellent treated surface has a defect that it loses water repellency when attacked by microorganisms such as bacteria in seawater. Once the water-repellent treatment surface loses its water repellency, marine organisms may rapidly adhere to the surface and may cause significant damage to artifacts.
Japanese Patent Laid-Open No. 2002-3776 JP 2000-248207 A JP 2002-348536 A JP 2002-80778 A

  It is an object of the present invention to provide an antifouling coating that does not lose its ability to prevent aquatic organisms from sticking even after long-term use. In addition, the antifouling coating of the present invention uses an aquatic organism adhesion prevention action that is not based on an adhesion prevention action that peels off aquatic organisms attached by decomposition and removal of the coating by hydrolysis, as in the conventional ship bottom paint, An object of the present invention is to provide an antifouling film with very little problem of marine contamination of hydrolyzate.

  That is, the present invention provides an antifouling coating to which aquatic organisms composed of a polymer hydrogel do not adhere.

  Further, the present invention is an antifouling object comprising a base material and an antifouling film provided on the outermost surface of the base material, wherein the antifouling film is the antifouling film described above. Provide an antifouling object to which aquatic organisms do not adhere.

  Furthermore, the present invention provides an antifouling paint to which aquatic organisms containing a vinyl polymer containing a hydrophilic monomer of 50 mol% or more, a crosslinking agent, an antifouling agent and an organic solvent do not adhere.

  Without being bound by any particular theory, a polymer hydrogel is constructed with a crosslinked polymer as a matrix, but water molecules are either trapped or trapped in the crosslinked polymer matrix. It is considered to be. Although water molecules exist in polymer hydrogels, they are not necessarily fixed and cannot move, and it is thought that there are many water molecules that exist with a certain degree of freedom. Yes. Therefore, it is considered that water molecules are replaced when the polymer hydrogel comes into contact with the water flow. Thus, the present inventor confirmed the fact that aquatic organisms are hardly attached to the polymer matrix in a state where water molecules can move, and came to make the present invention. For this state, the expression “poor scaffolding” for aquatic organisms can be used. In any case, when the polymer hydrogel matrix part is cross-linked and hard, but the part where water molecules are trapped is present in the presence of voids, aquatic organisms have poor scaffolding, It is predicted that it will be difficult to adhere.

  When a general antifouling agent is included in the antifouling coating composed of this polymer hydrogel, aquatic organisms are more difficult to adhere and the antifouling action is improved.

  The polymer hydrogel is formed by forming a polymer matrix portion by cross-linking a highly hydrophilic polymer in an organic solvent or a mixture of water and an organic solvent, and immersing the polymer matrix in water or seawater. be able to. Therefore, at the time of the first stage cross-linking reaction, the molecules trapped in the matrix are expected to be mainly organic solvent molecules (partly containing water molecules). In particular, if the molecules trapped in the matrix are organic solvent molecules, they are called organogels and can be distinguished from hydrogels. The highly hydrophilic polymer that is the basic constitution of the hydrogel is a vinyl polymer obtained by polymerizing a vinyl monomer containing a predetermined amount of a hydrophilic monomer, particularly 50 mol% or more, preferably 60 mol% or more. Good.

  The polymer hydrogel is formed by applying an antifouling paint containing the above-mentioned hydrophilic vinyl polymer, cross-linking agent, antifouling agent, water and / or organic solvent to the base material and crosslinking it, and then immersing it in water. Can do. Of course, it is not limited to these.

  As described above, the polymer hydrogel membrane of the present invention can extremely effectively prevent the attachment of aquatic organisms. The polymer hydrogel membrane of the present invention is basically not hydrolyzable, is not a self-polishing antifouling coating, and hardly causes water contamination due to the hydrolyzate. In addition, since the polymer hydrogel film is a three-dimensionally crosslinked polymatrix, it can retain its form for a long period of time, and the adhesion preventing action of aquatic organisms is longer than that of a self-polishing type antifouling film. Lasts for a period.

Polymer hydrogel membrane The antifouling coating of the present invention comprises a polymer hydrogel. The polymer hydrogel of the present invention is considered to have a structure in which highly hydrophilic polymer molecules are three-dimensionally crosslinked and water molecules are retained or trapped inside. The highly hydrophilic polymer is a monomer having a predetermined amount of a hydrophilic group in a general polymer skeleton (for example, vinyl polymer, silicone resin, acrylic / silicone copolymer resin), and the polymer is three-dimensionally crosslinked by a crosslinking action. An antifouling agent may be contained in the three-dimensional crosslinked matrix structure.

(1) Vinyl Polymer In the present invention, the polymer hydrogel film is mainly formed from a vinyl polymer that can swell with water to form a hydrogel. A vinyl polymer is preferable because it can be formed by polymerization of various monomers and various physical quantities (for example, molecular weight, hydrophilic group amount, etc.) can be easily controlled.

  The polymer matrix constituting the polymer hydrogel of the present invention is formed from a vinyl monomer containing 50 mol% or more, preferably 60 mol% or more of a hydrophilic vinyl monomer.

  Examples of suitable hydrophilic vinyl monomers include cationic vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, allylamine, N-methylallylamine, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl ( (Meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-hydroxy (meth) acrylamide and vinylpyridine, vinylimidazole, vinylpyrrolidone, etc .; anionic vinyl monomers such as (meth) acrylic acid and its salts, fumaric acid, maleic acid Citraconic acid, itaconic acid, crotonic acid, aconitic acid, 4-pentenoic acid, ω-undecenoic acid and their salts, vinyl sulfonic acid, vinyl benzyl sulfonic acid, 2-acrylic acid Bromide 2-methylpropanesulfonic acid, 2-acryloyl ethanesulfonic acid, 2-acryloyl propane sulfonic acid, 2-methacryloyloxy ethane sulfonic acid and salts thereof, furthermore, phosphoric acid and salts thereof; and the like.

  Other monomers that copolymerize with the hydrophilic vinyl monomer include N-alkyl substituted (meth) acrylamides: (meth) acrylamide, (meth) N-acrylol-L-alanine, (meth) aminopropyl acrylamide, (meta ) N-aminopropyl acrylamide, (meth) N-isopropylacrylamide, t-butyl (meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, ( (Meth) isobutylacrylamide, (meth) diacetone acrylamide, etc .; (meth) acrylic acid ester: for example, methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, (meth) acrylic acid i-butyl, ( N-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, i-octyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid isobornyl; or (meth) acrylic acid containing a hydroxyl group, for example, (meth) acrylic acid 2-hydroxypropyl, ( Examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) -1,4-cyclohexanedimethanol monoacrylate, and the like.

  The monomer copolymerized with the hydrophilic vinyl monomer for forming the polymer hydrogel requires a vinyl monomer for introducing a crosslinkable functional group into the vinyl polymer (1) in addition to the above-mentioned monomers.

  Examples of such monomers include two polymerizable vinyl monomers that introduce crosslinkable unsaturated groups into the vinyl polymer (1), such as vinyl (meth) acrylate, allyl (meth) acrylate, and (meth) acrylic. Examples include 2-butenyl acid and 3-methyl-2-butenyl (meth) acrylate, but are not limited thereto. When this monomer is used, a polymerizable unsaturated group is introduced into the vinyl polymer (1) and is cured at room temperature due to the presence of a curable catalyst called a so-called dryer.

  As another example of the monomer for introducing a crosslinkable functional group, glycidyl (meth) acrylate: for example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether Etc. These monomers are intended for crosslinking reaction with glycidyl groups.

  The monomer to be copolymerized may be a hydrophobic monomer or a water-repellent monomer in order to adjust the water swelling degree and water content of the coating. Examples of such monomers include (meth) alkylalkoxy acrylates: for example, ethyl 3-ethoxy (meth) acrylate, (meth) 2-ethoxyethyl acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) Acrylate, (meth) ethylene glycol methyl ether acrylate, etc .; polyethylene glycol (meth) acrylate: for example, polyethylene glycol mono (meth) having a degree of polymerization (n) of ethylene glycol of about 1 to 10, preferably a degree of polymerization of 1 to 3. Acrylate; (meth) alkyl acrylate containing fluorine: for example, (meth) -2,2,2-trifluoroethyl acrylate, (meth) -2,2,3,3-tetrafluoropropyl acrylate, (meth) -2 , 2,3,3,4,4,5,5-octafluoropentyl acrylate, etc. And silicone-containing acrylic monomers: for example, alkyl (meth) acrylate of polydimethylsiloxane, (meth) polydimethylsiloxane-grafted polyacrylate, etc .; or styrene, α-methylstyrene, vinyl acetate, vinyl propionate, benzoic acid Monomers that contain both vinyl, vinyltoluene, acrylonitrile, unsaturated dibasic acid distels (eg, crotonic acid esters, maleic acid diesters, itaconic acid diesters), and acid / base in the molecule (eg, Nonionic vinyl monomers such as (meth) acrylamidopropylsulfonic acid, (meth) acrylamidopropylsulfonic acid sodium) can also be used.

  The vinyl polymer (1) is polymerized by appropriately using at least one monomer among the reactive vinyl monomers by a conventional method, if necessary, using a solvent, a polymerization initiator (such as azoisobutyronitrile), or the like. Can be prepared. However, the hydrophilic monomer must be present in a specific amount as described above.

  The vinyl polymer (1) thus prepared is applied to the surface of an object to be coated and dried at room temperature when a monomer having two double bonds is used. As a result, cross-linking occurs due to oxidative polymerization or the like of the incorporated vinyl group, and a cross-linked polymer resin coating film having a highly hydrophilic polymer matrix formed therein is obtained. The polymer matrix contains the solvent used during preparation. In this case, a curing catalyst called a so-called dryer is necessary. Specific examples thereof include cobalt, lead, titanium, and nickel-based catalysts.

  Among these monomers, when the vinyl monomer (1) is prepared using a monomer having a glycidyl group or a monomer having an amino group, a crosslinking agent (for example, an amine compound or an aldehyde) is added and uniformly mixed during coating. You can do it. In this case, a three-dimensional crosslinked structure is formed inside by the action of the crosslinking agent. Examples of amine compounds include aromatic diamine compounds such as methylene bis (2-chloroaniline), trimethylene bis (4-aminobenzoate) 4-aminophenyl sulfone; aliphatic diamine compounds such as dimethylaminopropylamine, 1,2- Diaminopropane is mentioned. Examples of aldehydes include glutaraldehyde, phthalaldehyde, and 1,3-bis- (4-formylphenoxy) propane.

  The former (that is, a system in which no cross-linking agent is added) is more preferable because good coating workability can be provided.

  In the present invention, the polymer resin (1) may be used by mixing a silicone resin (SiR). For example, moisture reaction curable methylsiloxane rubber (generic name “RTV silicone rubber”) and the like can be mentioned.

  When the polymer matrix is immersed in water or seawater, the solvent in the three-dimensional cross-linked structure elutes and the water or seawater replaces it. As a result, the polymer hydrogel membrane of the present invention in which water or seawater is included in the three-dimensional crosslinked structure (that is, swollen with water or seawater) is obtained.

(2) Antifouling agent (antibacterial agent)
The antifouling coating film of the present invention may contain an antifouling agent (2) in the three-dimensional crosslinked structure of the polymer hydrogel. There are two types of antifouling agents, organic and inorganic. In the present invention, either one or both may be used in combination.

  The organic antifouling agent suitably used in the present invention may be a known one, and is selected from, for example, nitrile, pyridine, haloalkylthio, organic iodo, thiazole and benzimidazole antibacterial agents. Two or more types may be included. Specific examples of preferable antibacterial agents are listed below.

  (A) Nitrile antibacterial agents; haloisophthalonitrile compounds (for example, 2,4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluorophthalonitrile) and haloaryl nitrile compounds ,

  (B) Pyridine antibacterial agents: Halogenated pyridine derivatives (for example, 2-chloro-6-trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl- 6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridinemethanol, sulfonylhalopyridine compounds (2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 2,3,5-trichloro-4 -(n-propylsulfonyl) pyridine) and pyridinethiol-1-oxide compounds (eg, 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol-1-oxide zinc, di (2-pyridinethiol-1-oxide) )),

  (C) haloalkylthio antibacterial agents; haloalkylthiophthalimide compounds (for example, N-fluorodichloromethylthiophthalimide, N-trichloromethylthiophthalimide), haloalkylthiotetrahydrophthalimide compounds (for example, N-1,1,2,2-tetrachloroethylthio) Tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide), haloalkylthiosulfamide compounds (eg, N-trichlorothio-N- (phenyl) methylsulfamide, N-trichloromethylthio-N- (4-chlorophenyl) methylsulfami N- (1-fluoro-1,1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N- (1,1-difluoro-1,2,2-trichloroethylthio) -N- (phenyl) methylsulfamide), and haloalkylthiosulfimide compounds (eg, N, N-dimethyl) Tyl-N'-phenyl-N '-(fluorodichlorothio) sulfimide, N, N-dichlorofluoromethylthio-N'-phenylsulfimide, N, N-dimethyl-N'-(p-tolyl) -N ' -(Fluorodichloromethylthio) sulfimide),

  (D) Organic iodine-based antibacterial agents; iodosulfone compounds, iodinated unsaturated aliphatic compounds (for example, 3-iodo-2-propargylbutylcarbamic acid, 4-chlorophenyl-3-iodopropargyl formal, 3-ethoxycarbonyloxy- Bromo-1,2-diiodo-1-propene, 2,3,3-triiodoallyl alcohol), iodosulfenylbenzene compounds (eg diiodomethyl-p-trisulfone, 1-diiodomethylsulfonyl-4-methylbenzene) 1-diiodomethylsulfonyl-4-methylbenzene, 1-diiodomethylsulfonyl-4-chlorobenzene),

  (E) thiazole antibacterial agents; isothiazolin-3-one compounds (for example, 1,2-benzisothiazolin-3-one, 2- (n-octyl) -4-isothiazolin-3-one, 5-chloro-2- Methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one), benzthiazole compounds (for example, 2- ( 4-thiocyanomethylthio) -benzthiazole, 2-mercaptobenzthiazole sodium, 2-mercaptobenzthiazole zinc), and isothiazolin-3-one compounds, and

  (F) benzimidazole antibacterial agents; benzimidazole carbamate compounds (for example, methyl 1-H-2-benzimidazole carbamate, methyl butylcarbamoyl-2-benzimidazole carbamate, 6-benzoyl-1H-2-benzimidazole) Methyl carbamate), sulfur-containing benzimidazole compounds (eg, 1H-2-thiocyanomethylthiobenzimidazole, 1-dimethylaminosulfonyl-2-cyano-3-bromo-6-trifluoromethylbenzimidazole), cyclic benzimidazole Compound derivatives (eg, 2- (4-thiazolyl) -1H-benzimidazole, 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole, 2- (1- ( 3,5-dimethylpyrazolyl) -1H-benzimidazole, 2- (2-furyl) -1H-benzimidazole), benzimidazole Vammin acid compound, thiazolyl benzimidazole compound.

  Examples of the inorganic antifouling agent suitably used in the present invention, that is, the metal-containing antifouling agent include, for example, cuprous oxide, rhodan copper, copper naphthenate, copper stearate, zinc oxide, titanium oxide, iron oxide, Examples include zinc bis- (dimethyldithiocarbamate), ethylene-bis- (dithiocarbamate) zinc, ethylene-bis- (dithiocarbamate) manganese, and ethylene-bis- (dithiocarbamate) copper. The most commonly used is cuprous oxide.

  A part of the antifouling agent (2) may be ionically bonded within the three-dimensional crosslinked structure of the polymer hydrogel membrane of the present invention.

(3) Solvent and various additives The polymer hydrogel film of the present invention may further contain various additives such as a solvent, a plasticizer, a color pigment, an extender pigment, and an elution aid.

  The solvent suitably used in the present invention may be water or an organic water-soluble solvent. Examples of solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and propylene glycol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, 1,4-dioxane, diethyl ether and ethylene glycol diethyl ether And ethers such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone are preferably used.

  Plasticizers include phthalic acids such as dioctyl phthalate, dimethyl phthalate and dicyclohexyl phthalate, aliphatic dibasic acid esters such as diisobutyl adipate and dibutyl sebacate, glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl ester, Examples thereof include phosphate esters such as tricresyl phosphate and trichloroethyl phosphate, and epoxy systems such as epoxidized soybean oil and octyl epoxy stearate.

  As the color pigment, titanium oxide, zircon oxide, carbon black, bengara, phthalocyanine green, quinacridone, emerald green, phthalocyanine blue can be used.

  The extender pigments include talc, clay, silica white, alumina white, titanium white, bentonite, barite, precipitated barium sulfate, and the like.

  As an elution aid, paraffin or the like can be used.

Antifouling object The present invention also provides an object to which the polymer hydrogel film of the present invention is applied as a second embodiment. For the purpose of the present invention, an object to which the polymer hydrogel membrane of the present invention is applied is an object that comes into contact with water or seawater, and its function, performance, or operability, particularly when aquatic organisms adhere to its surface. It can be greatly influenced by such. Such objects specifically include ships (especially ship bottoms), seawater inlet pipes, for example, bay facilities, offshore drilling facilities, bridges, pipelines, offshore structures such as submarine bases, and fishnets.

Antifouling paint Another aspect of the present invention is an antifouling paint containing a hydrophilic vinyl polymer as a main component and containing a solvent and an additive. If necessary, an antifouling agent or a crosslinking agent may be added to the antifouling paint. The antifouling paint of the present invention is used to form the polymer hydrogel film of the present invention.

  The hydrophilic vinyl polymer that is the main component of the antifouling paint of the present invention may be blended in an amount of 1 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the antifouling paint.

  In the antifouling paint composition of the present invention, the antifouling agent (2) is further contained in an amount of 0 to 40% by weight, preferably based on the total weight of the antifouling paint composition, based on the total weight of the antifouling paint composition. 2 to 30% by weight, and the total amount of solvent and various additives is 35 to 99% by weight based on the total weight of the antifouling coating composition, preferably 45 to 90% based on the total weight of the antifouling coating composition. It may be blended in an amount of% by weight.

  When blending the antifouling agent (2), the solvent, and various additives (3), add them to the polymer resin (1) and use a mixer such as a ball mill, a roll mill, or a sand grind mill. By mixing, the antifouling coating composition of the present invention is obtained.

  After the preparation, the antifouling coating composition of the present invention may be appropriately diluted with a water-soluble solvent to a viscosity suitable for application.

  The antifouling paint of the present invention is applied to the surface of a ship, which is an object to be coated, and then dried at room temperature and crosslinked to form a crosslinked polymer resin coating film. The obtained crosslinked polymer resin coating film contains the solvent used at the time of preparation or preparation of the coating composition in the three-dimensional crosslinked structure inside.

  Next, the crosslinked polymer resin coating film is immersed in water or sea water (for example, for 0.5 to 7 days) together with the object to be coated covered with the film. During this time, the solvent contained in the three-dimensional crosslinked structure elutes and water or seawater is included in the structure instead. As a result, the polymer hydrogel membrane of the present invention in which water or seawater is included in the three-dimensional crosslinked structure (that is, swollen with water or seawater) is obtained.

  In the polymer hydrogel film formed by the method of the present invention, water or seawater can freely move. Therefore, the polymer hydrogel membrane of the present invention is unlikely to become a foothold for attachment of aquatic organisms (also referred to as “poor scaffold” for aquatic organisms), and as a result, aquatic organisms are difficult to attach. According to the present invention, adhesion of marine organisms can be more effectively prevented by including an antifouling agent in the polymer hydrogel film.

  In addition, since the polymer hydrogel membrane of the present invention has poor hydrolyzability, the membrane is difficult to collapse. If antifouling agents are optionally included, they are retained within the three-dimensional cross-linked structure within the membrane and are optionally ionically fixed and cannot be released into water unless the membrane is disrupted. . Thus, the polymer hydrogel membrane of the present invention not only extends the useful life of the membrane itself, but also prevents seawater contamination.

  That is, the polymer hydrogel film of the present invention can be used for a long period of time, for example, for at least 2 years, particularly for at least 3 years. It is possible to effectively prevent the attachment of marine organisms.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Parts indicate parts by weight.

Preparation of polymer resin varnish A 30 parts of dimethylacetamide and 10 parts of ethanol were placed in a 300 mL four-necked flask equipped with a stirrer, cooler, temperature controller, nitrogen inlet tube, and dropping funnel, and stirred while introducing nitrogen. . Subsequently, acrylic acid (0.076 mol), acrylamide (0.014 mol), N-isopropylacrylamide (0.009 mol), 2-acrylamido-2-methyl-1-propanesulfonic acid (0.010 mol), Allyl methacrylate (0.004 mol) and 0.03 part of azoisobutyronitrile as an initiator were added and heated at 60 ° C. for 24 hours under nitrogen. As a result, a transparent polymer resin varnish A was obtained.

Preparation of polymer resin varnish B 40 parts of dimethylacetamide was placed in a 300 mL four-necked flask equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube, and a dropping funnel, and stirred while introducing nitrogen. Subsequently, acrylic acid (0.031 mol), methacrylic acid (0.012 mol), acrylamide (0.028 mol), N-isopropylacrylamide (0.009 mol), 2-acrylamido-2-methyl-1- Propanesulfonic acid (0.010 mol), methyl methacrylate (0.010 mol), allyl methacrylate (0.004 mol), polydimethylsiloxane-graft polyacrylate (10% aqueous solution, manufactured by Aldrich) (1.15 × 10 6 ^-5 mol), 0.03 part of azoisobutyronitrile as an initiator was added and heated at 60 ° C. under nitrogen for 24 hours. Thereby, a transparent polymer resin varnish B was obtained.

Production Example of Coating Composition A To 10 parts of the polymer resin varnish A, 2.0 parts of n-butanol and 0.1 part of an antifouling agent (nitrile / pyridine) were added and stirred. Subsequently, 2.5 parts of cuprous oxide and 0.05 parts of catalyst (lead-based dry trade name DECATE ^{(registered trademark)} : manufactured by Dainippon Ink & Chemicals, Inc.) and 10 parts of glass beads are stainless steel bat (capacity: 100 mL). And dispersed with a disperser for 30 minutes while cooling. After the dispersion, the glass beads were removed by filtration to obtain the antifouling paint composition A of the present invention.

Production Example of Coating Composition B To 10 parts of a polymer resin varnish B, 2.0 parts of n-butanol and 0.1 part of an antifouling agent (nitrile / pyridine) were added and stirred. Subsequently, 1.5 parts of cuprous oxide and 0.05 parts of a catalyst (trade name Dekunate ^{(registered trademark)} : manufactured by Dainippon Chemical Industry Co., Ltd.) and 10 parts of glass beads were placed in a stainless steel vat (capacity: 100 mL). Dispersed for 30 minutes with a disperser while cooling. After the dispersion, the glass beads were removed by filtration to obtain an antifouling paint composition B of the present invention.

Example 1
The antifouling paint composition A prepared by the above method was applied with a brush to a test piece to which a rust preventive primer had been applied in advance. The film was dried at room temperature for 2 hours to obtain a coating film having a dry thickness of about 300 mμ.
Subsequently, the test piece coated with the coating film was immersed in artificial seawater (trade name Aqua Marine ^{(registered trademark)} : manufactured by Hachishu Pharmaceutical Co., Ltd.). After 12 hours, it was confirmed that the coating film was swollen (polymer hydrogel film formation).

Example 2
The antifouling paint composition B prepared by the above method was applied with a brush to a test piece to which a rust preventive primer had been applied in advance. The film was dried at room temperature for 24 hours to obtain a coating film having a dry thickness of 300 μm.

Subsequently, the test piece coated with the coating film was immersed in artificial seawater (trade name Aqua Marine ^{(registered trademark)} : manufactured by Hachishu Pharmaceutical Co., Ltd.). After 12 hours, it was confirmed that the coating film was swollen (polymer hydrogel film formation).

Claims (7)

  Antifouling coating that is composed of polymer hydrogel and does not adhere to aquatic organisms.   The antifouling film according to claim 1, comprising an antifouling agent in the polymer hydrogel.   The antifouling coating according to claim 1, wherein the polymer hydrogel is a three-dimensional cross-linked product of a vinyl polymer containing at least 50 mol% of a hydrophilic monomer.   The polymer hydrogel is formed by immersing in water after forming a film with an antifouling paint containing a vinyl polymer containing at least 50 mol% of a hydrophilic monomer, a crosslinking agent, an antifouling agent and an organic solvent. Antifouling coating.   It is an antifouling object comprised from a base material and the antifouling film provided in the surface outermost layer of this base material, and this antifouling film is an antifouling film in any one of Claims 1-4 Antifouling object that does not adhere to characteristic aquatic organisms.   The antifouling object according to claim 5, wherein the substrate is a ship, an underwater structure, a seawater introduction pipe, a fish net, or a submarine cable. An antifouling paint to which aquatic organisms containing a vinyl polymer containing a hydrophilic monomer in an amount of 50 mol% or more, a crosslinking agent, an antifouling agent and an organic solvent do not adhere.