WO2009104257A1 - Antifouling coating film free from attachment of aquatic organisms, method for obtaining the antifouling coating film and utilization of the same - Google Patents

Abstract

It is intended to provide an antifouling coating film wherein an antifouling agent, which is in the form of a monomer, is introduced into a high-molecule hydrogel matrix. Namely, an antifouling coating film that is made of a high-molecule hydrogel and free from the attachment of aquatic organisms, which is an antifouling coating film free from the attachment of aquatic organisms characterized in that the high-molecule hydrogel comprises an antifouling monomer as one of the constituents of the same.

Description

Antifouling film to which aquatic organisms do not adhere, means for obtaining antifouling film and use thereof

The present invention relates to an antifouling film to which aquatic organisms do not adhere, an antifouling paint for obtaining the antifouling film, a method for forming the antifouling film, and an antifouling object having the antifouling film on the surface.

人工 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, it is common to use a film having a self-polishing property and using a compound that decomposes and peels off itself even if aquatic organisms adhere thereto, or a compound having a repellent effect on aquatic organisms.

However, these conventional methods have problems such as short effect duration, possibility of marine pollution, and high production cost. Under such circumstances, the present inventor proposed an antifouling coating using a polymer hydrogel in JP-A-2005-34770 (Patent Document 1). A polymer hydrogel is a water molecule that is fluidly incorporated into an antifouling coating. From the viewpoint of aquatic organisms, it creates a so-called “bad scaffolding” state so that aquatic organisms do not adhere. is there. This method using a polymer hydrogel has few conventional drawbacks and is highly effective.

On the other hand, WO2006 / 035891 (Patent Document 2) and JP-A-2002-380907 (Patent Document 3) describe antifouling agents that are highly safe for fish and shellfish and that can be chemically synthesized relatively easily. Has been proposed. Although these antifouling agents are effective as antifouling agents, they still cannot avoid the problem of marine pollution.

JP 2005-34770 A WO2006 / 035891 JP 2002-380907 A

In view of the above situation, an object of the present invention is to provide an antifouling film in which an antifouling agent is monomerized and introduced into a matrix of a polymer hydrogel.

The present invention relates to an antifouling coating to which aquatic organisms composed of a polymer hydrogel do not adhere, wherein the polymer hydrogel has an antifouling monomer as one of its constituent components, and prevents aquatic organisms from adhering. The object is achieved by providing a dirty coating.

The antifouling monomer has the following chemical formula (1)

(Wherein R ¹ is hydrogen or a methyl group, R ² and R ³ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, p represents 0 or 1, and X represents O represents oxygen or —NH—, and Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and is an ether group, carbonyl group, ester group, amino group, amide group, imide group, sulfide A group, a sulfoxide group or a sulfone group may be interposed.)
The thing represented by these is preferable.

In the chemical formula (1) of the antifouling monomer, Y is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may interpose an ether group.

In the above formula (1), Y is preferably a linear, branched or cyclic alkyl group having 5 to 12 carbon atoms.

The polymer hydrogel of the present invention is a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer. May be obtained by three-dimensionally cross-linking.

The antifouling coating of the present invention may contain an antifouling agent in addition to the polymer hydrogel.

The present invention also provides a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer, Provided is an antifouling paint for forming an antifouling film containing a crosslinking agent, a catalyst and a solvent.

The present invention further provides a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer, Provided is a method for forming an antifouling film characterized in that an antifouling paint containing a crosslinking agent, a catalyst and a solvent is applied to form a film and then immersed in water.

The present invention is also an antifouling object composed of a base material and an antifouling film provided on the outermost surface of the base material, wherein the antifouling film is the specific antifouling film described above. Provided is an antifouling object to which characteristic aquatic organisms do not adhere.

The base material may be a ship, an underwater structure, a seawater introduction pipe, a fish net, or a submarine cable.

In the present invention, an antifouling monomer, that is, a monomer capable of exhibiting antifouling properties is synthesized as one of the monomer components at the time of the synthesis of the polymer hydrogel, and the antifouling component is contained in the matrix of the obtained polymer hydrogel. The antifouling film is introduced to keep the antifouling property, and the antifouling component is securely fixed in the antifouling film, so it does not elute into the water and there is an antifouling film As long as the antifouling property is maintained. Further, since the antifouling component is firmly held in the matrix, it does not elute in water, does not contaminate water, and hardly reaches the human body.

In general, it has been considered that when an antifouling agent is monomerized and introduced into a polymer matrix, the antifouling property (or repellency) does not appear or the performance of the antifouling agent is greatly reduced. If the antifouling monomer is introduced in such a large amount that the effect can be fully expressed, the membrane performance of the polymer matrix deteriorates. On the contrary, if the amount decreases, the antifouling property is not sufficiently expressed. Because. However, the present experimental results of the present inventors reverse the predictions of those skilled in the art, and it was confirmed that the antifouling property can be secured without impairing the membrane performance.

As the polymer hydrogel itself is clearly described in the application of Patent Document 1 already proposed by the present inventor and the effect is confirmed, the polymer hydrogel matrix portion is cross-linked and tough, Since trapped portions exist and water molecules may flow, aquatic organisms become so-called “poor scaffolding”, and adherence is drastically reduced.

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 cross-linked and water molecules can be retained or trapped therein. A highly hydrophilic polymer has a predetermined amount of hydrophilic groups in a general polymer skeleton (specifically, a vinyl polymer), and the vinyl polymer is three-dimensionally crosslinked by a crosslinking reaction. In the present invention, an antifouling monomer is blended during the synthesis of the polymer, and an antifouling part is introduced into the matrix of the resulting polymer hydrogel.

(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 vinyl monomers and various physical quantities (for example, molecular weight, hydrophilic group amount, etc.) can be easily controlled.

The vinyl polymer constituting the polymer hydrogel of the present invention comprises a hydrophilic vinyl monomer in an amount of 50 to 90 mol% (preferably 60 to 80 mol%), and an antifouling monomer 1 to 20 mol% (preferably 1 to 10 mol%). Mol%) and other copolymerizable monomers are formed from a vinyl monomer mixture containing 9 to 49 mol% (preferably 20 to 40 mol%). In addition, a vinyl monomer mixture is 100 mol% in total.

When the hydrophilic vinyl monomer is less than 50 mol%, the obtained vinyl polymer does not exhibit the performance as a hydrogel. On the other hand, when the amount of the hydrophilic vinyl monomer is more than 90 mol%, the water-resistant physical properties (physical properties such as Young's modulus, breaking strength, and elongation rate of the coating film swollen in seawater) of the obtained polymer hydrogel film are lowered. When the amount of the antifouling monomer is less than 1 mol%, the antifouling performance is not exhibited, and the effect of the antifouling coating of the present invention cannot be obtained. When there are more antifouling monomers than 20 mol%, the hydrophilic property of a coating film will fall and the swelling degree will be suppressed.

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-acetic acid Rumido 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.

The polymer hydrogel of the present invention contains an antifouling monomer as an essential component of the monomer mixture in addition to the hydrophilic monomer. The antifouling monomer may be various, but preferably the following chemical formula (1):

(Wherein R ¹ is hydrogen or a methyl group, R ² and R ³ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, p represents 0 or 1, and X represents O represents oxygen or —NH—, and Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and is an ether group, carbonyl group, ester group, amino group, amide group, imide group, sulfide A group, a sulfoxide group or a sulfone group may be interposed.)
Is mentioned. In the chemical formula (1), R ² and R ³ are preferably each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and more specifically, a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group and hexyl group. Y is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may intervene with an ether group, and more preferably a linear, branched or cyclic group having 5 to 12 carbon atoms. A cyclic alkyl group, more preferably a linear, branched or cyclic alkyl group having 6 to 11 carbon atoms.

Specific examples of the antifouling monomer include 4-isocyanocyclohexyl acrylate, 11-isocyano-11-methyldodecyl acrylate, N- (11-isocyano-11-methyl) dodecylacrylamide, N- (4-isocyanocyclohexyl) Acrylamide, 4-isocyano-4-methylcyclohexyl acrylate, N- (4-isocyano-4-methylcyclohexyl) acrylamide, 10-isocyano-10-methylundecyl acrylate, N- (10-isocyano-10-methyl) undecyl Acrylamide, 8-isocyano-8-methylnonyl acrylate, N- (8-isocyano-8-methyl) nonyl acrylamide, 6-isocyano-6-methylheptyl acrylate, N- (6-isocyano-6-methyl) heptyl Acrylamide, 4-isocyano-4-methyl-hexyl acrylate, N-(4-isocyano-4-methyl) hexyl acrylamide. More preferred antifouling monomers are 4-isocyanocyclohexyl acrylate, 11-isocyano-11-methyldodecyl acrylate, and N- (11-cyano-11-methyl) dodecyl acrylamide.

The hydrophilic vinyl monomer and the antifouling monomer may be copolymerized with other copolymerizable monomers that are copolymerized therewith. Examples of other copolymerizable monomers include N-alkyl substituted (meth) acrylamides: eg (meth) acrylamide, (meth) N-acrylol-L-alanine, (meth) aminopropylacrylamide, (meth) N-amino Propylacrylamide, (meth) N-isopropylacrylamide, t-butyl (meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) isobutylacrylamide , (Meth) t-butylaminoethyl acrylate, (meth) diacetone acrylamide, etc .; or (meth) acrylic acid ester: for example, methyl (meth) acrylate, ethyl (meth) acrylate, i- (meth) acrylate Propyl, ( T) i-butyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, i-octyl (meth) acrylate, stearyl (meth) acrylate, ( Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate; Etc.

The monomer copolymerized with the hydrophilic vinyl monomer for forming the polymer hydrogel is not limited to those described above, but a vinyl monomer for introducing a crosslinkable functional group into the obtained vinyl polymer (referred to as “crosslinkable monomer”). .) Is also necessary.

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

Another example of the crosslinkable monomer is glycidyl (meth) acrylate: for example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. It is done. These monomers are intended for crosslinking reaction with glycidyl groups. When a crosslinkable monomer having a glycidyl group is used, a monomer having a carboxyl group as a group capable of reacting with a glycidyl group (that is, an epoxy group) must be used as a part of the hydrophilic monomer.

Still other examples of crosslinkable monomers include hydroxyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2- (2-hydroxyethoxy) ethoxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, and these monomers are intended for crosslinking reaction with hydroxyl groups.

Further, the other copolymerizable monomer may be a hydrophobic monomer or a water-repellent monomer in order to adjust the water swelling degree and water content of the film. 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 (meta ) Acrylate, (meth) ethylene glycol methyl ether acrylate, etc .; polyethylene glycol (meth) acrylate: For example, polyethylene glycol mono (meth) with a degree of polymerization (n) of ethylene glycol of about 1 to 10, preferably 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 And silicone-containing acrylic monomers: for example, polydimethylsiloxane alkyl (meth) acrylate, (meth) polydimethylsiloxane-graft polyacrylate, etc .; or styrene, α-methylstyrene, vinyl acetate, vinyl propionate, benzoate Monomeric monomers containing both acid / base in the molecule (for example, crotonic acid ester, maleic acid diesters, itaconic acid diester, etc.) Nonionic vinyl monomers such as (meth) acrylamidopropyl sulfonic acid, sodium (meth) acrylamidopropyl sulfonate) can also be used.

The polymer hydrogel is prepared by polymerizing at least one monomer among the vinyl monomers by a conventional method, using a solvent or a polymerization initiator (such as azoisobutyronitrile) as necessary. Can be done. However, the hydrophilic monomer and the antifouling monomer must be present in specific amounts as described above.

The vinyl polymer thus prepared (sometimes referred to as “polymer hydrogel prepolymer”) is applied to the surface of the object to be coated when one having two double bonds in the crosslinkable monomer constituting the polymer is used. And dried at room temperature. 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 the crosslinkable monomers, when using a monomer having a glycidyl group, a monomer incorporating an amino group or a monomer having a hydroxyl group, a crosslinking agent (for example, an amine compound, an aldehyde, a polyisocyanate compound) is added at the time of coating. You may mix uniformly. In this case, a three-dimensional crosslinked structure is formed by the action of the crosslinking agent. Examples of amine compounds include alkylamines such as triethylamine, diethylamine, aromatic diamine compounds such as amine methylene bis (2-chloroaniline), trimethylene bis (4-aminobenzoate) 4-aminophenyl sulfone; aliphatic diamine compounds, Examples thereof include dimethylaminopropylamine and 1,2-diaminopropane. Examples of aldehydes include glutaraldehyde, phthalaldehyde, and 1,3-bis- (4-formylphenoxy) propane. The polyisocyanate compound includes known ones, but when water is contained as a solvent, measures to avoid reactivity with water are necessary.

The former (that is, a system in which a crosslinking agent is not added) is more preferable because good paint workability can be provided.

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

Since the polymer matrix has very little solvent remaining in the three-dimensional bridge structure after drying, the three-dimensional bridge structure is covered with water or seawater when immersed in water or seawater. 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 another antifouling agent in the three-dimensional crosslinked structure of the polymer hydrogel. In the present invention, since an antifouling monomer is used, an additional antifouling agent is not necessarily required, but the addition of the antifouling agent is not hindered. 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-di Methyl-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 Rubamin 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 may be ionically bonded in the three-dimensional cross-linked 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 preferably 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, and 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.

パ ラ Paraffin can be used as an elution aid.

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 introduction pipes, for example, bay facilities, offshore excavation 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 as 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 coating composition of the present invention, an additional antifouling agent is added in an amount of 0 to 40% by weight, preferably 2% with respect to the total weight of the antifouling coating composition. In an amount of ˜30% by weight, and the total amount of solvent and various additives is 35 to 99% by weight relative to the total weight of the antifouling coating composition, preferably 45 to 90% by weight relative to the total weight of the antifouling coating composition % May be included.

When blending the antifouling agent, the solvent and various additives, they are added to the polymer resin and mixed using a mixer such as a ball mill, roll mill, sand grind mill, etc. A dirty paint composition is obtained.

The antifouling paint composition of the present invention may be appropriately diluted after preparation with a water-soluble solvent up to an appropriate use viscosity 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 a very small amount of the solvent used during 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) (with the object coated with this film). High polymer resin coating. 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, since the antifouling monomer is contained in the matrix of the polymer hydrogel film, the polymer hydrogel alone exhibits sufficient antifouling performance without adding an additional antifouling agent. And attachment of aquatic organisms can be more effectively prevented. Since the antifouling monomer is a matrix of the polymer hydrogel, the antifouling agent is not eluted into the water, and the antifouling performance can be continued as long as the antifouling coating exists. Contamination due to elution of antifouling agent into water does not occur. Of course, this does not prevent the addition of a separate antifouling agent to the polymer hydrogel. In some cases, when a separate antifouling agent is added to the polymer hydrogel using the antifouling monomer, the performance improves and at the same time the sustainability may increase.

The polymer hydrogel film of the present invention is also poor in hydrolyzability, so that the film 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. . Therefore, the polymer hydrogel membrane of the present invention not only extends the useful life of the membrane itself but also prevents water 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.

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

Production of antifouling monomer Production Example 1 Production of antifouling monomer (4-isocyanocyclohexyl acrylate) trans-4-aminocyclohexanol (5.0 g, 43.4 mmol) was dissolved in ethyl formate (50 mL) Sulfonic acid monohydrate (75 mg, 0.43 mmol) was added and heated to reflux for 24 hours. The reaction mixture was concentrated, the residue was dissolved in pyridine (10 mL), acetic anhydride (10 mL) was added, and the mixture was stirred at room temperature for 18 hr. To the reaction solution was added saturated brine (50 mL), and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with 3M-hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was recrystallized from hexane-ethyl acetate to obtain trans-acetic acid-4-formaminocyclohexyl ester (3.92 g, 21.2 mmol) in a yield of 49%.

The obtained trans-acetic acid-4-formaminocyclohexyl ester (2.32 g, 12.6 mmol) was dissolved in pyridine (10 mL), paratoluenesulfonyl chloride (2.87 g, 15.1 mmol) was added, and the mixture was stirred at room temperature for 18 hours. . To the reaction solution was added saturated brine (50 mL), and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with 1M hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (Hexane: EtOAc = 3: 1) to obtain trans-acetic acid-4-isocyanocyclohexyl ester (260 mg, 1.56 mmol) in a yield of 12%. Obtained.

Trans-acetic acid 4-isocyanocyclohexyl ester (8.15 g, 48.7 mmol) was dissolved in methanol (100 mL), potassium carbonate (10.57 g, 76.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered under reduced pressure, concentrated, and ethyl acetate (200 mL) was added. The organic phase was washed with water and saturated brine, and then dried over sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (Hexane: EtOAc = 3: 1) to obtain trans-4-isocyanocyclohexanol (5.86 g, 46.8 mmol) in a yield of 96%. .

Dissolve trans-4-isocyanocyclohexanol (548 mg, 4.38 mmol) in methylene chloride (35 mL), add triethylamine (1.46 mL, 10.5 ア ク リ ル mmol), and ice-cool acrylic chloride (0.45 mL, 5.57 mmol) , DMAP (50 mg, 40.9 mmol) was added and stirred for 3 hours. To the reaction solution was added saturated brine (100 mL), and the mixture was extracted with ethyl acetate (250 mL). The organic phase was washed with 1M-hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 1) to give 4-isocyanocyclohexyl acrylate (547 mg, 3.1 mmol) in a yield of 70%.

The chemical formula is as follows:

¹ H NMR and ¹³ C NMR are as follows:
¹ H NMR (600 MHz, CDCl ₃ ) δ: 6.40 (dd, J = 17.2 and 1.1 Hz, 1H), 6.10 (dd, J = 17.2 and 10.6 Hz, 1H), 5.84 (dd, J = 17.2 and 10.6 Hz , 1H), 4.99-4.91 (m, 1H), 3.76-3.68 (m, 1H), 2.10-2.00 (m, 4H), 1.82-1.73 (m, 2H), 1.69-1.61 (2H, m).
¹³ C NMR (150.8 MHz, CDCl ₃ ) δ: 165.4, 155.3 (t, J = 6.2 Hz), 130.8, 128.5, 69.0, 50.4 (t, J = 6.2 Hz), 28.4, 26.7.

Production Example 2 Production of antifouling monomer (11-isocyano-11-methyldodecyl acrylate) 11-Bromoundecanoic acid (100.7 g, 380 mmol) was dissolved in methanol (200 mL), sulfuric acid (2 mL) was added, Heated to reflux for 18 hours. After completion of the reaction, the solvent was distilled off and ethyl acetate (400 mL) was added. The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 11-bromoundecanoic acid methyl ester (104 g, 372 mmol) in a yield of 98%.

The obtained 11-bromoundecanoic acid methyl ester (79.93 g, 286 mmol) was added dropwise to a stirred 3M-diethyl ether solution of methylmagnesium bromide (200 mL, 600 mmol) over 2 hours under ice cooling. After further stirring for 12 hours, an aqueous hydrochloric acid solution (200 mL) was added to the reaction mixture, and the mixture was stirred for 5 minutes, and then extracted with ethyl acetate (400 mL). The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated aqueous carbonate, and then dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 12-bromo-2-methyl-2-dodecanol (76 g, 272 mmol) in a yield of 95%.

The obtained 12-bromo-2-methyl-2-dodecanol (15.06 g, 53.9 mmol) was dissolved in methylene chloride (15 mL), TMSCN (8 mL, 60.0 mmol) was added, and methanesulfonic acid ( 4.5 mL, 69.3 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Then, methanesulfonic acid (5 mL, 77.0 mmol) was further added, and the mixture was further stirred for 1 hour. After confirming the disappearance of the raw materials by TLC, triethylamine (21 mL, 151 mL), methylene chloride (35 mL), pyridine (5 mL, 62.1 mL) were added to the reaction solution, and the mixture was stirred for 10 minutes, and then paratoluenesulfonyl chloride ( 11.82 g, 62.0 mmol) was added, and the mixture was further stirred for 80 minutes. Saturated brine (50 mL) was added to the reaction solution, and the mixture was stirred for 5 minutes, and then extracted with ethyl acetate (300 mL). The organic phase was washed with 3M-hydrochloric acid aqueous solution, saturated sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, filtered, and the solvent was evaporated. The residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 0-10: 1) to give 1-bromo-11-isocyano-11-methyldodecane (13.2 g, 45.8 mmol) in 85% yield. It was.

The obtained 1-bromo-11-isocyano-11-methyldodecane (12.26 g, 42.5 mmol) is dissolved in DMF (100 mL), triethylamine (12 mL, 85.4 mmol), acrylic acid (5 mL, 72.9 mmol) And stirred for 15 hours. The reaction solution was filtered to remove solids and then concentrated. The residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 0-3: 1) to give (11-isocyano-11-methyl) dodecyl acrylate (7.65 g, 27.4 mmol) in a yield of 64% .

The chemical formula is as follows:

¹ H NMR and ¹³ C NMR are as follows:
¹ H NMR (600 MHz, CDCl ₃ ) δ: 6.40 (dd, J = 17.2 and 1.1 Hz, 1H), 6.12 (dd, J = 17.2 and 10.6 Hz, 1H), 5.82 (dd, J = 10.6 and 1.1 Hz , 1H), 4.15 (t, J = 7.0 Hz, 2H), 1.67 (quint, J = 7.0 Hz, 2H), 1.57-1.52 (m, 2H), 1.49-1.40 (2H, m), 1.40 (t, J = 1.8 Hz, 6H), 1.41-1.33 (m, 2H), 1.33-1.26 (m, 10H).
¹³ C NMR (150.8 MHz, CDCl ₃ ) δ: 166.3, 152.8 (t, J = 5.0 Hz), 130.4, 128.6, 64.7, 57.4 (t, J = 5.0 Hz), 42.5, 29.5, 29.43, 29.42, 29.41, 29.2, 29.0, 28.6, 25.9, 24.1.

Production Example 3 Production of Antifouling Monomer (N- (11-Isocyano-11methyldodecyl) -acrylamide) 12-Bromo-2-methyl-2-dodecanol obtained in the same manner as in the synthesis of Production Example 2 ( 73.78 g, 264 mmol) was dissolved in DMF (200 mL), potassium phthalimide (59.05 g, 319 mmol) was added, and the mixture was heated to reflux for 6 hours. The reaction mixture was filtered, and further washed with ethyl acetate (400 mL). The organic phase was washed with 5% aqueous potassium hydroxide solution and saturated brine, and then dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 0-1: 1) to give 2- (11-hydroxy-11-methyldodecyl) isoindoline-1, 3-dione (85.02 g, 246 mmol) was obtained in 93% yield.

The obtained 2- (11-hydroxy-11-methyldodecyl) isoindoline-1,3-dione (53.24 g, 154 mmol) was dissolved in methylene chloride (50 mL), and TMSCN (25 mL, 187 mmol) was dissolved. In addition, methanesulfonic acid (50 mL, 770 mmol) was added under ice cooling, and the mixture was stirred at room temperature for 2 hours. Methylene chloride (100 メ チ レ ン mL) was added to the reaction solution, and triethylamine (110 mL, 792 mmol) and pyridine (15 mL, 186 mmol) were added under ice cooling, followed by stirring for 10 minutes, and then paratoluenesulfonyl chloride (36.2 g, 190 mmol) was added and stirred for 3 hours. To the reaction mixture was added saturated brine (100 ml), and the mixture was stirred for 5 minutes, and then extracted with diethyl ether (600 ml). The organic phase was washed with 3M-hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 0-10: 1) to give 2- (11-isocyano-11-methyldodecyl) isoindoline-1, 3-dione (46.7 g, 132 mmol) was obtained in 85% yield.

The obtained 2- (11-isocyano-11-methyldodecyl) isoindoline-1,3-dione (39.80 g, 112 mmol) was dissolved in methanol, and hydrazine monohydrate (11 mL, 226 mmol) was added. For 90 minutes. To the reaction solution was added saturated brine (100 mL), and the mixture was stirred for a while, extracted with ethyl acetate (300 mL), and dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by amino silica gel column chromatography (EtOAc: MeOH = 10: 1) to give 1-amino-11-isocyano-11-methyldodecane (24.88 g, 111 mmol). The yield was 99%.

The obtained 1-amino-11-isocyano-11-methyldodecane (24.88 g, 111 mmol) was dissolved in methylene chloride (200 、 mL), triethylamine (15.8 mL, 114 mmol) was added and stirred, and then ice-cooled. , Acroyl chloride (9 mL, 111 mL) was added and stirred for 3 hours. To the reaction solution was added saturated brine (100 mL), and the mixture was stirred for 5 minutes, and then extracted with ethyl acetate (200 mL). The organic phase was washed with 1M-hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine 50 ml, and then dried over sodium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (Hexane: EtOAc = 10: 0-10: 1), and N- (11-isocyano-11methyldodecyl) -acrylamide (11.57 g, 42 mmol) was obtained with a yield of 37%.

The chemical formula is as follows:

¹ H NMR and ¹³ C NMR are as follows:
¹ H NMR (600 MHz, CDCl ₃ ) δ: 6.27 (dd, J = 17.1 and 1.5 Hz, 1H), 6.09 (dd, J = 17.1 and 10.2 Hz, 1H), 5.75 (br s, 1H), 5.62 ( dd, J = 10.2 and 1.5 Hz, 1H), 3.32 (dt, J = 5.9 and 7.1 Hz, 2H), 1.59-1.49 (m, 4H), 1.48-1.37 (m, 2H), 1.40 (t, J = 1.7 Hz, 6H,), 1.36-1.22 (m, 12H).
¹³ C NMR (150.8 MHz, CDCl ₃ ) δ: 165.5, 152.6 (t, J = 5.0 Hz), 131.0, 126.0, 57.4 (t, J = 5.0 Hz), 42.4, 39.6, 29.5, 29.4, 29.31, 29.30, 29.2, 28.9, 26.7, 24.0.

Production of Polymer Hydrogel Prepolymer Production Example 4 Production of Polymer Hydrogel Prepolymer A Acrylic monomer (acrylic acid 12.2 g, t-butyl methacrylate 12.1 g, acrylamide 9.66 g, N, N′-dimethylaminopropylacrylamide 10.6 g, allyl 5.8 g of methacrylate and 3.02 g of antifouling monomer (4-isocyanocyclohexyl acrylate) produced in Production Example 1, 0.165 g of isobutyronitrile as an initiator, 37.6 g of 2-propanol, 37.6 g of methanol, and 18.8 g of water Was put into a 500 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, and heated at 60 ° C. for 90 minutes with stirring under nitrogen gas to obtain a polymer hydrogel prepolymer A.

Production Example 5 Production of Polymer Hydrogel Prepolymer B Acrylic monomer (acrylic acid 21.43 g, t-butyl methacrylate 21.14 g, acrylamide 16.961 g, N, N′-dimethylaminopropylacrylamide 18.58 g, glycidyl methacrylate 11.45 g and Example 2 5.7 g of antifouling monomer (11-isocyano-11-methyldodecyl acrylate) prepared in 1), 0.288 g of isobutyronitrile as an initiator, 70.2 g of 2-propanol, 70.3 g of methanol and 35.10 g of water as a stirrer, condenser Into a 500 ml glass reaction vessel equipped with a thermometer, the mixture was heated at 60 ° C. for 52 minutes with stirring under nitrogen gas to obtain 270 g of a polymer hydrogel prepolymer B.

Production Example 6 Production of Polymer Hydrogel Prepolymer C Acrylic monomer (acrylic acid 24.02 g, t-butyl methacrylate 23.65 g, acrylamide 18.933 g, N, N′-dimethylaminopropylacrylamide 20.8 g, glycidyl methacrylate 12.77 g and Production Example 3 Antifouling Monomer (N- (11-Isocyano-11methyldodecyl) -acrylamide) 6.6g, 0.327g of isobutyronitrile as initiator, 78.52g of 2-propanol, 79.12g of methanol, 39.55g of water Was put into a 500 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, and heated at 60 ° C. for 54 minutes with stirring under nitrogen gas to obtain 304 g of a polymer hydrogel prepolymer C.

Production Example 7 Production of Polymer Hydrogel Prepolymer D Acrylic monomer (acrylic acid 23.1 g, t-butyl methacrylate 22.71 g, acrylamide 13.634 g, N-isopropylacrylamide 7.233 g, N, N′-dimethylaminopropylacrylamide 9.98 g, dimethyl 6.34 g of acrylamide, 10.9 g of allyl methacrylate and 5.37 g of the antifouling monomer (11-isocyano-11-methyldodecyl acrylate) synthesized in Example 2, 0.315 g of isobutyronitrile as the initiator, and 73.23 g of 2-propanol as the solvent Then, 73.61 g of methanol and 37.42 g of water were placed in a 500 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer and heated at 60 ° C. for 52 minutes with stirring under nitrogen gas to give 285 g of a polymer hydrogel pre-polymer. Polymer D was obtained.

Production Example 8 Production of Polymer Hydrogel Prepolymers E-1 and E-2 (Production of E-1) Acrylic monomer (acrylic acid 28.8 g, t-butyl methacrylate 28.4 g, acrylamide 22.721 g, N-isopropylacrylamide 9.05 g, Reaction of 13.61 g of hexyl methacrylate, 15.34 g of glycidyl methacrylate, 0.385 g of isobutyronitrile as an initiator, 70.78 g of 2-propanol, 79.32 g of methanol, and 26.61 g of water, 500 ml of glass reaction equipped with a stirrer, condenser and thermometer The mixture was placed in a container and heated at 60 ° C. for 44 minutes with stirring under nitrogen gas to obtain 295 g of a polymer hydrogel prepolymer E-1.

(Production of E-2) Acrylic monomer (acrylic acid 25.93 g, t-butyl methacrylate 25.54 g, acrylamide 12.785 g, N, N'-dimethylaminopropylacrylamide 22.51 g, hexyl methacrylate 12.24 g, allyl methacrylate 12.24 g and Examples 10.05 g of the antifouling monomer (11-isocyano-11-methyldodecyl acrylate) prepared in 2 and 0.345 g of isobutyronitrile as an initiator, 66.12 g of 2-propanol, 67.62 g of methanol, and 14.96 g of water as a stirrer, It was put into a 500 ml glass reaction vessel equipped with a condenser and a thermometer, and heated at 60 ° C. for 109 minutes with stirring under nitrogen gas to obtain 270 g of a polymer hydrogel prepolymer E-2.

Production Example 9 Production of polymer hydrogel prepolymers F-1 and F-2 (Production of F-1) Acrylic monomers (22.38 g of acrylic acid, 22.02 g of t-butyl methacrylate, 24.21 g of acrylamide, 11.89 g of glycidyl methacrylate, Examples Antifouling monomer C (11-isocyano-11-methyldodecyl acrylate) 8.65 g prepared in 2 and 0.304 g of isobutyronitrile as an initiator, 52.81 g of 2-propanol, 53.4 g of methanol and 26.79 g of water as a stirrer In a 500 ml glass reaction vessel equipped with a condenser and a thermometer, the mixture was heated at 60 ° C. for 73 minutes with stirring under nitrogen gas to obtain 222 g of a polymer hydrogel prepolymer F-1.

(Production of F-2) Acrylic monomer (acrylic acid 17.99 g, t-butyl methacrylate 17.74 g, acrylamide 7.15 g, N, N'-dimethylaminopropylacrylamide 23.42 g, allyl methacrylate 8.51 g and the anti-protection produced in Example 2 13.96 g of soiling monomer (11-isocyano-11-methyldodecyl acrylate), 0.247 g of isobutyronitrile as an initiator, 53.61 g of 2-propanol, 60.03 g of methanol, and 20.03 g of water as a stirrer, condenser and thermometer It was placed in a 500 ml glass reaction vessel equipped and heated at 60 ° C. for 109 minutes with stirring under nitrogen gas to obtain 222 g of a polymer hydrogel prepolymer F-2.

Preparation of polymer hydrogel membrane and evaluation of immersion in seawater Example 1 Preparation of polymer hydrogel membrane A and evaluation of immersion in seawater Transfer 20 g of polymer hydrogel prepolymer A to a metal stirring vessel, add a cobalt-based reaction catalyst, and rotate about 2000 times. (Rpm) and mixed for 5 minutes. The obtained coating liquid was applied to a test piece made of vinyl chloride with a brush and dried overnight at room temperature to obtain a polymer hydrogel film A. When the obtained polymer hydrogel film A coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.

Example 2 Preparation of polymer hydrogel membrane B and evaluation of immersion in seawater Polymer hydrogel prepolymer B (20 g) was transferred to a metal stirring vessel, an amine-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes. The obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature. When the obtained polymer hydrogel membrane B-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.

Example 3 Preparation of polymer hydrogel membrane C and evaluation of immersion in seawater Polymer hydrogel prepolymer C, 20 g, was transferred to a metal stirring vessel, an amine-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes. . The obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature. When the obtained polymer hydrogel film-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.

Example 4 Preparation of polymer hydrogel membrane D and evaluation of immersion in seawater Polymer hydrogel prepolymer D (20 g) was transferred to a metal stirring vessel, a cobalt-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes. . The obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature. When the obtained polymer hydrogel membrane D-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.

Example 5 Preparation of polymer hydrogel membrane E and evaluation of immersion in seawater Polymer hydrogel prepolymer E-1, 10 g, polymer hydrogel prepolymer E-2, 10 g were transferred to a metal stirring vessel, and amine-based and cobalt-based The reaction catalyst was added and mixed for 5 minutes at about 2000 revolutions (rpm). The obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature. When the obtained polymer hydrogel-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.

Example 6 Preparation of polymer hydrogel membrane F and evaluation of immersion in seawater Polymer hydrogel prepolymer F-1, 10 g, polymer hydrogel prepolymer F-2, 10 g were transferred to a metal stirring vessel, and amine-based and cobalt-based The reaction catalyst was added and mixed for 5 minutes at about 2000 revolutions (rpm). The obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature. When the obtained polymer hydrogel-coated plate was immersed in the appropriate water for about 1 month, no adhesion of aquatic organisms was observed.

The antifouling coating of the present invention can be applied to any underwater structure and can suppress the adhesion of aquatic organisms for a long time. The method for forming the antifouling coating, the antifouling paint used for forming the antifouling coating, and the antifouling object having the antifouling coating have the same applicability.

Claims (10)

1. An antifouling film to which aquatic organisms composed of a polymer hydrogel do not adhere, wherein the polymer hydrogel has an antifouling monomer as one of its constituent components.
2. Antifouling monomer is represented by the following chemical formula (1)
   

   

   (Wherein R ¹ is hydrogen or a methyl group, R ² and R ³ each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, p represents 0 or 1, and X represents O represents oxygen or —NH—, and Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and is an ether group, carbonyl group, ester group, amino group, amide group, imide group, sulfide A group, a sulfoxide group or a sulfone group may be interposed.)
   The antifouling film according to claim 1 represented by
3. 3. The antifouling coating according to claim 2, wherein Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may interpose an ether group.
4. The antifouling coating according to claim 3, wherein Y is a linear, branched or cyclic alkyl group having 5 to 12 carbon atoms.
5. Polymer hydrogels are three-dimensional vinyl polymers obtained from vinyl monomer mixtures containing 50-90 mol% hydrophilic monomers, 1-20 mol% antifouling monomers and 9-49 mol% other copolymerizable monomers. The antifouling coating according to claim 1, wherein the antifouling coating is crosslinked.
6. The antifouling coating according to claim 1, further comprising an antifouling agent in addition to the polymer hydrogel.
7. Vinyl polymers, crosslinkers, catalysts and solvents obtained from vinyl monomer mixtures containing 50-90 mol% hydrophilic monomers, 1-20 mol% antifouling monomers and 9-49 mol% other copolymerizable monomers An antifouling paint for forming an antifouling film according to claim 1.
8. Vinyl polymers, crosslinkers, catalysts and solvents obtained from vinyl monomer mixtures containing 50-90 mol% hydrophilic monomers, 1-20 mol% antifouling monomers and 9-49 mol% other copolymerizable monomers The method for forming an antifouling film according to claim 1, wherein the film is formed by applying an antifouling paint containing, and then immersed in water.
9. An antifouling object comprising a base material and an antifouling coating provided on the outermost surface of the base material, wherein the antifouling coating is the antifouling coating according to any one of claims 1 to 8. Antifouling object that does not adhere to characteristic aquatic organisms.
10. 10. The antifouling object according to claim 9, wherein the base material is a ship, an underwater structure, a seawater introduction pipe, a fish net or a submarine cable.