JP6464509B2 - Antifouling coating with low frictional resistance against water or seawater - Google Patents

Description

  The present invention relates to an antifouling coating film having a small frictional resistance with water or seawater, and more particularly to an antifouling coating film for ships or the like that reduces the frictional resistance with seawater and does not adhere to aquatic organisms.

  The main role of the antifouling paint is to prevent algae and shellfish from adhering to help smooth navigation of ships, maintain high cooling efficiency for a long time in the case of waterways that introduce seawater such as power plants, etc. In the case of nets for fishery, clogging of the nets is prevented, and adhesion of marine organisms is performed to increase the service life of the underwater structure.

Although prevention of marine organisms such as ships is indispensable for smooth navigation of ships, there is a strong demand for coatings that realize not only adhesion prevention but also low fuel consumption navigation due to recent improvements in fuel efficiency. In addition, development of a coating film that achieves low frictional resistance with seawater is required in order to increase power energy efficiency in the conduit.

Such coating compositions that reduce friction with seawater are disclosed in the following Patent Documents 1 to 4. These patent documents disclose a resin composition for paint using an acrylic resin and an acrylic resin having a polyoxyethylene chain as a binder in the paint.

  In these patent documents, as a method for reducing frictional resistance, a technique for blending inorganic particles into an antifouling paint composition (Patent Document 1), a technique for blending composite particles of an organic polymer substance (Patent Document 2), and a hydrophilic surface. There are provided methods such as adding a polysaccharide binder (Patent Documents 3 to 4), and adding a polysaccharide binder, but none of these methods is sufficient as a friction reducing method.

JP-A-5-86309 JP 2007-169628 A Japanese Patent Laid-Open No. 11-29747 JP 2003-276991 A

  An object of the present invention is to provide an underwater friction-reducing coating film that can reduce frictional resistance with seawater in places where friction with seawater occurs, such as ships, waterways, and fishing nets. To do.

That is, the present invention is an antifouling coating film containing an antifouling agent in a coating film composed of a polymer hydrogel, wherein the antifouling coating film has a swelling degree of 10 to 80% and a Young's modulus of 500 to 500. An antifouling coating film having a low frictional resistance with water or seawater, characterized by having 30,000 N / cm ² .

  The antifouling agent is preferably cuprous oxide particles having an average particle size of 3 μm or less.

  The polymer hydrogel is preferably a chitosan polymer, a polyetherester polymer, or a vinyl polymer.

  The polymer hydrogel is also preferably a copolymer of a hydrophilic vinyl monomer and a monomer having a glycidyl group, and the crosslinking agent is preferably a triazine compound.

  The present invention also provides an object to which the above antifouling coating film is applied.

The present invention further includes 1 to 50% by weight of the hydrophilic vinyl polymer, 0 to 40% by weight of the antifouling agent, 20 to 70% by weight of the solvent and the crosslinking agent and other additives (the weight% is based on the total amount of the antifouling coating composition) ), Wherein the cured antifouling coating film has a degree of swelling of 10 to 80% and a Young's modulus of 500 to 30,000 N / cm ² . An antifouling paint composition that reduces frictional resistance is provided.

In the polymer hydrogel film formed by the method of the present invention, water or seawater can freely move. Therefore, the frictional resistance with water or seawater becomes small. In addition, the polymer hydrogel membrane of the present invention can move freely in water and seawater, so it is unlikely to become a foothold for attachment of aquatic organisms (also referred to as “poor scaffold” for aquatic organisms). The repellent triazine in the molecular skeleton of the gel inhibits the attachment of aquatic organisms. According to the present invention, adhesion of marine organisms can be extremely effectively prevented by including an antifouling agent in the polymer hydrogel membrane.

In addition, since the polymer hydrogel resin coating film of the present invention has poor hydrolyzability, the film is difficult to collapse. If an antifouling agent is 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 seawater contamination. In the present invention, the Young's modulus of the antifouling coating film is also defined. If the Young's modulus is not within a predetermined range, it is difficult to prevent long-term water resistance and adhesion of aquatic organisms.

That is, the contact resistance-reducing film of the present invention can be used for shellfish, coelenterate, tubulochaete, etc. on the surface of the object to be coated for at least 1 year or more, particularly for at least 2 to 4 years or more. The adhesion of marine organisms can be effectively prevented.

The graph which plotted the swelling degree (water content:%) and frictional resistance reduction rate (%) obtained in the Example of this invention is shown.

The antifouling coating film of the present invention has a film swelling degree (water content) of 10 to 80% and a Young's modulus of 500 to 30,000 N / cm ² .

Polymer hydrogel resin The antifouling coating binder of the present invention comprises a polymer hydrogel. The polymer hydrogel resin has three-dimensionally crosslinked polymer molecules with high hydrophilicity. Examples of hydrophilic hydrogels include chitosan gels made from natural polymers, methyl cellulose gels, hydrophilic polyether polyols, polyether ester polymers based on polyether polyols, and the like. Used as a binder alone or in combination with a vinyl polymer. However, a hydrophilic vinyl polymer synthesized using a vinyl monomer that is easy to synthesize and easy to handle as a raw material is preferred.

Chitosan polymer Chitosan polymer is used alone or in combination with a vinyl polymer as a binder for the antifouling coating of the present invention. The chitosan polymer can be easily obtained by dissolving a commercially available chitosan powder in an aqueous solution of an organic acid such as citric acid and then neutralizing with an alkali.

Polyether Ester Polymer The polyether ester polymer is used alone or in combination with a vinyl polymer as a binder for the antifouling coating of the present invention. The polyether ester polymer can be easily obtained by transesterification with a bifunctional carboxylic acid ester with a polyether polymer or the like.

Hydrophilic vinyl polymers synthesized from hydrophilic vinyl monomers as raw materials 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 these Salts, vinylsulfonic acid, vinylbenzylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloylethanesulfonic acid, 2-acryloylpropanesulfonic acid, 2-methacryloylethanesulfonic acid, and salts thereof, and Are phosphoric acid groups and salts thereof.

Examples of other monomers copolymerized with the hydrophilic vinyl monomer include N-alkyl substituted (meth) acrylamides; for example, (meth) acrylamide, (meth) N-acrylol-Lalanine, (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, (meth) methyl acrylate, ethyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic acid n -Butyl, (meth) acrylic acid t Butyl, lauryl (meth) acrylate, i-octyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, (meta ) Benzyl acrylate, isobornyl (meth) acrylate; or (meth) acrylic acid containing a hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 4 -Hydroxybutyl, (meth) 1,4-cyclohexanedimethanol monoacrylate and the like.

A hydrophilic vinyl polymer is prepared from the monomer species, and a three-dimensional structure is formed inside by the action of a crosslinking agent during coating. A repellent compound, particularly a triazine compound, is suitable as a cross-linking agent. For this reason, a triazine skeleton is coordinated to the cross-linking point of the formed three-dimensional structure, and the structure is difficult for marine organisms to adhere.

Examples of suitable triazine compounds are: 6- (4- (aminomethyl) piperidin-1-yl) -N ² , N ⁴ -diisopropyl-1,3,5-triazine-2,4-diamine, (4- (Aminomethyl) piperidin-1-yl) -N ² , N ⁴ -bis (2-methoxyethyl) -1,3,5-triazine-2,4-diamine, 6- (4- (aminomethyl) ) ^{piperidin-1-yl)} -N 2, ^{N 4} - bis (3- (methylthio) propyl) ^{-1,3,5-triazine-2,4-diamine,} N 2 - (2-aminoethyl) -N ⁴ , N ⁶ -Diisopropyl-1,3,5-triazine-2,4,6-triamine, N ² , N ⁴ -bis (2- (1H-indol-3-yl) ethyl) -N ^6- (2- Aminoethyl) -1,3,5-triazine-2 ^{4,6-triamine,} N 2 - ^{(2-aminoethyl)} -N 4, ^{N 6} - bis (2-methoxyethyl) ^{-1,3,5-triazine-2,4,6-triamine, N} 2 - ( 2- (1H-indol-3-yl) ^ethyl) -N 4, ^{N 6} - bis (2-aminoethyl) ^{-1,3,5-triazine-2,4,6-triamine,} N 2 - (2- (1H-indol-3-yl) ethyl) ^-N 4 - (2-aminoethyl) -N ⁶ - methyl ^-N 6 - (2- (pyridin-2-yl) ethyl) -1,3,5-triazine - 2,4,6-triamine and the like.

In the present invention, the polymer hydrogel may be used by mixing with another acrylic resin having a different curing system. Such a resin is a polymer having a polymerizable unsaturated group introduced therein, and is dried at room temperature in the presence of a curable catalyst called a dryer. Further, a silicone resin (SiR) may be mixed and used. For example, moisture curable methylsiloxane rubber (general name “RTV silicone rubber”) and the like can be mentioned.

When the polymer hydrogel of the present invention is immersed in water or seawater, the water or seawater penetrates into the three-dimensional crosslinked structure. As a result, the 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.

Antifouling agent (antibacterial agent)
The antifouling coating film of the present invention may contain an antifouling agent in the three-dimensional crosslinked structure of the polymer hydrogel. There are two types of antifouling agents, organic and inorganic. In the present invention, inorganic (for example, cuprous oxide) or organic antifouling agents 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 species 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-based antibacterial agents; halogenated pyridine derivatives (for example, haloalkylthio-2-chloro-6-trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloro) Methyl-6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridinemethanol, sulfonylhalopyridine compound (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 (for example, 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) methylsulfami And haloalkylthiosulfimide compounds (eg, N, N-dimethyl-N′-phenyl-N ′-(fluorodichlorothio) sulfimide, N, N-dichlorofluoromethylthio-N′-phenylsulfimide), N, N-dimethyl-N ′-(p-tolyl) -N ′-(fluorodichloromethylthio) sulfimide,

(D) Organic iodine-based antibacterial agent; iodosulfone compound, iodinated unsaturated aliphatic compound (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 diiodomethylsulfonyl-4-methylbenzene, 1-diiodomethylsulfonyl-4) -Chlorobenzene,

(E) thiazole antibacterial agent; inch azoline-3-one compound (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 luo 4-isothiazolin-3-one, benzthiazole compounds (eg 2- (4-thiocyanomethylthio) Benzthiazole, 2-mercaptobenzthiazole sodium, 2-mercaptobenzthiazole zinc), and isothiazoline-3-one compounds.

(F) benzimidazole antibacterial agent; benzimidazole carbamate compound (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 (for example, 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) 1H-benzimidazole, 2- (1- (3,5-dimethylpyrazolyl) -1H-benzimidazole, 2 -(Furyl) -1H- Lens imidazole), benzimidazole carbamic acid compounds, 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, Bis (dimethyldithiocarbamic acid) zinc, ethylene-bis- (dithiocarbamic acid) zinc, ethylene-bis- (dithiocarbamic acid) manganese, ethylene-bis- (dithiocarbamic acid) copper. Most preferred is cuprous oxide.

The inventors of the present invention studied in more detail about antifouling agents, particularly cuprous oxide, and reduced the blending amount by reducing the particle size of cuprous oxide and increasing the surface area. If the blending amount of cuprous oxide is reduced, the strength of the coating film is inferior and long-term water resistance in seawater cannot be ensured. For this reason, it is necessary to increase the strength of the binder resin, and by using the above-mentioned triazine compound instead of the aliphatic alkyl amine compound conventionally used as a crosslinking agent for the binder resin, the strength is insufficient due to reduction of cuprous oxide. In addition to covering, long-term antifouling properties were secured.

The antifouling property of cuprous oxide is due to the fact that cuprous oxide dissolves in seawater to produce copper ions. However, cuprous oxide dissolves very little in seawater. For this reason, in order to ensure antifouling property, a large amount of cuprous oxide is blended. On the other hand, it was confirmed that if the cuprous oxide particle size is reduced and the surface area is increased, antifouling properties can be obtained even with a small amount of cuprous oxide.

Cuprous oxide generally has a particle size (3 μm) reduced to about 0.5 μm (surface area increased 36 times), and the antifouling property can be ensured even if the blending amount is reduced to 1/10. The use of fine particles for ship bottom paint is expensive due to the difficulty of manufacturing, and the antifouling effect is questionable when combined with hydrolyzable resins, and handling is difficult, so it is considered in the industry's common sense It was not. Cuprous oxide thus has an average particle size of 3 μm or less, preferably 0.5 to 3 μm.

The amount of cuprous oxide used is usually about half that of the constituents of the coating film, so the amount of resin binder must be 50% or less. However, by using fine cuprous oxide (about 0.5 μm), the amount of the resin can be increased to 90% by mass or more, and the degree of swelling (water content) can be greatly increased. The inventors have also found that with the same weight of cuprous oxide, the swelling degree is increased by 10% or more by making the cuprous oxide fine particles.

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

Solvent and various additives The polymer hydrogel resin coating 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 The following ethers are preferably used: dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like.

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 include phosphoric acid ester systems such as tricresyl phosphoric acid and trichloroethyl phosphoric acid, and epoxy systems such as epoxidized soybean oil and octyl epoxy stearate.

As the coloring pigment, titanium oxide, zircon oxide, carbon black, bengara, phthalocyanine green, quinacridone, emerald green, and phthalocyanine blue are used.

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

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

In the present invention, the polymer hydrogel film needs to have a degree of swelling (water content) of 10 to 80% and a Young's modulus of 500 to 30,000 N / cm ² . The degree of swelling (moisture content) is determined by immersing a coated plate having a polymer hydrogel film in seawater for 12 hours, pulling it up, wiping excess water on the surface with a kim towel, and immediately measuring the weight. After drying at 90 ° C. for 3 hours, the weight is measured and calculated by (weight before drying−weight after drying) / weight before drying × 100. The degree of swelling is preferably 10 to 80%, more preferably 15 to 60%. Below 10%, there is no effect of reducing the frictional resistance with water. If it exceeds 80%, the Young's modulus of the polymer hydrogel film is greatly reduced.

The Young's modulus is obtained from the gradient between the tensile length and the stress applied at that time in the tensile test of the swollen coating film using Tensilon (a tensile tester). The Young's modulus is preferably 500 to 30,000 N / cm ² , and more preferably 1,000 to 25,000 N / cm ² . If it is less than 500 N / cm ² , aquatic organisms adhere. On the other hand, when it exceeds 30,000 N / cm ² , the coating film is brittle and causes a drawback such as causing a crack of the coating film with a simple impact. Further, the elongation rate is the tensile test of the swollen coating film with Tensilon, where the length before pulling (L1) and the length when the coating film breaks by pulling (L2): (L2-L1 / L1) × 100 ( %).

There are various methods for measuring the frictional resistance of a coating film, but the inventors rotate a cylindrical rotating drum (coating around) in a bath and are required to have a slight resistance (torque) generated by friction with water. Designed and manufactured. Painted on the outer circumference of a rotating drum (cylindrical; diameter: 26 cm, length: 20 cm), rotated at 300 rpm in artificial seawater at 20 ° C., and its resistance value (torque value: minimum unit: 0.001 cN · m) Obtained with a torque meter. The reduction rate (%) was compared with the resistance value of the commercially available coating film, and the reduced ratio was obtained.

Antifouling object The present invention also provides an object to which the polymer hydrogel film of the present invention is applied as a second aspect. 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. In particular, when aquatic animals adhere to the surface, its function, performance or operability It can be greatly influenced by such. Such objects specifically include ship (bottom) seawater inlet pipes, such as harbor facilities, offshore drilling facilities, bridges, pipelines, offshore structures such as submarine bases, and fishing nets.

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 resin coating film of the present invention.

The hydrophilic vinyl polymer which 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 45% by weight, based on the total weight of the antifouling paint.

In the antifouling coating composition of the present invention, the antifouling agent is further contained in an amount of 0 to 40% by weight, preferably 5 to 30% based on the total weight of the antifouling coating composition. In an amount of% by weight, and the total amount of solvent and various additives is 20 to 70% by weight, preferably 25 to 60% by weight, based on the total weight of the antifouling coating composition. It may be blended in an amount.

When blending the antifouling agent and various additives, the antifouling paint of the present invention is added to the polymer resin and mixed using a mixer such as a ball mill, a roll mill, or a sand grind mill. A composition is obtained.

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

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.

Next, the crosslinked polymer resin coating film is immersed in water or seawater (for example, for 0.1 to 7 days) (with the object coated with this film). During this time, water or seawater is included in the three-dimensional cross-linked structure. As a result, the polymer hydrogel resin coating film 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 unlikely to attach.
According to the present invention, adhesion of marine organisms is extremely effectively inhibited by using a highly repellent triazine skeleton in the molecular skeleton of the polymer hydrogel film and adding an antifouling agent.

In addition, since the polymer hydrogel resin coating film of the present invention has poor hydrolyzability, the film is difficult to collapse. If an antifouling agent is 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 situation but also prevents seawater contamination.

That is, the contact resistance-reducing film of the present invention can be used for a long period of time, for example, for at least 1 year, especially for at least 2 to 5 years. It is possible to effectively prevent the attachment of marine organisms.

  The present invention will be described in more detail with reference to examples. The present invention should not be construed as being limited to these examples.

Example 1
Preparation of polymer resin varnishes (A to D) (Table 1) 2-propanol 60 g, ethanol 60 g, ion exchange in a 500 ml four-necked flask equipped with a stirrer, cooler, temperature controller, nitrogen inlet tube, and dropping funnel 30 g of water was added and stirred while introducing nitrogen. Subsequently, the monomers in the composition table shown in Table 1 were added dropwise, 0.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as an initiator, and the mixture was heated by nitrogenization at 60 ° C. for 8 hours. did. As a result, transparent polymer resin varnishes A to E were obtained.

Preparation of polymer resin varnish (E) (Table 1) In the preparation of polymer resin varnishes (A to D), except that allyl methacrylate having an unsaturated group is used instead of a glycidyl monomer having a curing group Prepared. An organic cobalt compound was used as a curing catalyst.

Example 2
Preparation of chitosan polymer 2.63 g of chitosan powder was added to 30 g of 1% citric acid solution and dissolved with stirring at room temperature for 3 hours to obtain a viscous transparent liquid. A 2N potassium hydroxide solution was added little by little to the resulting liquid to make the pH pH 8 alkaline to obtain a white precipitate of chitosan gel. The precipitate was collected and applied uniformly on a vinyl chloride plate, and excess water on the surface of the precipitate was completely removed using a Kim towel. After measuring the weight after wiping, it was dried with a dryer (80 ° C.) for 3 hours. From the weight change before and after drying, the water content was 64%.

Example 3
Preparation of polyether polyester polymer
A 4-necked flask was charged with 37.62 g of 2,6-dimethylnaphthalate, 98.94 g of polyethylene glycol (molecular weight 2000), 17.75 g of 1,4 butanediol and 2 ml of tetrabutoxytitanium at 10 ppm (xylene solution), and purged with nitrogen. Warm while warming. A uniform liquid was obtained at a temperature of about 160 to 200 ° C. The reaction was carried out at 220 to 230 ° C. for about 7 hours to remove the distilled methanol. The obtained compound (which crystallizes at room temperature) was dissolved in tetrahydrofuran (concentration: about 15%), applied to a vinyl chloride plate and dried to obtain a polyester film. The membrane was immersed in distilled water for a whole day and night, and the moisture content of the membrane was determined from the change in weight before and after immersion.

Preparation of cuprous oxide (3μ, 1μ, 0.5μ) paste 50g of mixed solvent (20g of 2-propanol, 20g of ethanol, 10g of water) into a 200ml dispersion container, followed by acrylic pigment dispersant (concentration 50%) 2.4 g was added and dissolved. 50 g of cuprous oxide having an average particle diameter of 3 μm, 1 μm or 0.5 μm and 50 g of dispersed beads (made of zirconium) were placed in the dispersion solution, and dispersed for 20 minutes at a rotational speed of 2500 rpm on a disperser equipped with dispersion blades. After dispersion, the beads were removed with tea strainer to obtain a dispersion paste.

Example 4
Preparation of triazine compound (curing agent 1)
N, N-diisopropylethylamine (39.7 g) and isopropylamine (15.1 g) were added to a solution (350 ml) of cyanuric chloride (18.8 g) dissolved in the solvent terahydrofuran, followed by stirring at room temperature for 72 hours. Water was added to the reaction solution to precipitate the target product, and then suction filtration was performed to obtain 22.2 g of compound 6-chloro-N ² , N ⁴ -diisopropyl-1,3,5-triazine-2,4-diamine. It was. To a solution obtained by dissolving this compound in 150 ml of tetrahydrofuran were added 31.2 g of diisopropylamine and 27.6 g of 4- (aminomethyl) piperidine, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the reduced-pressure solvent was removed. The residue was purified by amino silica gel column chromatography (ethyl acetate: methanol = 3: 1) to give compound 6- (4- (aminomethyl) piperidin-1-yl) -N ² , N ⁴ -diisopropyl-1, 27 g of 3,5-triazine-2,4-diamine was obtained. This compound was then dissolved in 27 g of ethanol to obtain a 50% solution. The chemical formula of the curing agent 1 is as follows.

Preparation of triazine compound (curing agent 2)
To a solution (150 ml) of cyanuric chloride 15.0 g dissolved in tetrahydrofuran as a solvent, 21.1 g of N, N-diisopropylethylamine and 12.2 g of methoxyethylamine were added and stirred at room temperature for 72 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound 6-chloro-N ² , N ⁴ -bis (2-methoxyethyl) -1,3,5- 10.8 g (yield 51%) of triazine-2,4-diamine was obtained. 10.0 g of this compound was dissolved in 150 ml of tetrahydrofuran, 9.9 g of diisopropylethylamine and 8.75 g of 4- (aminomethyl) piperidine were added, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: methanol = 3: 1 containing 2% triethylamine) to give compound 6- (4- (aminomethyl) piperidin-1-yl) -N ² , N ⁴ -bis ( There were obtained 7.94 g (yield 61%) of 2-methoxyethyl) -1,3,5-triazine-2,4-diamine.

Preparation of triazine compound (curing agent 3)
N, N-diisopropylethylamine (5.9 g) and 3-methylthiopropylamine (4.8 g) were added to a solution (50 ml) of cyanuric chloride (4.21 g) dissolved in the solvent terahydrofuran, and the mixture was stirred at room temperature for 4 days. Water was added to the reaction solution to precipitate the desired product, which was then suction filtered, and compound 6-chloro-N ² , N ⁴ -bis (3- (methylthio) propyl) -1,3,5-triazine-2, 6.54 g (89% yield) of 4-diamine was obtained. To 50 ml of a tetrahydrofuran solution of this compound were added 6.57 g of diisopropylethylamine and 5.8 g of 4- (aminomethyl) piperidine, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: methanol = 1: 1 containing triethylamine 2%) to give compound 6- (4- (aminomethyl) piperidin-1-yl) -N ² , N ⁴ -bis ( 6.67 g (yield 82%) of 3- (methylthio) propyl) -1,3,5-triazine-2,4-diamine was obtained.

Preparation of triazine compound (curing agent 4)
Compound 6-Chloro-N ² , N ⁴ -diisopropyl-1,3,5-triazine-2,4-diamine in 1.0 g tetrahydrofuran solution (tetrahydrolane 15 ml) in diisopropylethylamine 4.5 g and N-acetylethylenediamine 22g was added and it heated and refluxed for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate), and the compound N- (2-((4,6-bis (isopropylamino) -1,3,5-triazin-2-yl) amino) ethyl) acetamide 1.09 g (yield 85%) was obtained. To a solution of this compound 12.4 g in ethanol (200 mL) was added 60% aqueous potassium hydroxide solution (200 mL), and the mixture was heated to reflux for 48 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: methanol = 5 1 Triethylamine 3% free), Compound ^N 2 - ^{(2-aminoethyl)} -N 4, ^{N 6} - diisopropyl 1,3,5 8.57 g (yield 81%) of triazine-2,4,6-triamine was obtained.

Preparation of triazine compound (curing agent 5)
To a solution of cyanuric chloride (11.5 g) in tetrahydrofuran (200 mL) were added diisopropylethylamine (16.15 g) and tryptamine (20.0 g), and the mixture was stirred at room temperature for 24 hours, followed by suction filtration, compound N ² , N ⁴ -bis (2- ( 26 g of 1H-indol-3-yl) ethyl-6-chloro-1,3,5-triazine-2,4,6-triamine was obtained, and 13.3 g of a tetrafuran solution (200 mL) was added to the compound. 47.8 g of diisopropylethylamine and 23.7 g of N-acetylethylenediamine were added, and the mixture was heated to reflux for 24 hours, concentrated, and then extracted with ethyl acetate, washed with saturated brine, and anhydrous sulfuric acid. After drying over magnesium, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate: methanol = 5: 1) to give a compound. 14.3 g of-(2-((4,6-bis ((2- (1H-indol-3-yl) ethyl) amino) -1,3,5-triazin-2-yl) amino) ethyl) acetamide) A 94% aqueous solution of potassium hydroxide (150 mL) was added to a solution of 14.3 g (28.7 mmol) of this compound in ethanol (150 mL), and the mixture was heated to reflux for 24 hours. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.The residue was subjected to amino silica gel column chromatography (ethyl acetate: methanol = 5: 1) to give compound ^N 2, ^{N 4} - bis (2-(1H-indol-3-yl) ethyl) ^-N 6 - (2-aminoethyl) -1,3,5-triazine-2,4 Thus, 10.7 g (82% yield) of 6,6-triamine was obtained.

Preparation of triazine compound (curing agent 6)
Compound 6-Chloro-N ² , N ⁴ -bis (2-methoxyethyl) -1,3,5-triazine-2,4-diamine In a solution of 15.0 g in tetrahydrofuran (150 mL), diisopropylethylamine 59.45 g, N -29.3 g of acetylethylenediamine was added, and the mixture was heated to reflux for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: methanol = 5: 1) to give compound N- (2-((4,6-bis ((2-methoxyethyl) amino) 1,3,5-triazine). There were obtained 8.9 g (yield 47%) of 2-yl) amino) ethyl) acetamide. A 60% aqueous potassium hydroxide solution (100 mL) was added to a solution of this compound 8.90 g in ethanol (100 mL), and the mixture was heated to reflux for 72 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue amino silica gel column chromatography (ethyl acetate: methanol = 5: 1 triethylamine 3% free) purified sushi, Compound N ² - (2-aminoethyl) -N 4, ^N 6 ^- bis (2-methoxyethyl) 7.08 g (yield 91%) of -1,3,5-triazine-2,4,6-triamine was obtained.

Preparation of triazine compound (curing agent 7)
To a solution of cyanuric chloride (1.00 g) in THF (20 mL) while cooling in an ice-salt bath, sodium hydrogen carbonate (0.68 g, 8.13 mmol) was added, and tryptamine (0.90 g) in THF (5 mL) was added dropwise, followed by 70 minutes. Stir. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound N- (2- (1H-indol-3-yl) ethyl) -4,6-dichloro-1 1.62 g of 3,5-triazine-2-amine was obtained. To a solution of 17.0 g (55.2 mmol) of this compound in THF (200 mL) were added 57.0 g of diisopropylethylamine and 28.2 g of N-acetylethylenediamine, and the mixture was heated to reflux for 24 hours, and then water was added to the reaction solution and extracted with ethyl acetate. . At this time, the emulsion part was separated separately and the solvent was distilled off under reduced pressure. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue of the organic layer and the emulsion portion were mixed and purified by silica gel column chromatography (ethyl acetate: methanol = 5: 1 containing 2% triethylamine) to obtain compound N, N ′-(((6-((2- (1H -Indol-3-yl) ethyl) amino) -1,3,5-triazine-2,4-diyl) bis (azanediyl)) bis (ethane-2,1-diyl)) diacetamide was obtained. . A 60% aqueous potassium hydroxide solution (150 mL) was added to a solution of this compound 13.5 g in ethanol (150 mL), and the mixture was heated to reflux for 72 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, the compound ^N 2 - (2- (1H- indol-3-yl) ^ethyl) -N 4, ^{N 6} - 10.2 g (94% yield) of bis (2-aminoethyl) -1,3,5-triazine-2,4,6-triamine was obtained.

Preparation of triazine compound (curing agent 8)
Compound N- (2- (1H-indol-3-yl) ethyl) -4,6-dichloro-1,3,5-triazin-2-amine 14.0 g in THF (150 mL) solution in diisopropylethylamine 23. 5 g and 22.4 g of betaustine methanesulfonate were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was stirred with warm methanol, the solid component was filtered, Compound ^N 2 - (2- (1H- indol-3-yl) ethyl) -6-chloro -N ⁴ - methyl ^-N 4 - (2- 14.6 g (neutral 79%) of (pyridin-2-yl) ethyl) -1,3,5-triazine-4,6-diamine were obtained. To a solution of 14.6 g (35.8 mmol) of this compound in THF (150 mL) were added 36.97 g of diisopropylethylamine and 18.3 g of N-acetylethylenediamine, and the mixture was heated to reflux for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: methanol = 5: 1 containing 2% triethylamine), and compound N- (2-((4-((2- (1H-indol-3-yl) ethyl) 13.6 g (80% yield) of amino) -6- (methyl (2- (pyridin-2-yl) ethyl) amino) -1,3,5-triazin-2-yl) amino) ethyl) acetamide was obtained. . A 60% aqueous potassium hydroxide solution (150 mL) was added to a solution of this compound 13.6 g in ethanol (150 mL), and the mixture was heated to reflux for 24 hours. The reaction mixture was concentrated, water was added, and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was recrystallized from ethyl acetate, the compound ^N 2 - (2- (1H- indol-3-yl) ethyl) ^-N 4 - (2-aminoethyl) -N ⁶ - methyl ^-N 6 - (2- ( 8.15 g (yield 66%) of pyridin-2-yl) ethyl) -1,3,5-triazine-2,4,6-triamine was obtained.

  The chemical formulas of curing agents 1-8 are as follows.

Example 5
Preparation of paints A-1 to E (Table 2)
According to the composition table in Table 2, add 100 to 172 g of resin solutions A to E, 22 to 80 g of cuprous oxide paste C, and 0.16 to 0.32 g of triazine catalyst to a 300 ml container, and stir well with a mixer. Thereafter, 6 to 20 g of a mixed solvent (ethanol / 2-propanol / water = 2/2/1) was added and stirred and diluted.

Example 6
Performance of coatings A-1 to E (Table 2)
A part of the paint (A-1 to E) prepared in Example 5 was applied to a rotating drum for measuring frictional resistance, dried at room temperature for 2 hours, and then measured. On the other hand, in order to investigate the antifouling property in seawater, it was applied to a 10 × 30 cm PVC plate and immersed in seawater. Also, for physical property measurement (Young's modulus, elongation), coated on glass plate, dried for 2 hours, soaked overnight in artificial seawater to swell, and the swollen coating film was immediately cut into strips from the glass plate and Tensilon (tensile) The physical properties were measured by a tensile test using a testing machine. The Young's modulus and the elongation were measured with Tensilon (tensile tester) as described above.

Measurement of Friction Resistance Friction resistance was obtained by designing and manufacturing a device that required a slight resistance (torque) caused by friction with water by rotating a cylindrical rotating drum (painted around) in a bathtub. Painted on the outer circumference of a rotating drum (cylindrical; diameter: 26 cm, length: 20 cm), rotated at 300 rpm in artificial seawater at 20 ° C., and its resistance value (torque value: minimum unit: 0.001 cN · m) Obtained with a torque meter. The reduction rate (%) was compared with the resistance value of the commercially available coating film, and the reduced ratio was obtained.

The antifouling property was immersed in seawater for 1 year, and the state of attachment of marine organisms was visually observed.
○ shows no adhesion of marine organisms and seaweed, and no deterioration of the membrane.
Δ indicates that marine organisms and algae are slightly attached, and the film is somewhat deteriorated.
× indicates that marine organisms and algae are attached and the film is significantly deteriorated.

Comparative Example 1
A commercially available coating material was prepared in the same manner as in Example 6 and subjected to a frictional resistance, antifouling property, and physical property test. The results are shown in Table 3.

Comparative Example 2
In the preparation of the coating material of Example 5 (B-2), a coating film was prepared in exactly the same manner except that diethylenetriamine was used instead of the triazine-based catalyst, and was subjected to various tests (friction resistance, antifouling properties, physical properties). . The results are shown in Table 3.

Comparative Example 3
In the preparation of the coating material of Example 5 (D-3), a coating film was prepared in exactly the same manner except that diethylenetriamine was used in place of the triazine-based catalyst, and subjected to various tests (friction resistance, antifouling properties, physical properties). . The measurement results for each example and comparative example are shown in Tables 2 and 3.

Measurement of Young's Modulus In a tensile test of a swollen coating film using a Tensilon (tensile tester), the Young's modulus is obtained from the gradient of the tensile length and the stress applied at that time.

Measurement of elongation rate In the tensile test of a swollen coating film with Tensilon, if the length before pulling (L1) and the length when the coating film was broken by pulling (L2): (L2-L1 / L1) × 100 ( %).

From the results in Tables 2 and 3, the frictional resistance was remarkably improved as compared with the commercially available coating film. In terms of physical properties, the Young's modulus and elongation were large, and as a film physical property, a coating film that was stronger and more flexible than a market coating film that was hard and brittle was obtained. Although the Young's modulus is somewhat low in the coating films B-3 and D-3, the physical properties can sufficiently withstand long-term immersion in seawater. On the other hand, in Comparative Examples 2 and 3, the coatings with poor Young's modulus maintained the physical properties, but adhesion of marine organisms and algae was observed.

In FIG. 1, the values of the degree of swelling (%) and the frictional resistance reduction rate (%) of the antifouling coating film of the examples described in Table 2 are shown, and the degree of swelling (%) is plotted with the frictional resistance reduction rate (%) on the vertical axis. ) On the horizontal axis. As shown in FIG. 1, it was found that the frictional resistance reduction rate increases in proportion to the degree of swelling of the coating film. This is a discovery that has not been known so far, and the present invention has been completed based on this discovery. It is clear that the coating of the present invention has excellent frictional resistance reduction in seawater. The present invention is a water-based paint with little environmental pollution, does not hydrolyze in seawater like conventional coatings, and the amount of cuprous oxide that is most effective for antifouling is greatly reduced, The provision of technology that significantly reduces seawater pollution.

  The antifouling coating film of the present invention is extremely effective for coating an object to be used on or in water, regardless of whether it is seawater or fresh water. In particular, when the antifouling coating film of the present invention is applied to a ship, not only the resistance to water is reduced and fuel is saved, but also it is possible to run faster and both time and cost are reduced.

Claims (6)

An antifouling coating film containing an antifouling agent in a coating film composed of a polymer hydrogel and a crosslinking agent,
The antifouling coating film has a degree of swelling of 10 to 80% and a Young's modulus of 500 to 30,000 N / cm ^2, and has a small frictional resistance with water or seawater,
The polymer hydrogel is a copolymer of a monomer mixture containing a hydrophilic vinyl monomer and a monomer having a glycidyl group,
The crosslinking agent is a triazine-based curing agent ,
Antifouling coating with low frictional resistance against water or seawater.   The antifouling coating film having a small frictional resistance with water or seawater according to claim 1, wherein the antifouling agent is cuprous oxide particles having an average particle size of 3 µm or less.   The hydrophilic vinyl monomer is one or more selected from the group consisting of a cationic vinyl monomer and an anionic vinyl monomer, and the monomer mixture includes other monomers that copolymerize with the hydrophilic vinyl monomer. An antifouling coating film having a small frictional resistance with water or seawater according to claim 1 or 2. The cationic vinyl monomer is dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, allylamine, N-methylallylamine, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) Acrylamide, N-hydroxy (meth) acrylamide and one or more selected from the group consisting of vinyl pyridine, vinyl imidazole and vinyl pyrrolidone, and the anionic vinyl monomer is (meth) acrylic acid and salts thereof, 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 sulfone One or more selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloylethanesulfonic acid, 2-acryloylpropanesulfonic acid, 2-methacryloylethanesulfonic acid, and salts thereof including,
The antifouling coating film with small frictional resistance with the water or seawater in any one of Claims 1-3.   The object which applied the antifouling coating film in any one of Claims 1-4. Antifouling containing 1 to 50% by weight of hydrophilic vinyl polymer, 0 to 40% by weight of antifouling agent, 20 to 70% by weight of solvent and crosslinking agent and other additives (weight% is based on the total amount of antifouling coating composition) A dirty paint composition,
The hydrophilic vinyl polymer is a copolymer of a monomer mixture containing a hydrophilic vinyl monomer and a monomer having a glycidyl group,
The crosslinking agent is a triazine-based curing agent ;
The cured antifouling coating film has a swelling degree of 10 to 80% and a Young's modulus of 500 to 30,000 N / cm ² ,
An antifouling paint composition that reduces frictional resistance with water or seawater.

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