JP2022130782A - Water-based antifouling paint composition, antifouling coating formed using the same, and fishing net, ship, and underwater structure having the coating on surface - Google Patents

Abstract

To provide a water-based antifouling paint composition that can exhibit excellent antifouling effect and can be stored for a long time, an antifouling coating formed using the same, and a fishing net and an underwater structure each having the coating on its surface.SOLUTION: Disclosed is a water-based antifouling paint composition containing: an emulsion resin or a water-soluble resin including an acidic functional group and having an acid value of 1 to 30 mgKOH/g; a base having the molar ratio of 15 to 300% relative to the acidic functional group; and one or more marine organism repellents.SELECTED DRAWING: None

Description

The present invention provides a novel water-based antifouling coating composition capable of preventing adhesion of marine organisms and seaweeds to aquaculture and stationary fishing nets, ship bottoms, underwater structures, buoys, etc., and a composition formed using the same. The present invention relates to antifouling coatings and fishing nets and underwater structures having such coatings on their surfaces.

Various marine organisms adhere to the surfaces of articles such as aquaculture nets, fixed nets, ship bottoms, underwater structures, and buoys used in the fields of fisheries, fisheries, marine transportation, and the like. In aquaculture nets, set nets, etc., marine organisms such as barnacles, hydroids, bryophytes, and Aegis stick to the nets and clog the nets, causing problems such as deterioration of water quality, fish disease, and damage to the nets. In the case of ships, the adhesion of barnacles and the like to the bottom of the ship causes various problems such as adverse effects on fuel consumption. Various antifouling paints have been used for the purpose of preventing adhesion of marine organisms to fishing nets, ships, underwater structures, etc., which cause such problems. In the past, antifouling paints containing organic tin compounds as antifouling components were used as ship bottom paints, etc., but their use is restricted due to their toxicity, and the development of alternative antifouling paints is desired. there is

In the paint industry, organic solvents have been widely used as solvents because of their quick-drying properties and dispersibility. The use of VOCs (volatile organic compounds) is restricted in consideration of their adverse effects on the environment. Along with this, the shift to water-based paint is being rapidly carried out.

As alternatives to organotin compounds, antifouling paints containing various low-toxic marine organism repellents or paints without marine organism repellents have been developed. For example, in Patent Document 1, a copolymer of a halogenated alkyl ester of acrylic acid or methacrylic acid and a copolymerizable monomer is included as a vehicle, and if necessary, cuprous oxide, copper thiocyanate, copper In addition to copper-based antifouling agents such as powders, other metal compounds such as lead, zinc, and nickel, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, and pyridine compounds are used. An antifouling paint composition that may be used is disclosed (claims, paragraphs 0008, 0013, examples).

In Patent Document 2, the constituent component of the binder contains an emulsion of polybutene having a number average molecular weight of 300 to 5,000, and if necessary, a metallic compound such as copper or zinc, a marine organism repellent such as a heterocyclic compound, or A water-based antifouling paint composition in which a marine organism inhibitor is compounded or dispersed is disclosed (claims, paragraphs 0025 and 0026).

Patent Document 3 describes an antifouling coating composition that uses a small amount of organic solvent when forming a coating film, maintains strength and self-polishing properties for a long period of time, and is capable of forming a coating film exhibiting excellent antifouling properties. discloses an antifouling coating composition containing an acrylic polymer, a radically polymerizable polymer and an organic peroxide, wherein at least one of the acrylic polymer and the radically polymerizable polymer has a divalent metal ester structure.

JP-A-11-148031 JP 2005-213336 A WO2011/125179

However, although the antifouling paint composition described in Patent Document 1 does not contain an organic tin compound, it uses an organic solvent such as xylene, and there is still the problem of adverse effects on the environment and workers' health. ing. The water-based antifouling coating composition described in Patent Document 2 has problems with long-term storage stability and drying properties. Moreover, the antifouling paint composition described in Patent Document 3 has a problem that the content and elution amount of copper ions as an antifouling component are insufficient.

In order to apply the water-based antifouling coating composition to fishing nets, etc., a coating film is formed by immersing the fishing net in the water-based antifouling coating composition, and the amount of the water-based antifouling coating composition is greater than the coating amount. must be used. It is desirable that the remaining antifouling coating composition can be stored and reused until the fishing season of the following year. It sometimes tends to gel, and there were problems in terms of long-term stability and economy.

The present invention has been made in view of such circumstances, and provides a water-based antifouling paint composition that exhibits an excellent antifouling effect over a long period of time and that can be stored for a long period of time. It is an object of the present invention to provide fishing nets, vessels and subsea structures having coatings on their surfaces.

A first aspect of the present invention in line with the above object is an emulsion resin or water-soluble resin containing an acidic functional group and having an acid value of 1 to 30 mgKOH/g, and an acid functional group having a molar ratio of 15 to 300%. The above problem is solved by providing a water-based antifouling paint composition comprising an amount of a base and one or more marine repellents.

In the water-based antifouling paint composition according to the first aspect of the present invention, the acidic functional group may be a carboxyl group or a silanol group.

In the water-based antifouling paint composition according to the first aspect of the present invention, the base is alkali hydroxide, aqueous ammonia, alkylamine, dialkylamine, trialkylamine, ω-hydroxyalkylamine and ω-aminoalkyltrialkoxy. silane, more specifically, sodium hydroxide, potassium hydroxide, aqueous ammonia, trimethylamine, triethylamine, 2-aminoethanol and ω-aminoalkyltrialkoxysilane. good.

The water-based antifouling paint composition according to the first aspect of the present invention may further contain any of ethylene glycol, propylene glycol and ethylene glycol dialkyl ether in an amount of less than 4% by mass.

A second aspect of the present invention solves the above problems by providing an antifouling coating formed by drying after applying the water-based antifouling coating composition according to the first aspect of the present invention. is.

A third aspect of the present invention solves the above problems by providing a fishing net having on its surface the antifouling coating according to the second aspect of the present invention.

A fourth aspect of the present invention solves the above problems by providing a ship having the antifouling coating according to the second aspect of the present invention on the bottom surface of the ship.

A fifth aspect of the present invention solves the above problems by providing an underwater structure having on its surface the antifouling coating according to the second aspect of the present invention.

According to the present invention, since no organic solvent is used, the danger of ignition, the burden on the environment, and the adverse effects on the health of workers are reduced, and it is possible to form a coating film that can exhibit excellent antifouling effects over a long period of time. Thus, a water-based antifouling coating composition is provided which does not cause problems such as gelation even in cold weather and is excellent in cold resistance and storage stability.

The water-based antifouling paint composition according to one embodiment of the present invention (hereinafter sometimes abbreviated as "water-based antifouling paint composition" or "antifouling paint composition") comprises (A) an acidic functional group and (B) a base and (C) a marine organism repellent, wherein the acid value is 1 to 30 mgKOH/g. Each component will be described in detail below.

(A) Emulsion resin or water-soluble resin Emulsion resin or water-soluble resin (water-dispersible resin) is used as the resin as the coating film-forming component of the water-based antifouling coating composition. "Water-soluble resin" refers to a resin that dissolves in water to form a uniform solution, and "emulsion resin" refers to a resin that is not water-soluble but disperses in water to form an emulsion. As the emulsion resin or water-soluble resin, one having an acidic functional group, which is a hydrophilic functional group, is used. Specific examples of preferred acidic functional groups include carboxyl groups and silanol groups. Specific examples of emulsion resins or water-soluble resins containing acidic functional groups include acrylic resins, silicone resins, alkyd resins, copolymers thereof, other resins (polyol resins, fluororesins, amino resins, etc.) and acidic functional groups. and copolymers with monomers containing.

As the emulsion resin, for example, an emulsion resin having a solid content of 10% or more and an MFT ((minimum film formation temperature) of 50° C. or less is preferable, and a temperature of 0 to 20° C. is particularly preferably used. A water-soluble resin having an average molecular weight of 1,000 to 1,000,000 is preferable, and a water-soluble resin having an average molecular weight of 50,000 to 200,000 is particularly preferable. The content of the resin in the water-based antifouling coating composition is, for example, 1 to 90% by mass in terms of solid content, and it is suitable according to the application, required performance, etc. adjusted.

Examples of emulsion resins having an MFT of 50° C. or lower include acrylic emulsion resins, acrylic silicone emulsion resins, acrylic urethane emulsion resins, etc. Specific examples include Boncoat Series 550EF, CE-6400, 40-418EF, 5400EF and CF. -2800, HY-364, U-40EF (DIC Corporation), Polydurex B3220, Polytron E2139 (Asahi Kasei Corporation) and the like. Examples of water-soluble resins having a weight average molecular weight of 1,000 to 100,000 include acrylic resins and alkyd resins. 2001, WJW-838, WC-201 (DIC Corporation) and the like.

The acid value of the emulsion resin or water-soluble resin is 1-30 mgKOH/g. The acid value is defined in JIS K5601-2-1: 1999 (Paint component test method-Part 2: Component analysis in solvent-soluble matter-Section 1: Acid value (titration method)) , "the amount (mg) of KOH required to neutralize the free acid in 1 g of the non-volatile content of the product", and the unit is "mg KOH/g". The acid value can be evaluated according to the titration method described in the standard.

(B) Base The water-based antifouling paint composition contains a base in order to stably retain the paint particles in the water-based antifouling paint composition for a long period of time. The amount of base is adjusted so that the molar ratio of base to acidic functional groups is 15-300%. Bases used in the water-based antifouling coating composition include alkali hydroxides, aqueous ammonia, alkylamines (primary amines), dialkylamines (secondary amines), trialkylamines (tertiary amines), ω- Hydroxyalkylamines and ω-aminoalkyltrialkoxysilanes are included. In the case of alkylamines, the number of carbon atoms in the alkyl group is preferably 5 or less because it is necessary to have water solubility. Specific examples of preferred bases include sodium hydroxide, potassium hydroxide, aqueous ammonia, trimethylamine, triethylamine, 2-aminoethanol and ω-aminoalkyltrialkoxysilanes.

(C) Marine organism repellent The marine organism repellent for preventing fouling due to adherence of marine organisms is appropriately selected according to the type of marine organisms to be prevented from adhering. Specific examples of marine organism repellents include cuprous oxide (copper (I) oxide), bis(2-sulfidopyridine-1-olato)copper, triphenylborane/amine complex compounds, tetraalkylthiuram disulfide compounds, Bis(N,N-dimethyldithiocarbamate) N,N'-ethylenebis(thiocarbamoylthiozinc) and copper glass. These may be used alone, or any two or more of them may be used in combination.

Specific examples of the triphenylborane/amine complex compound include triphenylborane/n-dodecylamine, triphenylborane/n-octylamine, triphenylborane/n-hexylamine, triphenylborane/n-butylamine, and triphenylborane. · n-propylamine, triphenylborane · n-octadecylamine, triphenylborane · 2-ethylhexylamine, triphenylborane · 3-ethoxypropylamine, triphenylborane · 3-(2-ethylhexyloxy) propylamine, tri Phenylborane/3-lauryloxypropylamine, Triphenylborane/3-stearyloxypropylamine, Triphenylborane/4-(2-ethylhexyloxy)butylamine, Triphenylborane/4-lauryloxybutylamine, Triphenylborane/8 -ethoxyoctylamine, triphenylborane/8-(2-ethylhexyloxy)octylamine, triphenylborane/2-ethylhexyloxyphenylamine, triphenylborane/lauryloxyphenylamine, and the like. Of these triphenylborane/amine complex compounds, particularly preferred is triphenylborane/[3-(2-ethylhexyl)]propylamine. The above triphenylborane-amine complex compounds may be used alone or in combination of any two or more.

Examples of the tetraalkylthiuram disulfide compounds include tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetra-sec-butylthiuram disulfide, tetraisobutylthiuram disulfide, and tetra-tert-butylthiuram disulfide. , tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptylthiuram disulfide, tetraoctylthiuram disulfide, tetra(2-ethylhexyl)thiuram disulfide and the like. Of these tetraalkylsulfide compounds, tetraethylthiuram disulfide is particularly desirable. The above tetraalkyldisulfide compounds may be used alone or in combination of any two or more.

Examples of other marine repellents include copper powder, copper rhodan, copper naphthenate, sodium pyrithione, soluble glass, bis(2-sulfidopyridine-1-olato)zinc, bis(N,Ndimethyldithiocarbamate). ) Bis N,N'-ethylenebis(thiocarbamoylthiozinc), bisdimethyldithiocarbamoyl, zinc ethylenebisdithiocarbamate, zinc methyldithiocarbamate, zinc ethylenedithiocarbamate, manganese ethylenebisdithiocarbamate, 2,4,5, 6-tetrachloroisophthalonitrile, 2,3-dichloro-N-(2′-ethyl-6′-methylphenyl)maleimide, 4,5-dichloro-2-n-octyl-isoazolin-3(2H)-one , 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, N,N'-dimethyl-dichlorophenylurea, N-(fluorodichloromethylthio)phthalimide, N,N'-dimethyl-N' antifouling agents such as -phenyl-(N-fluorodichloromethylthio)sulfamide, N'-dichlorofluoromethylthio-N',N'-dimethyl-NP-trisulfamide, and the like; These may be used alone or in combination of any two or more.

Deionized water, ion-exchanged water, distilled water, pure water, ultrapure water and the like can be appropriately used as the water serving as the base of the water-based antifouling coating composition, if necessary.

Other Additives The water-based antifouling paint composition may contain additives such as surfactants and elution modifiers, if necessary, in addition to the above components.

Surfactant A surfactant may be added to the water-based antifouling paint composition in order to improve the compatibility and dispersibility of the resin and the marine organism repellent and to improve the stability of the paint. The amount of surfactant added is 0.01 to 50% by mass in terms of the solid content of the paint.

Specific examples of surfactants include polyoxyethylene tridecyl ether, polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene lauryl ether, and polyoxyethylene styrenated phenyl ether. , polyoxyethylene isodecyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxylethylene oleyl cetyl ether, polyoxyethylene-polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly Nonionic surfactants such as oxyethylene oleate, polyoxyethylene diamine stearate, polyoxyethylene hydrogenated castor oil, glyceryl oleate, polyoxyethylene glyceryl isostearate, linear alkyl benzene sulfonate, sodium alpha olefin sulfonate , Phenolsulfonate, Sodium Lauryl Sulfate, Potassium Higher Fatty Acid, Ammonium Polyoxyethylenated Phenyl Ether Sulfate, Ammonium Polyoxyethylene Isodecyl Ether Sulfate, Sodium Polyoxyethylene Tridecyl Ether Sulfate, Ammonium Polyoxyethylene Tridecyl Sulfate, Polyoxyalkylene Content Sodium branched decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene oleyl cetyl ether sulfate, sodium polyoxyethylene oleyl cetyl ether sulfate, alkyl (C4) Sodium phosphate, ethanolamine salt of alkyl (C8) phosphate, disodium polyoxyethylene sulfosuccinate, anionic surfactants, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, octyldimethyl ethanesulfonate Cations such as ethylammonium, palmityldimethylethylammonium ethanesulfonate, didecyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylaminopropylamide, tributylbenzylammonium chloride, etc. Examples of surfactants include amphoteric surfactants such as lauryldimethylaminoacetate betaine, lauramidopropyl betaine, coconut oil fatty acid amidopropyl betaine, octanoamide propyl betaine, lauryldimethylamine oxide, and urethane surfactants. agents, silicone surfactants, and acrylic acid ester emulsions. These surfactants may be used alone or in combination of any two or more.

Elution modifier The water-based antifouling coating composition may contain an ethylene-α-olefin copolymer as an elution modifier. Specific examples of dissolution modifiers include polybutenes and isopolybutenes, liquid paraffin, solid paraffin, laurin, petrolatum, and dialkylpentasulfide. These dissolution modifiers may be used alone or in combination of any two or more.

As the dissolution modifier, a silicone compound can be used in addition to the above. Specific examples of silicone compounds include polyether-modified polydimethylsiloxanes with a hydrophilic-lipophilic balance (HLB) of 2 to 12, preferably HLB of 3 to 5.

Other Additives In addition to the emulsion resin or water-soluble resin having an acidic functional group, additives having an acidic functional group include, for example, polycarboxylic acid polymer surfactants, sodium dioctylsuccinate, potassium higher fatty acid, and dimethyl lauryl. Additives such as betaine aminoacetate, laurylamidopropyl betaine, coconut oil fatty acid amidopropyl betaine, octanoamide propyl betaine, styrene-maleic acid half ester copolymer ammonium salt may be contained. In addition, optional additives used in water-based paints, such as rheology modifiers and antifoaming agents, may be added as necessary.

Manufacture of the waterborne antifouling paint composition can be carried out using any known equipment and method. Application of the water-based antifouling coating composition to fishing nets, ships, and underwater structures can be carried out using any method such as immersion, brushing, doctor blade method, spraying, and the like. Since the water-based antifouling coating composition does not contain volatile organic compounds such as organic solvents, it does not require ventilation equipment or the like, thereby reducing adverse effects on the health of workers and the environment. After coating, the coating film is dried under any conditions such as natural drying or hot air drying to form an antifouling film.

The antifouling coating according to the second embodiment of the present invention (sometimes abbreviated as "antifouling coating") is the water-based antifouling coating according to the first embodiment of the present invention as described above. It is formed by applying a flexible coating composition to the surface of articles such as underwater structures, ship bottoms, and fishing nets, followed by drying.

Next, an example conducted to confirm the effects of the present invention will be described.
[1] Preparation of water-based antifouling paint composition As an example, the procedure for producing the water-based antifouling paint composition described in Example 6 in Table 1 below will be described. The water-based antifouling coating compositions according to other examples and comparative examples differ only in composition (see Tables 1 to 3 below), and the production procedure is the same.

(Example 6)
To 76.6 parts by mass of ion-exchanged water, 4.2 parts by mass of sodium linear alkylbenzene sulfonate (anionic surfactant) and 1.1 parts by mass of polyoxyethylene styrenated phenyl ether (nonionic surfactant) are added. Add in order under stirring, add 15 and 7 parts by mass of cuprous oxide and 4.0 parts by mass of bis(2-sulfidopyridine-1-orato) copper (marine organism repellent) and stir for 10 minutes, then urethane 2.3 parts by mass of a system surfactant (rheology modifier) and 1.4 parts by mass of a polyoxyalkylene lauryl ether surfactant are added under stirring and stirred for 30 minutes to obtain Boncoat 550EF (DIC Corporation) (emulsion Resin) 31.8 parts by mass were added, and while stirring was maintained, 0.4 parts by mass of 28% aqueous ammonia was added and stirred for 10 minutes in order to adjust the acid value neutralization degree of the resin to 50%. 0 parts by mass and 4.0 parts by mass of ether-modified polydimethylsiloxane were added with stirring, and after the completion of mixing, stirring was performed for 30 minutes, and 2.1 parts by mass of a vinyl polymer surfactant (antifoaming agent) was added for 30 minutes. After stirring and mixing, the mixture was taken out to prepare water-based antifouling paint compositions (Examples 1 to 19, Comparative Examples 1 to 6) having a solid content of 35%. In addition, a sea immersion test was conducted on fishing nets that had been dried after being coated with these water-based antifouling coating compositions, a commercially available organic solvent-based antifouling coating (Reference Example 1), and a commercially available water-based antifouling coating (Reference Example 2). . Compositions of water-based antifouling paint compositions according to Examples 1 to 19 and Comparative Examples 1 to 6, and results of sea immersion tests for Examples 1 to 19, Comparative Examples 1 to 6, and Reference Examples 1 and 2 are shown in Tables 1-3 below. The amount of each component added is shown in parts by weight (the sum of the weights of ion-exchanged water, emulsion resin and base is 100). In Tables 1 to 3, "prototype emulsion resin" is an acrylic emulsion resin (nonvolatile content 40%) similar to Boncoat (registered trademark) 500EF (DIC Corporation), and "amino-silane coupling agent" is It is 3-aminopropyltomethoxysilane (molecular weight 179.3), and the "base/acid molar ratio (%)" is the molar ratio of the base (ammonia or silane coupling agent) to the acidic functional groups in the emulsion resin (unit %).

In the evaluation results of long-term storage stability, "○" indicates that no precipitation or increase in viscosity is observed, and "○△" means that a slight precipitation occurs, but a uniform composition is obtained by stirring. . In addition, the evaluation result of the control effect is expressed by the adhesion rate (area ratio) of marine organisms after the underwater immersion test (after 180 days). "○△" means 10% or more and less than 20%, "△" means 20% or more and less than 30%, and "×" means 30% or more.

Of the marine organism repellents, cuprous oxide and bis(2-sulfidopyridine-1-olato)copper used in Examples 1 to 14 and Comparative Examples 1 to 4 are used to control barnacles. Bis(N,N-dimethyldithiocarbamic acid) N,N'-ethylenebis(thiocarbamoylthiozinc) used in Examples 15-19 and Comparative Examples 5 and 6 is used to control hydroid. There is. For Examples 1 to 19, high long-term storage stability and high control effect against target marine organisms are observed, whereas Comparative Example 1, in which the emulsion resin does not contain an acidic functional group, the acid value of the emulsion resin is In Comparative Example 2 exceeding 30 mg KOH / g, and Comparative Examples 3 to 6 in which the molar ratio of the base to the acidic functional group in the emulsion resin is less than 0.15, it was confirmed that the long-term storage stability or the pest control effect was inferior. was done.

Claims (9)

an emulsion resin or water-soluble resin containing an acidic functional group and having an acid value of 1 to 30 mgKOH/g;
a base in an amount such that the molar ratio to the acidic functional groups is 15 to 300%;
and one or more marine repellents. 2. A water-based antifouling paint composition according to claim 1, wherein said acidic functional group is a carboxyl group or a silanol group. 3. The base according to claim 1 or 2, wherein the base is any one of alkali hydroxide, aqueous ammonia, alkylamine, dialkylamine, trialkylamine, ω-hydroxyalkylamine and ω-aminoalkyltrialkoxysilane. A water-based antifouling paint composition as described. 4. The water-based antifouling according to claim 3, wherein the base is any one of sodium hydroxide, potassium hydroxide, aqueous ammonia, trimethylamine, triethylamine, 2-aminoethanol and ω-aminoalkyltrialkoxysilane. paint composition. 5. The water-based antifouling paint composition according to any one of claims 1 to 4, further comprising less than 4% by mass of any of ethylene glycol, propylene glycol and ethylene glycol dialkyl ether. An antifouling film formed by drying after applying the water-based antifouling coating composition according to any one of claims 1 to 5. A fishing net having the antifouling coating according to claim 6 on its surface. A ship having the antifouling coating according to claim 6 on the surface of the bottom of the ship. An underwater structure having the antifouling coating according to claim 6 on its surface.