JP5048929B2 - Antifouling paint composition for waterborne ship bottoms - Google Patents

Description

  The present invention relates to an aqueous paint composition having antifouling properties, and more particularly, an aqueous antifouling paint capable of forming a coating film that prevents adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. It is about.

  The coating film formed from the antifouling paint exhibits an antifouling effect when the antifouling chemical component contained therein elutes into the sea. When a coating film formed from a disintegrating antifouling paint using a rosin compound is immersed in the sea for a long time, the amount of elution gradually decreases, and the coating surface becomes uneven and non-eluting. As a result, the effect of preventing the adhesion of organisms such as marine organisms is significantly reduced. On the other hand, the coating film formed from self-polishing paint gradually renews the surface of the coating (self-polishing), and the antifouling component is always exposed on the coating film surface. The These antifouling paints contain a large amount of various organic solvents such as xylene and alcohol, and various water-based antifouling paints have been investigated in view of recent VOC (Volatile Organic Compounds) problems.

  For example, JP-A-60-237003 (Patent Document 1) and JP-A-8-81524 (Patent Document 2) disclose a water-based antifouling coating composition using a silicone emulsion. Has proposed a water-based antifouling paint composition comprising a composite resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in a silicone emulsion.

  In JP-A-2000-109729 (Patent Document 3), an aqueous emulsion having a carboxyl group and / or a metal carboxylate group in a resin molecule and having a resin acid value of 10 to 300 mgKOH / g obtained by emulsion polymerization. And if necessary, an aqueous antifouling paint containing an aqueous metal complex (a complex having a carboxylic acid and a divalent or higher metal) has been proposed.

Japanese Patent Application Laid-Open No. 9-52803 (Patent Document 4) comprises a resin aqueous emulsion obtained by emulsion polymerization of a (meth) acrylic monomer in an aqueous medium in the presence of a salt of an N-alkylpolyamine compound. Persistent underwater antifouling agents have been proposed.
JP-A-60-237003 JP-A-8-81524 JP 2000-109729 A JP-A-9-52803

  However, the antifouling paint containing silicone as described in Patent Document 1 and Patent Document 2 is intended to maintain the low surface tension of the coating film in seawater for a long period of time. There is a problem of poor adhesion.

  In Patent Document 3, the carboxyl group of the aqueous emulsion forms a metal and a metal carboxylate, and when the coating film touches seawater, the metal ion in the metal carboxylate group in the resin component on the coating film surface is sodium in water. It describes that it can exhibit antifouling properties over a long period of time because it is gradually solubilized by causing ion exchange with ions and the like. However, since the resin that forms the coating film has a high acid value and contains a large amount of aqueous metal complex coordinated with ammonia, the water resistance of the coating film is low, and the long-term antifouling property is insufficient. There is also a problem in the adhesion of the coating film.

  In Patent Document 4, a polyamine compound formed by forming a salt with an acid such as acetic acid is emulsion-polymerized in an aqueous medium as an emulsifier, and the salt of the polyamine compound does not have a chemical bond with the emulsion. The coating film easily absorbs water through salt, and there is a problem in water resistance and adhesion.

  An object of the present invention is to provide a water-based antifouling coating composition that is environmentally preferable, and is excellent in water resistance, can maintain an antifouling effect over a long period of time, and can form a coating film with excellent adhesion. It is to provide a coating composition.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

  That is, the present invention provides an aqueous resin dispersion comprising an organic hydrazine compound containing at least two hydrazine residues and a polymer containing a carbonyl group-containing ethylenically unsaturated monomer unit as a resin component. It is an antifouling paint composition.

  Moreover, this invention is said aqueous | water-based antifouling coating composition in which the said polymer further contains an ethylenically unsaturated carboxylic acid monomer unit and / or a polymerizable polyvalent metal salt monomer unit.

  Moreover, this invention is one of said water-based antifouling paint compositions in which the said polymer further contains a hydroxyalkyl (meth) acrylate unit and / or a polyoxyalkylene group containing (meth) acrylate unit.

  ADVANTAGE OF THE INVENTION According to this invention, the water-resistant antifouling coating material composition which can be excellent in water resistance, can maintain the antifouling effect over a long period of time, and can form the coating film excellent in adhesiveness can be provided.

  The aqueous antifouling coating composition of the present invention is a resin containing an organic hydrazine compound containing at least two hydrazine residues and a polymer containing a carbonyl group-containing ethylenically unsaturated monomer unit as a resin component. It consists of an aqueous dispersion. As this polymer, a vinyl polymer can be preferably used. Here, the vinyl polymer is a polymer obtained by so-called vinyl polymerization, in which a compound having a carbon-carbon double bond (ethylenically unsaturated monomer) is polymerized by opening the double bond. Say.

  The water-based antifouling coating composition of the present invention contains such a resin component and an organic hydrazine compound, so that the carbonyl group in the resin component and the organic resin dispersed in the aqueous resin dispersion are blended when the coating film is dried. A crosslinking reaction proceeds with the hydrazino group of the hydrazine compound, and a coating film excellent in antifouling durability, water resistance and adhesion is formed. Moreover, since the hydrazino group bridge | crosslinked by the coating-film surface layer hydrolyzes in seawater, since the self-polishing property of a coating film is obtained, antifouling property can be expressed, without impairing adhesiveness.

  The content of the carbonyl group-containing ethylenically unsaturated monomer unit in the resin component (polymer component) is 0.5 to 15 masses when the total of the monomer units constituting the polymer is 100 mass parts. It is preferable that it exists in the range of a part, and the range of 1-10 mass parts is more preferable. When the content is 0.5 parts by mass or more, the antifouling durability, water resistance and adhesion of the coating are improved, and when the content is 15% by mass or less, the coating is not reduced in water resistance. The self-polishing property and adhesiveness of the film can be obtained with a good balance.

  Examples of the carbonyl group-containing ethylenically unsaturated monomer include acrolein, diacetone acrylamide, formyl styrene, vinyl alkyl ketone, and the like. The vinyl alkyl ketone is preferably a vinyl alkyl ketone having 4 to 7 carbon atoms, and examples thereof include vinyl methyl ketone, vinyl ethyl ketone, and vinyl isobutyl ketone. In addition, ((meth) acryloxyalkyl) propanal having 1-10 carbon atoms in the alkyl group, (meth) acrylamide, pivalin aldehyde, diacetone (meth) acrylate, acetonitrile acrylate, acetoacetoxyethyl (meth) acrylate, etc. Can be mentioned. In view of polymerization reactivity and crosslinking reactivity, it is particularly preferable to use diacetone acrylamide, acrolein, and vinyl methyl ketone. These may be used alone or in combination of two or more as required.

  The resin component (polymer component) of the aqueous antifouling coating composition of the present invention is an ethylenically unsaturated carboxylic acid monomer from the viewpoints of storage stability of the resin aqueous dispersion, blending stability, and self-polishing properties of the coating film. It is preferable to contain a monomer unit and / or a polymerizable polyvalent metal salt monomer unit.

  The content of these monomer units in the polymer of the resin component is in the range of 0.1 to 10 parts by mass when the total of the monomer units constituting the polymer is 100 parts by mass. Is preferable, and the range of 0.5 to 8 parts by mass is more preferable. When the content is 0.1 parts by mass or more, the storage stability of the aqueous resin dispersion is improved, and when a pigment or the like is added to the aqueous vinyl resin dispersion of the present invention, aggregates are generated. The problem can be avoided and the self-polishing property of the coating film is manifested. Moreover, self-polishing property and water resistance can be improved, without reducing storage stability and mixing | blending stability as this content is 10 mass parts or less. In addition, this content shows the total content of both monomer units, when a polymer contains both monomer units.

  Examples of the ethylenically unsaturated carboxylic acid monomer include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, vinylbenzoic acid, Acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxypropyl (meth) acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate, Monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl phthalate (meth) acrylate, monohydroxyethyl maleate (meth) acrylate, hydroxypropyl maleate (meth) Acrylate, tetrahydrophthalic acid mono-hydroxybutyl (meth) acrylate. These may be used alone or in combination of two or more as required.

As the polymerizable polyvalent metal salt monomer, a polymerizable carboxylic acid-based polyvalent metal salt, more specifically, a carboxylic acid-based metal salt having a (meth) acrylic acid metal salt structure can be used. Examples of the metal include multivalent metals such as magnesium, zinc, and copper. For example, magnesium acrylate [(CH ₂ ═CHCOO) ₂ Mg], magnesium methacrylate [(CH ₂ ═C (CH ₃ ) COO) ₂ Mg], zinc acrylate [(CH ₂ ═CHCOO) ₂ Zn], methacryl Zinc acid [(CH ₂ ═C (CH ₃ ) COO) ₂ Zn], copper acrylate [(CH ₂ ═CHCOO) ₂ Cu], copper methacrylate [(CH ₂ ═C (CH ₃ ) COO) ₂ Cu] (Meth) acrylic acid polyvalent metal salt, magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, copper acetate (meth) acrylate, monochloromagnesium acetate (meth) acrylate, monochlorozinc acetate (meth) acrylate, monochloro Copper acetate (meth) acrylate, magnesium monofluoroacetate (meth) acrylate, zinc monofluoroacetate ) Acrylate, copper monofluoroacetate (meth) acrylate, magnesium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meth) acrylate, magnesium caproate (meth) acrylate, zinc caproate (meth) Acrylate, copper caproate (meth) acrylate, magnesium caprylate (meth) acrylate, zinc caprylate (meth) acrylate, copper caprylate (meth) acrylate, magnesium 2-ethylhexylate (meth) acrylate, zinc 2-ethylhexylate ( (Meth) acrylate, copper 2-ethylhexylate (meth) acrylate, magnesium caprate (meth) acrylate, zinc caprate (meth) acrylate, copper caprate (meth) acrylate, Magnesium saticate (meth) acrylate, zinc versatate (meth) acrylate, copper versatate (meth) acrylate, magnesium isostearate (meth) acrylate, zinc isostearate (meth) acrylate, copper isostearate (meth) acrylate, palmitic acid Magnesium (meth) acrylate, zinc palmitate (meth) acrylate, copper palmitate (meth) acrylate, magnesium cresotate (meth) acrylate, zinc cresotate (meth) acrylate, copper cresotate (meth) acrylate, magnesium oleate ( (Meth) acrylate, zinc oleate (meth) acrylate, copper oleate (meth) acrylate, magnesium elaidate (meth) acrylate, elaidic acid Zinc (meth) acrylate, copper elaidate (meth) acrylate, magnesium linoleate (meth) acrylate, zinc linoleate (meth) acrylate, copper linoleate (meth) acrylate, magnesium linolenate (meth) acrylate, zinc linolenate ( (Meth) acrylate, copper linolenate (meth) acrylate, magnesium stearate (meth) acrylate, zinc stearate (meth) acrylate, copper stearolate (meth) acrylate, magnesium ricinoleate (meth) acrylate, zinc ricinoleate (Meth) acrylate, copper ricinoleate (meth) acrylate, magnesium ricinoelaidate (meth) acrylate, zinc ricinoelaidate (meth) acrylate, copper ricinoelaidate (meth) acrylate , Magnesium brassinate (meth) acrylate, Zinc brassiete (meth) acrylate, Copper brassate (meth) acrylate, Magnesium erucate (meth) acrylate, Zinc erucate (meth) acrylate, Copper erucate (meth) acrylate , Α-magnesium naphthoate (meth) acrylate, α-naphthoate zinc (meth) acrylate, α-naphthoic acid copper (meth) acrylate, β-magnesium naphthoate (meth) acrylate, β-naphthoic acid zinc (meth) acrylate , Β-naphthoic acid copper (meth) acrylate, magnesium benzoate (meth) acrylate, zinc benzoate (meth) acrylate, copper benzoate (meth) acrylate, 2,4,5-trichlorophenoxy magnesium acetate (meth) acrylate, 2, , 5-trichlorophenoxyacetic acid zinc (meth) acrylate, 2,4,5-trichlorophenoxyacetic acid copper (meth) acrylate, 2,4-dichlorophenoxyacetic acid magnesium (meth) acrylate, 2,4-dichlorophenoxyacetic acid zinc (meta ) Acrylate, 2,4-dichlorophenoxyacetic acid copper (meth) acrylate, quinolinecarboxylate magnesium (meth) acrylate, quinolinecarboxylate zinc (meth) acrylate, quinolinecarboxylate copper (meth) acrylate, magnesium nitrobenzoate (meth) Acrylate, zinc nitrobenzoate (meth) acrylate, copper nitrobenzoate (meth) acrylate, magnesium nitronaphthalenecarboxylate (meth) acrylate, zinc nitronaphthalenecarboxylate (meth) acrylate, (Meth) acrylic acid such as copper nitronaphthalenecarboxylate (meth) acrylate, magnesium puruvate (meth) acrylate, zinc puruvate (meth) acrylate, copper puruvate (meth) acrylate and other carboxylic acids and polyvalent metals And a polymerizable composite polyvalent metal salt. These may be used alone or in combination of two or more as required.

  Among these, those containing zinc are preferable from the viewpoint that the obtained polymerization product is highly transparent and a coating film having a beautiful color tone is obtained. In particular, zinc acrylate, zinc methacrylate, zinc oleate (meth) acrylate and zinc versatate (meth) acrylate are preferred.

  The resin component (polymer) of the water-based antifouling coating composition of the present invention is composed of hydroxyalkyl (meth) acrylate units and / or polyoxy from the viewpoint of blending stability of the resin aqueous dispersion and self-polishing properties of the coating film. It preferably contains an alkylene group-containing (meth) acrylate unit.

  The content of these monomer units in the polymer of the resin component is in the range of 0.1 to 30 parts by mass when the total of the monomer units constituting the polymer is 100 parts by mass. Is preferable, and the range of 0.5 to 20 parts by mass is more preferable. When the content is 0.1 parts by mass or more, the blending stability of the aqueous resin dispersion and the self-polishing property of the coating film are improved. When the content is 30 parts by mass or less, the coating film is not deteriorated. Self-polishing property and water resistance can be improved. In addition, this content shows the total content of both monomer units, when a polymer contains both monomer units.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl ( And (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like. These may be used alone or in combination of two or more as required.

  Examples of polyoxyalkylene group-containing (meth) acrylates include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (polyethylene glycol-polypropylene glycol) mono (meth) acrylate, and poly (ethylene glycol-propylene glycol). ) Mono (meth) acrylate, (polyethylene glycol-polytetramethylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, (polypropylene glycol-polytetramethylene glycol) mono (meth) Examples include acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, and the like. These may be used alone or in combination of two or more as required.

  The resin component (polymer) of the aqueous resin dispersion in the present invention is composed of the above three groups of monomers: (1) a carbonyl group-containing ethylenically unsaturated monomer, and (2) an ethylenically unsaturated carboxylic acid. Among the acid monomer and / or polymerizable polyvalent metal salt monomer, (3) hydroxyalkyl (meth) acrylate and / or polyoxyalkylene group-containing (meth) acrylate, the unit of monomer (1) As an essential component, it is preferable to use the monomer (2) or the monomer (3) in combination, and it is particularly preferable to use both the monomer (2) and the monomer (3). Even more excellent effects can be obtained.

  The resin component (polymer component) of the aqueous resin dispersion in the present invention is not limited to the above-mentioned three groups of monomer units, and other ethylenically unsaturated monomers (4) as necessary. The unit may be contained. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- Octyl (meth) acrylate, n-nonyl (meth) acrylate, i-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Of 1 to 18 carbon atoms (Meth) acrylates having cycloalkyl; cycloalkyl (meth) acrylates such as cyclohexyl acrylate and pt-butylcyclohexyl (meth) acrylate; hydroxycycloalkyl (meth) acrylates such as p-hydroxycyclohexyl acrylate; lactone modification Hydroxyalkyl (meth) acrylates; aminoalkyl (2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, etc. (Meth) acrylates; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylol proppant Multifunctional (meth) acrylates such as (meth) acrylate; dimethylaminoethyl (meth) acrylate methyl chloride salt, allyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, ( Other (meth) acrylic monomers such as meth) acrylamide, N-methylol (meth) acrylamide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene; vinyl acetate, vinyl propionate, etc. An aliphatic vinyl compound is mentioned. These may be used alone or in combination of two or more as required.

  The content of the unit of the above-mentioned ethylenically unsaturated monomer (4) in the resin component can be the remainder excluding the units of the above-mentioned monomers (1), (2) and (3). .

  As the above-mentioned ethylenically unsaturated monomer (4), an alkyl (meth) acrylate having an alkyl group having 1 to 10 carbon atoms can be suitably used from the viewpoint of cost, polymerizability, and desired characteristics. It is preferable to use a highly hydrophilic alkyl (meth) acrylate having 1 to 4 carbon atoms. The content of the alkyl (meth) acrylate having 1 to 4 carbon atoms in the resin component is, for example, 45 to 99.3 parts by mass when the total of the monomer units constituting the polymer is 100 parts by mass. It can set to the range of 62-90 mass parts. Depending on the desired properties, alkyl (meth) acrylates having 1 to 4 carbon atoms and other ethylenically unsaturated monomers may be used in combination.

  The glass transition temperature of the resin component of the aqueous resin dispersion in the present invention is not particularly limited, but from the viewpoint of non-adhesiveness and stain resistance of the coating film, the calculated glass transition temperature (Tg) determined by the Fox formula. ) Is preferably −30 ° C. or higher, and more preferably −20 ° C. or higher. Moreover, 70 degreeC or less is preferable and 60 degreeC or less is more preferable from the point of the crack resistance in environments, such as a temperature change repeated temperature change and a freeze-thaw state change.

  Here, the formula of Fox is the following relational expression regarding the glass transition temperature (° C.) of the copolymer.

1 / (273 + Tg) = Σ (Wi / (273 + Tgi))
(In the formula, Wi represents the mass fraction of monomer i, and Tgi represents the Tg (° C.) of the homopolymer of monomer i. The Tg value of the homopolymer is “Chemical Handbook Application” edited by the Chemical Society of Japan, 2nd edition. , Maruzen, 1966, can be used.

  The resin component of the aqueous resin dispersion in the present invention can be obtained by polymerizing by a known polymerization method such as a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. In particular, it is possible to obtain a water-resin aqueous dispersion in the form of an emulsion by an emulsion polymerization method from the viewpoint of various physical properties such as storage stability as water-based antifouling paint, hardness of coating film, water resistance, weather resistance, and stain resistance. preferable.

  In order to obtain an emulsion by an emulsion polymerization method, for example, a method in which a monomer mixture is supplied into a polymerization system in the presence of a surfactant and polymerization is performed with a water-soluble initiator, or for example, an organic peroxide A known method such as a method of polymerizing with a redox initiator in which a reducing agent such as sodium thiosulfate is combined can be used.

  Examples of the polymerization initiator include inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide; benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl hydroperoxide, t Organic peroxides such as butylperoxybenzoate and cumene hydroperoxide; 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2, Azo compounds such as 4-dimethylvaleronitrile); redox catalysts represented by combinations of inorganic peroxides and sodium bisulfite or Rongalite, organic oxides and sodium hydrogensulfate or Rongalite, and the like.

  The emulsion obtained by the emulsion polymerization method, after the polymerization, the stability of the system is adjusted by adjusting the pH of the system to neutral to weakly alkaline, that is, about pH 6.5 to 10.0 by adding a basic compound. Can be increased. As this basic compound, ammonia, triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane, 2-dimethylaminoethanol, ethylaminoethanol, 2-diethylaminoethanol, 1-amino-2-propanol, 2-amino -1-propanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propylaminoethanol, ethoxy Examples include propylamine, aminobenzyl alcohol, morpholine, sodium hydroxide, potassium hydroxide and the like.

  When adjusting the molecular weight of the resin component of the aqueous resin dispersion, the molecular weight is adjusted by using a known chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, or α-methylstyrene dimer. Is possible.

  Moreover, it is preferable that 0.1-10 mass parts of surfactant is included with respect to 100 mass parts of resin components, and, as for resin aqueous dispersion, 0.5-8 mass parts is more preferable. When the surfactant is present in an amount of 0.1 part by mass or more, the storage stability as a water-based antifouling paint is improved, and when emulsion polymerization is performed in the presence of a surfactant, the stability during polymerization is also improved. Further, by setting the surfactant to 10 parts by mass or less, sufficient stability at the time of blending into a paint and stability over time can be obtained without impairing water resistance.

  Examples of the surfactant include various conventional anionic, cationic, or nonionic surfactants, and further a polymer emulsifier, and also has an ethylenically unsaturated bond in the surfactant component. So-called reactive emulsifiers can also be used.

  The water-based antifouling coating composition of the present invention can be obtained by blending an organic hydrazine compound containing at least two hydrazine residues with the aqueous resin dispersion obtained by the various methods described above. By blending such an organic hydrazine compound having a specific structure, the water resistance of the coating film is improved, and a particularly excellent balance between self-polishing properties and adhesiveness can be realized.

  The amount of the organic hydrazine compound containing at least two or more hydrazine residues is preferably in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin component of the aqueous resin dispersion. The range of 5 to 12 parts by mass is more preferable. When the content is 0.1 parts by mass or more, the antifouling durability, water resistance, and adhesion of the coating are improved, and when the content is 15% by mass or less, the coating is not reduced in water resistance. The self-polishing property and adhesiveness of the film can be obtained with a good balance. The hydrazine residue includes a hydrazino group.

  Examples of the organic hydrazine compound containing two or more hydrazine residues include 2 carbon atoms such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine. To 15 alkylene dihydrazine compounds; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, isophthalic acid dihydrazide hydrazide, etc. Dihydrazide of a dicarboxylic acid having 2 to 15 carbon atoms; 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 1,3-bis (hydrazinocarboethyl) -5- (2-methylmercaptoethyl) hydantoin , 1- Organic hydrazine compounds having a Dora Gino carboxymethyl ethyl-3 hydrazinocarboethyl-isopropyl-5- (2-methyl-mercaptoethyl) hydantoin skeleton such hydantoin and the like. These may be used alone or in combination of two or more as required. Among them, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin having the highest hydrophilicity is particularly preferable.

  The compounding ratio of the organic hydrazine compound to the resin component of the aqueous resin dispersion is such that the carbonyl group of the carbonyl group-containing ethylenically unsaturated monomer unit of the resin component is 1 mol of the hydrazino group of the organic hydrazine compound. It is more preferable to mix | blend so that it may become 0.5-4 mol, 0.5-3 mol is more preferable, and 1-3 mol is further more preferable. Thereby, as above-mentioned, at the time of drying of a coating film, a crosslinking reaction advances between a carbonyl group and a hydrazino group, and antifouling durability, water resistance, and adhesiveness of a coating film improve. Moreover, the self-polishing property, water resistance, and adhesiveness of the coating film can be obtained in a well-balanced manner by hydrolyzing the hydrazino group crosslinked in the coating film surface layer in seawater.

  The aqueous antifouling coating composition of the present invention is usually used in the range where the solid content in the aqueous resin dispersion is 20 to 80% by mass.

  The water-based antifouling coating composition of the present invention may further contain other antifouling agents as necessary. As this antifouling agent, it can be appropriately selected and used according to the required performance. For example, copper-based antifouling agents such as cuprous oxide, thiocyanic copper, copper powder, lead, zinc, nickel, etc. Metal compounds, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, pyridine compounds, and the like. These can be used singly or in combination of two or more. More specifically, Manganese ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroiso Phthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rhodan copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N , N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2,4, 6-trichlorophenylmaleimide 2,3,5,6-tetrachloro- 4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatrisulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4 -Thiazolyl) -benzimidazole, pyridine-triphenylborane.

  The water-based antifouling coating composition of the present invention is provided with lubricity on the surface of the coating film to prevent the adhesion of organisms, and silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbons. Etc. can be blended. Further, the antifouling coating composition of the present invention comprises various pigments, antifoaming agents, pigment dispersants, leveling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, slips Agents, preservatives, plasticizers, other emulsion resins, water-soluble resins, viscosity control agents, and the like.

  The coating film using the water-based antifouling coating composition of the present invention can be applied directly to the surface of a substrate such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base. It can be formed through a film. The undercoat film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, an intermediate coating, or the like. The method for forming a coating film is to apply the aqueous antifouling coating composition on the surface of the substrate or the base coating on the substrate by means of brush coating, spray coating, roller coating, submersion coating or the like. it can. The coating amount can generally be set to an amount that gives a thickness of 10 to 400 μm as a dry coating film. The coating film can be usually dried at room temperature, and may be heat-dried as necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these. In the following description, “part” is based on weight.

<Examples of acrylic emulsion production>
(Production Example A1)
100 parts by mass of a monomer mixture composed of monomers corresponding to the polymer composition shown in Table 1 below, 2 parts by mass of a surfactant and 35 parts by mass of deionized water are sufficiently mixed to prepare a pre-polymer in a uniform emulsified state. An emulsion (hereinafter abbreviated as “PE solution”) was prepared.

  In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 70 parts by mass of deionized water, 1 part by mass of a surfactant, and 10 parts by mass of PE solution are added, and the internal temperature of the reaction vessel is set to 80 ° C. After raising the temperature, 0.1 part by mass of ammonium persulfate dissolved in 1 part by mass of deionized water was added and maintained for 1 hour. This produced seed particles.

  Next, the remaining PE solution and 0.2 parts by weight of sodium persulfate dissolved in 10 parts by weight of deionized water were placed in the reaction vessel over 3 hours while maintaining the internal temperature of the reaction vessel at 80 ° C. Drops were added in parallel, and after completion of the addition, the internal temperature was maintained at 80 ° C. for 2 hours to complete the reaction.

  After completion of the reaction, the mixture was cooled to 60 ° C., and a 28 mass% aqueous ammonia solution was added so that the pH of the emulsion was between 8 and 10.

  While maintaining the internal temperature of the reaction vessel at 60 ° C., a solution prepared by dissolving 2.5 parts by mass of 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin in 8 parts by mass of deionized water was put into the reaction vessel. For 30 minutes to obtain the desired emulsion A1. The obtained emulsion A1 had a solid content of 45.1% by mass, a viscosity of 980 mPa · s, a pH of 9.3, and an average particle size of 120 nm.

(Production Examples A2 to A9, B2 to B4)
In the same manner as in Production Example 1, emulsions A2 to A9 and B2 having the compositions shown in Table 1 below were produced. The solid content, viscosity, and pH of the obtained emulsion are shown in Table 1 below.

(Production Example B1)
100 parts by mass of a monomer mixture composed of monomers corresponding to the polymer composition shown in Table 1 below, 2 parts by mass of a surfactant, and 35 parts by mass of deionized water are sufficiently mixed to form PE in a uniform emulsified state. A liquid was prepared.

  In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 70 parts by mass of deionized water, 1 part by mass of a surfactant, and 10 parts by mass of PE solution are added, and the internal temperature of the reaction vessel is set to 80 ° C. After raising the temperature, 0.1 part by mass of ammonium persulfate dissolved in 1 part by mass of deionized water was added and maintained for 1 hour. This produced seed particles.

  Next, the remaining PE solution and 0.2 parts by weight of sodium persulfate dissolved in 10 parts by weight of deionized water were placed in the reaction vessel over 3 hours while maintaining the internal temperature of the reaction vessel at 80 ° C. Drops were added in parallel, and after completion of the addition, the internal temperature was maintained at 80 ° C. for 2 hours to complete the reaction.

  After the completion of the reaction, the mixture is cooled to 60 ° C., 28 mass% aqueous ammonia solution and 6 parts by mass of deionized water are added so that the pH of the emulsion is between 8 and 10, and stirred for 30 minutes to obtain the desired emulsion B1. It was. The obtained emulsion B1 had a solid content of 44.8% by mass, a viscosity of 320 mPa · s, a pH of 9.1, and an average particle size of 125 nm.

DAAm: diacetone acrylamide,
t-BMA: Tertiary butyl methacrylate
MMA: methyl methacrylate MAA: methacrylic acid,
Zn (MAA) ₂ : zinc methacrylate 2-HEMA: 2-hydroxyethyl methacrylate,
Blemmer 70PEP350B: hydroxy (polyethylene glycol-polypropylene glycol) monomethacrylate (trade name, manufactured by NOF Corporation),
i-BMA: isobutyl methacrylate,
2-EHA: 2-ethylhexyl acrylate,
n-BA: normal butyl acrylate,
VDH (Amicure VDH): 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.),
ADH: adipic acid dihydrazide,
SANNOL NP-2030: an anionic emulsifier (trade name, manufactured by Lion Corporation),
ADEKA rear soap SE-10N: reactive anionic surfactant (trade name, manufactured by Asahi Denka Co., Ltd.).

<Preparation of water-based antifouling paint composition>
Next, using the emulsions A1 to A9 thus obtained, aqueous antifouling paint compositions (Examples 1 to 9) of the present invention were prepared according to the blending ratios shown in Table 2. Moreover, the aqueous | water-based antifouling paint composition of Comparative Examples 1-4 was prepared by the mixture ratio shown in Table 2 using emulsion B1-B4. The aqueous antifouling paint composition was prepared according to the following method.

  196.3 g of cuprous oxide, 2 g of pigment dispersant (trade name: OROTAN SG-1, manufactured by Rohm & Haas Co., Ltd.), antifoaming agent (trade name: Surfynol DF-58, manufactured by Air Products Co., Ltd.) 0 .3 g, 29.4 g of propylene glycol, 34.3 g of deionized water, and 1.8 g of 28% by weight aqueous ammonia solution are thoroughly mixed, and then glass beads are added and pigment dispersion is performed for 30 minutes with a high-speed disperser. Etc. were separated by filtration with a 300-mesh nylon scissor to obtain a mill base for evaluation.

  Next, 55 g of the above-mentioned mill base for evaluation, 2 g of a film-forming aid (trade name: Kyowanol M, manufactured by Kyowa Hakko Co., Ltd.), thickener (product) for 40 g of emulsion (based on a solid content of 45% by mass) Name: 0.5 g of RHEOLATE 350, manufactured by RHEOX Co., Ltd.) was mixed and sufficiently stirred, and 2.5 g of deionized water was added and stirred. Thereafter, filtration was again performed using a 300 mesh nylon bag to obtain an aqueous antifouling paint composition.

  Next, using each of the water-based antifouling paint compositions prepared as described above, a coating film wear degree test, an antifouling test, a water resistance test, and a cross-cut peel test (adhesion test) are performed as follows. It was.

(1) Degree of wear test of coating film Each coating composition was applied to a hard vinyl chloride plate of 50 mm x 50 mm x 2 mm (thickness) with an applicator so as to have a dry film thickness of 120 µm. The test plate was attached to a rotating drum installed in seawater, rotated at a peripheral speed of 7.7 m / s, and the consumed film thickness was measured every 6 months for 12 months. The results are shown in Table 3.

(2) Antifouling test Each water-based paint composition was applied to a sandblasted steel plate that had been coated with a rust-preventive paint in advance so that the dry film thickness was 120 μm. It was immersed in Hiroshima Bay in Hiroshima Prefecture for 24 months, and the adherent area (area ratio (%) with respect to the entire test plate) of the attached organisms was examined every 6 months. The results are shown in Table 3.

(3) Water resistance test The aqueous antifouling paint compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were applied on a sandblasted steel plate to which a rust preventive paint had been applied in advance so that the dry film thickness was 120 μm. Thus, a test plate was produced.

  The test plate was immersed in sterilized filtered seawater for 6 months, then dried at room temperature of 20 ° C. for 1 week, and the coating surface was observed.

  The case where there was no crack or peeling was indicated as ◎, the case where there was only a part of crack, ○, the case where there was partly peeled, Δ, and the case where crack occurred and peeling occurred over the entire surface. The results are shown in the table.

(4) Cross-cut peel test After a test plate prepared in the same manner as the above water resistance test is immersed in sterilized filtered seawater for 6 months, it is dried at room temperature of 20 ° C. for one week, and a cross-cut peel test is performed. went. The results are shown in Table 3.

Cross-cut peel test is to make 25 cuts of 2mm ² with cross cuts reaching the base material at intervals of 2mm, then apply cello tape (registered trademark) on it and peel off rapidly to determine the state of peeled cross-cuts did.

  The case where there is no crossing of the cross-cuts and the corners of the cross-cuts are marked ◎, and the case where only the corners of the cross-cuts are peeled off is ○, and the number of peeled cross-cuts is 1 to 12 Was marked with △, and the number of peeled grids was 13-25.

  Water-based antifouling paint composition (Comparative Example 2) using an emulsion (B2) containing no carbonyl group-containing ethylenically unsaturated monomer unit as a resin component, and containing at least two hydrazine residues in the molecule A water-based antifouling paint composition (Comparative Examples 3 and 4) using an emulsion (B3, B4) that does not contain an organic hydrazine compound, a resin component containing no carbonyl group-containing ethylenically unsaturated monomer unit, and The aqueous antifouling paint composition (Comparative Example 1) using the emulsion (B1) containing no organic hydrazine compound had low long-term antifouling properties and insufficient water resistance and adhesion.

  On the other hand, the emulsion contains an organic hydrazine compound containing at least two hydrazine residues in the molecule, and uses emulsions A1 to A9 containing a carbonyl group-containing ethylenically unsaturated monomer unit in the resin component. About the water-based antifouling coating composition (Examples 1 to 9), an appropriate degree of wear of the coating film was observed, the long-term antifouling property was good, and the water resistance and adhesion were also good. In particular, the coating compositions having a high degree of coating film consumption (Examples 5, 6 and 7) had good balance between water resistance and adhesion and long-term antifouling properties.

  The coating composition of the present invention has excellent water resistance in seawater, can maintain an antifouling effect over a long period of time, and can form a coating film having excellent adhesion, so that it is very useful as an antifouling agent for members used in seawater. Useful for.

Claims (5)

An organic hydrazine compound containing at least two hydrazine residues;
A resin component;
Including an antifouling agent,
The resin component is a polymer containing a monomer unit (1), a monomer unit (2) and a monomer unit (3),
The monomer unit (1) is a carbonyl group-containing ethylenically unsaturated monomer unit ,
The monomer unit (2) is an ethylenically unsaturated carboxylic acid monomer unit , or an ethylenically unsaturated carboxylic acid monomer unit and a polymerizable polyvalent metal salt monomer unit ,
Monomer units (3) are hydroxyalkyl (meth) acrylate unit and / or a polyoxyalkylene group-containing (meth) acrylate units,
The content of the monomer unit (3) is 0.1 to 30 parts by mass when the total of the monomer units constituting the polymer is 100 parts by mass,
The antifouling paint composition for an aqueous ship bottom, wherein the carbonyl group of the carbonyl group-containing ethylenically unsaturated monomer unit of the resin component is 0.5 to 4 mol with respect to 1 mol of the hydrazino group of the organic hydrazine compound.   2. The antifouling paint composition for an aqueous ship bottom according to claim 1, wherein the content of the organic hydrazine compound is in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin component.   The content of the carbonyl group-containing ethylenically unsaturated monomer unit in the resin component is in the range of 0.5 to 15 parts by mass with respect to 100 parts by mass in total of the monomer units constituting the resin component. The antifouling paint composition for an aqueous ship bottom according to claim 1 or 2.   The aqueous antifouling paint composition for an aqueous ship bottom according to any one of claims 1 to 3, wherein the carbonyl group-containing ethylenically unsaturated monomer unit is a unit of diacetone acrylamide.   The antifouling paint composition for an aqueous ship bottom according to any one of claims 1 to 4, wherein the ethylenically unsaturated carboxylic acid monomer unit is a unit of methacrylic acid.