JP2010077238A - Aqueous antifouling coating composition, antifouling coated film, ship and underwater structure, and antifouling method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous antifouling coating composition exhibiting extremely superior antifouling properties not only at the wholly immersed time but also at the water line part at a semi-submerged time, to provide an antifouling coated film comprising the aqueous antifouling coating composition, and to provide a ship and an underwater structure, having the antifouling coated film. <P>SOLUTION: The aqueous antifouling coating composition contains a first antifouling agent and binder resin particles (A), and the first antifouling agent is included in the binder resin particles (A). The antifouling coated film comprises the aqueous antifouling coating composition. The ship and the underwater structure have the antifouling coated film. The binder resin particle (A) preferably has curability. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous antifouling paint composition having improved antifouling properties. The present invention also relates to an antifouling coating film comprising the water-based antifouling coating composition, and a ship and an underwater structure having the antifouling coating film. The present invention further relates to an antifouling method using the aqueous antifouling coating composition.

  Marine creatures such as barnacles, mussels, and algae are likely to adhere to underwater structures such as ships and fishing nets, thereby causing problems such as hindering efficient operation and causing waste of fuel. In addition, problems such as clogging in fishing nets and shortened service life occur. In order to prevent organisms from adhering to these ships and underwater structures, an antifouling coating is formed on the surfaces of the ships and underwater structures. As an antifouling paint used for forming such an antifouling coating film, for example, an organic solvent type coating composition containing a non-curable resin has been used. Here, the “organic solvent-type coating composition” means a coating composition mainly using an organic solvent as a solvent.

Both the water-based antifouling coating compositions described in Patent Documents 1 and 2 contain an aqueous binder component having curability. In Patent Document 1, by selecting a curing system, and in Patent Document 2, by using an antifouling agent paste containing a water-soluble dispersion resin and an antifouling agent, an antifouling agent is obtained from each cured film. The agent can be eluted relatively easily. However, although it has excellent antifouling properties when all of the object to be coated is immersed in seawater (when fully submerged), the draft when part of the object to be coated is immersed in seawater (when semi-submerged) The antifouling property of the part was insufficient, and there was room for improvement regarding the antifouling property.
JP 2006-182955 A JP 2006-182956 A

  The present invention has been made in order to solve the above-mentioned problems, and the object thereof is an aqueous antifouling paint composition having excellent antifouling properties, which is only antifouling at the time of total immersion. In addition, an object is to provide a water-based antifouling paint composition having extremely good antifouling properties in the draft section during semi-submersion. Another object of the present invention is to provide an antifouling coating film comprising the water-based antifouling coating composition, and a ship and an underwater structure having the antifouling coating film. Still another object of the present invention is to provide an antifouling method using the water-based antifouling coating composition.

  As a result of intensive studies, the present inventors have found that the water-resistant antifouling paint composition described in Patent Documents 1 and 2 has an insufficient antifouling property in the draft portion of the water-based antifouling paint composition. Although the antifouling agent contained in the antifouling agent or antifouling agent paste is stably dispersed, it exists as a particle separate from the binder resin particles. It was thought that the area | region where a dirt agent exists and the area | region which does not exist are formed, and it originates in a marine organism beginning to start from the area | region where the said antifouling agent does not exist. And in order to solve the said subject, the antifouling agent should be included in the binder resin component itself constituting the antifouling coating film, thereby providing antifouling properties over the entire area of the antifouling coating film. In addition to obtaining the idea, it was confirmed that good antifouling properties were exhibited regardless of the curability of the binder resin, and the present invention was completed. That is, the present invention is as follows.

  The present invention relates to an aqueous antifouling coating composition containing a first antifouling agent and binder resin particles (A), wherein the first antifouling agent is encapsulated in the binder resin particles (A). It is a water-based antifouling paint composition characterized by being in contact. Here, the binder resin constituting the binder resin particles (A) may have curability. In addition, that binder resin has curability means having the property to harden | cure in presence or absence of a hardening | curing agent. When this binder resin does not have curability by itself, it is preferable that the water-based antifouling paint composition of the present invention further has a curing agent (B).

  Moreover, the water-based antifouling paint composition of the present invention may further contain a second antifouling agent that is not included in the binder resin particles (A), or the second antifouling agent and a water-soluble composition. An antifouling agent paste (C) containing an adhesive resin may be further contained.

  The mass ratio of the first antifouling agent to the solid content of the binder resin particles (A) (first antifouling agent / binder resin particles (A)) is 2/98 to 70/30. preferable.

  The mass ratio (first antifouling agent / second antifouling agent) between the content of the first antifouling agent and the content of the second antifouling agent is 3/97 to 40/60. Preferably there is.

  The first antifouling agent and the second antifouling agent are each independently zinc oxide, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt. , Triphenylboron pyridine salt, tetraethylthiuram disulfide (TET), stearylamine-triphenylboron, triphenyl [3- (2-ethylhexyloxy) propylamine] boron (OPA) and bisdaicene Or it is preferable that they are 2 or more types of antifouling agents.

  When the binder resin particles (A) contained in the aqueous antifouling paint composition of the present invention have curability and the aqueous antifouling paint composition of the present invention contains a curing agent (B), the binder resin particles (A) is preferably made of a resin having a functional group capable of reacting with at least one functional group or site of the curing agent (B). The functional group capable of reacting with at least one functional group or site of the curing agent (B) is one or more functional groups selected from the group consisting of a carbonyl group, an acetoacetoxy group and an alkoxysilyl group. It is preferably a group.

  Further, when the binder resin particles (A) have curability and the curing agent (B) is not used, the binder resin particles (A) are resins having a property of curing in the absence of the curing agent, that is, The binder resin is preferably made of a resin having a functional group capable of causing a curing reaction. Examples of such functional groups include higher unsaturated fatty acid-derived groups and alkoxysilyl groups, and the binder resin may contain one or more of these functional groups.

  The binder resin particle (A) enclosing the first antifouling agent polymerizes one or more monomers in an aqueous medium in the presence of the first antifouling agent and a polymerization initiator. It is preferable that it is obtained by this.

  The present invention also provides an antifouling coating film using the water-based antifouling coating composition described above, and a ship and an underwater structure having the antifouling coating film.

  Furthermore, this invention provides the antifouling method of the to-be-coated article which forms an antifouling coating film on the surface of the to-be-coated article using any of the above-described aqueous antifouling paint compositions.

  ADVANTAGE OF THE INVENTION According to this invention, not only the antifouling property at the time of full immersion but the antifouling property in the drafting part at the time of half immersion is very favorable is provided. Further, according to the present invention, it is possible to reduce the antifouling agent while maintaining the same antifouling property. According to the water-based antifouling paint composition of the present invention, it is applied to the surface of a ship or an underwater structure to form an antifouling coating film, thereby adhering marine organisms when fully submerged or semi-submerged. Can be effectively suppressed.

<< Water-based antifouling paint composition >>
The aqueous antifouling paint composition of the present invention is an aqueous antifouling paint composition containing a first antifouling agent and binder resin particles (A), wherein the first antifouling agent is the binder resin. It is characterized by being enclosed in the particles (A). By including the antifouling agent in the binder resin particles, the antifouling agent is present over the entire surface of the obtained antifouling coating film, so that the antifouling property, particularly when the article to be coated is semi-submerged. The antifouling property in the draft section is improved. Hereinafter, each component contained in the water-based antifouling coating composition of the present invention will be described in detail.

<Binder resin particles (A)>
The aqueous antifouling paint composition of the present invention contains binder resin particles (A) in which a first antifouling agent is included. Here, “the first antifouling agent is included” means a state in which the first antifouling agent has entered the binder resin particles (A). The inclusion of the first antifouling agent by the binder resin particles (A) should be confirmed using a transmission electron microscope (TEM), a field emission scanning electron microscope (FE-SEM) or solid state NMR. Can do. In the present specification, the “first antifouling agent” is distinguished from the following “second antifouling agent”, and the antifouling agent encapsulated in the binder resin particles (A). Say dirt. The “second antifouling agent” refers to an antifouling agent that is not included in the binder resin particles (A).

  The binder resin constituting the binder resin particles (A) may or may not have curability. When it has sclerosis | hardenability, the sclerosis | hardenability of binder resin to cure | harden at normal temperature when the usage form of a coating material is considered is preferable. The coating composition containing a binder resin that can be cured at room temperature can proceed with the curing reaction after coating, for example, by natural drying or forced drying by heating.

  The binder resin according to the present invention can be dispersed in water using an emulsifier or the like, or has a functional group in the resin for dispersion / emulsification in water, and can be dispersed / emulsified in water. ing. The functional group for dispersing and emulsifying in water is not particularly limited, and examples thereof include acidic groups such as carboxyl groups and sulfonic acid groups and basic groups such as amino groups. As the acidic group, a carboxyl group is particularly preferable. Further, a polyethylene oxide unit can be added to the resin and dispersed or emulsified in water. When the functional group for dispersing and emulsifying in water is an acidic group, these acidic groups are not particularly limited, but the acid value of the binder resin is preferably included in the range of 300 mgKOH / g or less, more preferably. Is 1-60 mg KOH / g. Also in the case of the basic group, it can be set in the same manner as the acidic group.

  When the functional group for dispersing and emulsifying in water is an acidic group, it can be dispersed and emulsified in water by adding a base to the binder resin and neutralizing. When the functional group for dispersing and emulsifying in water is a basic group, it can be dispersed and emulsified in water by adding an acid to the binder resin to neutralize it.

  When the binder resin does not have curability, the design needs to be designed so as to ensure water resistance when it is formed into a coating film. For example, when the binder resin is an emulsion resin, this design can be performed by adjusting the glass transition point and the solubility parameter of the monomer component used to obtain the emulsion resin.

  When the binder resin according to the present invention is curable, the binder resin contains a functional group that contributes to the curing reaction (hereinafter referred to as a cured functional group). When the water-based antifouling coating composition contains the curing agent (B), the curing functional group reacts with a specific functional group or site of the curing agent (B), and the curing reaction proceeds.

  Examples of the curing reaction exhibited by the binder resin include a dehydration condensation reaction, an addition reaction, and an oxidative polymerization reaction. Hereinafter, the binder resin showing each curing reaction will be described in more detail.

(Binder resin that cures by dehydration condensation reaction)
Since the dehydration condensation reaction is an equilibrium reaction that generates water, the curing reaction proceeds when water is removed by drying. Furthermore, when the coating film hardened | cured by the dehydration condensation reaction is immersed in water, decomposition | disassembly which is a reverse reaction of hardening reaction advances by the presence of a large amount of water. By balancing this curing / decomposition equilibrium, the antifouling agent can be efficiently released while maintaining water resistance.

  When the binder resin is cured by a dehydration condensation reaction, examples of the curing system include a carbonyl / hydrazide system, an acetoacetoxy / amine system, and an alkoxysilyl condensation system.

  The carbonyl / hydrazide curing system is, for example, a curing system utilizing a dehydration condensation reaction between a carbonyl group-containing resin that is a binder resin and a hydrazide compound that is a curing agent. The carbonyl group-containing resin is not particularly limited as long as it is a resin having at least one aldo group and / or keto group, acrylic resin, polyester resin (including alkyd resin), urethane resin, epoxy resin, and modified products thereof. / Complex etc. can be mentioned. Of these, a carbonyl group-containing acrylic resin is preferred from the standpoint of water resistance and physical properties of the coating film. The curing agent will be described later.

  The carbonyl group-containing acrylic resin is not particularly limited. For example, acrolein, diacetone acrylamide (diacetone acrylamide), diacetone methacrylamide (diacetone methacrylamide), formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone Aldo groups and / or keto groups such as acryloxyalkyl propanals, methacryloxyalkyl propanals, diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol acrylate acetyl acetate The ethylenically unsaturated monomer contained in the polymer is homopolymerized, or two or more of these listed monomers are selected for copolymerization. There can be prepared by copolymerization with other copolymerizable ethylenically unsaturated monomer.

  The ethylenically unsaturated monomer containing an aldo group and / or keto group is preferably used at a ratio such that the carbonyl group in the obtained resin is 0.02 to 2 mmol per 1 g of resin solid content. If it is less than 0.02 mmol, curing reactivity becomes insufficient, so that sufficient water resistance may not be obtained. If it exceeds 2 mmol, other performance may be adversely affected.

  The acid value of the carbonyl group-containing acrylic resin that is a binder resin is preferably 300 mgKOH / g or less, and more preferably 1 to 60 mgKOH / g.

  The other copolymerizable ethylenically unsaturated monomer is not particularly limited. For example, (meth) acrylic acid ester, styrene, vinyl toluene and other aromatic monomers, vinyl acetate, vinyl propionate, Examples include vinyl esters such as vinyl persate, vinyl cyanides such as (meth) acrylonitrile, vinyl halides such as vinyl chloride and vinylidene chloride, and butadiene. Furthermore, various functional monomers such as (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acid phosphooxyethyl methacrylate, methacrylic acid 3-chloro-2-acid phosphooxypropyl, methylpropanesulfonic acid acrylamide, divinylbenzene, (poly) oxyethylene mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, allyl (meth) acrylate, (poly ) Oxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, γ- (meth) acryloxypro It can be exemplified Le trimethoxysilane.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth). Examples thereof include dodecyl acrylate.

  As the carbonyl group-containing acrylic resin, a carbonyl group-containing acrylic resin as described above neutralized with a base such as an amine may be used. When neutralizing with a base, the pH is preferably 10 or less.

  The carbonyl group-containing acrylic resin preferably has a number average molecular weight of 3000 or more. If the number average molecular weight is less than 3000, the water resistance may be lowered. The number average molecular weight is more preferably 10,000 or more. The number average molecular weight can be appropriately adjusted to a desired range by using a chain transfer agent, or by adjusting the polymerization initiator amount, polymerization temperature and the like to polymerize the resin.

  Next, the acetoacetoxy / amine curing system will be described. The acetoacetoxy / amine curing system is, for example, a curing system that utilizes a dehydration condensation reaction between an acetoacetoxy group-containing resin that is a binder resin and an amine compound that is a curing agent. Although it does not specifically limit as acetoacetoxy group containing resin, It is preferable that it is an acrylic resin similarly to carbonyl group containing resin. The acetoacetoxy group-containing acrylic resin is obtained by homopolymerizing, for example, a monomer containing an ethylenically unsaturated monomer containing an acetoacetoxy group, or with another copolymerizable ethylenically unsaturated monomer. It can be prepared by copolymerization.

  The ethylenically unsaturated monomer containing an acetoacetoxy group is not particularly limited, and examples thereof include acrylic acid esters and methacrylic acid esters having an acetoacetoxy group. Specific examples include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate. As other copolymerizable ethylenically unsaturated monomers, those exemplified for the carbonyl group-containing acrylic resin can be used here. The curing agent will be described later. In addition, it is preferable that the acid value of the acetoacetoxy group containing acrylic resin which is binder resin is 300 mgKOH / g or less, and it is more preferable that it is 1-60 mgKOH / g.

  The alkoxysilyl condensation curing system is a curing system in which the binder resin is an alkoxysilyl group-containing resin. The alkoxy group of the alkoxysilyl group is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. One to three of these alkoxy groups may be bonded to one Si atom. In the case of an alkoxysilyl condensation curing system, a curing agent is not always necessary.

  The alkoxysilyl group-containing resin can be obtained, for example, by homopolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group or by copolymerizing with another copolymerizable ethylenically unsaturated monomer. it can. The ethylenically unsaturated monomer having an alkoxysilyl group is not particularly limited. For example, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- Acryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyl Diethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinylto Examples include triethoxysilane, vinylmethyldiethoxysilane, trimethoxysilylstyrene, dimethoxymethylsilylstyrene, triethoxysilylstyrene, diethoxymethylsilylstyrene, and the like. As other copolymerizable ethylenically unsaturated monomers, those exemplified for the carbonyl group-containing acrylic resin can be used here.

  The acid value of the alkoxysilyl group-containing acrylic resin that is a binder resin is preferably 300 mgKOH / g or less, and more preferably 1 to 60 mgKOH / g.

  When the binder resin has an alkoxysilyl condensation type curing system, the aqueous antifouling coating composition may contain an acid and / or a base as a curing catalyst. Although it does not specifically limit as the said acid and a base, For example, the compound which has acid groups, such as a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the compound which has basic groups, such as an amino group, can be mentioned. As the compound having an acid group, a compound having a phosphoric acid group or a sulfonic acid group may be used because of its strong catalytic activity. The amino group is preferably a tertiary group in which two alkyl groups are bonded to a nitrogen atom. The alkyl groups may be the same or different, but those having 1 to 8 carbon atoms are particularly preferable. Specific examples of such an amino group include a dimethylamino group, a diethylamino group, a methylethylamino group, a dibutylamino group, and a dioctylamino group. The compound having an acid group or a basic group may be a resin having an acid group or a basic group, such as an ethylenically unsaturated monomer having at least one acid group or basic group. Can be obtained by polymerization using

  Further, another specific example of the acid as the curing catalyst is not particularly limited. For example, orthophosphoric acid, butyl phosphoric acid, octyl phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, 2,4-xylenesulfonic acid, Examples include low molecular weight compounds such as isophthalic acid, terephthalic acid, hydrochloric acid, formic acid, acetic acid, and lactic acid. If it gives another specific example of the base as a curing catalyst, it is not particularly limited, for example, ammonia, triethylamine, tributylamine, dibutylamine, ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, diethanolamine, Triethanolamine, choline hydroxide, benzylamine and the like.

  The molar ratio between the amount of alkoxysilyl group contained in the alkoxysilyl-containing resin and the acid and / or base is preferably in the range of 1/10 to 1 / 0.01. When the molar ratio exceeds 1 / 0.01, the curability becomes insufficient and the water resistance may be lowered. On the other hand, if the molar ratio is less than 1/10, the amount of unreacted acid and / or base increases, and the water resistance may decrease. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  Among the curing systems based on the dehydration condensation reaction, a carbonyl / hydrazide system is preferable because of good self-polishing properties due to the progress of decomposition of the reverse reaction of the curing reaction. The combination of / semicarbazide compound is more preferable.

(Binder resin cured by oxidative polymerization reaction)
When the binder resin has a curing system by oxidative polymerization reaction, the binder resin is a resin having a group derived from a higher unsaturated fatty acid, and the curing reaction involves a group derived from a higher unsaturated fatty acid contained in the binder resin. Preferably there is. In the aqueous antifouling paint composition containing the binder resin particles (A) comprising such a binder resin, the antifouling coating film obtained by oxidation polymerization of the unsaturated bond in the higher unsaturated fatty acid-derived group has a long chain. Since the hydrocarbon group has a structure in which an oxygen atom is cross-linked, the antifouling agent is easily eluted. This is thought to be because the structure in which long-chain hydrocarbon groups are cross-linked has a gentle network as compared with the cross-linked structure obtained by other curing systems.

  Examples of the resin having a higher unsaturated fatty acid-derived group include acrylic resins and alkyd resins. The resin having a higher unsaturated fatty acid-derived group is obtained by homopolymerizing, for example, an ethylenically unsaturated monomer having a higher unsaturated fatty acid-derived group or another copolymerizable ethylenically unsaturated monomer. It can be prepared by copolymerization. As other copolymerizable ethylenically unsaturated monomers, those exemplified for the carbonyl group-containing acrylic resin can be used here.

  The ethylenically unsaturated monomer having a higher unsaturated fatty acid-derived group is not particularly limited, and examples thereof include those obtained by reaction of a higher unsaturated fatty acid and a glycidyl group-containing ethylenically unsaturated monomer. Can do. The higher unsaturated fatty acid is not particularly limited, and examples thereof include myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. In addition, non-conjugated double bonds such as linseed oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, eno oil fatty acid, hemp oil fatty acid, cottonseed oil fatty acid, tall fatty acid, etc. Examples thereof include dry oil fatty acids and semi-dry oil fatty acids. In addition, a part of fatty acids having a conjugated double bond such as tung oil fatty acid can be used in combination. The average carbon number of the hydrocarbon portion of the higher unsaturated fatty acid is preferably 13-23.

  The glycidyl group-containing ethylenically unsaturated monomer is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, and methyl glycidyl methacrylate.

  The iodine value of the ethylenically unsaturated monomer having a higher unsaturated fatty acid-derived group is preferably 60 to 180, and more preferably 70 to 150. Moreover, it is preferable that the iodine value of the binder resin which has higher unsaturated fatty acid origin group is 5-100. When the iodine value of the binder resin having a higher unsaturated fatty acid-derived group exceeds 100, the coating surface is dried too quickly, so that the coating surface is cracked or the coating is not sufficiently cured. There is a risk. The acid value of the resin having a higher unsaturated fatty acid-derived group that is a binder resin is preferably 300 mgKOH / g or less, and more preferably 1 to 60 mgKOH / g.

  When the binder resin has a curing system based on an oxidative polymerization reaction, the aqueous antifouling coating composition preferably further contains a dryer. The dryer functions to crosslink unsaturated bonds of higher unsaturated fatty acid-derived groups. The dryer is not particularly limited as long as it is usually used for paints, but cobalt, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, cerium, nickel, tin, etc. Naphthenates, octylates, resinates and the like. The amount of the dryer is usually 0.005 to 5 parts by mass with respect to 100 parts by mass of the binder resin solid content.

(Binder resin cured by addition reaction)
When the binder resin is cured by an addition reaction, examples of the curing system include a urethane / urea system, a carbodiimide / carboxyl system, and a Michael addition system.

  The urethane / urea curing system is, for example, a curing system that utilizes an addition reaction between a hydroxyl group and / or amino group-containing resin that is a binder resin and a polyisocyanate compound that is a curing agent. Examples of the hydroxyl group and / or amino group-containing resin include acrylic resins, polyester resins, urethane resins, polyether resins, and polycarbonate resins. The curing agent will be described later.

  The hydroxyl group and / or amino group-containing acrylic resin is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, 2-hydroxyethyl ( Ethylenically unsaturated monomers having a hydroxyl group such as ε-caprolactone adduct of (meth) acrylate (for example, “Placcel FM1”, “Placcel FA1” manufactured by Daicel Chemical Industries, Ltd.); Ethylene having an amino group such as allylamine and vinylamine It can be prepared by homopolymerizing a polymerizable unsaturated monomer or the like, or by copolymerizing with another copolymerizable ethylenically unsaturated monomer. As other copolymerizable ethylenically unsaturated monomers, those exemplified for the carbonyl group-containing acrylic resin can be used here.

  The acid value of the hydroxyl group and / or amino group-containing resin as the binder resin is preferably 300 mgKOH / g or less, and more preferably 1 to 60 mgKOH / g.

  The carbodiimide / carboxyl curing system is, for example, a curing system that utilizes an addition reaction between a carboxyl group-containing resin that is a binder resin and a polycarbodiimide compound that is a curing agent. The carboxyl group-containing resin is not particularly limited, and examples thereof include a carboxyl group-containing acrylic resin, a carboxyl group-containing polyester resin, a carboxyl group-containing alkyd resin, and a carboxyl group-containing polyurethane resin. When the carboxyl group-containing resin is an acrylic resin, an ethylenically unsaturated monomer containing a carboxyl group such as acrylic acid or methacrylic acid is homopolymerized, or other copolymerizable ethylenically unsaturated monomer and Can be prepared by copolymerization. As other copolymerizable ethylenically unsaturated monomers, those exemplified for the carbonyl group-containing acrylic resin can be used here.

  The Michael addition curing system utilizes, for example, an addition reaction between a compound having an active methylene group and / or an active methine group as a binder resin and a compound having a plurality of α, β-unsaturated carbonyl groups as a curing agent. It is a curing system. Examples of the compound having an active methylene group and / or an active methine group include acetoacetic acid, malonic acid, cyanoacetic acid, and derivatives thereof. The derivative is not particularly limited, and examples thereof include a reaction product of a polyol and the above compound.

  When the binder resin is cured by an addition reaction, if the addition reaction proceeds excessively, the antifouling agent encapsulated in the binder resin particles (A) may be difficult to elute. For this reason, when binder resin hardens | cures by addition reaction, it is preferable to control the elution property of an antifouling agent by adjusting the quantity of a hardening functional group. Moreover, it is also possible to control the elution property of an antifouling agent by using together the water-soluble resin mentioned later. The water-soluble resin used in this case is preferably one that does not participate in the addition reaction of the binder resin.

  The binder resin particles (A) made of the binder resin as described above enclose a first antifouling agent to be described later. The average particle diameter of the binder resin particles (A) is not particularly limited, but can be, for example, about 100 nm to 60 μm. In the present invention, the antifouling property of the antifouling coating composition can be improved regardless of the average particle diameter of the binder resin particles (A), but sufficient antifouling agent elution rate can be maintained. From the viewpoint of ensuring the effect of improving soiling properties, the average particle size of the binder resin particles (A) is preferably 150 nm to 25 μm. The particle size of the binder resin particles (A) can be controlled by appropriately adjusting conditions such as the stirring speed during emulsification, the initiator concentration, and the monomer concentration. In the present specification, the “average particle diameter of the binder resin particles (A)” means, for example, a binder resin particle (including a first antifouling agent) prepared by a method as described below ( It is a volume average particle diameter obtained when the aqueous emulsion resin liquid containing A) is measured using an electrophoretic light scattering photometer (for example, “ELS-800” manufactured by Otsuka Electronics Co., Ltd.).

<First antifouling agent>
It does not specifically limit as a 1st antifouling agent included in binder resin particle (A), A well-known thing can be used, for example, the organic compound which does not contain an inorganic compound, a metal, and a metal Etc.

  Specific examples of the antifouling agent include, for example, zinc oxide (zinc white), cuprous oxide, manganese ethylenebisdithiocarbamate, zinc dimethylcarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino -S-triazine, 2,4,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rhodan copper, 4,5, -dichloro-2-n-octyl-3 ( 2H) isothiazolone (for example, “Sea Nine 211” (trade name) manufactured by Rohm and Haas), N- (fluorodichloromethylthio) phthalimide, 1,1-dichloro-N-[(dimethylamino) sulfonyl] -1-fluoro -N-phenylmethanesulfenamide ("Prevento" manufactured by LANXESS) A4S "(trade name)), 1,1-dichloro-N-[(dimethylamino) sulfonyl] -1-fluoro-N- (4-methylphenyl) methanesulfenamide (" Preventol A5S "manufactured by LANXESS) (Trade name)), 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione), 2-pyridinethiol-1-oxide copper salt (copper pyrithione), tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propylbutylcarbamate, diiodomethylparatrisulfone, phenyl (bispyridyl) bismuth dichloride, 2- (4- Thiazolyl) -benzimidazole, triphenylboron pyridine salt, stearyl Min-triphenylboron, laurylamine-triphenylboron, tetraethylthiuram disulfide (TET), triphenyl [3- (2-ethylhexyloxy) propylamine] boron (OPA), bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate (bisdaicene) And the like. These may be used alone or in combination of two or more. Among these, zinc oxide (zinc white), cuprous oxide, 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione), 2-pyridinethiol-1-oxide copper salt (copper pyrithione), triphenylboronpyridine salt , Tetraethylthiuram disulfide (TET), stearylamine-triphenylboron, triphenyl [3- (2-ethylhexyloxy) propylamine] boron (OPA), bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate (bisdicene), etc. are preferably used. be able to.

  The mass ratio (first antifouling agent / binder resin particle (A)) between the first antifouling agent and the solid content of the binder resin particles (A) enclosing the first antifouling agent is 2 / It is preferably 98 to 70/30, more preferably 5/95 to 60/40, and particularly preferably 7/93 to 50/50. When the said mass ratio is less than 2/98, it exists in the tendency for antifouling property, especially the antifouling property in the drafting part at the time of semi-submersion to fall. Moreover, when the said mass ratio exceeds 70/30, there exists a possibility that the whole quantity of a 1st antifouling agent may not be included. In addition, at the time of manufacture of the binder resin particle (A) which includes the first antifouling agent, the monomer component constituting the binder resin is excessive, that is, the binder resin particle (A) cannot contain the entire amount. When the first antifouling agent is used, the excess antifouling agent is not included in the binder resin particles (A), but in the dispersion (emulsion) of the binder resin particles (A), It will be dispersed or will adhere to the outer surface of the binder resin particles (A). In the present invention, such an antifouling agent is grasped as a second antifouling agent described later. Therefore, the amount of the antifouling agent used in the production of the binder resin particles (A) enclosing the first antifouling agent is not particularly limited in this sense.

Next, the manufacturing method of the binder resin particle (A) in which the first antifouling agent is included will be described. The binder resin particle (A) in which the first antifouling agent is included is not particularly limited, but can be produced by, for example, the following method.
(I) A method in which one or more monomers constituting a binder resin exhibiting a desired curing system are polymerized in an aqueous medium in the presence of an antifouling agent and an oil-soluble polymerization initiator.
(Ii) A method in which one or more monomers constituting a binder resin exhibiting a desired curing system are polymerized in an aqueous medium in the presence of an antifouling agent and a water-soluble polymerization initiator.

  The monomer used in the polymerization reaction is as described above, and a monomer having a curing functional group corresponding to a desired curing system and / or another ethylenically unsaturated monomer copolymerizable therewith. Is selected.

  The polymerization initiator is not particularly limited, and in the case of the method (i), for example, azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2, Azo compounds such as 4-dimethylvaleronitrile); oil-soluble polymerization initiators such as redox peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and t-butyl perbenzoate. . In the case of the method (ii), for example, anions such as 4,4′-azobis (4-cyanovaleric acid) and 2,2′-azobis (N- (2-carboxyethyl) -2-methylpropionamidine) And water-based polymerization initiators such as peroxides such as potassium persulfate and ammonium persulfate.

  As the reaction solvent, water can be preferably used. Moreover, you may use together water-soluble organic solvents, such as alcohol, as needed. Although it does not specifically limit as polymerization temperature, For example, it can be set as about 20-95 degreeC, More preferably, it is about 40-85 degreeC.

  More specifically, in the method (i), for example, an aqueous mixture containing a monomer, an antifouling agent, and an oil-soluble polymerization initiator is added to an aqueous medium heated near the polymerization temperature. Can be applied. At this time, it is preferable to add an emulsifier and / or a water-soluble resin into the aqueous mixture and / or the aqueous medium in consideration of the uniform dispersibility of the reaction solution. In particular, it is preferable to pre-emulsify an aqueous mixture containing a monomer, an antifouling agent and an oil-soluble polymerization initiator using an emulsifier or the like.

  The emulsifier is not particularly limited, and may be any of anionic type, cationic type, and nonionic type. As the emulsifier, for example, Eleminol JS series (manufactured by Sanyo Kasei Co., Ltd.), Latemul S and K series (manufactured by Kao Corporation), Aqualon HS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap series (manufactured by Asahi Denka Co., Ltd.), Commercial products such as Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.) can be used.

  In the method (ii), for example, a method of adding an aqueous mixture containing a monomer and an antifouling agent and a water-soluble polymerization initiator to an aqueous medium heated near the polymerization temperature is applied. Can do. Also in this case, it is preferable to add an emulsifier and / or a water-soluble resin into the aqueous mixture and / or the aqueous medium in consideration of the uniform dispersibility of the reaction solution. In particular, it is preferable to pre-emulsify an aqueous mixture containing a monomer and an antifouling agent using an emulsifier or the like.

  After completion of the polymerization reaction, an acid or a base may be added to the resulting reaction solution to neutralize the reaction solution. Although it does not specifically limit as an acid used for neutralization, For example, a formic acid, an acetic acid, lactic acid etc. can be mentioned. Or as a base used for neutralization, ammonia, a triethylamine, a dimethylethanolamine etc. can be mentioned, for example.

  The binder resin particles (A) encapsulated with the first antifouling agent thus obtained are emulsion resins emulsified in an aqueous medium. The aqueous emulsion resin liquid can be used as it is as one component of the aqueous antifouling coating composition of the present invention. However, when it is visually confirmed that sedimentation has occurred due to the presence of a large amount of the first antifouling agent that is not included, it may be used after removing the sediment by decantation or the like. Good.

  In the case where the aqueous emulsion resin liquid contains an antifouling agent that is not included in the binder resin particles (A), in the measurement method of the “average particle diameter of the binder resin particles (A)” described above, Antifouling agents not included are also subject to particle size measurement.

  The blending amount (solid content) of the binder resin particles (A) encapsulated with the first antifouling agent can be, for example, 15 to 60% by mass in the solid content of the aqueous antifouling coating composition. In order to obtain sufficient antifouling properties, the content is more preferably 20 to 50% by mass.

<Curing agent (B)>
When the above-described binder resin has curability, the curing agent (B) is appropriately selected according to the curing system. Hereinafter, the curing agent that can be used in each curing system will be described.

  When the binder resin has a carbonyl / hydrazide cure system, the curing agent is a hydrazide compound. The hydrazide compound is not particularly limited, and a compound having a plurality of hydrazide groups or semicarbazide groups in one molecule can be used.

  Compounds having multiple hydrazide groups in one molecule include oxalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, glutamic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, etc. Dicarboxylic acid dihydrazide; carbonic acid polyhydrazide such as carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, 4,4'-oxybenzenesulfonylhydrazide, aliphatic, alicyclic, aromatic bissemicarbazide, aromatic dicarboxylic acid hydrazide; polyacrylic acid Examples thereof include polymer hydrazides such as hydrazide. Of these, adipic acid dihydrazide is preferable. These compounds may be used alone or in combination of two or more.

  The compound having a plurality of semicarbazide groups in one molecule is not particularly limited, and 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′ Examples thereof include semicarbazides such as-(methylene-di-P-phenylene) disemicarbazide and burette litri (hexamethylene-N, N-dimethylsemicarbazide). These compounds may be used alone or in combination of two or more.

  The molar ratio of the amount of the curing functional group contained in the carbonyl group-containing resin that is the binder resin and the amount of the curing agent functional group contained in the curing agent is preferably in the range of 1/10 to 1 / 0.05. When the molar ratio exceeds 1 / 0.05, the curability becomes insufficient and the water resistance may be lowered. On the other hand, if the molar ratio is less than 1/10, the amount of unreacted hydrazide compound increases, and the water resistance may be reduced. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  When the binder resin has an acetoacetoxy / amine curing system, the curing agent is an amine compound. The amine compound is not particularly limited. For example, 2-methylpentamethylenediamine, cyclohexanediamine, hexamethylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 1, 12-diaminododecane, 1,2-diaminocyclohexane, phenylenediamine, piperazine, 2,6-diaminotoluene, diethyltoluenediamine, N, N-bis (2-aminopropyl) ethylenediamine, N, N-bis (3-amino And a compound having a diamine group or a polyamine group such as propyl) -1,3-propanediamine.

  The molar ratio of the amount of the curing functional group contained in the acetoacetoxy group-containing resin that is the binder resin and the amount of the curing agent functional group contained in the curing agent is preferably in the range of 1/10 to 1 / 0.05. . When the molar ratio exceeds 1 / 0.05, the curability becomes insufficient and the water resistance may be lowered. On the other hand, if the molar ratio is less than 1/10, the amount of unreacted amine compound increases, and the water resistance may be reduced. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  When the binder resin has a urethane / urea curing system, the curing agent is a polyisocyanate compound. The polyisocyanate compound is not particularly limited. For example, aromatic diisocyanate compounds such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI); hexamethylene diisocyanate (HMDI), Isophorone diisocyanate (IPDI), 2,5- or 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane (aliphatic or alicyclic diisocyanate compounds such as norbornane diisocyanate (NBDI)); and these There may be mentioned polyisocyanate compounds such as dimers, trimers and trimethylolpropane adducts of diisocyanate compounds, etc. These are partly or entirely active hydrogens for controlling the reactivity. The blocking agent is not particularly limited, and examples thereof include aliphatic substances such as methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, and cyclohexanol. Examples thereof include alcohols; phenols such as phenol, nitrophenol, and ethylphenol; oximes such as methyl ethyl ketoxime; and lactams such as ε-caprolactam.

  The molar ratio between the amount of the curing functional group contained in the hydroxyl group and / or amino group-containing resin as the binder resin and the amount of the curing agent functional group contained in the polyisocyanate compound is within a range of 1/10 to 1 / 0.05. Preferably there is. When the molar ratio exceeds 1 / 0.05, the curability becomes insufficient and the water resistance may be lowered. If the molar ratio is less than 1/10, the amount of the unreacted polyisocyanate compound increases, and the water resistance may decrease. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  When the binder resin has a carbodiimide / carboxyl curing system, the curing agent is a polycarbodiimide compound. As the polycarbodiimide compound, a commercially available product such as V-02 manufactured by Nisshinbo Industries, Inc. can be used. Moreover, the polyisocyanate compound mentioned above can be carbodiimidized using phospholene oxide known as a carbodiimidization catalyst to obtain an isocyanate-terminated polycarbodiimide, which can be hydrophilized using this. .

  The molar ratio between the amount of the curing functional group contained in the carboxyl group-containing resin as the binder resin and the amount of the curing agent functional group contained in the polycarbodiimide compound is preferably in the range of 1/10 to 1 / 0.05. . If the molar ratio is out of the above range, the water resistance may decrease. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  When the binder resin has a Michael addition curing system, the curing agent is a compound having a plurality of α, β-unsaturated carbonyl groups. The compound having a plurality of α, β-unsaturated carbonyl groups is not particularly limited. For example, a compound having two or more methacrylate groups and / or acrylate groups per molecule, for example, between α and β carbons with respect to a carbonyl group. Examples thereof include those having two or more methacrylate groups and / or acrylate groups having a double bond. Specific examples include (meth) acrylic acid esters of polyols, such as ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-cyclohexyldimethanol di (meth) acrylate, 4,4′-isopropylidenedicyclohexanol di (meth) acrylate, bis (hydroxymethyl) tricyclo [ 5,2,1,0] decane di (meth) acrylate, 1,3,5-tris (2-hydroxyethyl) cyanuric acid tri (meth) acrylate, etc .; acrylic polyol poly (meth) acrylate resin, polyester Polyol (poly) acrylate resin, Poly (meth) acrylate resin of polyether polyol, Poly (meth) acrylate resin of epoxy polyol, Poly (meth) acrylate resin of polyurethane polyol, Poly (meth) acrylate resin of silicone polyol, etc. Can be mentioned.

  The molar ratio of the amount of the cured functional group contained in the compound having an active methylene group and / or an active methine group to the unsaturated bond contained in the compound having a plurality of α, β-unsaturated carbonyl groups is 1/10 to 1 / It is preferable to be within the range of 0.05. When the molar ratio exceeds 1 / 0.05, the curability becomes insufficient and the water resistance may be lowered. If the molar ratio is less than 1/10, the amount of the compound having a plurality of unreacted α, β-unsaturated carbonyl groups increases, and the water resistance may decrease. The molar ratio is more preferably in the range of 1 / 0.6 to 1 / 0.1 from the viewpoint of water resistance.

  The compounding quantity of a hardening | curing agent (B) is about 0.1-50 mass% normally in solid content of an aqueous | water-based antifouling paint composition, Preferably it is 0.5-20 mass%.

<Second antifouling agent>
In the present invention, it is preferable that the water-based antifouling coating composition contains a second antifouling agent separately from the first antifouling agent. Here, the “second antifouling agent” refers to an antifouling agent that is not included in the binder resin particles (A). As the second antifouling agent, those exemplified for the first antifouling agent can be similarly used. These may be used alone or in combination of two or more. Further, the second antifouling agent may be the same compound as the first antifouling agent or a different compound. By adding a 2nd antifouling agent, the further outstanding antifouling property, especially the antifouling property in the drafting part at the time of semi-submersion can be acquired.

  The mass ratio (second antifouling agent / binder resin particles (A)) between the second antifouling agent and the solid content of the binder resin particles (A) is 5/95 to 80/20. Preferably, it is 25/75 to 75/25. When the said mass ratio is less than 5/95, it exists in the tendency for the antifouling improvement effect by having added the 2nd antifouling agent to be hard to be acquired. Moreover, when the said mass ratio exceeds 80/20, defects, such as a crack and peeling, may arise in the antifouling coating film after hardening.

  Moreover, it is preferable that the total compounding quantity of a 1st antifouling agent and a 2nd antifouling agent is 10-80 mass% in solid content of an aqueous | water-based antifouling coating composition. If it is less than 10% by mass, the antifouling effect cannot be expected, and if it exceeds 80% by mass, defects such as cracks and peeling may occur in the coating film. As for the total compounding quantity of a 1st antifouling agent and a 2nd antifouling agent, it is more preferable that it is 10-60 mass%.

  Mass ratio of content of first antifouling agent and content of second antifouling agent in water-based antifouling paint composition (content of first antifouling agent / content of second antifouling agent The amount) is not particularly limited, but in order to ensure sufficient antifouling properties, the ratio is preferably 2/98 to 40/60, and 3/97 to 30/70. It is more preferable that the upper limit value be 40/60.

  Here, the second antifouling agent may be blended as an antifouling agent paste (C) comprising a water-soluble resin and the second antifouling agent. By using such an antifouling agent paste, the antifouling agent is released over time in water, and the antifouling effect can be exhibited stably. That is, since the antifouling agent paste contains a water-soluble resin, when the obtained coating film is placed in water, the portion where the water-soluble resin exists becomes a passage, and as a result, the antifouling agent located in the vicinity is Elution in water and antifouling effect is expressed.

  Although it does not specifically limit as said water-soluble resin, Although well-known water-soluble resin, such as an acrylic resin, a polyester resin, and a urethane resin, can be used, an acid value is 10-300 mgKOH / g and a number average molecular weight is 1000-20000. It is preferable to be within the range. When the acid value is less than 10 mgKOH / g, the water solubility may be lowered and the stability may be impaired. On the other hand, when the acid value exceeds 300 mgKOH / g, the hydrophilicity of the resin becomes too high, and the water resistance of the coating film may decrease. The upper limit of the acid value is more preferably 100 mgKOH / g. On the other hand, if the number average molecular weight is less than 1000, the molecular weight is too low and the antifouling agent may not be sufficiently dispersed. On the other hand, when the number average molecular weight exceeds 20000, there is a possibility that water solubility cannot be ensured or the viscosity becomes too high and handling becomes difficult. The lower limit of the number average molecular weight is more preferably 5000, and the upper limit of the number average molecular weight is more preferably 15000.

  More specifically, various water-soluble resins exist, and commercially available pigment dispersants can be used. Specific product names include Solsperse 20000, Solsperse 27000, Solsperse 41090 (above, manufactured by Avisia), Dispersic 180, Dispersic 181, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 190, Dispersic 191, Dispersic 192 (above, manufactured by BYK Chemie), polymer 450, polymer 451, polymer 452, polymer 453, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (above, manufactured by EFKA Chemical), floren G-700, Floren TG-720, Floren-730W, Floren 740W, Floren-745W (above, manufactured by Kyoeisha Chemical Co., Ltd.), Jonkrill 678, Di Nkuriru 679, Joncryl 62 (or more, Johnson Ltd. Polymer Co.), and the like.

  In the antifouling agent paste (C), the mixing ratio of the water-soluble dispersion resin and the antifouling agent is preferably in the range of 1/99 to 50/50 in terms of solid content. If the mixing ratio is outside this range, the dispersion viscosity of the antifouling agent paste may become too high, or the dispersibility of the antifouling agent may be lowered, resulting in insufficient stability. The antifouling agent paste (C) can be obtained, for example, by a method in which a water-soluble resin and an antifouling agent are mixed using a pigment dispersing machine such as a sand grinder mill. The antifouling agent paste (C) may contain conventional additives such as pigments and plasticizers in addition to the water-soluble resin and the antifouling agent. As the pigment and the plasticizer, for example, those described later can be used.

<Other additives>
The water-based antifouling coating composition can contain conventional additives such as plasticizers and pigments in addition to the above-described components. Examples of the plasticizer include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, and dicyclohexyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate; diethylene glycol dibenzoate, pentaerythritol alkyl Glycol ester plasticizers such as esters; Phosphate ester plasticizers such as tricylene phosphate and trichloroethyl phosphate; Epoxy plasticizers such as epoxy soybean oil and octyl epoxy stearate; Dioctyl tin laurate, Dibutyl tin laurate, etc. Organic tin-based plasticizers; trioctyl trimellitic acid, triacetylene and the like. These may be used alone or in combination of two or more.

  Examples of the pigment include extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white, bentonite; titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite, bengara, Examples thereof include colored pigments such as chrome yellow, phthalocyanine green, phthalocyanine blue, and quinacridone. These may be used alone or in combination of two or more. In addition to the above, other additives are not particularly limited. For example, monobasic organic acids such as monobutyl phthalate and monooctyl succinate, camphor, etc .; water binder, sagging agent; color separation inhibitor; Agents; antifoaming agents and the like.

  Additives such as plasticizers and pigments may be blended in the antifouling agent paste (C). When antifouling agent paste (C) contains a pigment, it is preferable that the compounding ratio of a pigment is 70 mass% or less by PWC in antifouling agent paste (C).

  The method for preparing the water-based antifouling paint composition is not particularly limited. For example, the emulsion of the binder resin particles (A) in which the first antifouling agent is included, and the second antifouling agent added as necessary. The fouling agent or antifouling agent paste (C), the curing agent (B) and other additives can be prepared by mixing using a mixer such as a ball mill, pebble mill, roll mill, sand grind mill or the like. When the second antifouling agent is used as an antifouling agent paste, the second antifouling agent and water-soluble resin, and further, a pigment, a plasticizer, and other additives are mixed in advance using a sand grinder mill or the like. Then, an aqueous antifouling paint composition is prepared by mixing these with an emulsion of binder resin particles (A) encapsulated with the first antifouling agent and a curing agent (B) added as necessary. can do.

  The water-based antifouling coating composition of the present invention preferably has a nonvolatile content of 10 to 90% by mass. If the nonvolatile content is less than 10% by mass, it may be difficult to increase the film thickness. If the non-volatile content exceeds 90% by mass, it may be difficult to adjust the viscosity during coating. The aqueous antifouling paint composition of the present invention preferably has a PWC of 50 to 90% by mass. If the PWC is less than 50% by mass, the room temperature drying property may decrease. On the other hand, when PWC exceeds 90 mass%, film formation may be difficult.

  The water-based antifouling coating composition of the present invention can form a dry antifouling coating film after being applied to the surface of an object to be coated according to a conventional method and then stripping off water at room temperature or by heat drying. Is. The antifouling coating film thus obtained effectively suppresses marine organisms from adhering to objects to be coated such as ships and underwater structures. Further, when the coating film is cured, the water resistance is particularly excellent. The antifouling coating film formed using the aqueous antifouling coating composition of the present invention is also one aspect of the present invention, and ships and underwater structures having the antifouling coating film are also one aspect of the present invention. Moreover, the antifouling method of the to-be-coated object by forming the said antifouling coating film using the water-based antifouling paint composition of this invention is also one of this invention. It does not specifically limit as an underwater structure, For example, various fish nets, a port facility, an oil fence, piping material, a bridge, a submarine base etc. can be mentioned.

  The antifouling coating film is formed, for example, by applying a water-based antifouling coating composition to the surface of a ship or an underwater structure by a conventionally known method such as dipping, spraying, brushing, roller, electrostatic coating, etc. Can do. After coating, it may be left to dry at room temperature, or forced drying at about 80 ° C. may be performed for several hours to about 1 day. The dry film thickness of the antifouling coating film is preferably in the range of 30 to 500 μm. It is preferable for the dry film thickness to be in this range because the balance between water resistance and antifouling property is good.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these. “Part” means “part by mass” unless otherwise specified.

<Preparation of antifouling agent inclusion binder resin particles>
[Production Example 1] Preparation of emulsion resin I 10 parts of diacetone acrylamide (DAAM), 30 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 30 parts of n-butyl acrylate (NBA), styrene ( ST) 9 parts, methacrylic acid (MAA) 1 part, cuprous oxide (NC-Tech NC-301, the same shall apply hereinafter) 50 parts, and lauroyl peroxide 4 parts monomer, antifouling agent (first antifouling agent) (Fouling agent) and a mixture of polymerization initiators were added to a solution obtained by mixing 100 parts of ion exchange water and 6 parts of Aqualon HS-10 (anionic reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) By emulsifying using a high-speed shearing emulsifier, a pre-emulsion which is a mixture of a monomer, an antifouling agent and a polymerization initiator was obtained. Next, 120 parts of ion-exchanged water and 2 parts of Aqualon HS-10 were charged into a reaction vessel equipped with a dropping funnel, a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Then, the pre-emulsion was dropped over 1 hour using a dropping funnel. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchange water and 1 part of dimethylethanolamine. The solid content of the emulsion resin I containing the binder resin particles encapsulated with cuprous oxide thus obtained was 41% by mass, and the average particle size of the binder resin particles was 320 nm. The average particle diameter was measured using an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.).

[Production Example 2] Preparation of emulsion resin II As an antifouling agent, 30 parts of cuprous oxide and bis (2-pyridinethiol-1-oxide) copper salt ((Copt), manufactured by Olin Co., Ltd., trade name “copper pyrithione” In the same manner as in Production Example 1, except that 20 parts were used, emulsion resin II was obtained. The solid content of the emulsion resin II containing the binder resin particles encapsulated with cuprous oxide and copper pyrithione (Cupt) thus obtained is 40% by mass, and the average particle size of the binder resin particles is 320 nm.

[Production Example 3] Preparation of emulsion resin III Emulsion resin III was obtained in the same manner as in Production Example 2 except that the amount of ion-exchanged water charged in the reaction vessel in advance was 130 parts. The solid content of the emulsion resin III was 37% by mass, and the average particle size of the binder resin particles was 320 nm.

[Production Example 4] Preparation of emulsion resin IV 10 parts of diacetone acrylamide (DAAM), 30 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 30 parts of n-butyl acrylate (NBA), styrene ( ST) 9 parts, methacrylic acid (MAA) 1 part, and cuprous oxide 20 parts, zinc pyrithione (Zpt, “Zinc Omazine” manufactured by Arch Chemical Co., Ltd., the same shall apply hereinafter) and Irgarol 1051 (chemical name: 2-methylthio- 4-t-butylamino-6-cyclopropylamino-s-triazine, trade name of Nippon Ciba-Geigy Co., Ltd., the same shall apply hereinafter) (Anionic reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a solution obtained by mixing 6 parts. Then, the pre-emulsion which is a mixture of a monomer and an antifouling agent was obtained by emulsifying using a high-speed shear emulsifier. Further, 0.3 part of ammonium persulfate was dissolved in 17 parts of ion-exchanged water to obtain a polymerization initiator aqueous solution. Next, a reaction vessel equipped with a dropping funnel, a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer was charged with 70 parts of ion-exchanged water and 2 parts of Aqualon HS-10, and heated to 80 ° C. in a nitrogen atmosphere. Subsequently, the said pre-emulsion and polymerization initiator aqueous solution were dripped simultaneously over 1 hour using the separate dripping funnel. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchange water and 1 part of dimethylethanolamine. The solid content of the emulsion resin IV containing the binder resin particles encapsulated with cuprous oxide, zinc pyrithione and irgarol 1051 thus obtained is 44% by mass, and the average particle diameter of the binder resin particles is It was 200 nm.

[Production Example 5] Preparation of emulsion resin V As an antifouling agent, 20 parts of cuprous oxide, 15 parts of copper pyrithione (Copt) and 4,5, -dichloro-2-n-octyl-3 (2H) isothiazolone (Rohm and) “Sea Nine 211” manufactured by Haas, the same applies hereinafter.) Emulsion resin V was obtained in the same manner as in Production Example 2, except that 15 parts were used and the amount of ion-exchanged water charged in the reaction vessel in advance was 70 parts. It was. The solid content of the emulsion resin V was 43% by mass, and the average particle size of the binder resin particles was 220 nm.

[Production Example 6] Preparation of emulsion resin VI Except that 25 parts of cuprous oxide and 25 parts of zinc pyrithione (Zpt) were used as an antifouling agent, and the amount of ion-exchanged water charged in the reaction vessel in advance was 110 parts. Emulsion resin VI was obtained in the same manner as in Production Example 4. The solid content of the emulsion resin VI was 41% by mass, and the average particle size of the binder resin particles was 290 nm.

[Production Example 7] Preparation of emulsion resin VII Emulsion resin VII was obtained in the same manner as in Production Example 2 except that 15 parts of cuprous oxide and 10 parts of copper pyrithione (Cupt) were used as an antifouling agent. The solid content of the emulsion resin VII was 35% by mass, and the average particle size of the binder resin particles was 290 nm.

[Production Example 8] Preparation of emulsion resin VIII As an antifouling agent, 20 parts of cuprous oxide, 15 parts of copper pyrithione (Cupt) and 1,1-dichloro-N-[(dimethylamino) sulfonyl] -1-fluoro-N Emulsion resin VIII was obtained in the same manner as in Production Example 4 except that 15 parts of-(4-methylphenyl) methanesulfenamide ("Pliventol A5S" manufactured by LANXESS, the same applies hereinafter) was used. The solid content of the emulsion resin VIII was 44% by mass, and the average particle size of the binder resin particles was 170 nm.

[Production Example 9] Preparation of emulsion resin IX Emulsion resin IX was obtained in the same manner as in Production Example 2 except that 50 parts of copper pyrithione (Cupt) was used as an antifouling agent. The solid content of the emulsion resin IX was 40% by mass, and the average particle size of the binder resin particles was 360 nm.

[Production Example 10] Preparation of emulsion resin X As an antifouling agent, triphenyl [3- (2-ethylhexyloxy) propylamine] boron (OPA, "OPA-SX" manufactured by Nitto Kasei Co., Ltd.), solid content 32.6% , The same shall apply hereinafter)), and the same amount as in Production Example 4 except that the amount of ion-exchanged water used for preparing the pre-emulsion and the amount of ion-exchanged water charged in the reaction vessel in advance were each 80 parts. Thus, an emulsion resin X was obtained. The solid content of the emulsion resin X was 35% by mass, and the average particle size of the binder resin particles was 200 nm.

[Production Example 11] Preparation of emulsion resin XI As an antifouling agent, 25 parts of OPA and 25 parts of tetraethylthiuram disulfide (TET, "Noxeller TET-G" manufactured by Ouchi Shinsei Chemical Co., Ltd., the same shall apply hereinafter) were used. Except that, emulsion resin XI was obtained in the same manner as in Production Example 10. The solid content of the emulsion resin XI was 36% by mass, and the average particle size of the binder resin particles was 170 nm.

[Production Example 12] Preparation of emulsion resin XII Emulsion resin XII was obtained in the same manner as in Production Example 11 except that 25 parts of OPA was used as an antifouling agent. The solid content of the emulsion resin XII was 36% by mass, and the average particle size of the binder resin particles was 230 nm.

[Production Example 13] Preparation of emulsion resin XIII 25 parts of OPA was used as an antifouling agent, and the amount of ion-exchanged water used for preparing the pre-emulsion and the amount of ion-exchanged water charged in advance into the reaction vessel were 75 parts each. Emulsion resin XIII was obtained in the same manner as in Production Example 4 except that the amount was 60 parts. The solid content of the emulsion resin XIII was 39% by mass, and the average particle size of the binder resin particles was 230 nm.

[Production Example 14] Preparation of emulsion resin XIV As an antifouling agent, 25 parts of OPA was used, and the amount of ion-exchanged water used for preparing the pre-emulsion and the amount of ion-exchanged water charged in advance into the reaction vessel were 75 parts each. Except that, emulsion resin XIV was obtained in the same manner as in Production Example 2. The solid content of the emulsion resin XIV was 39% by mass, and the average particle size of the binder resin particles was 600 nm.

[Production Example 15] Preparation of emulsion resin XV 10 parts of diacetone acrylamide (DAAM), 30 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 30 parts of n-butyl acrylate (NBA), styrene ( ST) 9 parts, methacrylic acid (MAA) 1 part, OPA 25 parts, lauroyl peroxide 4 parts monomer, antifouling agent (first antifouling agent) and polymerization initiator mixture, 75 parts of ion-exchanged water Is added to a solution obtained by mixing 6 parts of Kuraray Poval PVA-217EE (polyvinyl alcohol manufactured by Kuraray Co., Ltd.) and then emulsified using a stirrer to obtain a mixture of a monomer, an antifouling agent and a polymerization initiator. A pre-emulsion was obtained. Next, 75 parts of ion-exchanged water and 2 parts of PVA-217EE were charged into a reaction vessel equipped with a dropping funnel, a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Then, the pre-emulsion was dropped over 1 hour using a dropping funnel. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchange water and 1 part of dimethylethanolamine. The solid content of the emulsion resin XV containing the binder resin particles encapsulated in OPA thus obtained was 40% by mass, and the average particle size of the binder resin particles was 23 μm (23000 nm). .

[Production Example 16] Preparation of emulsion resin XVI As monomers, 10 parts of diacetone acrylamide (DAAM), 60 parts of methyl methacrylate (MMA), 10 parts of ethyl acrylate (EA), 10 parts of n-butyl acrylate (NBA) Emulsion resin XVI was obtained in the same manner as in Production Example 13 except that 9 parts of styrene (ST) and 1 part of methacrylic acid (MAA) were used. The solid content of the emulsion resin XVI was 40% by mass, and the average particle size of the binder resin particles was 200 nm.

[Production Example 17] Preparation of emulsion resin XVII As monomers, 10 parts of diacetone acrylamide (DAAM), 30 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 23 parts of n-butyl acrylate (NBA) Emulsion resin XVII was obtained in the same manner as in Production Example 13, except that 9 parts of styrene (ST) and 8 parts of methacrylic acid (MAA) were used. The solid content of the emulsion resin XVII was 39% by mass, and the average particle size of the binder resin particles was 180 nm.

[Production Example 18] Preparation of emulsion resin XVIII As monomers, 10 parts of diacetone acrylamide (DAAM), 25 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 30 parts of n-butyl acrylate (NBA) Emulsion resin XVIII was obtained in the same manner as in Production Example 13, except that 9 parts of styrene (ST), 1 part of methacrylic acid (MAA), and 5 parts of ethylene glycol dimethacrylate (EGDM) were used. The solid content of the emulsion resin XVIII was 40% by mass, and the average particle size of the binder resin particles was 230 nm.

[Production Example 19] Preparation of emulsion resin XIX As monomers, soybean oil fatty acid adduct of glycidyl methacrylate (GMA-SBO) 10 parts, methyl methacrylate (MMA) 30 parts, ethyl acrylate (EA) 20 parts, acrylic acid n -Emulsion resin XIX was obtained in the same manner as in Production Example 13 except that 30 parts of butyl (NBA), 9 parts of styrene (ST), and 1 part of methacrylic acid (MAA) were used. The solid content of the emulsion resin XIX was 40% by mass, and the average particle size of the binder resin particles was 200 nm.

[Production Example 20] Preparation of emulsion resin XX As monomers, 10 parts of 3-methacryloxypropyltriethoxysilane ("KBE-503" manufactured by Shin-Etsu Chemical Co., Ltd.), 30 parts of methyl methacrylate (MMA), ethyl acrylate ( Emulsion resin XX was obtained in the same manner as in Production Example 13 except that 20 parts of EA, 30 parts of n-butyl acrylate (NBA), 9 parts of styrene (ST) and 1 part of methacrylic acid (MAA) were used. . The solid content of the emulsion resin XX was 38% by mass, and the average particle size of the binder resin particles was 180 nm.

[Production Example 21] Preparation of emulsion resin XXI Emulsion resin XXI was obtained in the same manner as in Production Example 3 except that 50 parts of zinc pyrithione (Zpt) was used as an antifouling agent. The solid content of the emulsion resin XXI was 40% by mass, and the average particle size of the binder resin particles was 290 nm.

[Production Example 22] Preparation of emulsion resin XXII Production Example 3 was used except that 50 parts of triphenylboron pyridine salt ("PK" manufactured by Hokuko Chemical Co., Ltd., the same shall apply hereinafter) was used as an antifouling agent. Similarly, emulsion resin XXII was obtained. The solid content of the emulsion resin XXII was 40% by mass, and the average particle size of the binder resin particles was 290 nm.

[Production Example 23] Preparation of emulsion resin XXIII As an antifouling agent, zinc pyrithione (Zpt) 10 parts, zinc white ("Zinc oxide type 2" manufactured by Sakai Chemical Industry Co., Ltd., the same shall apply hereinafter) 15 parts, PK 15 parts Emulsion resin XXIII was obtained in the same manner as in Production Example 3, except that 10 parts of Priventol A5S was used. The solid content of the emulsion resin XXIII was 40% by mass, and the average particle size of the binder resin particles was 290 nm.

[Production Example 24] Preparation of emulsion resin XXIV Emulsion resin XXIV was obtained in the same manner as in Production Example 2 except that the amount of ion-exchanged water charged in the reaction vessel in advance was 130 parts. The solid content of the emulsion resin XXIV was 37% by mass, and the average particle size of the binder resin particles was 320 nm.

[Production Examples 25 to 29] Preparation of emulsion resins XXV to XXIX Emulsion resins XXV to XXV in the same manner as in Production Example 3 except that the antifouling agent was formulated so as to have the antifouling agent shown in Table 1. XXIX was obtained. The solid contents of the emulsion resins XXV to XXIX and the average particle size of the binder resin particles were as shown in Table 1, respectively. The bisdaicene used in Production Example 29 is bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate (“TOC-3204F” manufactured by Rohm and Haas) (hereinafter the same).

[Reference Production Example 1] Preparation of emulsion resin XXX 10 parts of diacetone acrylamide (DAAM), 30 parts of methyl methacrylate (MMA), 20 parts of ethyl acrylate (EA), 30 parts of n-butyl acrylate (NBA), styrene (ST) A monomer mixture consisting of 9 parts and 1 part of methacrylic acid (MAA) is obtained by mixing 60 parts of ion exchange water and 6 parts of Aqualon HS-10 (anionic reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). After adding to the obtained solution, the emulsion was emulsified using a stirrer to obtain a pre-emulsion as a monomer mixture. Further, 0.3 part of ammonium persulfate was dissolved in 17 parts of ion-exchanged water to obtain a polymerization initiator aqueous solution. Next, a reaction vessel equipped with a dropping funnel, a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer was charged with 70 parts of ion-exchanged water and 2 parts of Aqualon HS-10, and heated to 80 ° C. in a nitrogen atmosphere. Subsequently, the said pre-emulsion and polymerization initiator aqueous solution were dripped simultaneously over 3 hours using the separate dripping funnel. After completion of the dropwise addition, the reaction was continued for another 2 hours at the same temperature. After cooling, the mixture was neutralized with an aqueous basic neutralizing agent solution consisting of 7 parts of ion exchange water and 1 part of dimethylethanolamine. The solid content of the emulsion resin XXX containing the binder resin particles thus obtained was 40% by mass, and the average particle size of the binder resin particles was 90 nm.

  Table 1 summarizes the raw material composition used in each of the above production examples, the solid content of the obtained emulsion resin, and the average particle size of the binder resin particles.

  Moreover, about the emulsion resin I and the emulsion resin XXI of the said manufacture example 1 and the manufacture example 21, it confirmed that the antifouling agent was included by the binder resin particle | grains with the following method.

(1) Observation with Transmission Electron Microscope (TEM) The emulsion resin I of Production Example 1 containing cuprous oxide is placed on a grid of a transmission electron microscope (JEOL “JEM-2000FXII”), and the grid is set in a sample holder. Then, it was dried under reduced pressure in a vacuum dryer for 24 hours to completely remove moisture, and when observed with a transmission electron microscope (TEM), a dark region was observed in the binder resin particles, The presence of copper oxide was confirmed, and the same was true for the emulsion resin XXI containing zinc pyrithione.

  On the other hand, when the same transmission electron microscope (TEM) observation was performed about emulsion resin XXX, the dark area | region was not confirmed in the binder resin particle. Moreover, when the same transmission electron microscope (TEM) observation was performed about the binder resin particle which mixed emulsion resin I and XXX (50 wt% / 50 wt% by solid content ratio), the density in a binder resin particle differs. Two types of particles were observed.

(2) Field Emission Scanning Electron Microscope (FE-SEM) Measurement Regarding the emulsion resin I of Production Example 1 including cuprous oxide, a field emission scanning electron microscope (Hitachi High-Technologies Corporation “Hitachi Ultra High Resolution Electric Field” When elemental analysis was performed with an emission scanning electron microscope S-4800 "), copper (Cu) element was detected in the binder resin particles.

  Further, when the same field emission scanning electron microscope measurement was performed on the binder resin particles obtained by mixing the emulsion resins I and XXX (solid content ratio: 50 wt% / 50 wt%), copper element was detected in the binder resin particles. It was confirmed that there were some that were not detected and some that were not detected.

(3) Solid NMR Measurement Solid emulsion ¹³ X-NMR measurement was performed on the emulsion resin XXI from which water was removed. As a result, peaks were confirmed at 117 ppm, 137 ppm, and 160 ppm, which are characteristic peaks for zinc pyrithione. On the other hand, when the same solid NMR measurement was performed on the emulsion resin XXX, a peak characteristic of the antifouling agent was not confirmed.

<Preparation of antifouling agent paste>
[Production Example 30]
To 100 parts of ion-exchanged water, 300 parts of cuprous oxide as an antifouling agent (second antifouling agent), 25 parts of Bengala and 25 parts of talc are added, and further, BYK-190 (Bic Chemie Co., Ltd.) as a pigment dispersant. Manufactured, 40% by weight solid content) and 2.9 parts BYK-019 (manufactured by Pick Chemie) as an antifoaming agent, and dispersed with a sand grinder mill to give an antifouling agent having a solid content of 68% by weight and a particle size of 20 μm Agent paste P1 was obtained.

[Production Examples 31-50]
Antifouling agent pastes P2 to P21 were obtained in the same manner as in Production Example 30, except that the blending amounts of the antifouling agent, the pigment, the pigment dispersant, and the dehumidifying agent were the amounts shown in Table 2.

<Example 1>
364.96 parts of Emulsion Resin I of Production Example 1, 10.5 parts of Hardener SC (Asahi Kasei Co., Ltd. semicarbazide curing agent, solid content 50 mass%), 55.48 parts of antifouling agent paste P1 of Production Example 30, and PUR- An aqueous antifouling coating composition was obtained by dispersing 7.9 parts of 2150 (urethane associative thickener manufactured by Akzo Nobel, solid content of 35% by mass) with a disper.

<Examples 2 to 33, Comparative Examples 1 and 2>
A water-based antifouling paint composition was obtained in the same manner as in Example 1 except that the formulation shown in Table 3 was used. In addition, the antifouling agent total in Table 3 is the total amount (part by mass) of the first antifouling agent and the second antifouling agent.

(Evaluation of antifouling properties)
Brush the aqueous antifouling paint compositions of the above examples and comparative examples on an FRP plate (100 × 300 × 3 mm, with gel coat treatment) roughened with sandpaper (particle size 240) so that the dry coating film becomes 400 μm. And painted. After coating, a test coated plate was obtained by leaving it in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% for 1 day.

  Each test coating obtained was immersed in water at a depth of 1 m from the underwater shore at Nippon Paint Marine Co., Ltd., Rinkai Research Institute, Tamano City, Okayama Prefecture (all submerged), after 1 month, 3 months, 6 months, and 12 months. The surface state of the coating film was visually observed. The results are shown in Table 3. In addition, another test coating plate was installed from the underwater so that about half of the test coating plate was immersed in seawater (semi-immersion), and similarly, the coating film after 1 month, 3 months, 6 months, and 12 months The surface state of the draft portion was visually observed. The results are shown in Table 3.

The evaluation criteria for antifouling properties are as follows.
A: No attached organism.
B: Only the slime that can be easily removed adheres to the coating film (or the draft portion of the coating film).
C: Animals and plants adhere to less than 10% of the test coating plate area (or draft area).
D: Animals and plants adhere to 10% or more and less than 50% of the test coating plate area (or draft area).
E: Animals and plants adhere to 50% or more of the test coating plate area (or draft area).

  As can be seen from the antifouling property evaluation results shown in Tables 3A to 3D, according to the present invention, marine organisms are effectively prevented from adhering to the draft section during semi-submersion. Moreover, according to this invention, even if it is a case where the total amount of antifouling agents in a water-based antifouling paint composition is reduced, antifouling property can be improved compared with the past.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  Since the water-based antifouling paint composition of the present invention contains binder resin particles encapsulating an antifouling agent, it forms a coating film having a good antifouling effect, in particular, a good antifouling effect in the draft section. Can do. The water-based antifouling coating composition of the present invention can be widely applied to ships and underwater structures.

Claims (14)

An aqueous antifouling paint composition containing the first antifouling agent and the binder resin particles (A),
The aqueous antifouling paint composition, wherein the first antifouling agent is enclosed in the binder resin particles (A).   The water-based antifouling paint composition according to claim 1, wherein the binder resin particles (A) have curability.   The water-based antifouling paint composition according to claim 2, further comprising a curing agent (B).   The water-based antifouling paint composition according to any one of claims 1 to 3, further comprising a second antifouling agent not included in the binder resin particles (A).   The aqueous solution according to any one of claims 1 to 3, further comprising an antifouling agent paste (C) comprising a second antifouling agent not encapsulated in the binder resin particles (A) and a water-soluble resin. Antifouling paint composition.   The water-based antifouling paint composition according to any one of claims 1 to 5, wherein a mass ratio between the first antifouling agent and the solid content of the binder resin particles (A) is 2/98 to 70/30. .   The mass ratio of the content of the first antifouling agent and the content of the second antifouling agent is 3/97 to 40/60. Paint composition.   The first antifouling agent and the second antifouling agent are independently zinc oxide, cuprous oxide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt. , Triphenylboron pyridine salt, tetraethylthiuram disulfide, stearylamine-triphenylboron, triphenyl [3- (2-ethylhexyloxy) propylamine] boron and bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate The aqueous antifouling paint composition according to any one of claims 1 to 7, which is one or more antifouling agents.   The water-based antifouling paint according to any one of claims 3 to 8, wherein the binder resin particles (A) are made of a resin having a functional group capable of reacting with at least one functional group or part of the curing agent (B). Composition.   The functional group capable of reacting with at least one functional group or site of the curing agent (B) is one or more functional groups selected from the group consisting of a carbonyl group, an acetoacetoxy group and an alkoxysilyl group. The water-based antifouling paint composition according to claim 9.   The binder resin particles (A) that include the first antifouling agent polymerize one or more monomers in an aqueous medium in the presence of the first antifouling agent and a polymerization initiator. The water-based antifouling paint composition according to any one of claims 1 to 10, which is obtained by making it.   The antifouling coating film which uses the water-based antifouling paint composition in any one of Claims 1-11.   A ship or an underwater structure having the antifouling coating film according to claim 12.   The antifouling method of the to-be-coated object which forms an antifouling coating film on the surface of the to-be-coated object using the water-based antifouling paint composition according to any one of claims 1 to 11.