JPH1143629A - Antifouling paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling paint composition which can be stored for a long term and maintain an antifouling effect, when formed into a coated film, in seawater for a long term. SOLUTION: A non-aqueous dispersion resin (A) having 20-400 of acid value comprising a hydrophilic core component having acidic radicals and a hydrophobic shell component having no acid radicals dispersed in a hydrocarbon solvent is mixed with an antifouling agent including a metal (B) and a monobasic acid compound (C) having a carboxyl group. Further a ratio of acid group number in the non-aqueous dispersion resin (A) to a carboxyl group number in the monobasic acid compound (C) is 0.3-3.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antifouling paint composition. More specifically, the present invention relates to an antifouling paint composition that can be stored for a long period of time and retains antifouling performance in seawater for a long time after forming a coating film.

[0002]

2. Description of the Related Art Various types of marine organisms adhere to the bottom skin of ships below the sea level, marine structures, fishing nets, and other surfaces, which hinders efficient operation of ships. In the case of marine structures and fishing nets, there are problems such as a significantly shortened service life. As a countermeasure, an underwater antifouling paint composition containing various antifouling agents is applied.
Typical antifouling paints that have been used in the past include antifouling agents in vehicle components consisting of resins such as vinyl resins insoluble in seawater, alkyd resins, chlorinated rubber, and rosin soluble in seawater. Insoluble matrix type antifouling paints, and dissolved matrix type antifouling paints in which a metal-containing resin such as tin which gradually hydrolyzes in seawater is used as a vehicle component and an antifouling agent is added as necessary.

[0003] However, in the insoluble matrix type antifouling paint, since the antifouling agent elutes together with rosin in seawater, a stable antifouling effect cannot be expected for a long time.
Since the insoluble resin component remaining in the coating film forms a skeleton structure, particularly when applied to a ship, there is a drawback that the frictional resistance between seawater and the coated surface increases, resulting in a reduction in speed, an increase in fuel efficiency, and the like. On the other hand, the dissolving matrix type antifouling paint has an antifouling effect, but has problems in health and safety and environmental conservation. Further, as disclosed in JP-A-4-261473, etc., a non-aqueous dispersion resin having an acid group in a core component as a vehicle component, and a metal-containing antifouling agent is blended with an antifouling paint to form a coating film. Later, when the seawater comes into contact, the acid group and the metal react with each other, and as a result, the coating film hardly dissolves in the seawater, so that the antifouling effect cannot be sufficiently exhibited, and further, a skin component of the non-aqueous dispersion resin. In the case where has an acid group, there is a problem that the coating material is thickened and gelled and storage stability is deteriorated.

[0004]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of conventional antifouling paints and provides various underwater surfaces on the bottom skin of ships below the sea level, marine structures and fishing nets. An object of the present invention is to provide a coating composition that can effectively prevent organisms from adhering for a long period of time.

[0005]

Means for Solving the Problems The present inventors have conducted studies to solve the above problems, and as a result, have found that a non-aqueous dispersion resin having an acid group only in a core component, a metal-containing antifouling agent, By adding a monobasic acid containing a carboxyl group to antifouling paint containing, it is possible to store the paint for a long time, and after forming the coating, the coating gradually dissolves in seawater, so The knowledge that performance can be maintained for a long time was obtained.
The present invention has been completed based on such findings. Therefore, the present invention provides (A) a method of dispersing in a hydrocarbon solvent,
A non-aqueous dispersion resin having an acid value of 20 to 400, comprising a hydrophilic core component having an acid group and a hydrophobic skin component having no acid group, (B) a metal-containing antifouling agent, and (C) a carboxyl group. And a monobasic acid compound comprising:

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The non-aqueous dispersion resin (A), which is a vehicle component used in the present invention, includes various low-polar solvents such as hexane, heptane, xylene, toluene, cyclohexane, and mineral spirits such as aliphatic, aromatic, and alicyclic solvents. A mixture obtained by dispersing a hydrophilic core component, which is a high-polarity component, as a dispersion stabilizer using a hydrophobic skin component, which is a low-polarity component, as a dispersion stabilizer in a hydrocarbon solvent composed of a mixed system of, preferably, a particle size of 20 to 5000 nm. Resin. The non-aqueous dispersion resin that can be used in the present invention is not particularly limited, and typical examples include an acrylic resin, a polyester, an alkyd resin, and a silicone resin. The production of the non-aqueous dispersion can be carried out by a conventionally known method.For example, the core component and the skin component are polymerized by block copolymerization or graft copolymerization, and then the hydrocarbon solvent is added. A method of adding and producing, and a method of producing by reacting a skin component and a core component in a hydrocarbon solvent are exemplified. Explaining an acrylic resin-based non-aqueous dispersion resin as an example, for example, in a hydrocarbon-based solvent, in the presence of a dispersion stabilizer serving as a skin component, a polymerizable monomer containing a polymerizable monomer of an acid as an essential component The method of dispersion polymerization is suitable.

Examples of the polymerizable monomer for forming the core component include (meth) acrylic acid, acids such as crotonic acid, citraconic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride; ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid lauryl, alkyl (meth) acrylate having 1 to 24 carbon atoms in alkyl group such as dodecyl acrylate, alkyl methacrylates; other glycidyl (meth) acrylate, dimethylamino (meth) acrylate Ethyl, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene, vinyltoluene, (meth) acrylonitrile and the like are typical examples. By appropriately selecting, combining and polymerizing such polymerizable monomers, a hydrophilic core component having an acid group is formed.

[0008] The dispersion stabilizer is a polymer obtained by polymerizing a polymerizable monomer described below. The polymer is soluble in a hydrocarbon solvent and contains an acid group. In addition, it is a hydrophobic polymer obtained by selecting and polymerizing a monomer that does not contain a hydrophilic group as a polymerizable monomer, or even if it does contain a small amount of a hydrophilic group. The core component of the non-aqueous dispersion resin must have an acid group and be hydrophilic, so that the coating film gradually dissolves in (sea) water and exhibits antifouling properties. Become. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. On the other hand, the skin component of the non-aqueous dispersion resin needs to have no acid group and be hydrophobic. If it has an acid group similarly to the core component and is hydrophilic, the coating film will rapidly dissolve in (sea) water, and long-term antifouling properties cannot be expected.

[0009] The skin component can be produced by polymerizing or copolymerizing a vinyl polymerizable monomer having no acid group. Such vinyl polymerizable monomers include:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms, alkyl acrylates, alkyl methacrylates, other glycidyl (meth) acrylates, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Examples thereof include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, styrene, vinyl toluene, and (meth) acrylonitrile.

The weight ratio of the core component to the skin component is not particularly limited, but is usually 90/10 to 10/90, preferably
80/20 to 25/75 is suitable. The acid value of the non-aqueous dispersion resin comprising the core component and the skin component is suitably from 20 to 400, preferably from 50 to 200, and an excellent long-term antifouling coating film can be obtained in this range. The metal-containing antifouling agent (B) used in the present invention can be used without particular limitation as long as it is a conventionally used metal-containing antifouling agent. Specific examples thereof include cuprous oxide, basic copper carbonate, copper thiocyanate, copper hydroxide, cuprous rhodan, manganese ethylenebisdithiocarbamate, zinc pyrithione, zinc dimethyldithiocarbamate, and zinc ethylenebisdithiocarbamate. is there. These metal-containing antifouling agents can be used alone or in combination of two or more.

The monobasic acid compound (C) used in the present invention includes, for example, various carboxylic acids having a carboxyl group, such as aliphatic or aromatic carboxylic acids. Such a carboxylic acid may have, for example, another functional group such as a hydroxyl group in addition to the carboxyl group. Examples of such carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, caprylic acid, undecylic acid, lauric acid,
Tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachiic acid, linoleic acid, linolenic acid, oleic acid, arachidonic acid, elaidic acid, stearolic acid, salicylic acid, propiolic acid, glycolic acid Lactic acid, pivalic acid, dimethylacetic acid, cyclohexanecarboxylic acid, 1
Examples include 2-hydroxystearic acid, fluoroacetic acid, chloroacetic acid, palmitic acid, abietic acid, and naphthenic acid.

These monobasic acid compounds can be used alone or in combination of two or more. In the present invention, the monobasic acid compound (C) reacts when the acid group in the non-aqueous dispersion resin and the metal in the antifouling agent come into contact with seawater, and the coating film hardly dissolves. It is blended in order to prevent the long-term antifouling property from lowering.
To the coating composition of the present invention, a hydrocarbon-based solvent for dispersing the above-mentioned non-aqueous dispersion resin, and other various antifouling agents other than the metal-containing antifouling agent can be added as required. A specific example is 2-methylthio-4
-T-butylamino-6-cyclopropylamino-s-
Triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethylchlorophenylurea, 4,
5-dichloro-2-N-octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N'-phenyl (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, Examples include N- (3,4-dichlorophenyl) -N, N-dimethylurea and 2,4,6-trichlorophenylmaleimide.

The antifouling coating composition of the present invention may further contain, if necessary, various additives such as extender pigments, coloring pigments, plasticizers, foam inhibitors, anti-settling agents, leveling agents, other resins, And the like. The antifouling coating composition of the present invention comprises (A) a non-aqueous dispersion resin, (B)
The mixing ratio of the metal-containing antifouling agent and the (C) monobasic acid compound is usually 10 to 50% by weight, especially 12 to 50% by weight, based on the weight of the antifouling coating composition. The content is preferably 30% by weight, and (B) the metal-containing antifouling agent is usually 1 to 50% by weight, particularly 20 to 45% by weight.
And (C) the monobasic acid compound is preferably
(A) For the total acid groups of the non-aqueous dispersion resin,
(C) The ratio to the carboxyl group in the monobasic acid compound is 0.
It is added so as to be 3-3.0, especially 0.5-2.0. In addition,
When this ratio is 0.3 or less, the solubility of the coating film tends to decrease, and the antifouling effect tends to decrease. On the other hand, when it exceeds 3.0, the physical properties of the coating film tend to decrease.

The solid content of the antifouling coating composition is 40 to 40%.
90% by weight, preferably 50-80% by weight, is suitable. The antifouling coating composition of the present invention is prepared by mixing or dispersing the above-mentioned components in a lump or divided manner with a conventional coating equipment such as a ball mill or disperser. The antifouling coating composition of the present invention thus prepared, as it is, or after adjusting the viscosity with a solvent, or airless spray coating,
It is applied to ships and marine structures by air spray coating, roller coating, brush coating, etc. The antifouling coating composition of the present invention is preferably applied so as to have a dry film thickness of about 30 μm to 300 μm, preferably 100 to 200 μm.

[0015]

The present invention will be described in more detail with reference to the following examples. In Examples, “parts” and “%” are based on weight. <Preparation of dispersion stabilizer (skin component) A> In a four-necked flask equipped with a stir bar, a thermometer, and a reflux tube, 30 parts of xylene,
10 parts of n-heptane and 5 parts of mineral spirit were charged, and the temperature was maintained at 100 ° C., where 80 parts of n-butyl methacrylate and 15 parts of 2-ethylhexyl methacrylate were added.
, A mixed component of 5 parts of glycidyl methacrylate and 3 parts of azoisobutyronitrile was added dropwise over 3 hours with stirring and reacted, and after holding for 1 hour, azoisobutyronitrile 1
And a mixture of 10 parts of xylene were added dropwise over 1 hour to react. Thereafter, the temperature was raised to 130 ° C., and methacrylic acid 3.5
Parts, 0.05 parts of triethylamine and 0.05 parts of 1,4-benzenediol were added to the same flask and reacted for 6 hours.
A dispersion stabilizer A which was a light brown viscous liquid having an acid value of 0 and a solid content of 65% was prepared.

<Preparation of Dispersion Stabilizer B> In the same manner as in Dispersion Stabilizer A, from the components shown in Table 1 below, an acid value of 0 and a solid content of 6 were obtained.
5% of dispersion stabilizer B was prepared.

[0017]

[Table 1]Table 1 (Unit: parts) Dispersion stabilizer (skin component) A B n-butyl methacrylate 80.0 17.0 0 2-ethylhexyl methacrylate 1 5.0 80.0 glycidyl methacrylate 5.0 3.0 azoisobutyronitrile 4.0 4.0 methacrylic acid 3.5 1. 5 Triethyleneamine 0.05 0 .05 5 1,4-benzenediol 0.05 0 .05 Xylene 4 0.04 0 .0 n-heptane 1 0.0 .1 1 .0 Mineral spirit 5.0 5.0 Solid content (%) 6 5 6 5 <Preparation of Nonaqueous Dispersion Resin Solutions I to V> The following table
Based on the composition shown in 2, dispersion stabilizer (skin component), polymerization
Composed of a reactive monomer (core component), a polymerization initiator and a solvent.
The mixture was heated and reacted in the usual manner, and the characteristics shown in the lower part of Table 2 were used.
Of non-aqueous dispersion resin solutions I to V
did.

[0018]

[Table 2]Table 2 (Unit: parts) Non-aqueous dispersion resin solution I II III IV V Dispersion stabilizer A 153.8 230.7 Dispersion stabilizer B 230.7 153.8 77.0 Polymerizable monomer Methyl methacrylate 25.0 14.3 8.5 5.0 Methyl acrylate 60.0 5.0 60.0 40.0 40.0 Methacrylic acid 15.3 1.5 Acrylic acid 45.0 25.7 105.0 Azoisobutyronitrile 3.0 3.0 3.0 3.0 3.0 solvent Xylene 36.0 70.0 36.0 50.0 50.0 n-heptane 120.0 90.0 120.0 100.0 140.0 Mineral spirit 90.0 59.0 90.0 69.0 83.0 Characteristic Solid content (%) 40 40 40 40 40 Acid value of resin (KOHmg / g) 50 175 100 5 410 Average particle size of resin (nm) 180 250 200 110 290 Skin component / core component 50/50 75/25 50 / 50 75/25 25/75 (Solid content weight ratio)

Examples 1 to 5 and Comparative Examples 1 to 3 The components shown in Table 3 below were mixed and dispersed to produce antifouling paints of Examples 1 to 5 and Comparative Examples 1 to 3. Each of these antifouling paints was applied to a steel plate coated with an anticorrosive paint by air spray coating to a dry film thickness of 150 μm, and dried. When an abrasive test and an antifouling test were performed on the obtained test plate,
The results shown in Table 4 were obtained. In addition, the test was performed based on the following method. <Abrasiveness test> Rotor test (25 ° C, 15 knots)
Thereafter, the film thickness was measured with a micrometer, and the difference from the film thickness before the test was calculated. <Antifouling test> In Toba Bay, Toba City, Mie Prefecture, a test plate was submerged in the sea and the appearance of the coating film was observed. Evaluation criterion 5: No deposit was observed on the test plate. 4: Adhesion of thin slime was observed on the test plate. 3: Thick slime adhered to the test plate. 2: Adherence of large animals and plants is observed. 1: Large attachment of large animals and plants is observed.

[0020]

TABLE 3 (Unit: Part) implementation example comparisons example antifouling coating composition 1 2 3 4 5 1 2 3 nonaqueous dispersion resin solution I 30.0 30.0 II 30.0 III 30.0 30.0 30.0 IV ( Reference) 30.0 V (Reference) 30.0 Monobasic lauric acid 7.0 Oleic acid 3.0 10.0 2.5 19.3 Naphthenic acid 3.5 0.3 Metal-containing antifouling agent Cuprous oxide 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Zinc pyrithione 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Talc 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Petroleum 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Mineral spirit 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ratio of carboxyl groups Note 1) 1.0 / 1.0 / 1.0 / 1.0 / 1.0 / 1.0 / 1.0 / 1.0 / 1.5 0.9 1.2 0.5 0.8 0 1.4 1.0 Note 1) (Number of carboxyl groups in non-aqueous dispersion resin) / (number of carboxyl groups in monobasic acid)

[0021]

[Table 4] Table 4 Example Comparative Example 1 2 3 4 5 1 2 3 Abrasiveness test (μm) 3 months 15 15 35 25 27 25 5 75 6 months 32 28 66 49 58 39 7 140 9 months 48 41 98 73 85 42 8 150 or more 12 months 63 57 132 97 115 43 10- Antifouling test 3 months 5 5 5 5 5 5 4 5 6 months 5 5 5 5 5 4 4 5 9 months 5 5 5 5 5 3 3 3 12 months 5 5 5 5 5 2 2 Peeling 18 months 5 5 5 5 5 1 2-24 months 4 4 5 5 5 1 1- As is clear from Table 4 above, the antifouling paint composition of the present invention is In the coating films of Examples 1 to 5, the acid groups of the non-aqueous dispersion resin and the metal-containing antifouling agent did not react in seawater, and had excellent polishing properties and long-term antifouling properties, and were good. .

On the other hand, Comparative Example 1 containing no monobasic acid
Then, it is polished in the early stage, probably because the acid group of the non-aqueous dispersion resin and the metal-containing antifouling agent reacted in seawater,
It was not polished continuously and had poor long-term antifouling properties. Also,
In Comparative Example 2 in which the non-aqueous dispersion resin having a low acid value was mixed with a monobasic acid, the polishing property was low and the long-term antifouling property was poor. In Comparative Example 3 in which a non-aqueous dispersion resin having a high acid value and a monobasic acid were blended, the polishing property was large,
Peeled off.

[0023]

According to the present invention, an excellent antifouling paint having excellent polishing properties and long-term antifouling properties can be obtained.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroharu Sasaki 7-1414-46 Shimonagata, Nishinasuno-cho, Nasu-gun, Tochigi Prefecture

Claims (2)

[Claims] 1. A non-aqueous dispersion having an acid value of 20 to 400, comprising (A) a hydrophilic core component having an acid group and a hydrophobic skin component having no acid group, dispersed in a hydrocarbon solvent. An antifouling paint composition comprising a resin, (B) a metal-containing antifouling agent, and (C) a monobasic acid compound having a carboxyl group. 2. The method according to claim 1, wherein the ratio of the number of acid groups contained in the non-aqueous dispersion resin (A) to the number of carboxyl groups contained in the monobasic acid compound (C) is from 0.3 to 3.0. Antifouling paint composition.