JP2789684B2 - Underwater antifouling coating agent - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an underwater antifouling coating agent for preventing adhesion of underwater organisms to various objects immersed in water.

[Conventional technology]

Barnacles on the surface of underwater objects such as ship bottoms, buoys, fishing nets (cultured nets such as hamachi and scallops, fixed nets for salmon, etc.) immersed in water, underwater pollution prevention sheets, and various suction and drain pipes for cooling, Various obstacles occur due to the adhesion of Serpula, mussels, algae and the like. It is well known that an underwater antifouling coating is applied to the surface of an underwater immersion to prevent fouling by those organisms.

Typical examples of this type of underwater antifouling coating agent include those using an antifouling agent such as a compound having an effect of preventing adhesion to living organisms or cuprous oxide. For example, as for underwater antifouling coating agents using an organotin compound as an antifouling agent, Japanese Patent Publication No. 40-21426 and Japanese Patent Publication No. 44-957
No. 9, JP-B-46-13392, JP-B-49-20491, JP-B-51-11647, and JP-B-52-48170.

[Problems to be solved by the invention]

However, these known underwater antifouling coatings have the following drawbacks, and improvement thereof has been strongly desired.

Known underwater antifouling coating agents are roughly classified into the following two types. One type is a type of underwater antifouling coating agent in which the resin forming the film does not dissolve in water, and only the antifouling agent dissolves in water, thereby preventing the adhesion of organisms in water. This type of antifouling coating has a good initial antifouling effect. However, after the antifouling agent on the film surface is eluted and lost, the antifouling agent in the deep part of the film gradually elutes, but the elution rate of the antifouling agent is slower as the depth of the film becomes deeper, In the long term, the antifouling effect was insufficient.

Another type is an underwater antifouling coating agent in which both the resin forming the film and the antifouling agent dissolve in water. The antifouling effect of this coating agent may be due to only the antifouling agent or to both the antifouling agent and the resin component (organotin copolymer, etc.). The anti-fouling coating surface will be maintained,
The durability of the antifouling effect is recognized more than the former. However, even in this case, there is a limit to the consumption of the coating,
On the contrary, at present, sufficient effects have not been obtained due to excessive consumption.

[Means for solving the problem]

The present inventors have conducted intensive studies on the above points, and as a result, have solved the above-mentioned various drawbacks of the conventionally known underwater antifouling coating agent, and have further improved antifouling properties. And a new type of underwater antifouling coating agent in which an antifouling agent or a surface lubricant is further combined.

That is, the present invention provides the following general formula (I): ｛Wherein, Z is a hydrogen atom or a methyl group, m is a real number of 1 or more, and n is a real number of 0 or more. Further, expression of X Hatsugi _{(a); -C p H 2p} O- ... (a) ( In the formula, p is a is a real number of 2-4) is a group represented by the formula of Y Hatsugi ( b); Wherein R ₄ and R ₅ are each an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenyloxyl group or the following formula (c); (Wherein, R _{6 to} R ₈ are each selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a hexyl group, a substituted phenoxyl group or an organosiloxane group represented by the formula (c). Groups which may be the same or different from each other) and are the same or different from each other. Which may be a group]. Further, R _{1 to} R ₃ are all alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups,
It is a group selected from a phenoxyl group or a substituted phenoxyl group, and may be the same or different. And / or one or more of the vinyl polymerizable monomers B copolymerizable with one or more of the above monomers A and one or more of the above monomers A. The present invention relates to an underwater antifouling coating agent, which comprises a copolymer comprising at least one or more species and an antifouling agent as essential components.

Further, in the present invention, in addition to the above-mentioned polymer and / or copolymer and the antifouling agent, by further including a surface lubricant as an essential component, the durability of the antifouling effect is further improved. It can provide an underwater antifouling coating agent.

In the underwater antifouling coating composition of the present invention, the coating formed from the above-mentioned polymer or copolymer has a self-polishing property of gradually hydrolyzing from the surface in water, that is, the resin is gradually removed from the coating surface layer. By taking a mechanism in which the antifouling agent dispersed in the resin dissolves in water at the same time, a very excellent antifouling effect is exhibited for a long time. In addition, the combined use of a surface lubricating agent appropriately suppresses the hydrolyzability of the resin film, properly maintains the solubility of the film and the antifouling agent, and consequently improves the antifouling effect, and at the same time improves the antifouling effect. The agent itself also exerts an antifouling effect.

[Configuration of the invention]

In the underwater antifouling coating composition of the present invention, one or more polymers of the monomer A represented by the above general formula (I), that is, a homopolymer or a copolymer (hereinafter, referred to as one of the essential components) , Or a polymer A), or a copolymer of one or more of the monomers A and one or more of the vinyl polymerizable monomers B copolymerizable therewith ( Hereinafter, this is referred to as copolymer AB). Further, the above-mentioned polymer A and copolymer AB may be used in combination as needed.

Since such a polymer A and a copolymer AB both have a side chain derived from the monomer A, an organosilyl group or an organosiloxane group, and an ether bond composed of an alkylene oxide or a polyalkylene oxide, These groups or bonds are appropriately hydrolyzed in water, whereby the remaining resin is dissolved. At the same time, the antifouling agent and the surface lubricating agent are gradually released into the water, thereby effectively and continuously preventing biofouling on the surface of the underwater object. The present inventors have found that such an antiadhesion effect is more remarkably exhibited than the conventional underwater antifouling coating agent, as shown in Examples described later.

In addition, since the above-mentioned polymer A and copolymer AB are easily soluble in an organic solvent, a dissolved solution of this and an underwater antifouling coating agent including an antifouling agent and a surface lubricant is immersed in water. By coating and drying on the surface of the object to be formed, it is possible to easily form a uniform film.

The monomer A for obtaining the polymer A and the copolymer AB is, as shown by the above-mentioned general formula (I), an alkylene oxide or a polyalkylene together with an organosilyl group or an organosiloxane group in the molecule. shall apply those having oxide in the formula (I), Z is hydrogen atom or a methyl group, wherein the X Hatsugi (a); a group represented by _{-C p H 2p O- ... (a} ) is there.

In the above formula (a), p is a real number of 2 to 4,
In addition to ethylene oxide represented by p = 2, propylene oxide represented by p = 3, and butylene oxide represented by p = 4, one or more of these oxides are 1
Also included are those that are mixed and repeated in the molecule. Also,
M representing a repeating unit of these alkylene oxides is 1
Although the above real numbers can be taken, it is usually preferable that the number be up to about 5,000. Since the alkylene oxide group is introduced by dehydration condensation or the like, the monomer A is usually a mixture of alkylene oxide groups having different numbers of repetitions. Therefore, the above-mentioned m value should be expressed as an average value of these (), and the reason why it is expressed as the real number is also for this reason. From this point of view, the following embodiments are indicated by the above.

In the general formula (I), R _{1 to} R ₃ are all groups selected from the group consisting of alkyl, alkoxyl, phenyl, substituted phenyl, phenoxyl and substituted phenyl. The number of carbon atoms in the alkoxyl group is usually up to about 30, preferably up to about 18. Examples of the substituent of the substituted phenyl group and the substituted phenoxyl group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. These R _{1 to} R ₃ may be the same or different groups.

Further, in the general formula (I), Y is the following formula (b); Is a group represented by Here, R ₄ and R ₅ are the same groups as those of R _{1 to} R ₃ described above or the following formula (c); And n groups of R ₄ and R ₅ may be the same or different from each other. When R ₄ and R ₅ are the same groups as the above R _{1 to} R ₃ , it is needless to say that these groups and the groups R _{1 to} R ₃ may be the same or different. It is.

In the above formula (c), each of R _{6 to} R ₈ is selected from the group consisting of an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenoxyl group and an organosiloxane group represented by the formula (c). It is a selected group, and the above-mentioned alkyl group and alkoxyl group usually have up to about 30 carbon atoms, preferably up to about 18 carbon atoms. Examples of the substituent of the substituted phenyl group and the substituted phenoxyl group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. R _{6 to} R ₈ may be the same group or different groups.

The number of repetitions n of the group represented by the formula (b), that is, the organosiloxane group, can be a real number of 0 or more, but is usually preferably up to about 10,000. Since the organosiloxane group is introduced by a dehydration condensation or addition reaction, the monomer A is usually a mixture of organosiloxane groups having different numbers of repetitions. Therefore, the above-mentioned n value should be expressed as an average value thereof (), and it is for this reason that it is expressed as the real number. From this point of view, the following embodiments are indicated by the above.

Such a monomer A is easily available as a commercial product. Examples of synthesis include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-methacrylic acid
With hydroxypropyl, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, polybutylene acrylate, polybutylene methacrylate, and the like An organosiloxane having a di-substituted / monohydroxysilane group at one end, a tri-substituted / monohydroxysilane or the like, an organosilyl compound having the above-mentioned R _{1 to} R ₃ in the molecule or the above-described R ₁ to R _{1 in the} molecule. and organosiloxane compounds having a _5, a method of dehydration condensation, the same and corresponding chlorosilanes with unsaturated acid base (e.g., triethylamine, Imitazoru etc.) dehydrochlorination reaction in the presence of There is a method to.

Specific examples of such a monomer A include 2- (trimethylsiloxy) ethyl (meth) acrylate, 2- (triisopropylsiloxy) ethyl (meth) acrylate, diethylene glycol-mono (triisopropylsilyl) ether (meth) Acrylate, triethylene glycol-mono (t-butyl, dimethylsilyl) ether ((meth) acrylate, polyethylene glycol-
Mono (organosilyl) ether (meth) acrylate, polyethylene glycol-mono (organopolysiloxane) ether (meth) acrylate, 2- (trimethylsiloxy) propyl (meth) acrylate, 2-triisopropylsiloxy) propyl (meth) acrylate, Dipropylene glycol-mono (triisopropylsilyl) ether (meth) acrylate, tripropylene glycol-mono (t-butyl, dimethylsilyl) ether (meth) acrylate, polypropylene glycol-mono (organosilyl) ether (meth) acrylate, polypropylene Glycol-mono (organopolysiloxane) ether (meth) acrylate, 2- (trimethylsiloxy) butyl (meth) acrylate, 2-
(Triisopropylsiloxy) butyl (meth) acrylate, dibutylene glycol-mono (triisopropylsilyl) ether (meth) acrylate, tributylene glycol-mono (t-butyl, dimethylsilyl) ether (meth) acrylate, polybutylene glycol-
Mono (organosilyl) ether (meth) acrylate, polybutylene glycol-mono (organopolysiloxane) ether (meth) acrylate, monooxyethylene / monooxypropylene glycol-mono (trimethylsilyl) ether (meth) acrylate, monooxyethylene Monooxypropylene glycol-mono (triisopropylsilyl) ether (meth) acrylate, monooxyethylene / monooxypropylene /
Monooxybutylene glycol-mono (organosilyl) ether (meth) acrylate, monooxyethylene / monooxypropylene / monooxybutylene glycol-mono (organosiloxane) ether (meth) acrylate, polyoxyethylene / polyoxypropylene glycol-mono (Organosilyl) ether (meth) acrylate, polyoxyethylene polyoxypropylene glycol-mono (organosiloxane) ether (meth) acrylate, polyoxyethylene polyoxybutylene glycol-mono (organosilyl) ether (meth) acrylate, Polyoxyethylene / polyoxybutylene glycol-mono (organosiloxane) ether (meth) acrylate, polyoxypropylene / polyoxybutylene Glycol-mono (organosilyl) ether (meth) acrylate, polyoxypropylene / polyoxybutylene glycol-mono (organosiloxane) ether (meth) acrylate, polyoxyethylene / polyoxypropylene / polyoxybutylene glycol-mono (organosilyl) ) Ether (meth) acrylate, polyoxyethylene / polyoxypropylene / polyoxybutylene glycol-mono (organosiloxane) ether (meth) acrylate, and the like.

Examples of the vinyl polymerizable monomer B used together with the monomer A to obtain the copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Methacrylates such as 2-hydroxyethyl, acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, and maleic esters such as dimethyl maleate and diethyl maleate , Fumaric acid esters such as dimethyl fumarate, diethyl fumarate, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, fumarate Examples thereof include luic acid, crotonic acid, crotonic acid ester, itaconic acid, and itaconic acid ester.

Such a vinyl polymerizable monomer B acts as a modifying component for imparting various performances to the antifouling coating according to the purpose of use, and has a higher molecular weight than the monomer A alone. It is also a convenient component for obtaining coalescence. The amount of the monomer B is set in an appropriate range in consideration of the above performance and the antifouling effect based on the monomer A. Generally, monomer A
And the proportion of monomer B in the total amount of 95% by weight or less,
Preferably, it is 90% by weight or less. That is, if the proportion of the monomer A constituting the copolymer AB is at least 5% by weight, preferably at least 10% by weight, the antifouling effect based on the monomer A can be sufficiently exerted. The amount of the monomer B may be appropriately set within the above range.

The polymer A and the copolymer AB are prepared by subjecting the monomer A or the monomer B as described above to a monomer B in the presence of a vinyl polymerization initiator.
It can be obtained by polymerizing by various methods such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like according to a conventional method. Examples of the above vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide, and di-tert-
Peroxides such as butyl peroxide;

The weight average molecular weight of the polymer A and the copolymer AB obtained by the above method is generally desirably in the range of 1,000 to 1,500,000. If the molecular weight is too low, it is difficult to form a film that can withstand use. If it is too high, the viscosity when used as a coating agent is high, and since the resin solid content is low, only a thin film can be formed by one coating. It is not possible to obtain it, and there is a problem that several coatings are required to obtain a dried film of a certain degree or more.

The antifouling agent used as another one of the essential components in the present invention widely includes conventionally known ones including an organic compound containing a metal, an organic compound containing no metal, and an inorganic compound.

Examples of the organic compound containing a metal include an organic tin compound, an organic copper compound, an organic nickel compound, an organic zinc compound, and the like, and also include maneb, manceb, propineb, and the like. Organic compounds containing no metal include N-trihalomethylphthalimide, dithiocarbamic acid, N-arylmaleimide, and 3-substituted amino-1.
• 3-thiazolidine-2,4-dione, dithiocyano compounds, triazine compounds and the like. Furthermore, examples of the inorganic compound include cuprous oxide, copper powder, copper compounds such as copper thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, and nickel sulfate.

The organic tin-based compounds among the organic compounds containing the above-mentioned metals include triphenyltin chloride, triphenyltin halide such as triphenyltin fluoride, tricyclohexyltin chloride, tricyclohexyltin halide such as tricyclohexyltin fluoride, and tributyltin. Chloride, tributyltin fluoride such as tributyltin fluoride, triphenyltin hydroxide, tricyclohexyltin hydroxide, bis (triphenyltin)
-Α.α'-dibromosuccinate, bis (tricyclohexyltin) -α.α'-dibromosuccinate, bis (tributyltin) -α.α'-dibromosuccinate,
Bis- (triphenyltin) oxide, bis- (tricyclohexyltin) oxide, bis- (tributyltin) oxide, triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatic acid ester, triphenyl Examples include tin dimethyldithiocarbamate and triphenyltin nicotinate.

Examples of the organic copper-based compound include oxine copper, copper nonylphenol sulfonate, copper-bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, and bis (pentachlorophenolic acid).
Copper and the like. Further, the organic nickel-based compound includes nickel acetate, nickel dimethyldithiocarbamate, and the like, and the organic zinc-based compound includes zinc acetate, zinc carbazate, and zinc dimethyldithiocarbamate.

In addition, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide and the like as the N-trihalomethylphthalimide among the organic compounds containing no metal, and bis (dimethylthiocarbamoyl) disulphide as the dithiocarbamic acid , N-methyldithiocarbamate, ammonium ethylenebis (dithiocarbamate), milneb and the like, and N-arylmaleimides include N- (2
.4-6-trichlorophenyl) maleimide, N-4-
Tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N-
(Anilinophenyl) maleimide, N- (2,3-xylyl) maleimide, and the like, respectively.

Also, 3-substituted amino-1,3-thiazolidine-2.
As 4-dione, 3-benzylideneamino-1.3
-Thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino) -1,3-thiazolidine-2,4-
Dione, 3- (2-hydroxybenzylideneamino)-
1,3-thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideneamino) -1,3-thiazoline-2,4-dione, 3- (2.4-dichlorobenzylideneamino) -1.3 -Thiazolidine-2,4-dione and the like; dithiocyano-based compounds such as dithiocyanomethane and dithiocyanoethane; and 2,5-dithiocyanothiophene; and triazine-based compounds as 2-methylthio-4-t-. Butylamino-6-cyclopropylamino-s-triazine and the like are each mentioned.

Other organic compounds containing no metal include 2-amino-3-chloro-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, and 5,10-dihydro-5.
• 10-dioxanaphtho [2.3-b] -1.4-dithiin-2.3-dicarbonitrile and the like.

In the present invention, one or more of the various antifouling agents as described above are selected and used. The amount of the antifouling agent depends on the amount of the hydrolyzable agent of the polymer A and / or the copolymer AB. Is set in an appropriate range in consideration of the synergy between the antifouling effect of the antifouling agent and the chemical antifouling effect of the antifouling agent. Generally, it is desirable that the proportion of the antifouling agent in the total amount of the polymer A and / or the copolymer AB is 0.1 to 80% by weight. If the amount of the antifouling agent is too small, the above-mentioned synergistic effect cannot be expected. If the amount is too large, the formed underwater antifouling film tends to have film defects such as cracks and peeling, and it is difficult to obtain effective antifouling properties.

In the present invention, the antifouling effect can be further improved by appropriately using a surface lubricant in addition to the polymer A and / or the copolymer AB and the antifouling agent. The surface lubricant widely includes various substances known to impart a lubricating property to the coating surface.
Typical examples are petroleum wax specified in JISK2235, liquid paraffin specified in JISK2231,
Silicone oil having a kinematic viscosity of 55,000 centistokes or less at 5 ° C., fatty acid having 8 or more carbon atoms having a melting point of -5 ° C. or more and esters thereof, and having 12 to 20 carbon atoms
An organic amine having an alkyl or alkenyl group of
Polybutene having a kinematic viscosity of 60,000 centistokes or less at 25 ° C. can be used.

Examples of the above include paraffin wax, microcrystalline wax, petrolatum, and the like.Examples of the above include ISOVG10, ISOVG15, ISOVG32, and ISOVG10.
VG68 and ISOVG100 equivalents are, for example, KF96L-0.65 and KF96L manufactured by Shin-Etsu Chemical Co., Ltd.
−2.0, KF96−30, KF96H−50,000, KF965, KF50, KF5
4, KF69, trade name TSF440, TSF made by Toshiba Silicone Co., Ltd.
410, TSF440, TSF431, TSF433, TSF404, TFA4200, YF38
60, YF3818, YF3841, YF3953, TSF451, trade names SH200, SH510, SH3531, SH230, FS126 manufactured by Toray Silicone Co., Ltd.
5 and the like.

The most common silicone oil is dimethyl silicone oil, but other methylphenyl silicone oil, polyether silicone oil, cyclic polysiloxane oil, alkyl-modified silicone oil,
Other materials such as methyl chlorinated phenyl silicone oil, higher fatty acid modified silicone oil, and fluorosilicone oil may be used.

Further, as the above specific examples, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid, melissic acid, lauroleic acid, oleic acid, vaccenic acid, gadolinic acid,
Whale oil, shark oil, diuniperic acid, and the like. Further, as esters of these carboxylic acids, stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate,
Cetyl palmitate, seryl serotate, myricil palmitate, melisil meliseate, whale wax, dense wax, carnauba wax, montan wax, insect wax, tristearin,
Tolpalmitin, triolein, myristo-dilaurin,
Caprylo lauromyristin, stearopalmito olein, monostearin, monopalmitin, distearin,
Dipalmitin, beef tallow, lard, horse tallow, sheep tallow, cod liver oil, coconut oil, palm oil, wood wax, kaputsu oil, cocoa butter, china butter, iritsupe fat.

Further, specific examples of the above include todecylamine,
Tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, tallow, alkylamine,
Cocoalkylamines, soybean oil alkylamines, didodecylamines, ditallow hydrogenated alkylamines, dodecyldimethylamines, cocoalkyldimethylamines, tetradecyldimethylamines, hexamethyldimethylamines, octadecyldimethylamines, etc. Is Nitsan Polybutene 0N (trade name, manufactured by NOF Corporation)
06N, 015N, 3N, 5N, 10N, 30N, 200N, 0SH, 06SH, 015S
H, 3SH, 5SH, 10SH, 30SH, 200SH and the like.

In the present invention, one or more of the above-mentioned various surface lubricants are selected and used, and the amount of the above-mentioned polymer A and / or copolymer is used.
It is set in an appropriate range in consideration of the performance such as drying property and adhesion based on AB and the antifouling agent and the antifouling performance. Generally, the ratio of the surface lubricant to the total amount of the polymer A and / or the copolymer AB and the surface lubricant is 0.1 to 70%.
%, Preferably 0.5 to 50% by weight.

As described above, the underwater antifouling coating composition of the present invention contains the polymer A and / or the copolymer AB and the antifouling agent, or the antifouling agent and the above-mentioned surface lubricant as essential components. It is usually used after being diluted with an organic solvent. Therefore, as a polymerization method for obtaining the polymer A and / or the copolymer AB, it is particularly preferable to employ a solution polymerization method or a bulk polymerization method. In the solution polymerization method, the reaction solution after polymerization can be used as it is or diluted with a solvent, and in the bulk polymerization method, the reaction product after polymerization can be used after adding a solvent.

Examples of the organic solvent used for the above purpose include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol, and butyl alcohol. Alcohol solvents such as dioxane,
Examples thereof include ether solvents such as diethyl ether, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, or a mixture thereof.

The amount of the organic solvent used is such that the concentration of the polymer A and / or the copolymer AB in the solution is usually 5 to 90% by weight, preferably 15 to 90% by weight.
It is better to be in the range of ~ 85% by weight. The viscosity of the solution at this time is generally preferably 150 poise or less / 25 ° C., which facilitates film formation.

In the underwater antifouling coating composition of the present invention thus configured,
If necessary, a colorant such as a red iron oxide or a pigment such as titanium dioxide or a dye may be blended. Also, the usual anti-sagging agent,
An anti-separation agent, an anti-settling agent, an antifoaming agent and the like may be added.

Further, the polymer A and / or the copolymer AB used in the present invention are hydrolyzed by the presence of water, and therefore, when preparing a coating agent, the polymer A and / or the copolymer AB trap water contained in the antifouling agent and the pigment. It is desirable to add a so-called water binder to the system. Examples of such water binders include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate, and tributyl orthoformate; trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate, and tributyl orthoacetate; Trialkyl orthoborates such as trimethyl borate, triethyl orthoborate, and tributyl orthoborate; tetra (substituted) such as tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, tetra (2-methoxyethyl) silicate, and tetra (2-chloroethyl) silicate ) Alkyl silicates, tetra (substituted) aryl silicates such as tetraphenyl silicate and tetrabenzyl silicate, and the above-mentioned tetra (substituted) alkyl silicates and tetra (substituted) ) Condensates of aryl silicates (dimers, trimers, tetramers, hydrolyzable ester compounds such as hexamers, etc.), phenylalanine isocyanate include compounds having an isocyanate group such as benzene Huo isocyanate.

In order to form an antifouling film on the surface of an object to be immersed in water using the underwater antifouling coating agent of the present invention, for example, applying the coating agent as a solution to the surface of the object by appropriate means, It is only necessary to dry at room temperature or under heating to evaporate and remove the solvent.

[Action]

The polymer A and / or copolymer AB used in the present invention has an organosilyl group or an organosiloxane group derived from the monomer A and an alkylene oxide group or a polyalkylene oxide group. It imparts hydrolytic properties to the coating to be formed. The vinyl polymerizable monomer B is used for imparting a degree of hydrolysis to the coating of the copolymer AB if necessary.
It acts as a convenient regulatory component for obtaining higher molecular weight polymers as compared to alone.

The antifouling agent used in the present invention chemically prevents the adhesion of organisms in water. The antifouling agent obtained from the polymer A and / or the copolymer AB is appropriately hydrolyzed and dissolved, and simultaneously the antifouling agent is used. The soiling agent and the surface lubricant are also gradually eluted into water, so that the antifouling effect can be maintained for a long time. Further, the surface lubricant used in the present invention has a function of controlling the hydrolysis of the coating film and a physical antifouling function, and plays a large role in improving the antifouling property.

As described above, according to the combined use of the polymer A and / or the copolymer AB and the antifouling agent, or the combination of these with the surface lubricant in the present invention, the polymer A and / or the copolymer AB can be used as the antifouling agent. It has a function of appropriately adjusting excessive dissolution and insufficient dissolution of the agent, and it is considered that the antifouling performance of the coating film is stably maintained over the medium term.

〔The invention's effect〕

Since the underwater antifouling coating composition of the present invention has the characteristic properties as described above, it is necessary to prevent underwater biofouling, such as at the bottom of a ship, an underwater structure such as a fish net or a cooling water pipe, and even an underwater structure. When applied to a marine pollution control membrane or the like used for preventing sludge diffusion in civil engineering work, it exhibits a remarkable antifouling effect and can effectively prevent biological adhesion fouling of a submerged submerged substrate.

〔Example〕

Next, the present invention will be specifically described with reference to Production Examples, Examples and Comparative Examples of polymers. The parts in the examples are parts by weight, the viscosity is the measured value of the foam viscosity at 25 ° C., and the molecular weight is the weight average molecular weight by GPC.

Production Examples 1 to 8 A solvent a was charged into a flask equipped with a stirrer in accordance with the composition shown in Table 2 ((1) and (2)), and the temperature was raised to a predetermined reaction temperature. A mixed solution of B and the polymerization catalyst a was dropped into the flask in 6 hours, and after the completion of the dropping, the mixture was kept at the same temperature for 30 minutes. Then, a mixture of the solvent b and the polymerization catalyst b was added dropwise over 20 minutes, and stirring was continued at the same temperature for 5 hours to complete the polymerization reaction. Finally, a diluting solvent was added for dilution to obtain polymer solutions I to VIII.

Production Example 9 Monomer A, Monomer B and polymerization catalyst a were charged into a heat-resistant and pressure-resistant container according to the composition shown in Table 2 ((1) and (2)), and the reaction was carried out while completely sealing and shaking. The temperature was raised to this temperature, and shaking was continued at this temperature for 8 hours to complete the reaction. Next,
Add the diluent solvent and shake for 3 hours to dissolve, and polymer solution IX
I got

Production Example 10 In a flask equipped with a stirrer, a solvent a, a monomer A and a polymerization catalyst a were charged according to the composition shown in Table 2 ((1) and (2)), and the temperature was raised to a predetermined reaction temperature while stirring. Stirring was continued at the temperature for 6 hours to obtain a polymer solution X.

The monomers A (A _{1 to} A ₁₎ used in the above Production Examples 1 to 10 were used.
₁₀ ) are Z, X [p in formula (a)], m (), Y [R ₄ , R ₅ ] in formula (b), n
() And R _{1 to} R ₃ have the structures shown in Table 1 below.

Examples 1 to 56 The polymer solutions I to X were mixed and dispersed by a homomixer at 2,000 rpm according to the composition shown in the following Tables 3 to 5 (the numerical values in the table are% by weight) to obtain 56 types. Was prepared.

In the ingredients, Paraffin Wax 120P and Petrolatum No. 1 were JIS K2235 petroleum wax, ISOVG-10.
Is a liquid paraffin of JIS K2231. KF-69 is silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., and Nitsusan Polybutene 06N is polybutene manufactured by NOF Corporation.
These are all used as one kind of surface lubricant.

In addition, Oil Blue 2N [trade name of Orient Chemical Co., Ltd.] is a dye, DISPARON 6900-20X [trade name of Kusumoto Kasei Co., Ltd.] and AERILIL 300 [trade name of Nippon AERILIL CO., LTD.] All are additives for preventing sagging.

Comparative Examples 1 to 4 The same procedures as in Examples 1 to 56 were repeated except that an organic tin copolymer solution was used instead of the polymer liquids I to X.
Four types of underwater antifouling coating agents having the composition shown in the table were prepared.

The above-mentioned organic tin copolymer solution is a copolymer solution polymerized using 40 parts of methyl methacrylate, 20 parts of octyl acrylate, and 40 parts of tributyltin methacrylate, and the weight average molecular weight of the copolymer is 90,000 clear xylene 50% by weight solution.

Comparative Examples 5 to 7 In the same manner as in Examples 1 to 56 except that a hydrolyzable organosilicon copolymer solution was used instead of the polymer solutions I to X, the composition shown in the following Table 6 was used. Three types of underwater antifouling coatings were prepared.

The above-mentioned hydrolyzable organic silicon copolymer solution is a copolymer solution polymerized using 35 parts of trimethylsilyl methacrylate, 45 parts of methyl methacrylate, and 20 parts of n-butyl acrylate, and the weight of the copolymer. Average molecular weight 7,00
0 is a clear 50% by weight solution of xylene.

The following tests were performed for each of the underwater antifouling coatings of Examples 1 to 56 and Comparative Examples 1 to 7 described above. The results were as shown in Tables 7 and 8 below.

<Performance test> The storage stability, drying property and adhesion of each underwater antifouling coating agent were measured by the following methods.

A) Storage stability 200 g of each underwater antifouling coating agent was placed in a 250 cc mayonnaise bottle.
cc was put in, sealed and sealed. The temperature is 70 ° C and the humidity is 75%
Was stored in a thermo-hygrostat, and the storage stability was determined by the viscosity increase of each sample after 2 weeks. Initial viscosity (KU: about 70)
When the rate of increase was less than 10%, it was evaluated as ○, when it was 10% or more and less than 100%, it was evaluated as Δ, and when it was 100% or more, it was evaluated as ×.

B) Drying The drying was performed according to the method of JIS K5400.5.8. That is, the measurement was performed on each of the underwater antifouling coating agents applied to a glass plate with a film thickness of 100 μm using a film applicator. When the half-curing drying time was less than 1 hour, it was evaluated as ○, when it was 1 hour or more and less than 3 hours, and when it was 3 hours or more, x. Each test plate was dried in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 75%.

C) Adhesion Each water-based antifouling coating agent is applied to a polished copper plate (150 x 70 x 1 mm) with a film thickness of 100 µm using a film applicator, and is kept at a constant temperature and humidity of 20 ° C and 75% humidity for one week. The coating dried in the chamber was cut with a cutter knife to a length of 20 mm in a X-shape reaching the substrate. The center was extruded 10 mm from the back of the test plate with an Erichsen tester. At that time, the adhesion was judged based on the length of the film surface peeled from the center of the X-shaped cut portion. When there was no peeling, it was evaluated as ○, when less than 5 mm, as Δ, and when more than 5 mm, as ×.

<Anti-fouling performance test> Each underwater anti-fouling coating material was applied to a sand blasted steel sheet with a tar vinyl-based anti-corrosive paint applied in advance (100 × 2
(00 × 1 mm), spray-coated twice so that the dry film thickness is 120 μm on one side, and dried for one week in a constant temperature and humidity room at 20 ° C. and 75% relative humidity to produce a test plate did.

The test plate was immersed in seawater for 24 months in Aioi Bay, Aioi City, Hyogo Prefecture, which is a sea area where biofouling is severe, and the ratio of the occupied area (fouling area) of the fouling organisms on the test coating was measured over time. .

As is clear from the results in Tables 7 and 8 above, Example 1
The underwater antifouling coating compositions of Nos. To 56 of the present invention were all excellent in storage stability, drying property and adhesiveness, and did not show any adhesion of organisms in the antifouling performance test until after 24 months had passed.

In contrast, Comparative Examples 1 to 4 were organic tin copolymer based antifouling coatings in water, but were slightly inferior in storage stability and antifouling properties. In addition, in the coating agents of Comparative Examples 5 to 7, the dissolution of the antifouling agent also became faster, probably because hydrolysis and dissolution of the resin were considerably faster, and the durability of the antifouling performance was poor.

Claims (2)

(57) [Claims] 1. The following general formula (I): ｛Wherein, Z is a hydrogen atom or a methyl group,
m is a real number of 1 or more, and n is a real number of 0 or more. Also, X
Formula Hatsugi _{(a); -C p H 2p} O- ... (a) ( In the formula, p is a is a real number of 2-4) is a group represented by the formula of Y Hatsugi (b); Wherein R ₄ and R ₅ are each an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenyloxyl group or the following formula (c); (Wherein, R _{6 to} R ₈ are each selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenoxyl group or an organosiloxane group represented by the formula (c)) Groups which may be the same or different from each other) and are selected from among the organosiloxane groups represented by Or a group represented by the formula: Further, R _{1 to} R ₃ are all alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups,
It is a group selected from a phenoxyl group or a substituted phenoxyl group, and may be the same or different. And / or one or more of the vinyl polymerizable monomers B copolymerizable with one or more of the above monomers A and one or more of the above monomers A. An underwater antifouling coating agent comprising, as essential components, a copolymer comprising at least one or more species and an antifouling agent. 2. The underwater defence according to claim 1, further comprising a surface lubricating agent as an essential component in addition to the polymer and / or copolymer and the antifouling agent. Soil covering agent.