JP2600813B2 - Underwater antifouling coating agent - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an antifouling coating in water containing a polymer having an organosilyl group or an organosiloxane group in a side chain.

[Conventional technology]

Barnacles can be found on the surface of underwater objects such as ship bottoms, buoys, fishing nets (cultured nets such as hamachi and scallops, salmon fixed nets, etc.) immersed in seawater, underwater pollution control sheets, and various water suction and drain pipes for cooling. Various obstacles occur due to the adhesion of cerpula, mussels, algae and the like. It is well known that underwater antifouling coatings are applied to the surface of seawater immersions to prevent fouling by those organisms. This coating agent is roughly classified into the following two types.

B) An antifouling agent such as an organotin copolymer or cuprous oxide, which has an effect of preventing adhesion to living organisms and is slightly soluble in seawater.

For example, a coating agent using an organotin compound as an antifouling agent is disclosed in Japanese Patent Publication Nos.
No. 9, JP-B-46-13392, JP-B-49-20491, JP-B-51-11647, and JP-B-52-48170.

B) An antifouling coating agent that does not dissolve in seawater without using an antifouling agent.
Using silicone rubber to form a film.

For example, Japanese Patent Publication No. 53-35974 discloses a coating composition using a vulcanized silicone rubber as a coating agent, and Japanese Patent Laid-Open Publication No. Sho 51-96830 discloses an oligomeric silicone having a hydroxyl terminal group. The use of a mixture of rubber and silicone oil is shown. Further, JP-A-53-79980 discloses a mixture of a vulcanized silicone rubber and a metal-free and silicon-free fluid organic compound. Furthermore, Japanese Patent Publication No. 60-3433
Japanese Patent Application Laid-Open Publication No. 2002-122,197 discloses oligomeric room temperature-curable silicone rubbers (for example, trade names KE45TS, KE44 of Shin-Etsu Chemical Co., Ltd.).
RTV) and liquid paraffin or petrolatum are shown.

[Problems to be Solved by the Invention] These conventionally known underwater antifouling coating agents are capable of exhibiting performance according to the type thereof, and thus are properly used depending on the purpose, but all of them have disadvantages as described below. Therefore, these improvements have been strongly desired.

First, there are two more types of the coating agent of the above a. One type is a type of coating agent in which the resin forming the coating film does not dissolve in seawater, and only the antifouling agent dissolves in seawater, thereby preventing the adhesion of marine organisms. This type of antifouling coating has a good initial antifouling effect. However, after the antifouling agent on the surface of the coating film is eluted and lost, the antifouling agent in the deep part of the coating will gradually elute, but as the elution rate of the antifouling agent becomes deeper in the coating film, Due to its slowness, the antifouling effect has a shortcoming in the long run.

Another type is a type of coating in which both the resin forming the coating film and the antifouling agent dissolve in seawater. 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 (such as an organotin copolymer). The surface of the active antifouling coating film is maintained, and the antifouling effect is more persistent than the former. However, even in this case, there is a limit to the consumption of the coating film and the like, and conversely, the coating film is excessively consumed, so that a satisfactory effect cannot be obtained at present.

Further, the coating agent of the above item (b) utilizes the slipperiness of the surface coated with the silicone rubber to prevent the aquatic organisms from adhering to the surface. Although the silicone rubber for forming the coating has the following problems in that it forms a film by three-dimensionally cross-linking when used, although it has an advantage without any eluting components that may cause water pollution. ing.

First, there is the problem of curability after painting. For example,
When an underwater antifouling coating using an oligomeric room-temperature-curable silicone rubber that cures under the action of moisture in the air and forms a film as disclosed in JP-B-60-3433 is applied to the surface to be coated. The cross-linking agent, which affects the condensation reaction of silicone rubber, is activated by moisture and temperature in the atmosphere. Therefore, i) the surface of the coating film cures quickly, which hinders the curing of the deep part of the coating film. As a result, there is a high risk of peeling and blistering of the coating film from the surface to be coated. In addition, since the penetration of moisture into the inside is slow, the time required for curing becomes long. Ii) When such an underwater antifouling coating is used in a high-temperature, high-humidity place, only the hydrolysis of the cross-linking agent takes precedence, the cross-linking density does not increase, and the physical properties of the coating deteriorate. become. iii) Further, in a dry land, since the moisture in the atmosphere is small, hydrolysis of the crosslinking agent hardly occurs, and the curing of the film becomes extremely slow. In order to prevent this, a catalyst such as a tin compound or platinum may be used as a curing accelerator, but their catalytic effect tends to be insufficient at low temperatures.

Second, there is the problem of overcoating properties. Usually, the solvent of the coating material to be overcoated slightly improves the interlayer adhesion by slightly immersing the undercoating surface and mixing at the interface, but since the underlying silicone rubber is three-dimensionally cross-linked and cured, the solvent of the overcoating coating material is hardened. Does not attack the silicone rubber surface, and therefore has poor adhesion.

Third, there is the problem of pot life. The actual painting work may take longer than expected due to the size and structure of the object to be coated, or it may rain on the surface after the start of painting, and the surface to be coated may be painted, or the atmosphere may become humid. There may be situations where the coating is interrupted and the already opened and agitated coating must be placed for a longer time than expected. In such a case, a long-life potting agent is extremely inconvenient in the painting operation.

Fourth, there is the problem of storage stability. The underwater antifouling coating agent may be stored for a long time from the time it is manufactured until it is used, but the one that cures due to moisture or the like will have short storage stability unless dry nitrogen gas is enclosed during the manufacturing. Also,
Once the lid of the can is opened, there is a problem that moisture in the air enters and the surface of the coating material hardens and thickens, making it difficult to reuse.

[Means for solving the problem]

The present inventors have conducted intensive studies on the above points, and have found that there are no various problems with the conventionally known underwater antifouling coating agent of the above-mentioned b using silicone rubber alone or using a combination of silicone rubber and silicone oil or paraffin. In addition, a solvent that can be expected to have good antifouling properties, and in particular, can be expected to have better antifouling properties as compared with the underwater antifouling coating composition using the previously known antifouling agent-containing organotin copolymer described in (a) above. We have succeeded in obtaining a new type of underwater antifouling coating using a specific polymer in volatile form and combining this with an antifouling agent.

That is, the present invention provides the following general formula (a): (Where X ₁ is a hydrogen atom or a methyl group, m is 1
The above real numbers, R _{1 to} R ₅ are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group or a substituted phenoxyl group,
And m m R ₄ , R ₅ and R _{1 to} R ₃ may be the same or different groups, and the following general formula (b): (Where X ₂ is a hydrogen atom or a methyl group, and n is 0
More real, R '1 _{to R' 5} are both an alkyl group, an alkoxyl group, phenyl group, substituted phenyl group, shall apply in a group selected from among Fuenokishiru group or a substituted Fuenokishiru group, and n pieces of R ' _4, R _'5 and _R' 1 _{~R '3}
May be the same or different groups) and a monomer A ′ represented by the following general formula (c): [However, in the formula, X ₃ and X ₄ are a hydrogen atom or a methyl group, and both groups may be either a cis form or a trans form. One of Y ₁ and Y ₂ is the following equation (1); (Where p is 0 or 1 and r is a real number not less than 0, and R ″ _{1 to} R ″ ₂ are all alkyl, alkoxyl, phenyl, substituted phenyl, phenoxyl, substituted phenoxyl groups) Alternatively, r groups of R " ₄ , R" ₅ and R " _{1 to} R" ₃ may be the same groups or different groups selected from organosiloxane groups. And the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group or an organic group represented by the above formula (1). And / or two or more polymers selected from the monomers A "and / or one or two or more polymers selected from the monomers A, A 'and A" The present invention relates to an underwater antifouling coating composition comprising, as an essential component, a copolymer consisting of one or two or more kinds of vinyl polymerizable monomers B copolymerizable therewith and an antifouling agent.

Incidentally, prior to the present invention, the present applicant assumed that the methylene group (—CH ₂ —) in the above general formula (b), that is, the above group interposed between the Si atom and the ester-forming portion had the same number of carbon atoms. An essential component is a polymer or copolymer using a monomer having a structure substituted with 2 to 4 alkylene groups (particularly, having a trimethylsilyl group or a polydimethylsiloxane group), and further adding an antifouling agent thereto. An underwater antifouling coating has already been proposed as Japanese Patent Application No. 61-311221.

In this prior invention, the reason why the lower limit of the number of carbon atoms of the alkylene group of the monomer is set to 2 is that if the number is less than 2, the bondability of the ester forming portion is weakened, and the ester bond at the polymerization stage or when used as a coating agent. Was dissociated and the antifouling performance and its sustainability were reduced.

However, according to the subsequent studies by the present inventors, even if the alkylene group has a monomer having less than 2 carbon atoms,
That is, even in the case of the monomer A 'represented by the general formula (b), which is a methylene group having 1 carbon atom, such an alkylene group is completely interposed between the Si atom and the ester forming portion. Not represented by the monomer A represented by the general formula (a)
However, even if the polymerization is carried out in a state where the water in the solvent and the raw material monomer is sufficiently removed during the polymerization, a desired polymer that does not dissociate in the polymerization stage can be obtained. Was completed.

The film formed from this polymer has a self-polishing property that gradually hydrolyzes from the surface in water and seawater, that is, the film gradually hydrolyzes from the surface layer and dissolves, It has been found that the antifouling agent dispersed in the water has a mechanism of dissolving into the sea, thereby exhibiting a very excellent antifouling effect.

Further, in a further study based on the above findings, a polymer using the monomer A ″ represented by the general formula (c) also shows that an antifouling agent is contained in a film formed therefrom. By containing the same, as in the case of the polymer using the monomers A and A ', it exhibits good antifouling performance based on hydrolysis from the coating surface and its durability. And finally completed the present invention.

Examples of this type of antifouling coating agent include US Pat. Nos. 4,594,365 and 4,593,055 by M & T,
Although the use of a trialkylsilyl acrylate-based polymer is described, this coating agent has a hydrolysis rate that is too fast and the coating is consumed in a short time, so that the antifouling effect is long as in the present invention. It does not last and is not practical.

[Configuration of the invention]

In the underwater antifouling coating composition of the present invention, as one of its essential components, the monomer A, the monomer A 'represented by the above-mentioned general formulas (a), (b) and (c) and the monomer One or two or more polymers selected from the group A ", that is, a homopolymer or a copolymer (hereinafter, referred to as a polymer A), or the monomer A, the monomer A And a copolymer of one or more selected from monomers A "and one or more vinyl polymerizable monomers B copolymerizable therewith (hereinafter, these will be referred to as copolymers). (Referred to as union AB). Further, the above-mentioned polymer A and copolymer AB
May be used in combination as needed.

Since both the polymer A and the copolymer AB have an organosilyl group or an organosiloxane group derived from the monomers A, A ′, A ″ in the side chain, a film containing the organosilyl group or the antifouling agent is contained. Effectively hydrolyzes the organosilyl and organosiloxane groups, dissolves the residual resin, and gradually releases the antifouling agent into the sea, effectively and continuously preventing biofouling on the surface of underwater objects. We have:
It has been found that such an anti-adhesion effect is more remarkably exhibited than the conventional underwater antifouling coating agent as shown in Examples described later.

Further, since the above-mentioned polymer A and copolymer AB are easily soluble in an organic solvent, a solvent solution of this and a coating agent containing an antifouling agent is applied to the surface of an object to be immersed in seawater and dried. By doing so, it is possible to easily form a uniform film. Moreover, since the above-mentioned polymer A and copolymer AB are essentially non-reactive, different from the above-mentioned conventional reaction-curing type, the above-mentioned film formation is carried out under atmospheric humidity and temperature. It does not depend on the temperature, and has excellent pot life as a solution and storage stability. Furthermore, when the same type or another film is overcoated on this film, the above-mentioned film is eroded by the solvent of the overcoating agent, so that the interlayer adhesion with the overcoating film is excellent. That is, the disadvantages of the conventional underwater antifouling coating agent can be completely eliminated by using the polymer A and / or the copolymer AB.

Polymer A and copolymer AB exhibiting such effects
Monomer A among monomers A, A 'and A "for obtaining the above is an unsaturated acid monoester having an organosiloxane group in the molecule as represented by the general formula (a). And the monomer A 'is an unsaturated acid monomer having an organosilyl group (n = 0) or an organosiloxane group (n = 1 or more) in the molecule as represented by the general formula (b). And the monomer A ″ is an unsaturated acid ester having an organosilyl group (r = 0) or an organosiloxane group (r = 1 or more) in the molecule represented by the general formula (c). It is.

In the general formulas (a) and (b) representing the monomers A and A ′,
m and n are the number of repeating organosiloxane groups, and m
Can be a real number of 1 or more and n can be a real number of 0 or more. Since the organosiloxane group is introduced by dehydration condensation or the like, the monomers A and A 'are usually a mixture of organosiloxane groups having different numbers of repetitions. Therefore, the above m, n values should be expressed as their average value (,), and the reason why they are expressed as the real numbers is also for this reason. From this point of view, the following examples are represented by the above.

In the general formulas (a) and (b), X ₁ and X ₂ represent a hydrogen atom or a methyl group, and R _{1 to} R ₅ and R ′ _{1 to} R ′ ₅ each represent an alkyl group, an alkoxyl group, a phenyl group. A group selected from a group, a substituted phenyl group, a phenoxyl group or a substituted phenoxyl group. The above-mentioned alkyl group and alkoxyl group usually have up to about 5 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. Here, m R ₄ , R ₅ and R _{1 to} R ₃ may be the same or different from each other, and similarly, n R ′ ₄ , R ′ ₅ and R ′ _{1 to} R ' ₃ may be the same or different.

In the general formula (c) showing the monomer A ″, X ₃ and X ₄ are a hydrogen atom or a methyl group, and both groups can take either a cis form or a trans form as geometric isomerism. In the formula, _one of Y ₁ and Y ₂ is the following formula (1); And the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group or an organic group represented by the above formula (1). The number of carbon atoms of the above alkyl group is usually up to about 5, and the substituent of the above substituted phenyl group is halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, an acyl group and the like. .

In the above formula (1), p is 0 or 1, and r is the number of repetitions of the organosiloxane group, and 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 dehydration condensation or an addition reaction, the monomer A ″ is usually a mixture of organosiloxane groups having different numbers of repetitions. It is for this reason that these values should be expressed as an average value (), and are expressed as the above-mentioned real numbers, and from this point of view, they will be described above in the following embodiments.

Further, in the formula (1), R ″ _{1 to} R ″ ₅ each represent an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group,
It is a group selected from a phenoxyl group, a substituted phenoxyl group or an organosiloxane group. The above-mentioned alkyl group and alkoxyl group usually have up to about 5 carbon atoms, and the above-mentioned substituted phenyl group and substituted phenoxyl group are preferably halogen, alkyl groups having up to about 5 carbon atoms, alkoxyl groups. And an acyl group.
Here, r R " ₄ , R" ₅ and R " _{1 to} R" ₃ may be the same or different groups.

One example of the synthesis of such monomers A, A ′, A ″ is acrylic acid, methacrylic acid, maleic acid monoester and the like, and an organosiloxane having a di-substituted / monohydroxysilane group at one end. R _{1 to} R ₃ , R ′ _{1 to} R ′ ₃ or R ″ _{1 to} R ″ in a molecule comprising trisubstituted / monohydroxysilane, organosiloxane having one end having a hydroxymethyl group, or trisubstituted silane.
_And an organosilyl compound having ₃ or a group represented by R ₁ to
There is a method of dehydrating and condensing an organosiloxane compound having R ₅ , R ′ _{1 to} R ′ ₅ or R ″ _{1 to} R ″ ₅ .

Further, in order to obtain a copolymer AB, the above monomers A, A ',
Examples of the vinyl polymerizable monomer B used together with A ″ include methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate. Acrylates such as butyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate; maleic esters such as dimethyl maleate and diethyl maleate; fumaric esters such as dimethyl fumarate and diethyl fumarate , Styrene, vinyltoluene,
α-methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid and the like.

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 is compared with the monomers A, A ', and A "alone. The amount of the monomer B is determined in consideration of the above performance and the antifouling effect based on the monomers A, A 'and A ". Therefore, it is set to an appropriate range. In general, the proportion of the monomer B in the total amount of the monomers A, A 'and A "is 95% by weight or less, particularly preferably 90% by weight or less. If the proportion of the monomers A, A ′, A ″ constituting the polymer AB is at least 5% by weight, particularly preferably at least 10% by weight, the monomers A, A ′,
Since the antifouling effect based on A ″ can be sufficiently exhibited, the amount of the monomer B to be used may be appropriately set within the above range.

The polymer A and the copolymer AB are the monomers A,
A ′, A ″ or a monomer B is polymerized in the presence of a vinyl polymerization initiator by various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization in accordance with a conventional method.
Obtainable. As the above vinyl polymerization initiator,
Examples include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, and peroxides such as benzoyl peroxide and ditert-butyl peroxide. In the above polymerization reaction, as described above, water contained in the raw material monomers and the solvent is removed as much as possible, and the monomers A, A ′, and A ″ are hydrolyzed during the polymerization. It is important to prevent decomposition.

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 be used, and if it is too high, the viscosity becomes high when used as a coating agent, and the resin solid content is low, so that only a thin film can be obtained by one coating. In addition, there is a problem that several coatings are required to obtain a dry film thickness of a certain value or more.

The antifouling agent used as another one of the essential components in the present invention widely includes conventionally known ones. Roughly speaking, there are organic compounds containing metals, organic compounds containing no metals, and inorganic compounds.

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-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, and 3-substituted amino-
There are 1.3-thisozolidine-2.4-dione, dithiocyano 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 compounds 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, among the organic compounds containing no metal, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide and the like as N-trihalomethylthiophthalimide, and bis (dimethylthiocarbamoyl) disulphide as dithiocarbamic acid Ammonium N-methyldithiocarbamate, ammonium ammonium bis (dithiocarbamate), milneb and the like include N-arylmaleimides such as N-arylmaleimide.
(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, and dithiocyano-based compounds include dithiocyanomethane, dithiocyanoethane, 2.5-dithiocyanothiophene and the like.

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 ratio of the antifouling agent to the total amount of the polymer A and / or the copolymer AB is 0.1 to 65% by weight. If the amount of the antifouling agent is too small, the antifouling effect cannot be expected. If the amount is too large, film defects such as cracks and peeling are likely to occur in the formed underwater antifouling film, and it becomes difficult to obtain effective antifouling properties.

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 as essential components, and is usually prepared using an organic solvent. Used after dilution. For this reason, 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 and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alone or in combination.

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 in the range of 5 to 80% by weight, particularly preferably 30 to 70% by weight. At this time, the viscosity of the solution is preferably not more than 150 boise / 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-segregation agent, an anti-settling agent, an antifoaming agent, etc. may be added.

To form an antifouling film on the surface of an object to be immersed in seawater using the underwater antifouling coating agent of the present invention, for example, after 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.

(Operation)

Since the polymer A and / or the copolymer AB used in the present invention each have an organosilyl group or an organosiloxane group derived from the monomers A, A ′, A ″, a coating film to be formed is formed. The vinyl polymerizable monomer B is used for imparting an appropriate degree of hydrolyzability to the coating of the copolymer AB, if necessary, and the monomers A, A ', A "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 attachment of marine organisms, and the film is gradually formed due to the hydrolyzability of the film obtained from the polymer A and / or the copolymer AB. By dissolving the antifouling agent simultaneously with dissolution, the antifouling effect can be maintained for a long time.

As described above, according to the combination system of the polymer A and / or the copolymer AB and the antifouling agent in the present invention, the polymer A and / or the copolymer AB excessively elutes and elutes the antifouling agent. It has the function of excessively adjusting the shortage, and it is considered that the antifouling performance of the coating is stably maintained over a long period of time.

〔The invention's effect〕

The above-mentioned specific polymer used in the underwater antifouling coating agent of the present invention has a non-reactive itself, has a solvent volatile type drying property, and forms a thermoplastic film which is soluble in seawater. The underwater antifouling coating composition of the present invention has the following advantages as compared with the conventional anti-fouling coating compositions of A and B types.

First, at the time of production of the coating agent, there is no danger of deterioration due to the antifouling agent, and the coating agent is stable. There is no need to fill an inert gas when canning, and there is no limitation on the pot life. It is quick-drying, and is not affected by poor curing at the deep part of the film or humidity or temperature at the time of drying, so that blistering and peeling hardly occur. Excellent interlayer adhesion when the same or another coating is applied over the coating. When the coating comes into contact with seawater, hydrolysis occurs gradually from the surface, and the resin dissolves, and simultaneously the antifouling agent is released to the coating surface, so that the antifouling performance can be maintained for a long time.

For this reason, the present invention can be obtained by the present invention in ship bottoms, underwater structures such as fish nets and cooling water pipes that require prevention of underwater biological pollution, and in marine pollution prevention membranes used for preventing sludge diffusion in marine civil engineering works. The coating exhibits a significant antifouling effect and can prevent biofouling of submerged submerged substrates.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Production Examples, Examples, and Comparative Examples of a polymer. 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 10 Into a flask equipped with a stirrer, a solvent a was charged in accordance with the composition shown in Table 3 ((1) and (2)), the temperature was raised to a predetermined reaction temperature, and the monomers A and A ′ were stirred. , A ″, monomer B and polymerization catalyst a were dropped into the flask in 6 hours, and after the completion of the dropping, the mixture was kept at the same temperature for 60 minutes. The polymerization reaction was completed by continuing stirring at the same temperature for 5 hours and finally diluting with a diluting solvent to obtain polymer solutions I to X.

Production Examples 11 and 12 Monomers A and A ', a monomer B and a polymerization catalyst a were charged into a heat and pressure resistant container in accordance with the composition shown in Table 3 (Nos. 1 and 2).
The temperature was raised to a predetermined reaction temperature while shaking completely, and shaking was continued at the same temperature for 8 hours to complete the reaction. Next, add a diluting solvent and shake for 3 hours to dissolve,
Polymer solutions XI and XII were obtained.

The monomer A (A) used in Production Examples 1 to 5, 11, and 12 was used.
₁ to A ₅₎ and the monomer _{A '(A' 1 ~A '} 4) , the formula (a), X ₁ in _{(b), X 2, m} (), n (), R 1 ~
R ₅ , R ′ _{1 to} R ′ ₅ have a structure as shown in Table 1 below.

In addition, the monomer A ″ used in the above Production Examples 6 to 10 was used.
(A ″ _{1 to} A ″ ₅ ) are X ₃ and X ₄ in the general formula (c), cis-trans geometric isomers thereof, Y ₁ and Y ₂ [one or both of which are represented by the formula (1) P, r when the organic group is represented
(), R ″ _{1 to} R ″ ₅ ] have the structure shown in Table 2 below.

Examples 1 to 12 Polymer solutions I to XII were mixed and dispersed by a homomixer at 2,000 rpm according to the following composition shown in Table 4 (the values in the table are% by weight), and 12 types of water were used. An antifouling coating was prepared.

Oil Blue 2N (trade name of Orient Chemical Co., Ltd.) is a dye, and DISPARON 6900-20X (trade name of Kusumoto Kasei Co., Ltd.) and AERILIL 300 (trade name of Nippon AERILIL CO., LTD.) Is also an anti-sagging additive.

Comparative Example 1 Examples 1 to 12 were repeated except that KE45TS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd .; oligomeric cold-curable silicone rubber 50% by weight toluene solution) was used instead of polymer solutions I to XII. In the same manner as described above, an underwater antifouling coating composition having the composition shown in Table 4 was prepared.

Comparative Example 2 The following fourth step was performed in the same manner as in Examples 1 to 12, except that the organotin copolymer solution was used instead of the polymer solutions I to XII.
An underwater antifouling coating agent having the composition shown in the table was 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.

The coating materials of Examples 1 to 12 and Comparative Examples 1 and 2 were subjected to the following physical performance tests and antifouling performance tests to evaluate their performance. The results were as shown in Table 5 below.

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

A) Storage stability 200 cc of each coating agent was placed in a 250 cc capacity mayonnaise bottle,
Covered and sealed. This was stored in a thermo-hygrostat at a temperature of 70 ° C. and a humidity of 75%, and after 2 weeks, the viscosity of each sample increased.
Storage stability was determined. When the rate of increase from the initial viscosity was less than 10%, it was evaluated as ○, when it was 10% or more and less than 100%, Δ, and when it was 100% or more, ×.

B) Drying The drying was performed according to the method of JIS K5400.5.8. That is,
Wet each coating with a film applicator to a wet film thickness of 10
The measurement was performed on a glass plate having a thickness of 0 μm. 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 The adhesion was measured in accordance with the cross-cut test method of JIS K5400.6.15.
That is, each coating agent is applied to a polished steel plate (150 × 70 × 1 mm) with a film thickness of 100 μm using a film applicator, and dried for one week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. The film was cut with a cutter knife to a length of 20 mm in a cross to reach the substrate. Extrusion of 10 mm was performed from the back of the test plate at the center using an Erichsen tester.
At that time, the adhesion was determined based on the length of the film surface peeled off from the center of the cross cut portion. When peeling was 0, it was evaluated as ○, when it was less than 5 mm, it was evaluated as Δ, and when it was 5 mm or more, it was evaluated as ×.

<Anti-fouling performance test> A coating plate (100 x 200 x 1 m
m) was applied twice by spray coating on both sides so that the dry film thickness was 120 μm on one side, to produce a test plate.

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

As is clear from the results in Table 5 above, Examples 1 to 12
The antifouling coating composition of the present invention has good storage stability, drying property and adhesiveness, and further, no adhesion of organisms in the antifouling performance test was observed at least until after 24 months.

On the other hand, Comparative Example 1 is a silicone rubber-based coating agent, which has drawbacks in storage stability, drying properties and adhesion, and also has unsatisfactory antifouling properties. Comparative Example 2 was an organotin copolymer-based antifouling coating agent, which was slightly inferior in storage stability and inferior in antifouling property to that of the present invention.

Claims (1)

(57) [Claims] 1. The following general formula (a): (Where X ₁ is a hydrogen atom or a methyl group, m is 1
The above real numbers, R _{1 to} R ₅ are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group or a substituted phenoxyl group,
And m m R ₄ , R ₅ and R _{1 to} R ₃ may be the same or different groups, and the following general formula (b): (Where X ₂ is a hydrogen atom or a methyl group, and n is 0
More real, R '1 _{to R' 5} are both an alkyl group, an alkoxyl group, phenyl group, substituted phenyl group, shall apply in a group selected from among Fuenokishiru group or a substituted Fuenokishiru group, and n pieces of R ' _4, R _'5 and _{R'1~R' 3}
May be the same or different groups) and a monomer A ′ represented by the following general formula (c): [However, in the formula, X ₃ and X ₄ are a hydrogen atom or a methyl group, and both groups may be either a cis form or a trans form. One of Y ₁ and Y ₂ is the following equation (1); (Where p is 0 or 1, r is a real number not less than 0, and R ″ _{1 to} R ″ ₅ are all alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups, phenoxyl groups, substituted phenoxyl groups. Alternatively, r groups of R " ₄ , R" ₅ and R " _{1 to} R" ₃ may be the same groups or different groups selected from organosiloxane groups. The other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group or the above-mentioned formula (1)
Is an organic group represented by And / or one or more polymers selected from the monomers A ″ represented by the following formulas: and / or the monomers A, A ′, A ″
Water containing, as essential components, a copolymer consisting of one or more kinds selected from among the above and one or more kinds of vinyl polymerizable monomers B copolymerizable therewith, and an antifouling agent Antifouling coating.