JP2003211081A - Coating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating method using a coating material composition which forms no residual layer on the surface of a coated film even after long- term immersion, generates no defect such as crack and peeling with respect to coated film property, keeps coated film consumability without changing the consumability with time, exhibits marine organism deposition preventing performance for a long time at a constant rate or more and has a satisfactory reapplying property and an excellent marine organism deposition preventing performance corresponding to installation time. <P>SOLUTION: In this coating method, a ship coated with the coating material composition which indispensably consists of a rosin compound (A) comprising rosin and a rosin derivative or a rosin metallic salt, an organic silyl ester group- containing polymer (B) comprising a homopolymer or copolymer of a monomer M having triorgano silyl group in which at least one of three alkyl groups or allyl groups R<SP>1</SP>-R<SP>3</SP>is a 3C group or more, or a copolymer between the monomer M and a pomerizable monomer other than the same and an antifouling agent (C) is placed in commission in a prescribed term and the coating material composition is reapplied to the ship after the commission. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating method using a coating composition for preventing organisms from adhering to the surface of objects in the sea.

[0002]

BACKGROUND OF THE INVENTION Barnacles, mussels, sea breams, buoys, buoys, fishnets (fixed nets, aquaculture fishnets, etc.) underwater contamination prevention membranes, water supply and drainage pipes for cooling, etc. Various obstacles occur due to the adhesion of cerpra, algae and the like. It is well known that a paint is applied to the surface of an undersea object to prevent the organisms from adhering to prevent the organisms from being contaminated. At present, resins used in paints for preventing the adhesion of marine organisms are roughly classified into hydrolyzable polymer type and rosin type.

The most typical type of hydrolyzable polymer system is an organic tin polymer. In the coating material made of an organotin polymer, the coating film is consumed by the hydrolysis of the organotin group bonded to the polymer in seawater, and the surface activity of the coating film is maintained. In addition, since the hydrolyzed organotin compound also functions as an antifouling agent, the adhesion of marine organisms can be prevented over a long period of time. However, organotin compounds have high accumulation in the environment, and their use is regulated because of concern over environmental pollution. As a hydrolyzable polymer which replaces the organotin polymer, Japanese Patent Publication No. 52324/1993, Japanese Patent Laid-Open No. 63-32433.
Many polymers containing an organic silyl group, such as those disclosed in JP-A-215780 and JP-A-7-102193, have been proposed.

In the rosin-based paint, rosin has a slight solubility in an alkaline solution and dissolves in weakly alkaline seawater (pH≈7.8 to 8.2) (seawater of pH = 8.1). 8.6 × 10 ⁻⁵ mol / liter), the antifouling agent can be effectively and slowly released into seawater. Because of its low solubility in seawater, rosin is widely used in marine organism adhesion prevention paints, and its use is described in many publications. For example, "Handbook of Coloring Material Engineering" (p. 821-: edited by Coloring Material Association), "Painting and Paint of Ships" (p. 70-: Manabu Nakao, Ship Engineering Association) and the like.

However, rosin is fragile in its physical properties by itself (it has a remarkably low film-forming ability due to its low molecular weight), so that it is necessary to blend another synthetic resin or the like to supplement it. To compensate for this weakness, a polymer that has a good compatibility with rosin must be used. If the compatibility is poor, the rosin and the polymer are separated from each other, and the fragile portion of the rosin exhibits physical weakness.

Blending a rosin with another polymer is proposed in Japanese Patent Laid-Open No. 135125/1975, and when a polymer having good compatibility is used as a blending polymer, The fact that the consumable property (self-polishing property) is easily controlled is reported in JP-A-60-28456.

[0007]

However, even when a polymer having good compatibility with rosin is blended, the initial coating film physical properties are good, but after long-term immersion, the coating film wearability is reduced and It was revealed that there were problems such as the occurrence of physical defects and a decrease in the effect of preventing adhesion of marine organisms. Also,
Especially in ships, new paint is applied to the old paint film after it has been in service for a certain period (about 1 to 3 years). Was found to be defective.

These defects or defects have a low solubility or a low solubility in seawater of the polymer itself having good compatibility with rosin as compared with rosin. Is caused by the formation of a so-called surface residual layer as a film that is dissolved (extracted) in advance.

Since the blended polymer supplements the physical weakness of rosin, a polymer having a better film forming performance than rosin, that is, a polymer having a higher molecular weight than rosin is required. This difference in molecular weight causes a difference in solubility between the rosin and the blend polymer. Since this residual layer increases due to immersion, deterioration of the coating film depletion, physical property defects of the coating film due to internal cohesive force within the residual layer, reduction of marine organism adhesion prevention effect caused by these, Deterioration of the property occurs.

Thus, although rosin has a property of being slightly soluble in seawater, which is very suitable as a paint for preventing adhesion of marine organisms, there has been a paint composition which makes the best use of the property for a long time. I have never done it.

Further, it is a hydrolyzable polymer which replaces the organic tin polymer, and is disclosed in Japanese Patent Publication No. 52324/1993 and Japanese Unexamined Patent Publication No. 63 (1989).
The polymer having an organic silyl group as a hydrolyzable group disclosed in JP-A-215780 does not dissolve in a coating film, and the coating film falls off when immersed in seawater and is not suitable as a marine organism adhesion preventing paint. Is defective.

[0012] Therefore, the inventors of the present invention disclosed in Japanese Unexamined Patent Publication No. 7-102.
In 193, it was found that a specific polymer having an alkoxy or aryloxy polyethylene glycol group together with an organic silyl group can eliminate the above defects. However, in subsequent research, even with the above-mentioned specific polymer, the performance after immersion in seawater for a long time,
In particular, it was found that there was a problem with the re-collection property, and there was a problem with the marine organism adhesion prevention performance for the outfitting period, which is required during the outfitting period.

The above outfitting period is a period for constructing a ship interior part by constructing a ship outer plate inside the dock and then floating the hull in the ocean outside the dock when the ship is constructed.
Usually about 3 months. During this period, the hull is exposed to the ocean around the shipyard (unlike the open ocean, which is a region with severe biofouling unlike the open ocean), so it is possible to cope with the outfitting period, which is a higher level of marine organism adhesion prevention performance than usual. The marine organism adhesion prevention performance is required.

After the outfitting is completed, will the ship continue to operate?
Re-enter the dock, finish, and then enter service. If biofouling occurs during the outfitting period, the efficiency of fuel consumption will decrease from the start of service. In addition, even if the ship docks in the dock again, it means that the adhered organisms will be removed before it goes into service, which means that it cannot serve as a marine organism adhesion preventive paint during the outfitting period. This is the same as not applying paint.

As a method for evaluating the performance of preventing attachment of marine organisms to the outfitting period, the inventors of the present invention ensure that the start of the immersion test is in the summer when the biofouling is most severe (the marine organism adhesion inhibitor elutes immediately after immersion. However, since it elutes after a certain period of time, if the period immediately after the start of immersion is when there is severe biological fouling, there is a high possibility that organisms will adhere, and the marine organism adhesion prevention performance evaluation that is usually adopted by the present inventors. At Owase Bay in Mie Prefecture, where the degree of biofouling is more severe than that at Aioi Bay in Hyogo Prefecture, which is the sea area, from July to September 1996 for three months,
A test method was devised in which the immersion is usually performed vertically to the sea surface, while the immersion is horizontally performed so that the influence of sunlight is large. According to this test method, the above-mentioned JP-A-7-102 is used.
As a result of evaluating the polymer disclosed in Japanese Patent No. 193, it was found that there is a problem in the performance of preventing attachment of marine organisms for the outfitting period.

Therefore, according to the present invention, since no residual layer is formed on the surface of the coating film even after long-term immersion, defects such as cracking and peeling do not occur in the physical properties of the coating film, and the wear resistance of the coating film changes with time. We have developed and used a coating composition that does not change and is at a certain speed or more, that can exhibit marine organism adhesion prevention performance over a long period of time, and that has good reticulability and marine organism adhesion prevention performance for outfitting period. The purpose is to provide a new coating method.

[0017]

Means for Solving the Problems The present inventors have developed a desired coating composition by paying attention to the following points. This coating composition can be developed by not forming a residual layer on the surface of the coating film. For this purpose, the solubility of the polymer having good compatibility with rosin in seawater must be increased after the immersion in seawater. The expression of such a function is possible only in a polymer that undergoes a chemical change before and after immersion in seawater. The polymer with chemical change has good compatibility with the rosin-based resin before immersion in seawater, and after immersion in seawater, only the surface of the coating film becomes hydrophilic and a good dissolution rate can be obtained.

The present inventors, as a blend polymer,
Attention was paid to a polymer in which a carboxylic acid was protected with an organic silyl group. This polymer has good compatibility with rosin, which has low polarity, due to the low polarity of the organic silyl group, and due to the hydrolyzability of the organic silyl group, it undergoes a chemical change after immersion in seawater and has a solubility in seawater. Changes greatly from insoluble to soluble. Organotin polymers with similar hydrolyzability are
Since the polarity is higher than that of the silyl-based polymer, the compatibility with rosin is poor and it is not possible to exhibit the function of the silyl-based polymer. Poor polarity and hydrolyzability in seawater are very important for blending with rosin.

As a result of extensive studies on these points, a rosin compound such as rosin and its derivatives, an organic silyl ester group-containing polymer having an organic silyl group as a hydrolysis point, and an antifouling agent are used. By doing so, it has been found that the problems of the conventional technology can be solved perfectly. That is, since there is no formation of a residual layer on the surface of the coating film even after long-term immersion, the physical properties of the coating film are not cracked, and defects such as peeling do not occur, and the coating film consumability does not change over time and is at a certain rate or higher, The ability to prevent the adhesion of marine organisms can be demonstrated over a long period of time.
In addition, we have succeeded in developing a rosin-based coating composition that has good recoverability and good performance for preventing marine organisms from being outfitted, and have arrived at a new coating method using this composition.

That is, the present invention relates to 1) a rosin compound comprising rosin, a rosin derivative or a rosin metal salt.
And two or more kinds, and B) the following general formula; (Wherein R ^{1 to} R ³ are all alkyl groups or ar-
Although they may be the same group or different groups, at least one of R ^{1 to} R ³ is a group having 3 or more carbon atoms. X is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group,
It is a fumaroyloxy group, an itaconoyloxy group or a citraconoyloxy group. ) 1 of the monomer M represented by
From one or more polymers, and / or from one or more polymers of the above-mentioned monomer M and one or more polymers of a polymerizable monomer other than the above-mentioned monomer M A vessel coated with a coating composition containing the following organic silyl ester group-containing polymer and C) an antifouling agent as essential components is operated for a certain period of time, and the above-mentioned coating composition is recoated on the vessel after the operation ( Recoating). Further, the present invention can provide an antifouling coating film formed on a ship by this coating method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the coating composition of the present invention, the rosin compound of component A used as an essential component is rosin, a rosin derivative or a rosin metal salt. For example, as rosin, tolurosin, gum rosin, utudrosine, etc., as rosin derivatives, hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride,
Formylated rosin, polymerized rosin and the like, examples of rosin metal salts include zinc chloride, calcium rosinate, copper rosinate, magnesium rosinate, and reaction products of rosin with other metal compounds. .

In the present invention, one kind or two or more kinds are selected and used from such rosin-based compounds. The amount of the rosin-based compound and the organic silyl ester group-containing polymer as the component B is used. The solid content ratio is usually 1/99 by weight.
It is 99/1, preferably 5/95 to 95/5. If the amount of A component is too small, the effect of preventing marine organisms from attaching,
In particular, we cannot expect the effect of preventing marine organisms from adhering during the outfitting period.
Defects such as peeling are likely to occur, and it is difficult to obtain effective marine organism adhesion prevention performance.

The organic silyl ester group-containing polymer of the component B used as an essential component in the coating composition of the present invention is one or more of the monomers M represented by the general formula (1). It is a polymer and / or a polymer of one or more kinds of the monomer M and one or more kinds of polymerizable monomers other than the monomer M.

As represented by the general formula (1), the monomer M has an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly a monoalkyl group] as an unsaturated group (X) in the molecule. (C1-6 ester maleinoyloxy group), fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group],
Itaconoyloxy group (mainly monoalkyl (C1-C1
6) Ester itaconoyloxy group] or a citraconoyloxy group [mainly a monoalkyl (C 1 to C 6) ester citraconoyloxy group] and a triorganosilyl group.

In the triorganosilyl group, the three alkyl groups or aryl groups (R ^{1 to} R ³ ) may be the same or different, but at least one of them is a group. Is a group having 3 or more carbon atoms. Specifically, a linear or branched alkyl group having 20 or less carbon atoms such as methyl, ethyl, propyl, and butyl; a cyclic alkyl group such as cyclohexyl and substituted cyclohexyl;
There are aryl groups and substituted aryl groups. Examples of the substituted aryl group include halogen, an alkyl group having up to about 18 carbon atoms, an aryl group substituted with an acyl group, a nitro group or an amino group.

Of these monomers M, those having a (meth) acryloyloxy group in the molecule include tri-n-propylsilyl (meth) acrylate and tri-i.
-Propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-i-butylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-n- Amylsilyl (meth) acrylate, tri-n-hexylsilyl (meth)
Acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) ) Acrylate and tribenzylsilyl (meth) acrylate.

Further, as another example having a (meth) acryloyloxy group in the molecule, n-butyldimethylsilyl (meth) acrylate, di-i-propyl-n-butylsilyl (meth) acrylate, n -Octyldi-n-butylsilyl (meth) acrylate, di-i-propylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate , Lauryldiphenylsilyl (meth) acrylate, t-butyl-m-nitrophenylmethylsilyl (meth) acrylate, and the like.

Further, those having a maleinoyloxy group in the molecule include tri-n-propylsilyl-n-
Propyl maleate, tri-n-butyl silyl-n-butyl maleate, tri-n-amyl silyl-n-amyl maleate, tri-n-hexyl octyl silyl maleate, tri-n-octyl silyl dodecyl maleate, Tri-n-
Dodecyl silyl methyl maleate, triphenyl silyl methyl maleate, tri-p-tolyl silyl ethyl maleate
, Triisopropylsilyl isoamyl maleate, triisobutyl silyl phenyl maleate, t-butyl dimethyl silyl methyl maleate, t-butyl diphenyl silyl methyl maleate, n-octyl di-n-butyl silyl methyl maleate -T.

Further, those having a fumaroyloxy group in the molecule include tri-n-propylsilyl-n-propyl fumarate, tri-n-butylsilyl-n-butyl fumarate and tri-n-amylsilyl-n-amyl fumarate. -Tri-n-hexylsilyl-n-hexyl fumarate, tri-n-octylsilyl dodecyl fumarate
, Tri-n-dodecylsilylmethyl fumarate, triphenylsilylmethyl fumarate, tri-p-methylphenylsilylmethyl fumarate, triisopropylsilylmethyl fumarate, triisobutylsilylmethyl Fumarate, tri-2-chloroisopropylsilylmethyl fumarate, tri-t-butylsilylmethyl fumarate,
Examples thereof include n-butyldimethylsilylmethyl fumarate and n-octyldi-n-butylsilylmethyl fumarate.

Further, those having an itaconoyloxy group in the molecule include tri-n-propylsilyl-n-propylitaconate, tri-n-butylsilyl-n-butylitaconate and tri-n-amylsilyl. -N-amyl italyneate, tri-n-hexyl silyl-n-hexyl lytaconate, tri-n-octyl silyl dodecyl itaconate, tri-n-dodecyl silylmethyl itaconate, triphenyl silyl methyl itaconate , Tri-p-fluorophenylsilylmethyl itaconate, triisopropylsilylmethyl itaconate, triisobutylsilylmethyl itaconate, tri-2-cyanoisopropylsilylmethyl itaconate, tri-t-butylsilylmethyl itaconate -To, n-butyldimethylsilylmethylitacone- , N- octyl di -n- butyl silyl itaconate Ne - such bets and the like.

Further, those having a citraconoyloxy group in the molecule include tri-n-propylsilyl-n.
-Propyl citracone, tri-n-butylsilyl-
n-butyl citracone, tri-n-amylsilyl-
n-amyl citracone, tri-n-hexyl silyl-n-hexyl citrate, tri-n-octyl silyl dodecyl citrate, tri-n-dodecyl silyl methyl citrate, triphenyl silyl methyl citrate Connect, tri-p-hydroxyphenylsilylmethyl citraconate, triisopropylsilylmethyl citraconate, triisobutylsilylmethyl citraconate, tri-2-bromoisopropylsilylmethyl citracone, tri -T-Butylsilylmethyl citracone, n-butyldimethylsilylmethyl citracone
And n-octyldi-n-butylsilylmethyl citraconate.

The polymerizable monomer other than the monomer M is another monomer copolymerizable with the above-mentioned monomer M, such as acrylic acid and methyl acrylate, ethyl acrylate,
N-Butyl acrylate, t-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 2-acrylate Acrylic esters such as methoxyethyl, 2-ethoxyethyl acrylate, methacrylic acid and methyl methacrylate, n-methacrylic acid
Butyl, t-butyl methacrylate, s-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate,
Examples thereof include methacrylic acid esters such as 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, and 2-ethoxyethyl methacrylate.

Other examples of the polymerizable monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, Veova 9 and Veova 10 [Showa Shell Science Co., Ltd.].
Product name], dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-i-propyl maleate, di-2-maleate.
Maleic acid esters such as methoxyethyl, dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, di-i-propyl fumarate, di-2-methoxyethyl fumarate and other fumarate esters, crotonic acid Esters, itaconic acid esters, citraconic acid esters, styrene, vinyltoluene, α-methylstyrene,
Acrylonitrile and the like are also included.

In the organic silyl ester group-containing polymer of the component B, the proportion of the monomer M represented by the general formula (1) and the polymerizable monomer other than the above depends on the purpose of use of the coating composition. It can be appropriately set depending on the case, but in general, the monomer M is 1 to
It is preferable that the amount of the polymerizable monomer is 100% by weight and the amount of the other polymerizable monomer is 99 to 0% by weight.

The organic silyl ester group-containing polymer as the component B is prepared by subjecting such a mixture of monomers to various methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization in the presence of a polymerization catalyst according to a conventional method. It can be obtained by polymerizing by a method. When the B component-containing organic silyl ester group-containing polymer is used for paints, it is preferable to dilute it with an organic solvent to obtain a polymer solution having an appropriate viscosity. For that purpose, a solution polymerization method or a bulk polymerization method is used. It is desirable to adopt.

Examples of the above-mentioned polymerization catalyst include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t.
-Peroxides such as butyl peroxyisopropyl carbonate.

As the above-mentioned organic solvent, aromatic hydrocarbon solvents such as xylene and toluene, hexane,
Aliphatic hydrocarbon solvents such as heptane, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol
Examples of the solvent include alcohol solvents such as alcohol and butyl alcohol, ether solvents such as dioxane and diethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. One or two of them The above is used.

The organic silyl ester group-containing polymer of component B thus obtained has a weight average molecular weight of 1,0.
It is preferably in the range of 00 to 150,000. If the molecular weight is too low, it is difficult to form a normal coating film. On the other hand, if it is too high, the viscosity of the coating composition will be high, so it will have to be diluted with thinner and only a thin coating film can be obtained with a single coating, so the problem of requiring a greater number of coatings will occur. Come on. The viscosity of the polymer solution of the component B is
It is expediently not more than 150 poise at 25 ° C., for which the solids content of the polymer solution should be in the range 5 to 90% by weight, preferably 15 to 85% by weight.

In the coating composition of the present invention, the component C used as another one of the essential components is an antifouling agent, which widely includes conventionally known ones. Broadly speaking, there are organic compounds containing an inorganic compound and a metal, and organic compounds containing no metal. Among these, as the inorganic compound, for example, cuprous oxide, copper powder, cuprous thiocyanate, copper carbonate,
Copper compounds such as copper chloride and copper sulfate, zinc sulfate, zinc oxide,
Nickel sulfate, copper-nickel alloy and the like can be mentioned.

Examples of the organic compound containing a metal include organic copper compounds, organic nickel compounds and organic zinc compounds, and other compounds such as manneb, manceb,
Propineb can also be used. Organic copper compounds include oxine copper, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate), copper acetate, copper naphthenate, and bis (pentachlorophenolic acid) copper. , Copper pyrithione and the like, organic nickel compounds such as nickel acetate and dimethyldithiocarbamate nickel, and organic zinc compounds such as zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione and zinc ethylenebisdithiocarbamate. , Respectively.

Examples of the metal-free organic compound include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compound, There are triazine compounds and others.

Examples of N-trihalomethylthiophthalimide include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide, and examples of dithiocarbamic acid include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamine). Acid) ammonium, milneb and the like, respectively.

As the N-arylmaleimide, N-
(2,4,6-Trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N
Examples thereof include-(anilinophenyl) maleimide and N- (2,3-xylyl) maleimide.

3-Substituted amino-1,3-thiazolidine-
As 2,4-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
-Zeon and the like.

Examples of dithiocyano compounds include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene, and examples of triazine compounds include 2
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and the like, respectively.

Other organic compounds containing no metal include 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-N'-dichlorophenylurea,
4,5-Dichloro-2-n-octyl-isoazoline-
3-one, N, N-dimethyl-N'-phenyl- (N-
Fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2-propynylbutylcarbamate, 2- (methoxycarbonylamino) benzimidazole, 2,3,5,6-tetrachloro -4- (Methylsulfonyl) pyridine, diiodomethyl paratolyl sulfone, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, triphenylboron pyridine and the like can be mentioned.

In the present invention, one kind or two or more kinds are selected from the various antifouling agents and used.
The amount of the antifouling agent in the coating solid content is usually 0.1 to 80% by weight, preferably 1 to 60% by weight. If the amount of the antifouling agent is too small, the antifouling effect cannot be expected, and if the amount of the antifouling agent is too large, defects such as cracks and peeling are likely to occur in the formed coating film, and it is difficult to obtain effective antifouling properties.

In the coating composition of the present invention thus constituted, coloring agents such as pigments and dyes such as rouge, zinc oxide and talc, water binders, anti-sagging agents commonly used in coatings,
Plasticizers such as chlorinated paraffin, dioctyl phthalate and tricresyl phosphite, UV absorbers such as benzophenone compounds and benzotriazole compounds,
Various additives such as a color separation preventing agent, an anti-settling agent, an antifoaming agent, silanol, polysiloxane, and alkoxysilane can be appropriately blended.

To form an antifouling coating film on the surface of an object immersed in seawater using the coating composition of the present invention, it is applied to the surface of the object by an appropriate means and then at room temperature or under heating. The solvent may be removed by volatilization with, and a dry coating film can be easily formed on the surface of the object by this method. The coating method of the present invention is characterized in that a ship coated with the above-mentioned coating composition as described above is put into service for a certain period of time, and the above-mentioned coating composition is recoated on the ship after the service. Is. Further, the present invention can provide an antifouling coating film formed by being repainted on a ship in this way.

[0050]

EXAMPLES Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. The parts in the examples are parts by weight, and the molecular weight is the polystyrene-converted weight average molecular weight by GPC (gel permeation chromatography). Further, the monomers M _{1 to} M ₉ used in Production Examples are the monomers M represented by the general formula (1), and R ^{1 to} R ³ and X in the general formula (1) are As shown in Table 1.

[0051]

[Table 1]

Production Examples 1 to 4 A flask equipped with a stirrer was charged with the solvent a in accordance with the formulation shown in Table 2, the temperature was raised to a predetermined reaction temperature, and the monomer M, other monomers and polymerization were carried out with stirring. The mixed solution of the catalyst a was dropped into the flask over 3 hours, and after the dropping was completed, the mixture was stirred at the same temperature for 30 hours.
Hold for minutes. Then, the 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 2 hours to complete the polymerization reaction. Finally, a diluting solvent was added to dilute the solution to obtain each polymer solution S _{1 to} S ₄ .

Production Examples 5 to 8 A monomer M, other monomers and a polymerization catalyst were charged in a heat and pressure resistant container according to the formulation of Table 3, completely sealed and shaken at a predetermined reaction temperature. The temperature was raised to 0, and shaking was continued at the same temperature for 8 hours to complete the reaction. Next, a diluent solvent is added and shaken for 1 hour to dissolve, and each polymer solution S _{5 to} S ₈ is dissolved.
Got

Production Examples 9 to 16 A flask equipped with a stirrer was charged with a solvent, a monomer M, other monomers and a polymerization catalyst in accordance with the formulations shown in Tables 4 and 5, and the mixture was stirred at a predetermined reaction temperature. The temperature was raised, and stirring was continued at the same temperature for 6 hours to complete the reaction. Then diluted with a dilution solvent, to obtain each polymer solution S ₉ to S _16.

In Tables 2 to 5, "Veoba 9" and "Veoba 10" (trade names, manufactured by Showa Ciel Kagaku Co., Ltd.) are all vinyl ester monomers and "perbutyl". "I" (trade name of NOF CORPORATION) is an organic peroxide.

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

Examples 1 to 20 Using the polymer solutions S _{1 to} S ₁₆ , the components were mixed according to the compounding compositions shown in Tables 6 to 10 (numerical values in the tables are% by weight), and the mixture was mixed at 2,000 rpm. Mix and disperse with a homomixer, 2
Zero coating compositions were prepared.

Comparative Examples 1 to 6 Polymer solution S ₇ , polyisobutylene, "Laroflex MP-15" (trade name of BASF, vinyl chloride resin), "Pryolite S-5B" (GoodYear)
Company name, styrene butadiene rubber), "Toyo Parax A-70" [trade name of Toyo Soda Kogyo Co., Ltd., chlorinated paraffin resin], "Polyzol EVA-AD-"
3 ”(trade name of Showa Highpolymer Co., Ltd., ethylene-vinyl acetate copolymer (50% by weight solution)), and the composition shown in Table 11 (numerical values in the table are% by weight). The components were mixed and mixed with a homomixer at 2,000 rpm to disperse them to prepare 6 kinds of coating compositions.

In Tables 6 to 11, "Dimarex" (trade name of Ha-Quilles Co., Ltd.) is a polymerized rosin.
"Days Palon A630-20X", "Days Palon 4
300 "[trade name of Kusumoto Kasei Co., Ltd.] and" Benton SD-2 "[trade name of National Red Co., Ltd.]
Is an additive for preventing sagging, "KMP590" [trade name of Shin-Etsu Chemical Co., Ltd.] is a silicone resin powder, and "Tinuvin 900" [trade name of Ciba-Gaigi Co., Ltd.] is an ultraviolet absorber. Is.

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

[Table 11]

The above Examples 1 to 20 and Comparative Examples 1 to 6
For each coating composition of the above, the coating layer residue layer confirmation test, coating layer wear test, antifouling performance test, adhesion test, crack resistance test, recortability test, and marine organisms compatible with the outfitting period are performed as follows. An adhesion prevention performance test was conducted. The results are as shown in Tables 12 to 20.

<Coating Surface Residual Layer Confirmation Test> A blast steel plate (100 mm × 200 mm × 1 mm) is spray-coated twice with a tar-epoxy rust-preventive coating so that a dry film thickness of 125 μm per time is applied. Further, a tar vinyl-based sealer coat was applied so that the dry film thickness would be 70 μm.
On top of this, each coating composition was coated with a dry film thickness of 10
It was applied twice by spray coating so as to have a thickness of 0 μm, and dried for 1 week in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 75% to prepare 6 test pieces for each coating composition.

The thus-prepared test piece was immersed in artificial seawater, pulled up after 3 months, 6 months, 12 months, 18 months and 24 months, and the test piece was cut. After polishing the cut surface, the coated cross section was observed with a stereomicroscope to measure the residual layer formed on the coating film surface.

<Coating Film Depletion Test> Each coating composition was spray-coated on the surface of a steel plate (100 mm × 100 mm × 1 mm) with anticorrosion coating on both sides so that the dry coating film thickness would be 200 μm once. It was applied twice and dried in a room at a temperature of 20 ° C. for 1 week to prepare a test piece.

After fixing the above test piece to the outer surface of a cylindrical drum having a diameter of 50 cm, 1 below the sea surface of Yura Bay, Sumoto City, Hyogo Prefecture
It is immersed in m and is rotated with a motor so that the peripheral speed of the drum becomes 16 knots, and the consumed film thickness is increased to 2 every 3 months.
It was measured for 4 months. Also, the average speed of film thickness consumption (μm /
Month) was calculated for the period of 6 months and the period of 6 months to 24 months. The average speed of coating film thickness consumption is 3 μm /
Months correlate with good antifouling performance. If the average speed of coating thickness consumption from 6 months to 24 months is within the range of average speed of coating thickness consumption of 6 months ± 1 (μm / month),
It shows that the coating film is consumed at a constant speed.

<Anti-fouling performance test> Each coating composition was coated on a sandblasted steel sheet with a tar vinyl anticorrosive coating in advance on both sides of a coated sheet (100 mm x 200 mm x 1 mm) with a dry film thickness on one side. It was applied twice by spray coating so as to have a thickness of 240 μm, and dried for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% to prepare a test piece. This test piece was immersed in seawater for 24 months in Aioi Bay, Aioi City, Hyogo Prefecture, and the ratio of the area occupied by adherent organisms (adhered area) on the test coating film was measured over time.

<Adhesion Test> A blasted steel plate was spray-coated twice with a tar-epoxy rust-preventive coating so that a dry film thickness of 125 μm was obtained, and then a tar vinyl-based sealant was applied. -Coating was performed so that the dry film thickness was 70 μm. On top of this, each coating composition was applied twice by spray coating so that the dry film thickness was 100 μm per time, and dried for 1 week in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 75%, and tested. Pieces were made.

This test piece was dipped in artificial seawater and pulled up after 3 months, 6 months, 12 months, 18 months and 24 months, and a 2 mm-interval goggles test was carried out.
Adhesion is evaluated by the number of peeled pieces by this test is 0/25
When the number of peeled pieces was 1 or more / 25 pieces, the case was ◯ (pass), and when the number of peeled pieces was 1 or more, it was x (fail).

<Crack resistance test> In the adhesion test, when the test piece was pulled up from the artificial seawater, the coating film was visually observed to check for the occurrence of cracks. Those without cracks were marked with O (pass), and those with cracks were marked (fail).

<Recoatability Test> Each coating composition was spray-coated on the surface of a steel plate (100 mm × 100 mm × 1 mm) with rust-proof coating on both sides so that the dry film thickness was 100 μm per time. 2 times and dried in a room at a temperature of 20 ° C. for 1 week to prepare two test pieces for each coating composition.

This test piece was immersed in artificial seawater, pulled up after 12 months and 24 months, washed with distilled water,
It was dried in a room at a temperature of 20 ° C. for 1 week. Then, the surface of each test piece was coated twice with the same coating composition by spray coating so that the dry film thickness was 100 μm per time, and dried in a room at a temperature of 20 ° C. for one week. After fixing these test pieces to the outer surface of a cylindrical drum with a diameter of 50 cm, they were immersed in 1 m below the sea surface of Yura Bay, Sumoto City, Hyogo Prefecture, and rotated with a motor so that the peripheral speed of the drum was 16 knots. Let After one week, this was pulled up, and the presence or absence of peeling between the new coating film and the old coating film was confirmed. Those without peeling were evaluated as ◯ (pass), and some were evaluated as x (fail).

<Marine organism adhesion prevention performance test for outfitting period> Each coating composition was previously applied to a sandblasted steel plate.
Painted board coated with vinyl-based anticorrosive paint (100 mm x
(300 mm x 1 mm) with a dry film thickness of 240 μm on each side
2 times by spray coating at a temperature of 20
A test piece was prepared by drying in a thermo-hygrostat at a temperature of 75 ° C. and a humidity of 75% for 1 week. This test piece was immersed in seawater at a position 1 m below the surface of the water so that it would be horizontal to the surface of the sea in Owase Bay, Mie Prefecture. The ratio of the area occupied by adherent organisms (adhered area) was measured over time.

In order to compare the degree of biofouling in Owase Bay, Mie Prefecture, during the above period with that in Aioi Bay, Hyogo Prefecture, and to compare the dipping direction in the vertical and horizontal directions with respect to the sea level, Rubin-based anticorrosive paint applied to the test piece,
Immersion was carried out in both of the above-mentioned sea areas in both of the above-mentioned dipping directions, and the amount of attached organisms was compared by weight.

[0082]

[Table 12]

[0083]

[Table 13]

[0084]

[Table 14]

[0085]

[Table 15]

[0086]

[Table 16]

[0087]

[Table 17]

[0088]

[Table 18]

[0089]

[Table 19]

[0090]

As is clear from the results of Tables 12 to 20, the coating composition of Comparative Example 1 using a vinyl chloride resin as the blend polymer with rosin, styrene-butadiene rubber, chlorinated paraffin resin, The coating compositions of Comparative Examples 2, 3 and 6 using an ethylene-vinyl acetate copolymer (all correspond to the examples of JP-A-60-28456), and Comparative Example 5 using polyisobutylene. the coating composition (corresponding to example of JP-a-50-135125), addition polymer solution antifouling agent added to S _7, the coating composition of Comparative example 4 which has failed blended rosin (Patent 7- 102
(Corresponding to those described in Japanese Patent No. 193), some of them exhibit good coating film wearability for several months after the start of immersion, but after a long period of immersion, a residual layer is formed on the surface of the coating film. ,
Unsatisfactory results were obtained for both the coating consumption rate and antifouling performance, and defects were also found in the crack resistance, adhesion, retortability, and performance of preventing marine organisms from attaching during the outfitting period.

On the other hand, various rosin compounds and hydrolyzable organic silyl ester group-containing polymer solutions S _{1 to} S
_In each of the coating compositions of Examples 1 to 20 in which ₁₂ was used in combination, a residual layer was not formed on the surface of the coating film even after long-term immersion, and the coating film consumption rate, antifouling performance, crack resistance, adhesiveness, and coating Satisfactory results are shown in any of the tests on the anti-adhesion property and the marine organism adhesion preventing performance corresponding to the outfitting period, which shows that the coating composition of the present invention has excellent performance.

[0093]

As described above, the coating composition of the present invention is
It can be used for ship bottoms that need to prevent biological contamination in the sea, underwater structures such as fishnets and cooling water pipes, and for preventing sludge diffusion in marine civil engineering work.The coating film remains on the coating surface even after long-term immersion. Since there is no layer formation, defects such as cracks and peeling do not occur in the physical properties of the coating film, and the wear resistance of the coating film does not change over time and is above a certain speed, and the marine organism adhesion prevention performance is demonstrated over a long period of time. In addition, it is also excellent in the performance of preventing marine organisms from adhering during the outfitting period, and it also exhibits good recoverability. Therefore, in the present invention,
Making use of the characteristics of the above coating composition, a ship coated with this coating composition is put into service for a certain period of time, and a coating method characterized by recoating (recoating) the above coating composition on a ship after the service, The antifouling coating film formed by this can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shigeo Fukuda             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory (72) Inventor Yoshihisa Kawakami             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory (72) Inventor Yoshiro Matsubara             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory (72) Inventor Yasushi Kawamura             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory (72) Inventor Shigeru Masuoka             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory (72) Inventor Yoshihiro Honda             296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan             Oil and fat Co., Ltd. Totsuka factory F-term (reference) 4D075 CA34 DA23 DA37 DB02 DC08                       EB42

Claims (2)

[Claims] 1. A) one or more rosin-based compounds consisting of rosin, a rosin derivative or a rosin metal salt, and B) the following general formula; (Wherein R ^{1 to} R ³ are all alkyl groups or ar-
Although they may be the same group or different groups, at least one of R ^{1 to} R ³ is a group having 3 or more carbon atoms. X is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group,
It is a fumaroyloxy group, an itaconoyloxy group or a citraconoyloxy group. ) 1 of the monomer M represented by
From one or more polymers, and / or from one or more polymers of the above-mentioned monomer M and one or more polymers of a polymerizable monomer other than the above-mentioned monomer M A vessel coated with a coating composition containing the following organic silyl ester group-containing polymer and C) an antifouling agent as essential components is operated for a certain period of time, and the above-mentioned coating composition is recoated on the vessel after the service. A coating method characterized by that. 2. An antifouling coating film formed on a ship by the coating method according to claim 1.