JPH1030071A - Paint composition - Google Patents

Abstract

(57) [Summary] [Problem] Even after long-term immersion, there is no formation of a residual layer on the coating film surface, and there is no defect such as cracking or peeling in the coating film physical properties, and the coating film consumability changes with time. It is able to demonstrate the marine organism adhesion prevention performance for a long time,
Further, the present invention provides a coating composition having good recyclability and excellent marine organism adhesion prevention performance for an outfitting period. SOLUTION: A rosin compound, an organic silyl ester group-containing polymer and an antifouling agent are used as essential components of a coating composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for preventing organisms from adhering to the surface of an underwater object.

[0002]

2. Description of the Related Art Barnacles, mussels, etc. are placed on the surface of underwater objects such as ship bottoms, buoys, fish nets (stationary nets, fish nets etc.) that are immersed in seawater, anti-pollution membranes for water, and various plumbing pipes for cooling. Various obstacles occur due to adhesion of serpula, algae and the like. It is well known that in order to prevent fouling by these organisms, paints are applied which prevent the organisms from adhering to the surface of the underwater objects. At present, resins used for paints for preventing the adhesion of marine organisms are broadly classified into hydrolyzable polymer-based resins and rosin-based resins.

[0003] The most typical hydrolyzable polymer system is an organic tin polymer. In a coating composed of an organic tin polymer, the coating is consumed by the hydrolysis of the organic tin groups bonded to the polymer in seawater, and the activity of the coating surface is maintained. In addition, since the hydrolyzed organic tin compound also functions as an antifouling agent, the adhesion of marine organisms can be prevented over a long period of time. However, organotin compounds are highly accumulative in the environment, and their use is regulated due to concerns about environmental pollution. Japanese Patent Publication No. Hei 5-32433 and Japanese Patent Application Laid-Open No.
Many organic silyl group-containing polymers, such as those disclosed in JP-A-215780 and JP-A-7-102193, have been proposed.

[0004] In addition, rosin-based paint has a low solubility in an alkaline solution and is dissolved in weakly alkaline seawater (pH ≒ 7.8 to 8.2) (pH = 8.1 seawater). 8.6 × 10 ^-5 mol / liter), and the antifouling agent can be effectively slowly released into seawater. Rosin is widely used in marine organism antifouling paints due to its low solubility in seawater, and its use has been described in many publications. For example, "Handbook of Coloring Material Engineering" (pages 821 to: edited by the Coloring Materials Association), "Painting and Paints for Ships" (pages 70 to: Manabu Nakao, Ship Technology Association) and the like can be mentioned.

However, rosin is fragile in physical properties by itself (it has a remarkably low film-forming performance due to its low molecular weight), and it is necessary to blend another synthetic resin or the like in order to compensate for it. To compensate for this weakness, a polymer with good rosin compatibility must be used. If the compatibility is poor, separation between the rosin and the polymer occurs, and the rosin aggregates exhibit physical weakness.

[0006] The blending of rosin with other polymers is proposed in Japanese Patent Application Laid-Open No. 50-135125, and if a polymer having good compatibility with the polymer to be blended is used, the coating of the coating film is reduced. It is reported in JP-A-60-28456 that the wear property (self-polishing property) is easily controlled.

[0007]

However, even when a polymer having good compatibility with rosin is blended, the initial coating film properties are good, but after immersion for a long time, the coating film has a reduced consumption of the coating film. It has been found that physical defects occur, and that the effect of preventing marine organisms from adhering is reduced. Also,
In particular, for ships, after a certain period of service (approximately one to three years), new paint is re-coated on the old paint film. Was found to be defective.

These problems or defects are caused by the fact that a polymer having good compatibility with rosin has a low solubility in seawater compared to rosin or has little solubility. This is because a so-called surface residue layer is formed as a film dissolved (extracted) in advance.

[0009] Since the blend polymer compensates for the physical weakness of rosin, it is required to have a polymer having better film forming performance than rosin, that is, a polymer having a higher molecular weight than rosin. This difference in molecular weight causes a difference in solubility between the rosin and the blend polymer. Since the residual layer increases due to immersion, the depletion of the coating film is reduced, the physical property defects of the coating film are generated due to the internal cohesion in the residual layer, and the effect of preventing the adhesion of marine organisms caused by these is reduced. The deterioration of the performance occurs.

As described above, although rosin has a very low solubility in seawater, which is a very suitable property as an anti-adhesion coating for marine organisms, there has been a coating composition which makes use of its performance for a long time. It was not.

Also, a hydrolysis-type polymer replacing the organic tin polymer is disclosed in Japanese Patent Publication No.
The polymer having an organic silyl group as a hydrolyzable group disclosed in JP-A-215780 does not dissolve the coating film, and when immersed in seawater, the coating film falls off and has no suitability as a marine organism adhesion preventing paint. There are defects.

Therefore, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 7-102.
In Japanese Patent Publication No. 193, it has been found that the above-mentioned defects can be solved by a specific polymer having an alkoxy or aryloxy polyethylene glycol group together with an organic silyl group. However, subsequent studies have shown that, even with the above specific polymers, their performance after long-term immersion in seawater,
In particular, it was found that there was a problem with the recoatability, and that there was a problem with the marine organism adhesion prevention performance required during the outfitting period.

The above-mentioned outfitting period is a period in which a ship outer plate is built in a dock when the ship is built, and then the ship is floated in the ocean outside the dock to build a ship interior part.
Usually about 3 months. During this period, the ship's hull is exposed to the ocean around the shipyard (in contrast to the open sea, it is a sea area with severe biofouling) while anchored, so it is compatible with the outfitting period, which is an unusual and more advanced marine organism adhesion prevention performance The marine organism adhesion prevention performance is required.

After completion of the outfitting, the ship will go into service
Enter the dock again, and after finishing, enter service. If biofouling occurs during the outfitting period, the fuel efficiency will decrease from the start of service, and therefore, service will not be possible in such a state. In addition, even when re-entering the dock, it is necessary to remove the attached organisms before entering service, which means that they cannot serve as a marine organism adhesion prevention paint during the outfitting period. It is the same as not applying paint.

The present inventors evaluated the marine organism adhesion prevention performance corresponding to the outfitting period so that the start of the immersion test would be in summer, when the biological fouling was most severe (the marine organism adhesion inhibitor was eluted immediately after immersion. Rather, it elutes after a certain period of time, so if the time immediately after the start of immersion is a period of severe biofouling, the possibility of organisms being attached increases, and the marine organism adhesion prevention performance evaluation that is generally adopted by the present inventors is evaluated. In Owase Bay, Mie Prefecture, where the degree of biofouling is even more severe than Aioi Bay, Hyogo Prefecture, which is a sea area, for three months from July to September 1996,
A test method has been devised in which immersion is performed vertically so that it is normally immersed in the sea surface, but immersed horizontally so that the influence of sunlight increases. According to this test method, the above-mentioned JP-A-7-102 was used.
As a result of evaluating the polymer disclosed in Japanese Patent Publication No. 193, it was found that there was a problem in the marine organism adhesion prevention performance corresponding to the outfitting period.

Therefore, according to the present invention, since there is no formation of a residual layer on the surface of the coating film even after long-term immersion, defects such as cracks and peeling do not occur in the coating film properties, and the consumption of the coating film decreases with time. The purpose of the present invention is to develop a coating composition which does not change and has a certain speed or more, can exhibit marine organism adhesion prevention performance over a long period of time, and has a good re-coating property and good marine organism adhesion prevention performance corresponding to the outfitting period.

[0017]

Means for Solving the Problems The present inventors have focused on the following points and have developed a target coating composition. The development of this coating composition can be achieved by not forming a residual layer on the coating film surface. For this purpose, the solubility of the polymer having good compatibility with rosin in seawater must be increased after immersion in seawater. Expression of such a function is possible only with a polymer that undergoes a chemical change before and after immersion in seawater. The polymer accompanied by the chemical change has good compatibility with the rosin-based resin before immersion in seawater, and after immersion in seawater, changes to hydrophilicity only on the surface of the coating film and can have a good dissolution rate.

The present inventors have proposed a blend polymer as:
Attention was paid to a polymer in which a carboxylic acid is protected by an organic silyl group. Due to the low polarity of the organic silyl group, this polymer has good compatibility with low-polarity rosin, and due to the hydrolyzability of the organic silyl group, it undergoes a chemical change after immersion in seawater, resulting in its solubility in seawater. Greatly changes from insoluble to soluble. Organotin polymers having similar hydrolyzability are
Since it has a higher polarity than the above silyl polymer, it has poor compatibility with rosin, and cannot exhibit functions like silyl polymer. Low polarity and hydrolyzability in seawater are very important for blending with rosin.

As a result of intensive studies on these points, it was found that a rosin-based compound such as rosin or a derivative thereof, an organic silyl ester group-containing polymer having an organic silyl group as a hydrolysis point, and an antifouling agent were used. As a result, it was found that the problems of the prior art can be solved satisfactorily.
In other words, even after long-term immersion, there is no formation of a residual layer on the surface of the coating film. , The marine organism adhesion prevention performance can be demonstrated for a long time,
In addition, we successfully developed a rosin-based coating composition with good recoiling properties and good marine organism adhesion prevention performance for outfitting periods.

That is, the present invention relates to A) a rosin compound comprising a rosin, a rosin derivative or a rosin metal salt;
Species or two or more, and B) the following general formula: (Wherein, R ^{1 to} R ³ are all an alkyl group or an aryl group)
And may be the same or different groups. X is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group, an itaconoyloxy group or a citraconoyloxy group. And / or one or more polymers of monomer M and / or one or more of monomers M and a polymerizable monomer other than monomer M The present invention relates to a coating composition comprising, as essential components, an organic silyl ester group-containing polymer composed of one or more polymers and C) an antifouling agent.

[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, tol rosin, gum rosin, utsdrodin, etc., as rosin derivatives, hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride,
Formylated rosin, polymerized rosin, and the like, and rosin metal salts include zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, and other reaction products of a metal compound with rosin. .

In the present invention, one or two or more of such rosin compounds are selected and used. The amount of the rosin compound used is determined by the amount of the rosin compound and the organic silyl ester group-containing polymer of the B component. Solid content ratio is usually 1/99 ~ by weight ratio
99/1, preferably 5/95 to 95/5. If the amount of A is too small, the effect of preventing marine organisms from adhering,
In particular, it is not possible to expect the marine organism adhesion prevention effect corresponding to the outfitting period, and if it is excessive, the coating film forming ability will decrease and the coating film will crack,
Defects such as peeling are likely to occur, and it is difficult to obtain effective marine organism adhesion prevention performance.

In the coating composition of the present invention, the organic silyl ester group-containing polymer of the component B used as an essential component 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 of the above-mentioned monomers M and one or more of polymerizable monomers other than the above-mentioned monomers 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 (having 1 to 1 carbon atoms)
6) an ester itaconoyloxy group] or a citraconoyloxy group (mainly a monoalkyl (C1-6) 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. 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; an aryl group and a substituted aryl group and so on. Examples of the substituted aryl group include halogen, an alkyl group having up to about 18 carbon atoms, an acyl group, a nitro group or an amino group.
And the like.

Among such monomers M, those having a (meth) acryloyloxy group in the molecule include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, and tri-n-propyl. Silyl (meth) acrylate, 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, tribenzylsilyl (meth)
There are acrylates.

Other examples having a (meth) acryloyloxy group in the molecule include ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth)
Acrylate, di-i-propyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, di-i-propylstearylsilyl (meth) acrylate, dicyclohexyl LF Enylsilyl (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 trimethylsilylmethyl maleate.
, Triethylsilylethyl maleate, tri-n-propylsilyl-n-propyl maleate, tri-n-butylsilyl-n-butyl maleate, tri-n-amylsilyl-n-amyl maleate, tri-n- Hexyl octyl silyl maleate, tri-n-octyl silyl decyl maleate, tri-n-dodecyl silyl methyl maleate, triphenyl silyl methyl maleate, tri-p-tolyl silyl ethyl maleate, triisopropyl Silyl isoamyl maleate, triisobutylsilyl phenyl maleate, t
-Butyldimethylsilylmethyl maleate, t-butyldiphenylsilylmethyl maleate, n-octyldi-n-
Butylsilylmethyl maleate;

Further, those having a fumaroyloxy group in the molecule include trimethylsilylmethyl fumarate,
Triethylsilylethyl fumarate, tri-n-propylsilyl-n-propylfumarate, tri-n-butylsilyl-n-butylfumarate, tri-n-amylsilyl-n-amylfumarate, tri-n-hexyl Silyl-n-hexyl fumarate, tri-n-octyl silyl decyl fumarate, tri-n-dodecyl silyl methyl fumarate, triphenyl silyl methyl fumarate, tri-p-methyl phenyl silyl methyl Fumarate, triisopropylsilylmethyl fumarate, triisobutylsilylmethyl fumarate, tri-2-chloroisopropylsilylmethyl fumarate, tri-t-butylsilylmethyl fumarate, ethyldimethyl Silyl methyl fumare
N-butyldimethylsilylmethyl fumarate, n-
Octyl di-n-butylsilylmethyl fumarate and the like can be mentioned.

Further, those having an itaconoyloxy group in the molecule include trimethylsilylmethylitacone-
G, triethylsilylethyl itaconate, tri-n-
Propylsilyl-n-propylitanate, tri-n
-Butylsilyl-n-butylitaconate, tri-n-
Amylsilyl-n-amylyl itaconate, tri-n-hexylsilyl-n-hexylitaconate, tri-n-
Octyl silyl decyl itaconate, tri-n-dodecylsilylmethyl itaconate, triphenylsilylmethyl itaconate, tri-p-fluorophenylsilylmethyl itaconate, triisopropylsilylmethyl itaconate, triisobutylsilyl Methyl itacone
G, tri-2-cyanoisopropylsilylmethyl itaconate, tri-t-butylsilylmethyl itaconate,
Ethyldimethylsilylmethylitaconate, n-butyldimethylsilylmethylitanate, n-octyldi-
and n-butylsilylmethyl itaconate.

Further, those having a citraconoyloxy group in the molecule include trimethylsilylmethylcitracone, triethylsilylethylcitracone, and tri-n-propylsilyl-n-propylcitracone.
G, tri-n-butylsilyl-n-butylcitracone
G, tri-n-amylsilyl-n-amylcitracone
Tri-n-hexylsilyl-n-hexylcitracone, tri-n-octylsilyldecylcitracone, tri-n-dodecylsilylmethylcitracone
G, triphenylsilylmethyl citrate, tri-
p-hydroxyphenylsilylmethyl citracone,
Triisopropylsilylmethylcitracone, triisobutylsilylmethylcitracone, tri-2-bromoisopropylsilylmethylcitracone, tri-t
-Butylsilylmethylcitracone, ethyldimethylsilylmethylcitracone, n-butyldimethylsilylmethylcitracone, n-octyldi-n-butylsilylmethylcitracone, and the like.

The polymerizable monomer other than the monomer M is another monomer copolymerizable with the above-mentioned monomer M, for example, 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-acrylic acid Acrylic esters such as methoxyethyl and 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 include methacrylates 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, VEOBA 9 and VEOBA 10 [Showa Ciel Science Co., Ltd.]
Trade names], dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-i-propyl maleate, di-2-maleate
Maleic esters such as methoxyethyl, fumaric esters such as dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, di-i-propyl fumarate, di-2-methoxyethyl fumarate, crotonic acid Esters, itaconic esters, citraconic esters, styrene, vinyltoluene, α-methylstyrene,
Acrylonitrile and the like can also be mentioned.

In the organic silyl ester group-containing polymer of the component B, the ratio of the monomer M represented by the general formula (1) to the other polymerizable monomer depends on the intended use of the coating composition. Although it can be set appropriately according to, generally, the monomer M is 1 to
It is preferable that 100% by weight and the other polymerizable monomer be 99 to 0% by weight.

The polymer containing an organic silyl ester group as the component B is prepared by subjecting such a monomer mixture 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 organic silyl ester group-containing polymer of the component B is used for coatings, it is preferable to dilute it in an organic solvent to obtain a polymer solution having an appropriate viscosity. For this purpose, a solution polymerization method or a bulk polymerization method is used. It is desirable to adopt.

Examples of the polymerization catalyst include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-butylperoxybenzoate, and the like.
Peroxides such as -butylperoxyisopropyl carbonate.

The organic solvents include aromatic hydrocarbon solvents such as xylene and toluene, hexane, and the like.
Aliphatic hydrocarbon solvents such as heptane, ester solvents such as ethyl acetate and butyl acetate, isopropyl alcohol
Alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane and diethyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and one or two of these. The above is used.

The organic silyl ester group-containing polymer of the component B thus obtained has a molecular weight of 1,0 by weight average.
Desirably, it is 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 becomes high, and it must be diluted with a thinner, and only a thin coating film can be obtained with one coating, so that there is a problem that a larger number of coatings is required. Come. The viscosity of the polymer solution of the component B is as follows:
Conveniently, it is less than 150 poise at 25 ° C., for which purpose the solids content of the polymer solution should be in the range of 5 to 90% by weight, preferably 15 to 85% by weight.

In the coating composition of the present invention, the C component used as one of the other essential components is an antifouling agent, and a wide variety of conventionally known components are included. Roughly speaking, there are an organic compound containing an inorganic compound and a metal and an organic compound containing no metal. Among them, 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.

Examples of the organic compound containing a metal include an organic copper-based compound, an organic nickel-based compound and an organic zinc-based compound.
Propineb can also be used. Examples of organic copper compounds include oxine copper, copper nonylphenolsulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, and copper bis (pentachlorophenolate) , Copper pyrithione, etc., as organic nickel-based compounds, nickel acetate, nickel dimethyldithiocarbamate, etc., as organic zinc-based compounds, zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, zinc ethylenebisdithiocarbamate, etc. , Respectively.

Examples of the organic compound containing no metal include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, There are triazine compounds and others.

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

As N-arylmaleimide, 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.

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
-Dione and the like.

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

Other metal-free organic compounds 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, diiodomethylparatolylsulfone, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, triphenylboronpyridine and the like.

In the present invention, one or more of these various antifouling agents are selected and used.
The amount of the antifouling agent in the solid content of the paint 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. If the amount 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.

The coating composition of the present invention thus constituted includes a red pigment, a coloring agent such as a pigment or a dye such as zinc oxide or talc, a water binder, a sagging agent commonly used in paints,
Plasticizers such as chlorinated paraffin, dioctyl phthalate, tricresyl phosphate, ultraviolet absorbers such as benzophenone compounds and benzotriazol compounds,
Various additives such as a color separation preventing agent, an anti-settling agent, an antifoaming agent, silanol, polysiloxane, and alkoxysilane can be appropriately compounded.

In order to form an antifouling coating film on the surface of an object immersed in sea water using the coating composition of the present invention, the film is applied to the surface of the object by an appropriate means, and is then subjected to normal temperature or heating. The solvent can be volatilized and removed, and a dry coating film can be easily formed on the surface of the object by this method.

[0050]

EXAMPLES Next, the present invention will be described specifically with reference to Production Examples, Examples and Comparative Examples. The parts in the examples are parts by weight, and the molecular weight is the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). The monomers M _{1 to} M ₉ used in the 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 It is as shown in Table 1.

[0051]

[Table 1]

Production Examples 1 to 4 A solvent a was charged into a flask equipped with a stirrer according to the composition shown in Table 2, and the temperature was raised to a predetermined reaction temperature. The mixed solution of the catalyst a was dropped into the flask in 3 hours.
Hold for 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 2 hours to complete the polymerization reaction. Finally, was diluted with a diluting solvent, 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 into a heat-resistant and pressure-resistant container according to the composition shown in Table 3, and the container was completely sealed and shaken at a predetermined reaction temperature. And shaking was continued at the same temperature for 8 hours to complete the reaction. Next, a diluting solvent was added and shaken for 1 hour to dissolve, and each polymer solution S _{5 to} S _{8 was} dissolved.
I got

Production Examples 9 to 16 Into a flask equipped with a stirrer, a solvent, a monomer M, other monomers and a polymerization catalyst were charged according to the formulations shown in Tables 4 and 5, and the mixture was heated to a predetermined reaction temperature while stirring. The temperature was raised, and stirring was continued at the same temperature for 6 hours to complete the reaction. Next, each polymer solution was diluted with a diluting solvent to obtain each of polymer solutions S _{9 to} S ₁₆ .

In Tables 2 to 5, "Veoba 9" and "Veoba 10" (trade names manufactured by Showa Ciel Science Co., Ltd.) are all vinyl ester monomers, and "Perbutyl". "I" (trade name, manufactured by 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 respective components were mixed according to the composition shown in Tables 6 to 10 (the numerical values in the tables are% by weight), and the mixture was mixed at 2,000 rpm. Mix and disperse with a homomixer and add 2
Zero coating compositions were prepared.

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

In Tables 6 to 11, "Dymalex" (trade name, manufactured by Hazukires Co., Ltd.) is a polymerized rosin.
"Dayspalon A630-20X", "Dayspalon 4
300 "(trade name, manufactured by Kusumoto Kasei Co., Ltd.) and" Benton SD-2 "(trade name, manufactured by National Red Co., Ltd.)
Are all additives for preventing sagging, "KMP590" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) is silicone resin powder II, "Tinuvin 900" (trade name, manufactured by Ciba Geigy Corporation) is an ultraviolet absorber It 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 of the paint compositions, the following procedures were used to confirm the residual layer of the paint film, the wear test of the paint film, the antifouling performance test, the adhesion test, the crack resistance test, the recoatability test, and the marine life corresponding to the outfitting period. An adhesion prevention performance test was performed. These results were as shown in Tables 12-20.

<Test for confirming residual layer of coating film surface> A blast steel plate (100 mm x 200 mm x 1 mm) was spray-coated twice by spray coating to a dry film thickness of 125 µm per coat. Further, a tar vinyl sealer coat was applied so that the dry film thickness became 70 μm.
On this, each coating composition was dried at a dry film thickness of 10
Coating was performed twice by spray coating to a thickness of 0 μm, and the coating was dried for one week in a constant temperature / humidity room at a temperature of 20 ° C. and a humidity of 75%, to prepare six test pieces for each coating composition.

The test piece thus prepared was immersed in artificial seawater, pulled up after 3 months, 6 months, 12 months, 18 months and 24 months, and cut. After polishing the cut surface, the residual layer formed on the coating film surface was measured by observing the coating cross section with a stereoscopic microscope.

<Coating film wear test> Each coating composition was spray-coated on the surface of a steel plate (100 mm x 100 mm x 1 mm) coated on both sides with rust prevention so that the thickness of one dry coating film was 200 µm. It was coated twice and dried in a room at a temperature of 20 ° C. for one week to prepare a test piece.

After fixing the above test piece on the outer surface of a cylindrical drum having a diameter of 50 cm, the test piece was placed under the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture.
m and rotated by a motor so that the peripheral speed of the drum becomes 16 knots.
It was measured for four months. In addition, the average thickness consumption rate of the coating film (μm /
) Was calculated for the period up to six months and for the period from six months to 24 months. The average speed of consumption of the coating film thickness was 3 μm /
If it is a month, it correlates with good antifouling performance. If the average thickness of the coating film from 6 months to 24 months is within the range of the average thickness of the coating film from 6 months to 1 month (μm / month),
This indicates that the coating film is consumed at a constant speed.

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

<Adhesion Test> A blast anti-corrosive paint was applied twice to the blasted steel sheet by spray coating so as to give a dry film thickness of 125 μm each time, and then a tar vinyl-based sealer was applied. The paint was applied to a dry film thickness of 70 μm. Each of the coating compositions was applied twice by spray coating so that the dry film thickness was 100 μm each time, and dried for one week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. Pieces were made.

The test piece was immersed in artificial seawater, pulled up after 3 months, 6 months, 12 months, 18 months and 24 months, and subjected to a 2 mm-square test.
The evaluation of the adhesion was such that the number of peeled pieces by this test was 0 pieces / 25.
場合 (pass) when the number was one, and × (fail) when the peeled number was 1 or more / 25.

<Crack Resistance Test> In the adhesion test, when the test piece was pulled out of artificial seawater, the coating film was visually observed to check for the occurrence of cracks. A sample without cracks was evaluated as ○ (pass), and a sample with no crack was evaluated as x (fail).

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

The 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 one week. Thereafter, the same coating composition was applied twice on the surface of each test piece by spray coating so that the dry film thickness was 100 μm each time, and dried in a room at a temperature of 20 ° C. for one week. After fixing these test pieces on the outer surface of a cylindrical drum having a diameter of 50 cm, they were immersed 1 m below the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture, and rotated by a motor so that the peripheral speed of the drum became 16 knots. I let it. One week later, it was lifted up, and the presence or absence of peeling between the new coating film and the old coating film was confirmed. A sample without peeling was evaluated as ○ (pass), and a test sample was evaluated as x (fail).

<Marine organism adhesion prevention performance test corresponding to the outfitting period>
Painted plate coated with ruvinyl-based rust preventive paint (100mm ×
(300mm x 1mm) Both sides have a dry film thickness of 240μm on one side
Spray paint twice so that the temperature becomes 20
The sample was dried for one week in a constant temperature and humidity room at 75 ° C. and a humidity of 75% to prepare a test piece. The test piece was immersed in seawater for 3 months from July to September 1996 in Owase Bay, Mie Prefecture, at a position 1 m below the water surface so as to be horizontal with respect to the seawater surface. The ratio of the area occupied by the attached organisms (the attached area) was measured over time.

Further, in order to compare the degree of biofouling in Owase Bay in Mie Prefecture during the above period with Aioi Bay in Hyogo Prefecture, and to compare the direction of immersion vertically and horizontally with respect to the sea surface, Specimens coated with only ruvinyl-based rust-proof paint
The immersion was performed in both the immersion directions in the two sea areas, 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] (All adhesion areas are 100%)

As is apparent from the results of Tables 12 to 20, the coating composition of Comparative Example 1 using a vinyl chloride resin as a blend polymer with rosin, styrene butadiene rubber, chlorinated paraffin resin, Each of the coating compositions of Comparative Examples 2, 3, and 6 using an ethylene-vinyl acetate copolymer (all correspond to Examples in 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
193), all of which show good paint consumption for several months after the start of immersion, but a residual layer is formed on the surface of the paint after long-term immersion. ,
Both the wear rate of the coating film and the antifouling performance were unsatisfactory, and some defects were found in the crack resistance, adhesion, recovability and marine organism adhesion prevention performance corresponding to the outfitting period.

On the other hand, various rosin compounds and the 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 No. ₁₂ was used in combination, no residual layer was formed on the coating film surface even after long-term immersion, and the coating film consumption rate, antifouling performance, crack resistance, adhesion, and recoating The test shows that the coating composition of the present invention has excellent performance in both the test of the marine organism adhesion prevention performance corresponding to the outfitting period and the outfitting period.

[0093]

As described above, the coating composition of the present invention comprises:
It can be used for underwater structures such as ship bottoms and fish nets and cooling water pipes that need to prevent underwater biofouling, and for preventing the spread of sludge in marine civil engineering works.The coating remains on the coating even after long-term immersion. Since there is no layer formation, there are no defects such as cracks or peeling in the physical properties of the coating film, and the coating film consumption does not change over time and is at a certain speed or higher, and the marine organism adhesion prevention performance is exhibited over a long period of time. It is also excellent in the marine organism adhesion prevention performance corresponding to the outfitting period, and also exhibits good recoverability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiro Matsubara 296, Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Japan Oil & Fat Co., Ltd. (72) Inventor Yasushi Kawamura 296, Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan Inside the Totsuka Plant Co., Ltd. (72) Inventor Shigeru Masukaka 296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan Inside the Totsuka Plant (72) Inventor Yoshihiro Honda 296 Shimokurata-cho, Totsuka-ku, Yokohama-shi, Kanagawa Japan Oil and Fat Co., Ltd. Inside the Totsuka factory

Claims (1)

[Claims] 1. A) one or more rosin compounds comprising rosin, a rosin derivative or a rosin metal salt, and B) the following general formula: (Wherein, R ^{1 to} R ³ are all an alkyl group or an aryl group)
And may be the same or different groups. X is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group, an itaconoyloxy group or a citraconoyloxy group. And / or one or more polymers of monomer M and / or one or more of monomers M and a polymerizable monomer other than monomer M A coating composition comprising, as essential components, an organic silyl ester group-containing polymer comprising one or more polymers and C) an antifouling agent.