JPH0619070B2 - Underwater antifouling coating agent - Google Patents

Description

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

[Conventional technology]

The surface of underwater objects such as ship bottoms, buoys, fishing nets (culture nets such as yellowtail and scallops), underwater pollution prevention sheets, and various intake and drainage pipes for cooling that are immersed in water include barnacles, serpra, mussels, Various obstacles occur due to adhesion of algae and the like. It is well known that an underwater antistatic coating is applied to the surface of an underwater immersion product in order to prevent the stains from being caused by those organisms.

Currently, as an underwater antifouling coating agent, one using an antifouling agent such as an organotin copolymer or cuprous oxide is often used.

However, due to the problem of environmental pollution, a pollution-free underwater antifouling coating agent has been demanded, and for example, Japanese Patent Publication No. 53-3597.
Japanese Unexamined Patent Publication No. 4-96830 discloses a material using vulcanized silicone rubber as a coating agent.
The publication discloses the use of a mixture of an oligomeric silicone rubber having hydroxyl end groups and a silicone oil. Further, JP-A-53-79980 discloses a mixture of a vulcanized silicone rubber and a fluid organic compound containing no metal and containing no silicon. Furthermore, Japanese Patent Publication No. 60-3433 discloses that
A mixture of oligomeric cold-curing silicone rubber and fluid paraffin or petrolatum is shown.

[Problems to be Solved by the Invention]

These conventionally known underwater antifouling coatings utilize the low surface tension of the silicone rubber-coated surface to prevent the adhesion of aquatic organisms to the surface. Difficulty was observed in the antifouling effect, especially in antifouling durability.

Therefore, the present invention solves the above conventional problems,
It is intended to provide an underwater antifouling coating material having a greater antifouling effect.

[Means for Solving the Problems]

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, by using a specific hydrophilic polymer in combination with a reaction-curable silicone rubber, and by further adding a surface lubricant to it. Then, they have found that an underwater antifouling coating agent having a large antifouling effect, particularly excellent antifouling durability can be obtained, and thus completed the present invention.

That is, the present invention provides a reaction-curable silicone rubber and the following general formula (1); (Wherein, X is a hydrogen atom or a methyl group, R is a hydrogen atom, an alkyl group or an acyl group, m is a real number of 2 to 4, and n is a real number of 1 or more). One or more polymers, and / or a copolymer composed of one or more monomers of the above-mentioned monomer A and one or more monomers of a vinyl-polymerizable monomer B copolymerizable therewith. The present invention relates to an underwater antifouling coating agent containing as an essential component, and an underwater antifouling coating agent obtained by adding a surface lubricant to the above both components as an essential component.

[Constitution / Operation of Invention]

The reaction-curable silicone rubber used in the present invention is
A polyorgano having a siloxane bond in the molecule that chemically reacts and cures into a rubber-like elastic body when exposed to the atmosphere, mixed with a catalyst, heated, or irradiated with ultraviolet rays. It is mainly composed of siloxane.

Examples of commercially available products of such silicone rubber include TSE370RTV and YE3, trade names, manufactured by Toshiba Silicone Co., Ltd.
085, TSE382RTV, TSE388W, TSE
385RTV, TSE3851, Tosseal 371, Tosseal 381, Tosseal 380, Tosseal 10,
Tosukoto 10, TSE3033, TSJ3130, T
SJ3150, TSE350RTV, TSE3562,
Toss Seal 361, TSE3434RTV, YE562
6, TSE322, TSE325, TSE3360, T
LM1025, TUV6000, TUV6020, YE
5505 etc. and Shin-Etsu Chemical Co., Ltd. product name KE4
1, KE42TS, KE44, KE45, KE45T
S, KE347, KE3475 and the like.

In the present invention, together with the above reaction-curable silicone rubber, one or more polymers of the monomer A represented by the general formula (1), that is, a homopolymer or a copolymer (hereinafter, These are referred to as a polymer A), and / or a copolymer of one or more of the above-mentioned monomers A and one or more of a vinyl-polymerizable monomer B copolymerizable therewith (hereinafter, These are referred to as copolymers AB).

Since both the polymer A and the copolymer AB have an alkylene oxide group derived from the monomer A in the side chain of the molecule, they impart appropriate hydrophilicity to the antifouling coating so that the surface of the coating is submerged in water. It has a function of weakening, and it is difficult for organisms to adhere to the coating surface weakened in this way, and since the hydrophilicity-imparting group is present in the side chain of the olimer molecule, The molecule's function is activated, which is one of the factors that hinder the attachment of organisms.

Therefore, when such a polymer A and / or copolymer AB is used in combination with the above reaction-curable silicone rubber to form an antifouling coating, the above-mentioned polymer A and copolymer AB based on Combined with the low surface tension based on silicone rubber, a large antifouling effect with extremely excellent antifouling durability is exhibited.

In the present invention, the monomer A for obtaining the above-mentioned polymer A and / or copolymer AB is an unsaturated acid monoester containing an alkylene oxide group in the molecule represented by the above general formula (1). Is. In the general formula (1), m is represented by a real number of 2 to 4, and n can be a real number of 1 or more, but it is usually up to about 5000. Further, R is a hydrogen atom or an alkyl group or an acyl group having usually about 18 carbon atoms.

In addition to the ethylene oxide group represented by m = 2, the propylene oxide group represented by m = 3, and the butylene oxide group represented by m = 4, the alkylene oxide group includes two or more kinds of these groups in one molecule. These groups may be mixed, and since these groups are introduced by dehydration condensation, the monomer A is usually a mixture of the above-mentioned one or more alkylene oxide groups having different repeating numbers. ing.

Therefore, the above-mentioned m and n values should be expressed as their average values () and (), respectively, and this is why they are expressed as the real numbers.

Specific examples of the monomer A include 2-methoxyethyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, 2-ethoxyethyl (meth)
Acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tetraethylene glycol monoethyl ether (meth) acrylate,
Polyethylene glycol monoethyl ether (meth) acrylate, 2-propoxyethyl (meth) acrylate, diethylene glycol monopropyl ether (meth) acrylate, triethylene glycol monopropyl ether (meth) acrylate, tetraethylene glycol monopropyl ether (meth) acrylate , Polyethylene glycol monopropyl ether (meth) acrylate, 2-acetoxyethyl (meth) acrylate, diethylene glycol monoacetate (meth) acrylate, triethylene glycol monoacetate (meth) acrylate, tetraethylene glycol monoacetate (meth) acrylate, polyethylene glycol Monoacetate (meth) acrylate, 2-methoxypropyl (meth) a Relate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetrapropylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, 2-ethoxypropyl (meth) acrylate, Dipropylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monoethyl ether (meth) acrylate, tetrapropylene glycol monoethyl ether (meth) acrylate, polypropylene glycol monoethyl ether (meth) acrylate, 2-propoxypropyl (meth ) Acrylate, dipropylene glycol monopropyl ether (meth) ac Rate, tripropylene glycol monopropyl ether (meth) acrylate, tetrapropylene glycol monopropyl ether (meth) acrylate, polypropylene glycol monopropyl ether (meth) acrylate, 2-
Acetoxypropyl (meth) acrylate, dipropylene glycol monoacetate (meth) acrylate, tripropylene glycol monoacetate (meth) acrylate, tetrapropylene glycol monoacetate (meth) acrylate, polypropylene glycol monoacetate (meth) acrylate, 2-methoxybutyl (Meth) acrylate, dibutylene glycol monomethyl ether (meth) acrylate, tributylene glycol monomethyl ether (meth) acrylate, tetrabutylene glycol monomethyl ether (meth) acrylate, polybutylene glycol monomethyl ether (meth) acrylate, 2-ethoxybutyl ( (Meth) acrylate, dibutylene glycol monoethyl ether (meth) acrylate Tributylene glycol monoethyl ether (meth) acrylate, tetrabutylene glycol monoethyl ether (meth) acrylate, polybutylene glycol monoethyl ether (meth) acrylate, 2-propoxybutyl (meth) acrylate, dibutylene glycol monopropyl ether ( (Meth) acrylate, tributylene glycol monopropyl ether (meth) acrylate, tetrabutylene glycol monopropyl ether (meth) acrylate, polybutylene glycol monopropyl ether (meth) acrylate, 2-acetoxybutyl (meth) acrylate, dibutylene glycol mono Acetate (meth) acrylate, tributylene glycol monoacetate (meth) acrylate, tetrabutylene glyco Monoacetate (meth) acrylate, polybutylene glycol monoacetate (meth) acrylate, monoethylene monopropylene glycol monoethyl ether (meth) acrylate, triethylene dipropylene glycol monomethyl ether (meth) acrylate, monoethylene monopropylene monobutylene glycol monomethyl Ether (meth) acrylate, polyethylene polypropylene glycol monomethyl ether (meth) acrylate,
Polyethylene polybutylene glycol monoethyl ether (meth) acrylate, polypropylene polybutylene glycol monoethyl ether (meth) acrylate,
Polyethylene polypropylene Polybutylene glycol monoethyl ether (meth) acrylate, 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2 -Hydroxybutyl (meth)
Acrylate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, polybutylene glycol (meth) acrylate, monoethylene monopropylene glycol mono (meth) acrylate, triethylene Dipropylene glycol mono (meth) acrylate, monoethylene monopropylene monobutylene glycol mono (meth) acrylate, polyethylene polypropylene glycol mono (meth) acrylate, polyethylene polybutylene glycol mono (meth) acrylate, polypropylene polybutylene glycol mono (meth) acrylate , Polyethylene polypropylene polybutylene glycol mono (meta)
Acrylate, etc.

Further, as the vinyl polymerizable monomer B used together with the above-mentioned monomer A to obtain the copolymer AB, there are methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-dimethylaminoethyl methacrylate, methacrylic acid. Acid 2-diethylaminoethyl, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-dimethylaminoethyl acrylate,
(Meth) acrylic acid esters such as 2-diethylaminoethyl acrylate, methyl crotonic acid, crotonic acid esters such as ethyl crotonic acid, methyl itaconate,
Itaconic acid esters such as ethyl itaconate, maleic acid esters such as dimethyl maleate and diethyl maleate, fumaric acid esters such as dimethyl fumarate and diethyl fumarate, styrene, vinyltoluene, α-methylstyrene, chlorostyrene , Vinyl chloride, vinyl acetate, vinylidene chloride, ethylene, butadiene, cyclohexene, acrylamide, acrylonitrile, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and their acid salts.

The above (meth) acrylate means that either acrylate or methacrylate may be used, and similarly (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used. .

The vinyl-polymerizable monomer B acts as a modifying component for imparting various performances to the antifouling coating depending on the purpose of use, and the amount used is a hydrophilic component based on the monomer A. It is set in an appropriate range in consideration of the effect. Generally, the proportion of the monomer B in the total amount of the monomer A is 90% by weight.
Hereafter, it is preferably 70% by weight or less.

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

Polymer A and copolymer AB obtained by such a method
Generally has a weight average molecular weight of 1,000 to 1,500,
It is preferably in the range of 000. If the molecular weight is too low, it is difficult to form a coating that can be used, and if it is too high, the viscosity of the coating agent becomes too high, which is not preferable.

In the present invention, the above reaction-curable silicone rubber and the above polymer A and / or copolymer AB are used in combination, but the combination ratio of both is in order to better exhibit the functions of both components. Polymer A in the total amount of components
And / or the proportion of copolymer AB is usually from 0.1 to 70
It is good to set it as the weight%, preferably 0.5 to 50 weight%. If this proportion is too large, the compatibility of both components will deteriorate and it will be difficult to obtain a normal coating.

In the present invention, the excellent antifouling effect can be exhibited only by using the above-mentioned reaction-curable silicone rubber in combination with the polymer A and / or the copolymer AB, but with these, a surface lubricant is one of the essential components. By using it, the antifouling effect, especially its sustainability, can be further improved.

As the surface slip agent used in the present invention, there are various substances known to impart surface slip properties to the coating film. Typical examples thereof include petroleum wax and JIS specified in JIS-K2235. -Fluid paraffin specified by K2231, silicone oil having a kinematic viscosity of 55,000 centistokes or less at 25 ° C,
Fatty acids having 8 or more carbon atoms and esters thereof having a melting point of -5 ° C or higher, organic amines having an alkyl group or an alkenyl group having 12 to 20 carbon atoms, polybutene having a kinematic viscosity of 60,000 centistokes or less at 26 ° C, etc. There is.

Specific examples of the above include JIS-K2235 120
P, 125P, 130P, 135P, 140P, 145
Paraffin wax such as P, 150P, 155P, J
IS-K2235 150M, 160M, 170M, 1
Examples include microcrystalline waxes such as 80M and 190M and petrolactams such as JIS-K2235 Nos. 1, 2, 3 and 4. Further, as the above specific examples, ISOVG10, ISOVG15, ISOV
Examples include parts corresponding to G32, ISOVG68, and ISOVG100.

Specific examples of the above include trade names KF96L-0.65, KF96L-2.0, and KF96 manufactured by Shin-Etsu Chemical Co., Ltd.
-30, KF96H-50,000, KF965, KF
503, KF54, KF69, product names TSF440, TSF410, TSF444 manufactured by Toshiba Silicone Co., Ltd.
0, TSF431, TSF433, TSF404, TF
A4200, YF3860, YF3818, YF396
5, YF3841, YF3953, TSF451, TS
F400, FQF501, trade names SH200, SH510, SH3531, SH23 manufactured by Toray Silicone Co., Ltd.
0, FS1265, etc.

The above-mentioned silicone oil is most commonly dimethyl silicone oil, but other methyl phenyl silicone oils, polyether silicone oils, cyclic polysiloxane oils, alkyl modified silicone oils, methyl chlorinated phenyl silicone oils, higher fatty acids. Other materials such as modified silicone oil and fluorosilicone oil may be used.

Specific examples of the above, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid, melissic acid, lauroleic acid, oleic acid, vaccenic acid, caderic acid, whale oil acid, shark Examples thereof include oily acid and diuniperic acid. Also,
These carboxylic acid esters include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate,
Cetyl palmitate, ceryl cerotate, myricil palmitate, melisil merisate, whale wax, beeswax, carnauba wax, montan wax, mulberry wax, tristearin,
Tolpalmitin, triolein, myristodilaurin,
Caprylolauromyristin, stearopalmitoolein, monostearin, monopalmitin, distearin,
There are dipalmitin, beef tallow, lard, horse fat, sheep fat, cod liver oil, coconut oil, palm oil, wood wax, capoque oil, cacao oil, cacao butter, Chinese fat, and Ilitsupe fat.

Specific examples of the above include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
Oleylamine, tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, di-beef hydrogenated alkylamine, dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, octadecyldimethylamine, etc. is there.

Specific examples of the above include trade names Nitsusan Polybutene 0N, 06N, 015N, 3N, 5N manufactured by NOF CORPORATION.
10N, 30N, 200N, 0SH, 06SH, 015
SH, 3SH, 5SH, 10SH, 30SH, 200S
There are H etc.

In the present invention, one kind or two or more kinds are selected and used from the above-mentioned various surface lubricants, and the amount thereof is such that the reaction curable silicone rubber and the polymer A and / or the copolymer AB are used. It is set in an appropriate range in consideration of the performance such as dryness and adhesion based on and the antifouling performance. Generally, the proportion of the surface-lubricating agent in the total amount of the reaction-curable silicone rubber, the polymer A and / or the copolymer AB and the surface-lubricating agent is 70% by weight or less, particularly 50% by weight or less. Is preferred.

As described above, the underwater antifouling coating material of the present invention comprises a reaction-curable silicone rubber, a polymer A and / or a copolymer AB.
It contains either or as an essential component, or further contains the above-mentioned surface lubricant as an essential component, and is usually diluted with an organic solvent before use. For this reason,
As a polymerization method for obtaining the polymer A and / or the copolymer AB, it is particularly preferable to adopt 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 after being diluted with a solvent, and in the bulk polymerization method, a solvent can be added to the reaction product after polymerization and used.

The organic solvent used for the above purpose, xylene, aromatic hydrocarbon solvents such as toluene, hexane, aliphatic hydrocarbon solvents such as heptane, ethyl acetate, ester solvents such as butyl acetate, isopropyl alcohol, butyl alcohol Alcohol-based solvents such as, ether solvents such as dioxane and diethyl ether, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. Is mentioned.

In the underwater antifouling coating agent of the present invention which is used by diluting in this manner, coloring pigments, extender pigments, anticorrosion pigments, dyes, anti-sagging agents, plasticizers, color separation preventing agents, anti-settling agents, You may add antifoaming agents, antifouling agents, etc.

In order 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, the above coating agent as a solution is applied to the surface of the object by an appropriate means. The solvent may be removed by volatilization at room temperature or under heating, and the silicone rubber may be cured. As a result, an antifouling coating film which is hydrophilic and has good slipperiness is uniformly formed.

〔The invention's effect〕

As described above, in the present invention, by using the reaction-curable silicone rubber in combination with the polymer A and / or the copolymer AB, and by adding a surface lubricant to these components, It is possible to provide an underwater antifouling coating material having a greater antifouling effect as compared with the silicone rubber alone or a combination system thereof with a silicone oil or petrolatum.

Therefore, the underwater antifouling coating material of the present invention can be applied by applying it to a ship bottom that requires prevention of aquatic biological pollution, an underwater structure such as a fishing net or various cooling water pipes, and a marine pollution prevention film. It can greatly contribute to the prevention of biofouling contamination of these submerged submerged substrates.

〔Example〕

The present invention will be specifically described below with reference to polymer production examples, examples and comparative examples. Parts in the examples are parts by weight, viscosity is the measured value of foam viscosity at 25 ° C., and molecular weight is the weight average molecular weight by GPC.

Production Examples 1 to 7 A flask equipped with a stirrer was charged with the solvent a according to the formulation in Table 2.
Was charged, the temperature was raised to a predetermined reaction temperature, the mixed solution of the monomer A, the monomer B and the polymerization catalyst a was dropped into the flask with stirring for 10 hours, and after completion of the dropping, at the same temperature for 30 minutes. Held Then, a mixture of the solvent b and the polymerization catalyst b is added to 2
The mixture was added dropwise over 0 minutes, and stirring was continued at the same temperature for 5 hours to complete the polymerization reaction. Finally, a diluting solvent was added to dilute each to obtain polymer solutions I to VII.

Production Examples 8 and 9 In a container with heat and pressure resistance, in accordance with the composition of Table 2, the monomer A,
The monomer B and the polymerization catalyst a were charged, completely sealed, heated to a predetermined reaction temperature while shaking, and further shaken at the same temperature for 8 hours to complete the reaction. Next, a diluting solvent was added and the mixture was shaken for 3 hours to dissolve, and polymer solutions VIII and IX were added.
Got

Production Example 10 In a flask with stirring, according to the formulation of Table 2, the solvent a,
The monomer A and the polymerization catalyst a were charged, the temperature was raised to a predetermined reaction temperature while stirring, and stirring was continued at the same temperature for 6 hours to obtain a polymer solution X.

In addition, the monomer A (A _1-
A ₁₀ ) has a structure in which X, m, n and R in the general formula (1) are as shown in Table 1 below. In Table 1, the types of alkylene oxide groups contained in each monomer are also shown for reference. Among them, EO is an ethylene oxide group, PO is a propylene oxide group, and BO is a butylene oxide group.

Here, the monomer A ₆ is a mixture of EO with m = 2, PO with m = 3, and BO with m = 4, and is represented as an average value at an average number of repetitions of these alkylene oxide groups = 1,200. However, it will be 3.2. Similarly, the monomer A ₈ is a mixture of EO with m = 2 and BO with m = 4, which is represented as an average value of these alkylene oxide groups at an average number of repetitions = 23, but is 3, or The monomer A ₉ is a mixture of EO with m = 2 and PO with m = 3, and is represented as an average value when the average number of repetitions of these alkylene oxide groups = 32, but is 2.5.

Examples 1 to 19 Using the reaction-curable silicone rubber and the polymer solutions I to X, mixing and dispersing with a homomixer of 2,000 rpm according to the compounding composition shown in the following Table 3 (numerical values in the table are% by weight). Then, 19 kinds of underwater antifouling coating materials were prepared.

In addition, YE3085 (50 wt% toluene solution) and YE5505 (50 wt% toluene solution) in the blended components
Is KE45TS (50% by weight) manufactured by Toshiba Silicone Co., Ltd.
Toluene solution) and KE3475 (100% by weight)
Are trade names of reaction-curable silicone rubbers manufactured by Shin-Etsu Chemical Co., Ltd.

Paraffin wax 120P and petrolatum 1 are petroleum wax of JIS-K2235.
OVG10 and ISOVG68 are JIS-K2231
It is a fluid paraffin of. Further, KF-69 [trade name of Shin-Etsu Chemical Co., Ltd.] and TSF433 [trade name of Toshiba Silicone Co., Ltd.] are silicone oils, and Nitsusan Polybutene 06N and 200N [NOF CORPORATION].
Trade name] is polybutene.

In addition, Oil Blue 2N [trade name of Orient Chemical Co., Ltd.] is a dye, Disparlon 6900-20X [Kusumoto Kasei]
The trade name of manufactured by Nippon Aerogel Co., Ltd. and the trade name of Aerozil 300 manufactured by Nippon Aerozil Co., Ltd. are both anti-sagging additives.

Comparative Examples 1 to 4 In the same manner as in Examples 1 to 19, four types of underwater antifouling coating agents having the composition shown in Table 3 below were prepared.

An antifouling performance test was conducted on each of the coating materials of Examples 1 to 19 and Comparative Examples 1 to 4 described above by the method described below.

That is, a coated plate (100 mm x 200 mm) prepared by applying a tar vinyl anticorrosive paint to a sandblasted steel plate in advance.
X 1 mm) on both sides, each coating has a dry film thickness of 120μ on one side
A test plate was prepared by spraying twice so as to have a thickness of m.

This test plate was immersed in water for 24 months in Yura Bay, Sumoto City, Hyogo Prefecture, and the ratio of the area occupied by adherent organisms (adhered area) on the test coating film was measured over time.

As is clear from the results of Table 4 above, Examples 1, 2, and
With respect to 5, 6 and 9, only 1% of the biological attachment was observed after 24 months, but no biological attachment was observed up to 18 months, which was good. In addition, Example 3,
In Nos. 4, 7, 8 and 10 to 19, no adhesion of organisms was observed even after 24 months, which was extremely good.

On the other hand, in Comparative Example 1, the adherence of organisms was already observed after the lapse of 3 months, and in Comparative Examples 2 to 4 also, the adherence of the organisms was observed after the lapse of 6 months, indicating a poor antifouling performance. .

Claims (2)

[Claims] 1. A reaction-curable silicone rubber and the following general formula (1); (Wherein, X is a hydrogen atom or a methyl group, R is a hydrogen atom, an alkyl group or an acyl group, m is a real number of 2 to 4, and n is a real number of 1 or more). One or more polymers, and / or a copolymer composed of one or more monomers of the above-mentioned monomer A and one or more monomers of a vinyl-polymerizable monomer B copolymerizable therewith. An underwater antifouling coating agent containing as an essential component. 2. A reaction-curable silicone rubber and the following general formula (1); (Wherein, X is a hydrogen atom or a methyl group, R is a hydrogen atom, an alkyl group or an acyl group, m is a real number of 2 to 4, and n is a real number of 1 or more). One or more polymers, and / or a copolymer composed of one or more monomers of the above-mentioned monomer A and one or more monomers of a vinyl-polymerizable monomer B copolymerizable therewith. An underwater antifouling coating composition containing a surface lubricant and an essential component.