JPH08259856A - Coating composition for preventing aquatic organism from adhering - Google Patents

Abstract

PURPOSE: To obtain a coating composition having low toxicity and larger antifouling effect which continues for a long time by allowing to contain an oxyalkylene silyl ether having a specific structure. CONSTITUTION: This coating composition for preventing aquatic organisms from adhering preferably contains 0.5-80wt.% of at least one compound selected from among oxyalkylene silyl ethers of formula I and formula II [A and B are each a 2-3C alkylene, etc.; (n) and (t) are each >=1 integer; X is H, OH, etc.; R<1> to R<3> are each OH, a 1-20C alkyl, etc.; (q) is 1-10; Y is H, a 6-12C aryl, etc.; R<4> and R<5> are each OH, acetoxyl, etc.; R<6> to R<8> are each OH, phenoxy, etc.]. The compound of formula I or formula II can be preferably obtained by reacting a silane compound with an oxyalkylene compound containing a (poly)oxyethylene chain or a (poly)oxypropylene chain having a reactive group containing an active hydrogen on the A terminal. As the component A, e.g. ethylene glycol and as the component B, e.g. dimethyldichlorosilane can be cited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater organism adhesion preventing coating composition used in marine structures, industrial water systems and the like to prevent the aquatic organisms from adhering and being damaged by reproduction.

[0002]

BACKGROUND OF THE INVENTION Underwater structures such as ships, marine structures, aquaculture fishing nets, buoys, and industrial water systems are constantly exposed to the water in which living organisms live, so bacteria, etc. , And organisms such as barnacles, mussels, sea bream, and diatoms adhere. If the surface of an undersea structure is covered by these, corrosion of the part concerned, deterioration of fuel efficiency of the ship due to increase of seawater friction resistance of the ship, large amount of hay death of seafood due to clogging of fishing net, sedimentation due to decrease of buoyancy of buoy , Damage such as reduced work efficiency will occur.

Further, in industrial water systems such as cooling water using natural water such as river water and lake water, and circulation type cooling devices using inside and tap water, bacteria, diatoms, cyanobacteria, etc. breed and water quality is increased. Cause deterioration of cooling efficiency and deterioration of cooling efficiency due to adherence to vessel walls, blockage of water pipes, decrease in flow rate, etc.

As a method for preventing the attachment of these pests, a method of coating an antifouling paint has been conventionally used, and an inorganic copper compound, an organic tin compound or the like is mainly used as an antifouling agent in the above antifouling paint. There is. The antifouling paint contains rosin as a part of the paint vehicle, and the antifouling agent is added to the rosin to prevent adhesion of aquatic organisms.

Further, a hydrolyzable antifouling paint containing a trialkyltin polymer as an antifouling component is used. This is because the trialkyltin polymer is hydrolyzed in a slightly alkaline atmosphere in water. In addition to elution of the organotin compound, the paint vehicle becomes water-soluble and the compounded antifouling agent elutes.

All of the antifouling agent components thus eluted are highly toxic, and due to this toxicity, antifouling performance is exhibited by killing harmful aquatic organisms attached or injuring them to a state where they cannot be attached. . All of the conventional antifouling paints contain a compound harmful to the living body as described above, which is a safety and health problem for workers. Furthermore, it was a serious problem from the viewpoint of environmental pollution.

In recent years, many silicone antifouling paints have been proposed, which utilize the water repellency and low surface energy of the coated surface. The silicone antifouling paint is
Although the degree of toxicity to the human body and environmental pollution is small, there are many problems such as poor adhesion with the coating base, insufficient coating film strength, and difficulty in coating and repair coating.For example, in some special areas such as nuclear power generation. It is only used in.

Japanese Unexamined Patent Publication (Kokai) No. 60-170673 discloses a coating agent composed of a polymer of a polymerizable unsaturated monomer containing a polyoxyethylene group, which is gradually eluted in water. , It prevents the adhesion of aquatic organisms and other materials to the surface of the material that comes into contact with water, and keeps the coated surface in a uniform state. Further, in Japanese Patent Laid-Open No. 5-320539,
A technique is disclosed in which polyoxyethylene chains are oriented on the surface of a coating film to make it hydrophilic and prevent adhesion of aquatic organisms.

All of these techniques bring about the antifouling effect by increasing the solubility or hydrophilicity of the coating film in water without using a highly toxic antifouling agent. In this way, the method of utilizing the high hydrophilicity of the coating film has a long-lasting effect such that the antifouling effect is significantly reduced once aquatic organisms are attached and covered with bacteria and contaminants in the water. I had a problem with. In addition, the elution of coating film components is a key point in exhibiting the antifouling effect, which makes it difficult to control the elution rate.

Japanese Unexamined Patent Publication (Kokai) No. 3-128302 discloses an aquatic organism adhesion preventing coating composition using a phenol derivative having an alkyl group introduced therein. The above-mentioned phenol derivative having an alkyl group introduced has a considerably high antifouling effect and low toxicity. However, in order to maintain the antifouling effect for a long period of time, it is indispensable to devise such as using a compound having water repellency together.

[0011]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a coating composition for preventing aquatic organisms from adhering, which has a low toxicity, a larger antifouling effect, and a longer-lasting antifouling effect. The purpose is.

[0012]

The gist of the present invention is to construct an aquatic organism adhesion preventing coating composition, and an oxyalkylene silyl ether represented by the following general formula (1) and the following general formula (2). At least one of the oxyalkylene silyl ethers represented by

[0013]

Embedded image

In the formula, A represents alkylene having 2 or 3 carbon atoms. n represents an integer of 1 or more. X is a hydrogen atom,
Hydroxyl group, C1-C20 alkyl group, C1-C20
Alkoxy group, aryl group having 6 to 12 carbon atoms, aryl group substituted with alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, phenoxy group, straight chain having 1 to 20 carbon atoms, or Phenoxy group substituted with branched alkyl group, phenoxy group substituted with 1-methyl-1-phenylethyl group, unsaturated hydrocarbon ether group having 2 to 30 carbon atoms, alkyl ester group having 1 to 20 carbon atoms ,
Alternatively, it represents an unsaturated hydrocarbon ester group having 2 to 30 carbon atoms. R ¹ , R ² and R ³ are the same or different and are a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 1 carbon atom.
An aryl group substituted with an alkyl group of -20, carbon number 1
~ 20 cycloalkyl group, acetoxyl group, carbon number 2
-12 alkylketoxime group, C1-C20 cycloalkylamino group, propenyloxy group, phenoxy group, phenoxy group substituted with a C1-C20 linear or branched alkyl group, 1-methyl A phenoxy group substituted with a -1-phenylethyl group or a group represented by X- (AO) n- (in the formula, A, n and X are the same as the above). B represents alkylene having 2 or 3 carbon atoms. t
Represents an integer of 1 or more. q represents an integer of 1 to 10. Y is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or 6 to 1 carbon atoms.
An aryl group having 2 carbon atoms, an aryl group substituted with an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms,
Phenoxy group, phenoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, 1-methyl-1-
Phenoxy group substituted with phenylethyl group, carbon number 2
Represents an unsaturated hydrocarbon ether group having 30 to 30 carbon atoms, an alkyl ester group having 1 to 20 carbon atoms, or an unsaturated hydrocarbon ester group having 2 to 30 carbon atoms. R ⁴ and R ⁵ are the same or different and each represent a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Substituted aryl group, cycloalkyl group having 1 to 20 carbon atoms, acetoxyl group, alkyl ketoxime group having 2 to 12 carbon atoms, cycloalkylamino group having 1 to 20 carbon atoms, propenyloxy group, phenoxy group, carbon number A phenoxy group substituted with a linear or branched alkyl group of 1 to 20, a phenoxy group substituted with a 1-methyl-1-phenylethyl group, or Y- (BO) t- (wherein B, t and Y are the same as defined above). R ⁶ , R ⁷ and R ⁸ are the same or different and each represent a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. Aryl group substituted by alkyl group, cycloalkyl group having 1 to 20 carbon atoms, acetoxyl group, alkyl ketoxime group having 2 to 12 carbon atoms, cycloalkylamino group having 1 to 20 carbon atoms, propenyloxy group, phenoxy group , A phenoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a phenoxy group substituted with a 1-methyl-1-phenylethyl group, or Y-BO- (wherein B, Y is the same as the above).

The oxyalkylene silyl ether used in the present invention has a structure represented by the above general formula (1) or a structure represented by the above general formula (2). The oxyalkylene silyl ether having the structure represented by the general formula (1) or the structure represented by the general formula (2) is oxyethylene or polyoxy having a reactive group having an active hydrogen such as a hydroxyl group at the terminal. Reacting an oxyalkylene compound (a) having an ethylene chain or an oxypropylene or polyoxypropylene chain with a silane compound (b) which reacts with the reactive group having active hydrogen to form a silyl ether bond. Can be obtained by

The oxyalkylene compound (a) has an active hydrogen at the terminal and a hydrogen atom, a hydroxyl group at the other terminal,
C1-C20 alkyl group, C1-C20 alkoxyl group, C6-C12 aryl group, C1-2
An aryl group substituted with an alkyl group of 0, having 1 to 2 carbon atoms
0 cycloalkyl group, phenoxy group, 1 to 20 carbon atoms
, A phenoxy group substituted with a linear or branched alkyl group, a phenoxy group substituted with a 1-methyl-1-phenylethyl group, an unsaturated hydrocarbon ether group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Or an oxyethylene or polyoxyethylene chain having an unsaturated hydrocarbon ester group having 2 to 30 carbon atoms, or an oxypropylene or polyoxypropylene chain.

Examples of the oxyalkylene compound (a) include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monomethyl ether. Oleyl ether, diethylene glycol monododecyl ether, diethylene glycol monophenoxy ether, diethylene glycol monononyl phenoxy ether, diethylene glycol mono (1-methyl-1-phenylethyl) phenoxy ether, triethylene glycol monoethyl ether, polyethylene glycol, Triethylene glycol monobutyl cetyl ether, polyethylene glycol mono dodecyl ether, polyethylene glycol mono oleyl ether,
Polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooctyl phenyl ether, polyethylene glycol monononyl phenyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monostearate , Dipropylene glycol, dipropylene glycol monomethyl ether, polypropylene glycol and the like.

As the silane compound (b), for example, a chlorosilane compound, an alkoxysilane compound or the like is usually used, but in addition thereto, for example, a silazane compound, a silylacetamide compound, a silylimidazole compound, a silylurea compound, a propenyloxysilane. It is also possible to use compounds, alkylketoxime silane compounds, acetoxysilane compounds, silanol compounds and the like.

Examples of the silane compound (b) include dimethyldichlorosilane, octadecyltrichlorosilane, trimethylchlorosilane, t-butyldimethylchlorosilane, hexamethyldisilazane, N-trimethylsilylacetamide, N, O-bis (trimethylsilyl). Trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, N-trimethylsilylimidazole, N, N'-bis (trimethylsilyl) urea,
N-trimethylsilyl-N, N'-diphenylurea,
Methyltripropenyloxysilane, methyltris (methylethylketoxime) silane, methyltriacetoxysilane, dimethyldiacetoxysilane, trimethylsilanol, triethylsilanol, triphenylsilanol, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxy Silane,
Methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, triphenylmethoxysilane , Methyl-2- (3-cyclohexenyl) dimethoxysilane, methylcyclohexylethoxysilane, n-propyltrimethoxysilane, trimethoxysilylphenoxide, trimethoxysilylnonylphenoxide,
Examples thereof include trimethoxysilyl (1-methyl-1-phenylethyl) phenoxide and 1,6-bis (trimethoxysilyl) hexane.

The reaction between the oxyalkylene compound (a) and the silane compound (b) can be carried out by a known silylation reaction or the like. For example, as a silane compound,
When an alkoxysilane compound is used, an oxyalkylene compound and an alkoxysilane compound are mixed in a suitable solvent, if necessary, and heated and stirred in the presence of a catalyst such as an organic metal oxide to generate alcohols. It is possible to preferably employ a method such as removing the outside of the system.

The aquatic organism adhesion preventing coating composition of the present invention comprises
The structure represented by the general formula (1) or the general formula (2)
One or more oxyalkylene silyl ethers having a structure represented by
It is contained in the range of% by weight. If the content is less than 0.5% by weight, the antifouling effect cannot be expected, and if it exceeds 80% by weight, it becomes difficult to form a normal coating due to thickening. In the present invention, the content of the oxyalkylene silyl ether can be determined according to the antifouling performance required within the above range.

The coating composition for preventing aquatic organisms from adhering to the present invention may contain, if necessary, a coating resin which is usually used for the purpose of enhancing the strength of the coating film and the adhesion with the undercoat. . As the resin for coating material, as an organic solvent-based resin, for example, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin , Polyamide resin, petroleum-based resin, silicone resin, silicone rubber-based resin, wax, paraffin, rosin ester, rosin-based resin, and the like. Further, metal elements such as tin, copper, zinc and tellurium are used as side chains. The resin etc. which it contains can be mentioned. Examples of the water-based resin include acrylic emulsion resin, epoxy emulsion resin, vinyl acetate resin and the like. These can be used in combination of two or more.

In preparing the aquatic organism adhesion preventing coating composition of the present invention, a known antifouling agent may be further added as an antifouling aid. In addition, a plasticizer, a coloring pigment, an extender pigment, a solvent and the like which are generally used in coating compositions can be added. The aquatic organism adhesion preventing coating composition can be prepared by a method known in the paint manufacturing technical field, such as a method of charging in a reaction vessel and reacting.

[0024]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Production Example 1 Production of Oxyalkylene Silyl Ether A reaction vessel equipped with a rectification device was charged with each compound in the composition shown in Table 1, and the temperature was raised to 120 ° C. for 30 minutes under normal pressure. The condensation reaction was carried out at 150 ° C. for about 4 hours.
The amount of methanol distilled was 92 g. The reaction was confirmed by the infrared absorption spectrum by the disappearance of an absorption peak near 3400 cm ⁻¹ due to the hydroxyl group of diethylene glycol monobutyl ether. The obtained oxyalkylene silyl ether was a transparent liquid and had a viscosity of 6 centipoise.

Production Example 2 Production of Oxyalkylene Silyl Ether The reaction was carried out in the same manner as in Production Example 1 except that the formulation shown in Table 1 was used. The distilled amount of methanol was 63 g. The obtained oxyalkylene silyl ether was a transparent liquid and had a viscosity of 50 centipoise.

Production Example 3 Production of Oxyalkylene Silyl Ether The reaction was carried out in the same manner as in Production Example 1 except that the formulation shown in Table 1 was used. Distilled methanol was 93 g. The obtained oxyalkylene silyl ether was a transparent liquid and had a viscosity of 50 centipoise.

Production Example 4 Production of oxyalkylene silyl ether A reaction was carried out in the same manner as in Production Example 1 except that the composition was as shown in Table 1. The amount of methanol distilled was 125 g.
The obtained oxyalkylene silyl ether was a transparent liquid and had a viscosity of 20 centipoise.

Production Example 5 Production of oxyalkylene silyl ether A reaction was carried out in the same manner as in Production Example 1 except that the formulation shown in Table 1 was used. The amount of methanol distilled was 125 g.
The obtained oxyalkylene silyl ether was a transparent liquid and had a viscosity of 40 centipoise.

Examples 1 to 6 and Comparative Example 1 Each raw material having the composition shown in Table 2 was charged in a closed container and homogenized by high-speed stirring to obtain aquatic organism adhesion preventing coating compositions of each Example and Comparative Example. As the petrolatum, a JIS K 2235 petrolatum 4 equivalent product was used. In Table 2, KE-45
TS is KF-96, a room temperature reaction curable deoxime type silicone rubber varnish (50% volatile content) manufactured by Shin-Etsu Chemical Co., Ltd.
Represents polydimethylsiloxane oil manufactured by Shin-Etsu Chemical Co., Ltd., and KF-53 represents polymethylphenylsiloxane oil manufactured by Shin-Etsu Chemical Co., Ltd., respectively.

Antifouling test Steel sheets for immersion test, to which the underwater organism adhesion preventing coating compositions obtained in Examples 1 to 6 and Comparative Example 1 were previously coated with an anticorrosion coating and an intermediate coating for silicone rubber type antifouling coating. (300
(× 100 × 1.6 mm) was spray-coated so as to have a dry film thickness of 200 μm, and then subjected to antifouling coating. This one
After air-drying for a week, it was immersed at a depth of 1 m in the sea off Tamano City, Okayama Prefecture, and the time-dependent change in the degree of contamination by attached organisms was examined. The results are shown in Table 3. The numerical values in Table 3 represent the ratio (%) of the area contaminated by the attached organisms.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

EFFECTS OF THE INVENTION The coating composition of the present invention has a low toxicity and a strong effect of preventing the attachment of aquatic organisms for a long period of time due to the above constitution.

Claims (1)

[Claims] 1. Water containing at least one of an oxyalkylene silyl ether represented by the following general formula (1) and an oxyalkylene silyl ether represented by the following general formula (2): Biofouling prevention coating composition. Embedded image In the formula, A represents alkylene having 2 or 3 carbon atoms. n
Represents an integer of 1 or more. X represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 1 to 20 carbon atoms.
An aryl group substituted with an alkyl group having 1 to 20 carbon atoms
Cycloalkyl group, phenoxy group, phenoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, phenoxy group substituted with 1-methyl-1-phenylethyl group, 2 to 30 carbon atoms Represents an unsaturated hydrocarbon ether group, an alkyl ester group having 1 to 20 carbon atoms, or an unsaturated hydrocarbon ester group having 2 to 30 carbon atoms. R ¹ ,
R ² and R ³ are the same or different and each represent a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Substituted aryl group, cycloalkyl group having 1 to 20 carbon atoms, acetoxyl group, alkyl ketoxime group having 2 to 12 carbon atoms, cycloalkylamino group having 1 to 20 carbon atoms, propenyloxy group, phenoxy group, carbon number A phenoxy group substituted with a linear or branched alkyl group of 1 to 20, a phenoxy group substituted with a 1-methyl-1-phenylethyl group, or X- (AO) n- (wherein A, n and X are the same as the above). B represents alkylene having 2 or 3 carbon atoms. t
Represents an integer of 1 or more. q represents an integer of 1 to 10. Y is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or 6 to 1 carbon atoms.
An aryl group having 2 carbon atoms, an aryl group substituted with an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms,
Phenoxy group, phenoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, 1-methyl-1-
Phenoxy group substituted with phenylethyl group, carbon number 2
Represents an unsaturated hydrocarbon ether group having 30 to 30 carbon atoms, an alkyl ester group having 1 to 20 carbon atoms, or an unsaturated hydrocarbon ester group having 2 to 30 carbon atoms. R ⁴ and R ⁵ are the same or different and each represent a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Substituted aryl group, cycloalkyl group having 1 to 20 carbon atoms, acetoxyl group, alkyl ketoxime group having 2 to 12 carbon atoms, cycloalkylamino group having 1 to 20 carbon atoms, propenyloxy group, phenoxy group, carbon number A phenoxy group substituted with a linear or branched alkyl group of 1 to 20, a phenoxy group substituted with a 1-methyl-1-phenylethyl group, or Y- (BO) t- (wherein B, t and Y are the same as defined above). R ⁶ , R ⁷ and R ⁸ are the same or different and each represent a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. An aryl group substituted with an alkyl group, a cycloalkyl group having 1 to 20 carbon atoms, an acetoxyl group having 1 to 30 carbon atoms, an alkyl ketoxime group having 2 to 12 carbon atoms,
Substituted with a cycloalkylamino group having 1 to 20 carbon atoms, a propenyloxy group, a phenoxy group, a phenoxy group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, and a 1-methyl-1-phenylethyl group. Or a group represented by Y-BO- (wherein B and Y are as defined above).