AU734678B2 - Industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms containing a cyanoacrylate compound - Google Patents

Description

SPECIFICATION

INDUSTRIAL ANTIBACTERIAL AND ANTIFUNGAL AGENTS, ALGICIDES AND AGENTS FOR PREVENTING ADHESION OF ORGANISMS CONTAINING A CYANOACRYLATE COMPOUND Technical Field The present invention relates to antibacterial and antifungal agents and algicides for industrial products, to antibacterial and antifungal agents and algicides all of which are used in the production process of industrial products and to agents for preventing adhesion of organisms for preventing the attachment of harmful aquatic organisms such as shellfish.

Background Art Antibacterial and antifungal agents and algicides for industrial use are used to eliminate various evil influences of the growth and propagation of bacteria, fungi and algae in various kinds of industrial products and industrial facilities.

Heretofore, organic nitrogen-containing compounds, organic nitrogen-sulfur-containing compounds, organic halogen-containing compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used as these antibacterial and antifungal agents and algicides for industrial use.

Agents for preventing adhesion of organisms are used to prevent harmful aquatic organisms such as shellfish from adhering to a fishing net, the bottom of ship, equipment placed in the sea such as a buoy, marine construction, the cooling water system of a condenser at a thermal power plant or atomicpowerplant, the inlet channel of cooling water in the heat exchanger for the chemical industry, under-water construction, reservoir or the like.

When an aquatic organism is adhered to a culture net, the meshes of the net are clogged and the growth of cultured fish is inhibited along with deterioration in the circulation of seawater, attacking fish with diseases frequently.

The adhesion of aquatic organisms to a ship causes an increase in fluid resistance with the result of a reduction in sailing speed, increases in fuel consumption and costs for cleaning the bottom of the ship and a loss caused by the suspension of service.

The adhesion of aquatic organisms to marine equipment, or a marine or water construction causes an increase in weight and marked inconvenience in handling operation, and the adhesion of aquatic organisms to an inlet channel causes a reduction in heat conductivity, the blockage of the inlet channel and a reduction in the amount of intake water.

Heretofore, to prevent the adhesion and propagation of seawater and freshwater aquatic organisms, an antifouling coating containing an organic tin compound such as bis(tributyltin) oxide, or copper compound such as copper sulfate or cuprous oxide has been used.

As the prior art relevant to the cyanoacrylate compound of the present invention, a cyanoacrylate compound having herbicidal activity as a photosynthesis inhibitor is disclosed in Pesticide Science vol. 32, pp.329-338, 1991, Agricultural and Biological Chemistry vol. 45, pp.2769-2773, 1981, Agricultural and Biological Chemistry vol. 48, pp.55-88, 1984 and US Patent No. 3981717.

However, there is no description in the above publications that the compoundisusedasindustrialantibacterialandantifungalagents, algicides and agents for preventing adhesion of organisms for industrial use.

(Problems to be solved by the Invention) The above-mentioned organic nitrogen-containing compounds, organic nitrogen-sulfur-containing compounds, organic halogen-containing compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds contain a chemical which is stimulative and causes a problem from a viewpoint of the Labor Safety Law, a chemical which is used in quantity and causes a problem from a viewpoint of environmental protection, a chemical which liberates formalin or halogen and has the possibility of environmental pollution or an influence upon the human body or a chemical which has the possibility of environmental pollution with aheavymetal. Therefore, it cannot be said that all the antibacterial and antifungal agents and algicides for industrial use are composed of favorable chemicals only.

Although the above-mentioned organic tin compound as agents for preventing adhesion of organisms is effective in preventing the

I

adhesion of aquatic organisms, it has high toxicity, accumulates in particular in the body of fish or shellfish markedly and is now regulated because it promotes environmental pollution.

For example, use of organic tin ship coatings in ships as long as 65 feet or less is prohibited by the organic tin antifouling coating regulation law (1987) in US and use of tributyltin-containing agents for preventing adhesion of organisms in ships as long as 25 m or less and marine agriculture is prohibited by the food environmental protection law (1987) in UK.

In Japan, tributyltin oxide is designated as a specified chemical substance of the first kind, and triphenyltin compounds and tributyltin compounds are designated as specified chemical substances of the second kind by the chemical examination law (1990).

Thus, use of these compounds in fishing nets is prohibited.

Further, a measure for the control of use of tributyltin-containing coatings in the bottom of a ship is taken (official notice from the Ministry of Transport, 1990).

The above-mentioned copper compounds are widely used in antifouling coatings for an inlet channel and the bottom of a ship.

However, sincethecoppercompoundscontain, liketin compounds, copper which is a heavy metal, future environmental pollution is apprehended and it cannot be said that the copper compounds make favorable agents for preventing adhesion of organisms.

Summary of the Invention The inventors of the present invention have made intensive investigation with a view to solve the above problems and have found that a cyanoacrylate compound represented by the general formula below can be industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms which has high safety, exhibits a wide spectrum with a small amount from a viewpoint of environmental pollution prevention and has high practical applicability. Thus, the present invention has been accomplished based on the finding.

Thus, the present disclosure relates to industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms, characterised by containing a cyanoacrylate compound of the general formula

X

CN

S N-CH< CN

(I)

CH C02 R 2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group.

"o Accordingly, in one aspect of the invention there is provided a method of preventing S• or suppressing growth of bacteria, fungi or algae, said method comprising contacting said bacteria, fungi or algae, or a locus of said algae, fungi or bacteria with an agent having as an active ingredient at least one cyanoacrylate compound of general formula

X

Y

CN

N-CH 2 (I) R C2R wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to suppress said growth of bacteria, fungi or algae.

According to a second aspect of the invention there is provided a method of preserving wood or cutting oil, said method comprising treating said wood or cutting oil [R:\LIBH]08731.doc:mcc with an agent having as an active ingredient at least one cyanoacrylate compound of general formula

X

Y CI\ N-CHz< 2

(I)

I CO

R

2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant.

According to a third aspect of the invention there is provided a method of mildewproofing surfactants, said method comprising treating said surfactant with an agent having as an active ingredient at least one cyanoacrylate compound of general formula

X

Y -N-CH =C (1) I \C02R wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, 2 1i R represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to mildewproof said surfactant.

According to a fourth aspect of the invention there is provided a method of sterilising or preventing formation of slime in cooling systems, said method comprising contacting said cooling system with an agent having as an active ingredient at least one cyanoacrylate compound of general formula C N S-ON-CH=

(I)

i1 CO 2

R

wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally L together with a suitable carrier, diluent or adjuvant, in an amount sufficient to sterilise and prevent formation of slime in cooling systems.

[R:\LIBH]08731.doc:mcc According to a fifth aspect of the invention there is provided a method of protecting fibres, fabrics or leathers, said method comprising contacting said fibres, fabrics or leathers with an agent having as an active ingredient cyanoacrylate compounds of general formula

X

SY N-CH C 2 C02R2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally 0o together with a suitable carrier, diluent or adjuvant, in an amount sufficient to prevent the attack of bacteria, fungi and algae.

According to a sixth aspect of the invention there is provided a method of protecting a surface or product, said method comprising contacting said surface or product with an antibacterial agent, antifungal agent or an algicide having as an active ingredient S 15 cyanoacrylate compounds of general formula X 2 C02R 2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, 20 alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to protect said surface.

According to a seventh aspect of the invention there is provided a method of deodorising or sterilising washing production equipment, sewage treatment plants or night soil treatment plants, said method comprising contacting said washing production equipment, sewage treatment plants or night soil treatment plants with an agent having as an active ingredient at least one cyanoacrylate compound of general formula

X

-N-CH2

(I)

R1 CO 2 R i C0R 2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each [R:\LIBH]08731 .doc:mcc independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to deodorise or sterilise.

According to a eighth aspect of the invention there is provided an anti-fouling coating composition comprising a cyanoacrylate compound of general formula

X

Y N-CH cCN

(I)

R11 \CO 2 R2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each to independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, together with a coating film forming agent.

According to a ninth aspect of the invention thee is provided a method for preventing adhesion of aquatic organisms to a surface, said method comprising contacting is said surface with an agent having as an active ingredient at least one cyanoacrylate compound of general formula N-CH (CN 2

(I)

SR1 CO 2

R

Swherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,

R

2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally S.together with a suitable carrier, diluent or adjuvant, or a composition according to any one of claims 26 to 28, in an amount sufficient to prevent adhesion of aquatic organisms to said surface.

Each of the substituents shown in the general formula will be described in concrete terms.

[R:\LIBH]08731 .doc:mcc In the specification, means normal, iso, secondary and tertiary.

Examples of the halogen atom are fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having i to 3 carbon atoms are methyl, ethyl, n-propyl, i-propyl and cyclopropyl. Examples of the alkyl group having 1 to 10 carbon atoms include n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, l-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1, l-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1, 2-dimethyl-cyclopropyl, 2, 3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, l,2-trimethyl-n-propyl, l,2,2-trimethyl-n-propyl, 1-ethyl-l-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, 2-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2, 2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-l-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl and n-decyl in addition to the above groups.

Examples of the alkoxy group having 1 to 3 carbon atoms are methoxy, ethoxy, n-propoxy, i-propoxy and cyclopropoxy.

The industrial antibacterial and antifungal agents, algicides andagents forpreventingadhesionof organisms of thepresent invention may contain a cyanoacrylate compound represented by the above general formula as an active ingredient.

Preferred examples of the compound of the general formula (1) contained as an active ingredient of the industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms of the present invention are compounds of the formula in which X and Y each independently represent a hydrogen atom or trifluoromethyl group. Other preferred examples of the compound of the general formula are listed in Table 1 below. However, the compound used in the present invention is not limited to these.

Symbols in the table mean the following.

Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-i: isopropyl group, Bu-n: normal butyl group, Bu-s: secondary butyl group, Bu-i: isobutyl group, Bu-t: tertiary butyl group, Pen-n: normal pentyl group, Hex-n: normal hexyl group, Hep-n: normal heptyl group, Oct-n: normal octyl group, Non-n: normal nonyl group, Dec-n: normal decyl group, 2-Et-Hex: 2-ethylhexyl group, OMe: methoxy group, OEt: ethoxy group, OPr-n: normal propoxy group, OPr-i: isopropoxy group.

8 Xr-'t- c" Table 1 x 4

N-LH=C<

s 6C( Substituent on the benzene ring(X and Y) R R' 2-position 3-position 4-position 5-position 6-position H H H H H H Me H H H H H H Et H H H H H H Pr-n H H H H H H Pr-i H H H H H H Bu-n H H H H H Me Me H H H H H Me Et H H H H H Me Pr-n H H H H H Me Pr-i H H H H H Me Bu-n H H H H H Me Bu-s H H H H H Me Bu-i H H H H H Me Bu-t H H H H H Me Pen-n H H H H H Me Hex-n H H H H H Me Hep-n H H H H H Me Oct-n H H H H H Me Non-n H H H H H Me Dec-n H H H H H Me 2-Et-Hex H H H H H Et Me H H H H H Et Et H H H H H Et Pr-n H H H H H Et Pr-i H H H H H Et Bu-n H H H H H Et Bu-s H H H H H Et Bu-i H H H H H Et Bu-t H H H H H Et Pen-n H H H H H Et Hex-n Table 1(continuation) Substituent on the benzene ring(X and Y) R' R 2 2-position 3-position 4-position 5-position 6-position H H H H H Et Hep-n H H H H H Et Oct-n H H H H H Et Non-n H H H H H Et Dec-n H H H H H Et 2-Et-Hex H H H H H Pr-n Me H H H H H Pr-n Et H H H H H Pr-n Pr-n H H H H H Pr-n Pr-i H H H H H Pr-n Bu-n H H H H H Pr-n Bu-s H H H H H Pr-n Bu-i H H H H H Pr-n Bu-t H H H H H Pr-n 2-Et-Hex H H H H H Pr-i Me H H H H H Pr-i Et H H H H H Pr-i Pr-n H H H H H Pr-i Bu-n H H H H H Pr-i 2-Et-Hex F H H H H Me Me H F H H H Me Me H H F H H Me Me F H H H F Me Et H F F H H Me Et Cl H H H H Me Et H Cl H H H Me Et H H CI H H Me Et Cl H H H Cl Me Me H Cl Cl H H Me Me Cl H Cl H H Me Me H Br H H H Me Et H H Br H H Me Pr-n H Br Br H H Me Bu-n F H H H Cl Me Me H F CI H H Me Et Table 1(continuation) Substituent on the benzene ring(X and Y) R- R- R R 2 2-position 3-position 4-position 5-position 6-position Br

I

H

Me

H

H

Me

H

Me Et

H

H

Me

H

Et Me

H

F

Pr-n

H

OMe

H

H

OMe

H

OMe OEt

H

H

OMe

H

Me OPr-n

H

OMe

H

H

H

H

Me

H

Me Me

H

H

Et

H

Et Et

H

Cl Me

H

H

Pr-i

H

OMe

H

OMe OMe

H

H

OEt

H

Me Me

H

H

OPr-i Cl

CI

H

I

H

H

Me

H

Me

H

H

H

Et

H

Me

H

H

Br

H

H

H

H

H

OMe

H

OMe

H

H

H

OEt

H

OMe

H

H

H

H

H

H

H

H

H

H

H

H

Me

H

H

H

H

H

Me

H

H

Me

H

H

H

H

H

H

H

OMe

H

H

H

H

H

OMe

H

H

H

Me Et Me Me Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Me Et Table 1(continuation) Substituent on the benzene ring(X and Y) R' R2 2 -position 3-position 4-position 5-position 6-position H Br OMe H H Me Et F H H H OMe Me Et N02 H H H H Me Et H NO2 H H H Me Et H H NO 2 H H Me Et Me N02 H H H Me Et H N02 Me H H Me Et NOz H H H Me Me Et

NO

2 Cl H H H Me Et H N02 Br H H Me Et F H H H N02 Me Et CF3 H H H H Me Et H CF3 H H H Me Et H H CF 3 H H Me Et Me CF3 H H H Me Et H Me CF 3 H H Me Et CF3 H H H Me Me Et CF3 CI H H H Me Et H CF3 Br H H Me Et F H H H CF3 Me Et

CF

3 H H H H H Et H CF3 H H H H Et H H CF 3 H H H Et The cyanoacrylate compound of the present invention can be synthesized with reference to the above-mentioned Pesticide Science vol. 32, pp.329- 338 1991, Agricultural and Biological Chemistry vol. 45, pp.276 9 2 7 7 3 1981, Agricultural and Biological Chemistry ol. 48, pp.55- 88 1984 and US Patent No. 3981717.

The target compounds obtained by the above method can be made into a pure product through purification by recrystallization with an appropriate solvent or by column chromatography, etc.

The cyanoacrylate compound used as an active ingredient in the present invention may be used alone or may further contain other known industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms as required and may be used as mixed agents when the industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms of the present invention is used.

Typical examples are given below. However, the present invention is not limited to these: cuprous oxide, quaternary ammonium compounds, allylisothiocyanate, 2-amino-3-chloro-l,4-naphthoquinone, ethylene-bis-thiocyanate, 2-n-octyl-3-isothiazolone, glutaraldehyde, 5-chloro-2-n-decyl-3-isothiazolone, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 5-chloro-2-methyl-3-isothiazolone, 2,3-dichloro-l,4-naphthoquinone, diiodomethyl-p-tolylsulfone, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide, N-(3,4-dichlorophenyl)-N'-methylurea, N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, zinc dimethyldithiocarbamate, 2, 6-dichloro-3, 5-dicyano-4-phenylpyridine, 2, 4-dichloro-6- (o-chloroanilino) -s-triazine, 4, 5-dichloro-2- (4-chlorobenzyl) -3-isothiazolone, 4, 5-dichloro-2-(4-chlorophenyl) -3-isothiazolone, 4, 5-dichloro-2-n-hexyl-3-isothiazolone, 4, 5-cichloro-2-n-octyl-3-isothiazolone, 1, 2-dibromo-2, 4-dicyanobutane, 2, 2-dibromo-3-nitrilopropionamide, 2-thiocyanomethylthiobenzothiazole, 2- (4-thiazolyl)benzimidazole, thiabendazole, tetrafluoroisophthalonitrile, 2,3,5, 6-tetrachloro-4- (methylsulfonyl)pyridine, tetraphenyl borane pyridine salts, tetramethyithiuram disulfide, tetraethylthiuram disulfide, tetraisopropyithiuram disulfide, tetra-n-butylthiuram disulfide, tetrachloroisophthalonitrile, tetrachlorophthalonitrile, Cu-lO% Ni solid-solution alloy, N-trichloromethylthiotetrahydrophthalimide, N-trichlorornethylthiophthalimide, 2, 3,6-trichloro-4-propylsulfoflyl pyridine, N- 6-trichlorophenyl)maleimide, 4, 5-trimethylene-2-methyl-3-isothiazolofle, 2-pyridinethiol-l-oxide zinc salts, 2,3,3-triiodoallyl alcohol, N- (fluorodichloromethylthio) phthalimide, ,bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, N-phenethyldichloromaleimide, 2-bromo-2-nitropropanediol, 5-bromo-5-nitro-1,3-dioxane, bromochlorodimethylhydantoin, N-benzyldichloromaleimide, 1,2-benzisothiazolin-3-one, 2-(methoxycarbonylamino)benzimidazole, 4-methyl-5-chloro-2-n-octyl-3-isothiazolone, 2-methylthio-4-t-butylamino-6-cyclopropylamin'o-s-triazine, N-2-methyl-6-ethylphenyldichloromaleimide, 2-methyl-3-isothiazolone, methylene-bis-thiocyanate, O-3-iodo-2-propynyl-N-butylcarbamate, N-3-iodo-2-propynyl-O-butylcarbamate Further, the cyanoacrylate compound used as an active ingredient in the present invention may be a single compound or a mixture of several kinds of cyanoacrylate compounds.

The cyanoacrylate compound used as an active ingredient in the present invention may be added alone to a system for the above-mentioned application purpose or as a mixture of an active ingredient and an appropriate carrier or solvent as required, or as an aqueous emulsion or dispersion.

When the formulations of the industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms of the present invention are given an outline in the application field of industrial antibacterial and antifungal agents and algicides, the cyanoacrylate compound used as an active .ingredient in the present invention is mixed with appropriate carriers and auxiliaries, for example, a surfactant, binder and stabilizerandformedintowettablepowder, emulsifiableconcentrate, sol (flowable) formulation and other appropriate formulations by commonly used methods.

When these formulations are to be made, the cyanoacrylate compound as an active ingredient has no upper limit of concentration if wettable powder, emulsifiable concentrate, liquid formulation, sol formulation and other appropriate formulations can be made.

However, the cyanoacrylate compound is contained in an amount of 1 to 90 wt%, preferably 3 to 40 wt% based on the weight of each of the formulations.

The carrier usable may be solid or liquid if it is commonly used in industrial antibacterial and antifungal agents, and algicides and is not limited to a particular kind.

Examples of the solid carrier include mineral powders such as kaolin, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphorus lime, white carbon, slaked lime, quartz sand, ammonium sulfate and urea, and plant powders such as soybean meal, starch, crystal celluloses, alumina, silicates, sugar polymers, highly dispersible silicic acid and waxes.

Examples of the liquid carrier include water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol and benzyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene and methylnaphthalene, or halogenated hydrocarbons such as chloroform, dichloromethane and ethylene dichloride, ethers such as ethyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethylene glycol acetate and amyl acetate, nitriles such as acetonitrile, propionitrile and acrylonitrile, sulfoxides such as dimethyl sulfoxide, alcohol-ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, amines such as triethylamine, as well as aliphatic and alicyclic hydrocarbons such as n-hexane and cyclohexane and the like, and further industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum fractions (paraffins, kerosene, light oil, etc.) and the like.

In the case of formulation of an emulsifiable concentrate, a wettable powder and a sol (flowable) formulation and so on, a surfactant is blended for emulsion, dispersion, solubilization, wetting, foaming or spreading. Examples of the surfactant are given below but the surfactant is not limited to these.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters and sorbitan alkyl esters.

Examples of anionic surfactants include alkyl benzene -ulfonates, alkyl sulfosuccinates, alkylsulfates, polyoxyethylene alkylsulfates, aryl sulfonates and lauryl sulfates.

Examples of cationic surfactants include alkylamines (lauryl amine, stearyl trimethylammonium chloride and alkyldimethylbenzylammonium chloride).

Examples of ampholytic surfactants include carboxylic acid (betaine type) sulfuric acid esters.

Besides these, a thickener and various auxiliaries such as polyvinyl alcohol (PVA), carboxylmethyl cellulose (CMC), Arabian rubber, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, zansanth gum, hydroxypropyl cellulose may be blended.

A stabilizer such as an antioxidant or ultraviolet absorber may be further added in an appropriate amount as required.

The industrial antibacterial and antifungal agents, and algicides containing a cyanoacrylate compound as an active ingredient of the present invention can be used for the following purposes: the suppression of growth of bacteria, fungi and algae in emulsion products such as aqueous coatings, adhesives, latexes and acryl, slurry products such as starch, pigments and calcium carbonate, and joint cement; preservation of wood in construction materials (for building construction materials and civil engineering construction materials); preservation of cutting oil; smildewproofing of surfactants; sterilization and the prevention offormationofslimeinthecoolingtowersoftheproductionequipment of plants and building air conditioning systems, and pulp and paper plants; antibacterial and antifungal treatments by spraying or immersing fibers, fabrics and leather: protection fromthe attack of bacteria, fungi and algae which grow while coating films, particularly coating films of exterior coatings are exposed to the weather; the protection of interior and exterior materials (for housings and medical equipment materials, etc.) made from resins such as vinyl chloride, polyurethane, polyethylene, polypropylene, silicone, modified silicone, nylon and epoxy, building materials (for construction and civil engineering), home electric appliances, domestic sundries and sport goods from bacteria, fungi and algae; the prevention of accumulation of slime in cane and beet sugar production equipment; the prevention of accumulation of bacteria in air washers, scrubber systems and industrial freshwater supply systems; the maintenance of sanitary environment at food plants and the like; deodorization and sterilization for washing production equipment, sewage treatment plants and night soil treatment plants; the prevention of pollution and accumulation of bacteria in petroleum well cutting oil, muddy water and secondary oil recovery process; the prevention of growth of bacteria and fungi in paper coating materials and coating processing; the prevention of pollution of cosmetics and toiletry products by .bacteria and fungi; the suppression of growth of algae in swimming pools and the like; the prevention of pollution of agricultural blends, electrodeposition systems, diagnostic and pharmaceutical products, medical equipment and the like from bacteria and fungi; and the prevention of accumulation of bacteria and fungi in photographic treatment.

The agents for preventing adhesion of organisms containing a cyanoacrylate compound as an active ingredient can be used to prevent the adhesion of harmful aquatic organisms such as shellfish exemplified by blue mussel (Mytilus edulis), barnacle, oyster, hydrozoan, hydra, serpula, ascidian, bryozoan and pond snail, and algae such as exemplified by, Ulva sp., Enteromorpha sp., and Ectocarpus sp. to a fishing net, the bottom of a ship, equipment placed in the sea such as a buoy, marine construction, the cooling water system of a condenser at a thermal power plant or atomic power plant, the inlet channel of cooling water in the heat exchanger for the chemical industry, water construction such as accessory equipment at a dam, reservoir or the like.

Examples of formulation when the cyanoacrylate compound of the present invention is used as industrial antibacterial and antifungal agents, or algicides are given below. The proportions of active ingredients and the types and amounts of carriers and auxiliaries are not limited to these.

Formulation example 1 (emulsion formulation) ingredients wt% compound of general formula dimethyl sulfoxide methyl isobutyl ketone Sorpole 800 A (emulsifying agents of Toho Kagaku Co.) 100 An emulsifiable concentrate containing 5 of active ingredient was obtained by mixing and melting the above ingredients.

Formulation example 2 (wettable powder) ingredients wt% compound of general formula lauryl sulfate 7 clay 73 100 A wettable powder containing 20 of active ingredient was obtained by mixing and milling the above ingredients uniformly.

Formulation example 3 (flowable formulation) ingredients wt% compound of general formula lauryl sulfate 2 zansanth gum 2 hydroxypropyl cellulose 1 distilled water 100 A flowable formulation containing 20 of active ingredient was obtained by placing the above ingredients in a ball mill to mill and mix for 12 hours.

The formulated industrial antibacterial and antifungal agents and algicides of the present invention may be used in accordance with industrial antibacterial and antifungal agents and algicides use methods which have been generally carried out, including one in which these formulations are added to and mixed with various industrial raw materials or products directly or after they are diluted with water or an appropriate organic solvent, one in which they are applied or sprayed onto the surfaces of various industrial raw materialsandproducts, andoneinwhichindustrialrawmaterials and products are immersed in a diluted solution of the industrial antibacterial and antifungal agents and algicides of the present invention. The present invention is not limited to these specific methods.

When the formulations of the industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms of the present invention are outlined in the application 4ield of agents for preventing adhesion of organisms, the cyanoacrylate compound used as an active ingredient in the present invention is formulated in the form of a coating, solution, emulsion or the like.

General formulation can be employed for the formulation of the coating, solution, emulsion or the like.

When the agents for preventing adhesion of organisms of the present invention is used in the form of an antifouling coating, for example, the cyanoacrylate compound as an active ingredient is blended into a coating film forming agents to prepare a coating which is then coated on the bottom of a ship, marine construction, intake channel for cooling, under-water construction and the like to prevent the adhesion and propagation of aquatic organisms.

Oil varnish, synthetic resins, artificial rubber and the like are used as the coating film forming agent.

Asolvent, pigment andthe likemaybe furtherusedas required.

When the coating is to be formulated, the cyanoacrylate compound as an active ingredient has no upper limit of concentration if it can form a coating film. However, it is used in an amount of 1 to 50 wt%, preferably 5 to 20 wt% based on the weight of the antifouling coating.

Examplesofformulationwhentheagentsforpreventingadhesion of organisms of the present invention is used as an antifouling pating are given below. The present invention is not limited to these.

Formulation example 4 ingredients wt% compound of general formula 8 VYHH (vinyl type synthetic resin from UCC Co.) 7 rosin 7 tricresyl phosphate 3 talc barium sulfate red iron oxide xylene methyl isobutyl ketone 100 Formulation example ingredients wt% compound of general formula (chlorinated rubber resin from Asahi Denka Co.) 13 zinc white talc plasticizer 2 red iron oxide xylene 100 When the agents for preventing adhesion of organisms of the present invention is used in the form of a solution, for example, a solution of the cyanoacrylate compound as an active ingredient and a coating film forming agents dissolved in a solvent is prepared and applied to a culture net or fixed shore net to prevent the adhesion and propagation of aquatic organisms.

The coating film forming agents is a synthetic resin, artificial rubber, natural resin or the like and the solvent is xylene, toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone or acetone.

An additive such as a plasticizer may be further used as required.

When a solution is tobe formulated, the cyanoacrylate compound as an active ingredient has no upper limit of concentration if a solution can be formed but it is used in an amount of 1 to 50 wt%, preferably 5 to 30 wt% based on the weight of the solution.

Examplesof formulation when the agents for preventing adhesion of organisms of the present invention is used as an agent for preventing adhesion of organisms solutionaregivenbelow. However, the present invention is not limited to these.

i.

Formulation example 6 ingredients wt% compound of general formula acrylic resin (50 xylene solution) xylene 100 Formulation example 7 ingredients wt% compound of general formula acrylic resin (50 xylene solution) di-tertiary nonyl pentasulfide liquid paraffin xylene 100 When the agents for preventing adhesion of organisms of the present invention is used in the form of an emulsion, in accordance with a general method which is normally used to formulate an emulsion, a desired emulsion can be formulated by adding a surfactant to a solution of the cyanoacrylate compound as an active ingredient, and the surfactant used is not limited to a particular kind.

The formulated emulsion can be kneaded into a raw material, ,for example, a polymer resin or the like for culture nets and fixed shore nets used in the sea or water.

When an emulsion is to be formulated, the cyanoacrylate compound as an active ingredient has no upper limit of concentration if an emulsion can be formed but it is used in an amount of 1 to wt%, preferably 3 to 30 wt% based on the weight of the emulsion.

The above solution or emulsion of the present invention may be added to service water, reservoir water and the like to prevent the adhesion and propagation of aquatic organisms in the intake channel of cooling water or reservoir.

Best Mode for carrying out the Invention The present invention will be described in detail and specifically with reference to the following compounds 1 to 7 and Examples. However, the present invention is not limited to these.

Compounds 1 to 7 were synthesized with reference to the above-described Pesticide Science vol. 32, pp.329-338, 1991, Agricultural and Biological Chemistry vol. 45, pp.2769-2773, 1981, Agricultural and Biological Chemistry vol. 48, pp.55-88, 1984 and US Patent No. 3981717.

The melting points and structural formulas of the compounds 1 to 7 are given below.

compound 1 (melting point of 94.0 to 95.0 0

C)

compound 2 (melting point of 92.0 to 94.0 0

C)

=--pound 3 (melting point of 128.0 to 129.0°C) compound 4 (melting point of 109.0 to compound 5 (melting point of 88.0 to 89.0 0

C)

compound 6 (melting point of 52.0 to 53.0 0

C)

compound 7 (melting point of 59.0 to 60.0 0

C)

Me M e N compound I O N

CO

2 Et

CO

2 Pr-I

CF

3

CF

3 NK CN 0 _Me H Ncompound 3 C

CO

2 %Et

CO

2 Et compound 2 compound 4 Me N compound 5

CO

2 Me MIe Q-N CN

CO

1 Pr-n compound 6 O- Me, \N CN

CO

2 %Bu-n compound 7 Example 1 (evaluation of activity of inhibiting propagation of freshwater green algae) A predetermined amount of each of compound 1, compound 2, compound 6 and compound 7 was dissolved in a culture medium containing 5 /ml of freshwater green alga [Selenastrum capricornutum] at a logarithmic propagation period to prepare a sample having a compound concentration in the medium of 500 ppb and 50 ppb respectively and the sample was left to stand and cultured at 23±1 0 C for 24 hours under continuous illumination.

After 72 hours, a hemacytometer was applied to count the number of cells to obtain propagation rate.

The propagation inhibiting rate was calculated from comparison with an untreated lot.

The results are shown in Table 2.

Table 2 activity against freshwater green alga compound No. propagation inhibiting rate concentration 500 ppb concentration 50 ppb 1 87 2 90 81 6 98 82 7 97 79 Example 2 (evaluation of activity of inhibiting propagation of sea water diatom) A predetermined amount of each of compound 2, compound 6 and compound 7 was dissolved in a culture medium containing 10 5 /ml a sea water diatom [Nitzschia closterium] at a logarithmic propagation period to prepare a sample having a compound concentration in the medium of 500 ppb and the sample was left to stand and cultured at 22±10C for 24 hours under continuous illumination.

After 72 hours, cells were collected by centrifugation and methanol was added to smash the cells to extract chlorophyll, and the amount of chlorophyll was measured from absorbance using a spectrophotometer to obtain propagation rate.

The propagation inhibition rate was calculated from comparison with an untreated section.

The results are shown in Table 3.

Table 3 activity against sea water diatom compound No. propagation inhibiting rate concentration 500 ppb 2 6 92 7 92 Example 3 (evaluation of activity of inhibiting propagation of freshwater algae) A predetermined amount of compound 1 was dissolved in a culture medium containing 10 5 /ml of a freshwater alga at a logarithmic propagation period to prepare a sample having a compound 1 concentration in the medium of 500 ppb, and shaking culture was carried out at 100 rpm at 20±20C for freshwater diatoms and at -2±2°C for other algae under continuous illumination for 24 hours.

After 72 hours and 168 hours, the total volume of cells was measured using a hemacytometer to obtain propagation rate.

The propagation inhibiting rate was calculated from comparison with an untreated lot.

The results are shown in Table 4. Symbols in the table mean the following.

A: freshwater green alga [Chlorella pyrenoidosa] B: freshwater diatom [Diatoma elongatum] C: freshwater green alga [Scenedesmus pannonicus] D: freshwater green alga [Ankistrodesmus falcutus] E: freshwater green alga [Chlamydomonas reinhardii] F: freshwater green alga [Coccomyxa elongata] Table 4 activity against freshwater algae propagation inhibiting rate type of alga concentration 500 ppb time 72 hr time 168 hr A B 100 97 C 56 D 95 100 E 90 84 F 46 61 Example 4 (evaluation of antifouling activity against Mytilus edulis) Compound 7 was completely dissolved in 1 ml of acetone and the resulting solution was uniformly applied on the inside of a 4 cm-diameter zone drawn on a testing plate.

A zone coated with acetone only as blank and zones coated with mg and 0.5 mg of copper sulfate as a comparison chemical were formed.

After drying, four Mytilus edulis having a shell length of about 2 to 2.5 cm were bonded around each zone using a rubber piece as a spacer.

The thus prepared testing plate was immersed in a water tank into which sea water ran and left to stand in the dark for 3 hours.

The antifouling effect (adhesion repellent activity) was obtained from comparison with copper sulfate as a comparison chemical.

The evaluation of adhesion repellent activity was based on "Evaluation method of adhesion repellent substance to marine adhesion organisms using Mytilus edulis" written by Kazuo Ina and Hideo Etoh (Chemistry and Biology, vol. 28 (No. pp.132-138, 1990) The results are shown in Table 5. Symbols in the table mean the following.

not adhered in the zone and strong repellent effect is observed adhesion in zone is observed but most of them adhered outside zone and repellent effect is observed adhered inside and outside zone alike and repellent effect is not observed Table 5 repellent activity against Mytilus edulis Compound amount of chemical(mg) judgment compound 7 2.0 copper sulfate 1.0 Blank Industrial Applicability The cyanoacrylate compound represented by the general formula has high safety and exhibits a wide spectrum with a small amount, so that it is useful as industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms.

Claims (27)

1. A method of preventing or suppressing growth of bacteria, fungi or algae, said method comprising contacting said bacteria, fungi or algae, or a locus of said algae, fungi or bacteria with an agent having as an active ingredient at least one cyanoacrylate compound of general formula X S .CN r C (I) R/ 1 00 2 R 2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to suppress said growth of bacteria, fungi or algae.

2. The method of claim 1, wherein in said cyanoacrylate compound X and Y are independently a hydrogen atom or trifluoromethyl group. i5

3. A method of preserving wood or cutting oil, said method comprising treating said wood or cutting oil with an agent having as an active ingredient at least one cyanoacrylate compound of general formula x Y CN 0.N-CH= R (I) R/ i1 CO2R 2 wherein R 1 represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, 20 R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant.

4. The method of claim 3, wherein in said cyanoacrylate compound of formula I X and Y are independently a hydrogen atom or trifluoromethyl group.

A method of mildewproofing surfactants, said method comprising treating said surfactant with an agent having as an active ingredient at least one cyanoacrylate compound of general formula X Y R CN S N-CH (I) Ri CO 2 R 2 (I:\DayLib\LIBH]0B729.doc:mcc wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to mildewproof said surfactant.

6. The method of claim 5, wherein in said cyanoacrylate compound of formula I, X and Y are independently a hydrogen atom or trifluoromethyl group.

7. A method of sterilising or preventing formation of slime in cooling systems, said method comprising contacting said cooling system with an agent having as an active ingredient at least one cyanoacrylate compound of general formula X CH CN -CH O<2R2 (I) wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each 15 independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to sterilise and prevent formation of slime in cooling systems.

8. The method of claim 7, wherein in said cyanoacrylate compound of formula I X and Y are independently a hydrogen atom or trifluoromethyl group.

9. A method of protecting fibres, fabrics or leathers, said method comprising contacting said fibres, fabrics or leathers with an agent having as an active ingredient cyanoacrylate compounds of general formula X CN -NCH 2 (I) o i CO2R 2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to prevent the attack of bacteria, fungi and algae. L/

10. The method of claim 9, wherein in said cyanoacrylate compound of formula I o X and Y are independently a hydrogen atom or trifluoromethyl group. [I:\DayLib\LIBJ08729.doc:mcc

11. The method of claim 9 or 10, wherein said contacting comprises spraying or immersing.

12. A method of protecting a surface or product, said method comprising contacting said surface or product with an antibacterial agent, antifungal agent or an algicide having as an active ingredient cyanoacrylate compounds of general formula X Y^T- __CN Y N-CH CN2R (I) R CO 2 R wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, o0 alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, in an amount sufficient to protect said surface.

13. The method of claim 12, wherein said surface is a coating film.

14. The method of claim 12, wherein said product is selected from the group 15 consisting of interior or exterior products made from resin, building materials, home electrical appliances and sports goods.

15. The method of claim 14, wherein said resin is selected from the group consisting of vinyl chloride, polyurethane, polyethylene, polypropylene, silicone, modified silicone, nylon and epoxy.

16. The method of any one of claims 12 to 15, wherein in said cyanoacrylate compound of formula I X and Y are independently a hydrogen atom or trifluoromethyl group.

17. A method of deodorising or sterilising washing production equipment, sewage treatment plants or night soil treatment plants, said method comprising contacting said 25 washing production equipment, sewage treatment plants or night soil treatment plants with an agent having as an active ingredient at least one cyanoacrylate compound of general formula X Y (I -CN S 1 CH C 2 R 2 (I) wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each t" independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, Salkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally [I:\DayLib\LIBH]08729.doc:mcc together with a suitable carrier, diluent or adjuvant, in an amount sufficient to deodorise or sterilise.

18. The method of claim 17, wherein in said cyanoacrylate compound of formula I X and Y are independently a hydrogen atom or trifluoromethyl group.

19. An anti-fouling coating composition comprising a cyanoacrylate compound of general formula X Y l CN -CH 02R2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, together with a coating film forming agent.

The anti-fouling coating composition of claim 19, wherein the coating film forming agent is selected from the group consisting of oil varnish, synthetic resins, and artificial rubber.

21. The anti-fouling coating composition of claim 19 or 20 further comprising a solvent and/or a pigment.

22. A method for preventing adhesion of aquatic organisms to a surface, said 0: method comprising contacting said surface with an agent having as an active ingredient at least one cyanoacrylate compound of general formula X N-CH (I) 1 C2R2 wherein R' represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, SR 2 represents alkyl group having 1 to 10 carbon atoms, and X and Y are each Sindependently a hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or trifluoromethyl group, optionally together with a suitable carrier, diluent or adjuvant, or a composition according to any one of claims 26 to 28, in an amount sufficient to prevent adhesion of aquatic organisms to said surface.

23. The method of claim 22, wherein said aquatic organisms are selected from shellfish and algae. [1:\DayLib\LIBH]08729.doc:mcc

24. The method of claim 23, wherein said shellfish are selected from the group consisting of blue mussel (Mytilus edulis), barnacles, oysters, hydrozoan, hydra, seprula, ascidian, bryozoan and pond snails.

The method of claim 23, wherein said algae is selected from the group consisting of Ulva sp., Enteromorpha sp., and Ectocarpus sp.

26. The method of any one of claims 22 to 25, wherein said surface is a fishing net, ship hull, or underwater equipment.

27. The method of any one of claims 22 to 26, wherein in said cyanoacrylate compound of formula I X and Y are independently a hydrogen atom or trifluoromethyl to group. Dated 9 April, 2001 Nissan Chemical Industries, Ltd Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON b* C o C 0 I. Co CC* [I:\DayLib\LIBH]08729.doc:mcc