NZ503079A - Cyanoacrylate-containing antibacterial and antifungal agents, algicides and antifouling agents - Google Patents

Cyanoacrylate-containing antibacterial and antifungal agents, algicides and antifouling agents

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Publication number
NZ503079A
NZ503079A NZ503079A NZ50307998A NZ503079A NZ 503079 A NZ503079 A NZ 503079A NZ 503079 A NZ503079 A NZ 503079A NZ 50307998 A NZ50307998 A NZ 50307998A NZ 503079 A NZ503079 A NZ 503079A
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New Zealand
Prior art keywords
agents
algicides
organisms
compound
cyanoacrylate compound
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NZ503079A
Inventor
Shinichi Igarashi
Mitsugu Futagawa
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Nissan Chemical Ind Ltd
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Publication of NZ503079A publication Critical patent/NZ503079A/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)

Abstract

An industrial antibacterial and antifungal agent, algicides or agent for preventing adhesion of organisms comprises a cyanoacrylate of formula (I) wherein R1 is H or alkyl; R2 is alkyl and X and Y are H, halo, alkyl, alkoxy, nitro or trifluoromethyl.

Description

New Zealand Paient Spedficaiion for Paient Number 503079 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, 1 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, 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 2 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 compound is usedas industrial antibacterial and antifungal agents, 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 a heavy metal. 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 3 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, since the copper compounds contain, like tin 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. 4 Summary of the Invention The inventors of the present invention have made intensive investigation with view to solve the above problems and have found that a cyanoacrylate compound represented by the general formula (1) 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.
That is, the present invention relates to industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms, characterized by containing a cyanoacrylate compound of general formula (1): wherein R1 represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R2 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.
Each of the substituents shown in the general formula (1) will be described in concrete terms.
X (1) In the specification, "n" means normal, "i" iso, "s" secondary and wt" tertiary.
Examples of the halogen atom are fluorine, chlorine, bromine and iodine.
Examples of the alkyl group having 1 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, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1.1-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, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-l-methyl-n-propyl, l-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 for preventing adhesion of organisms of the present invention may contain a cyanoacrylate compound represented by the above general formula (1) 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 (1) in which X and Y each independently represent a hydrogen atom or trifluoromethyl group. Other preferred examples of the compound of the general formula (1) 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 Table 1 H F* N-C=\ ;R1 C02R2 ;Substituent on the benzene ring(X and Y) ;-position ;3-position ;4-position ;5-position ;6-position ;Iv ;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 ;9 ;Table 1(continuation) ;Substituent on the benzene ring(X and Y) ;! -position ;3-position ;4-position ;5-position ;6-position ;R' ;R2 ;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 ;CI ;H ;H ;H ;H ;Me ;Et ;H ;CI ;H ;H ;H ;Me ;Et ;H ;H ;CI ;H ;H ;Me ;Et ;CI ;H ;H ;H ;CI ;Me ;Me ;H ;CI ;CI ;H ;H ;Me ;Me ;CI ;H ;CI ;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 ;CI ;Me ;Me ;H ;F ;CI ;H ;H ;Me ;Et ;10 ;Table 1(continuation) ;Substituent on the benzene ring(X and Y) ;R i R! ;!-position ;3-position ;4-position ;5-position ;6-position ;Br ;H ;CI ;H ;H ;Me ;Et ;I ;H ;H ;H ;H ;Me ;Me ;H ;H ;I ;H ;H ;Me ;Et ;Me ;H ;H ;H ;H ;Me ;Et ;H ;Me ;H ;H ;H ;Me ;Et ;H ;H ;Me ;H ;H ;Me ;Et ;Me ;Me ;H ;H ;H ;Me ;Et ;H ;Me ;Me ;H ;H ;Me ;Et ;Me ;H ;H ;H ;Me ;Me ;Et ;Et ;H ;H ;H ;H ;Me ;Et ;H ;Et ;H ;H ;H ;Me ;Et ;H ;H ;Et ;H ;H ;Me ;Et ;Me ;Et ;H ;H ;H ;Me ;Et ;H ;Et ;Me ;H ;H ;Me ;Et ;Et ;H ;H ;H ;Me ;Me ;Et ;Me ;CI ;H ;H ;H ;Me ;Et ;H ;Me ;Br ;H ;H ;Me ;Et ;F ;H ;H ;H ;Me ;Me ;Et ;Pr-n ;H ;H ;H ;H ;Me ;Et ;H ;Pr-i ;H ;H ;H ;Me ;Et ;OMe ;H ;H ;H ;H ;Me ;Et ;H ;OMe ;H ;H ;H ;Me ;Et ;H ;H ;OMe ;H ;H ;Me ;Et ;OMe ;OMe ;H ;H ;H ;Me ;Et ;H ;OMe ;OMe ;H ;H ;Me ;Et ;OMe ;H ;H ;H ;OMe ;Me ;Et ;OEt ;H ;H ;H ;H ;Me ;Et ;H ;OEt ;H ;H ;H ;Me ;Et ;H ;H ;OEt ;H ;H ;Me ;Et ;OMe ;Me ;H ;H ;H ;Me ;Et ;H ;Me ;OMe ;H ;H ;Me ;Et ;Me ;H ;H ;H ;OMe ;Me ;Et ;OPr-n ;H ;H ;H ;H ;Me ;Et ;H ;OPr-i ;H ;H ;H ;Me ;Et ;OMe ;CI ;H ;H ;H ;Me ;Et ;11 ;Table 1(continuation) ;Substituent on the benzene ring(x and Y) ;R1 R2 ;-position ;3-position ;4-position ;5-position ;6-position ;1\ ;H ;Br ;OMe ;H ;H ;Me ;Et ;F ;H ;H ;H ;OMe ;Me ;Et ;NO 2 ;H ;H ;H ;H ;Me ;Et ;H ;NO 2 ;H ;H ;H ;Me ;Et ;H ;H ;NO2 ;H ;H ;Me ;Et ;Me ;NO2 ;H ;H ;H ;Me ;Et ;H ;NO2 ;Me ;H ;H ;Me ;Et ;N02 ;H ;H ;H ;Me ;Me ;Et ;NO2 ;CI ;H ;H ;H ;Me ;Et ;H ;NO2 ;Br ;H ;H ;Me ;Et ;F ;H ;H ;H ;NO 2 ;Me ;Et ;CFs ;H ;H ;H ;H ;Me ;Et ;H ;CFs ;H ;H ;H ;Me ;Et ;H ;H ;CFs ;H ;H ;Me ;Et ;Me ;CFs ;H ;H ;H ;Me ;Et ;H ;Me ;CFs ;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 ;CFs ;Me ;Et ;CFs ;H ;H ;H ;H ;H ;Et ;H ;CF 3 ;H ;H ;H ;H ;Et ;H ;H ;CFs ;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. 27 69-2773, 1981, Agricultural and Biological Chemistry vol. 48, pp.55-88, 1984 and US Patent No. 3981717. ;12 ;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, ;13 ;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-dichloro-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, tetramethylthiuram disulfide, ;tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, ;tetra-n-butylthiuram disulfide, tetrachloroisophthalonitrile, ;tetrachlorophthalonitrile, Cu-10% Ni solid-solution alloy, ;N-trichloromethylthiotetrahydrophthalimide, ;N-trichloromethylthiophthalimide, ;2,3,6-trichloro-4-propylsulfonyl pyridine, ;N-(2,4,6-trichlorophenyl)maleimide, ;4,5-trimethylene-2-methyl-3-isothiazolone, ;2-pyridinethiol-l-oxide zinc salts, 2,3,3-triiodoallyl alcohol, N-(fluorodichloromethylthio)phthalimide, ;bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, ;14 ;N-phenethyldichloromaleimide, 2-bromo-2-nitropropanediol, 5-bromo-5-nitro-l,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-cyclopropylamino-s-triazine, N-2-methyl-6-ethylphenyldichloromaleimide, 2-methyl-3-isothiazolone, methylene-bis-thiocyanate, 0-3-iodo-2-propynyl-N-butylcarbamate, N-3-iodo-2-propynyl-0-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 ;15 ;carriers and auxiliaries, for example, a surfactant, binder and stabilizer and formed into wet table powder, emulsif iable concentrate, 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, calciumcarbonate, 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 ;16 ;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 sulfonates, alkylsulfosuccinates, alkylsulfates, polyoxyethylene ;17 ;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 m 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; mildewproofing of surfactants; sterilization and the prevention ;18 ;of formation of slime in the cooling towers of the production equipment 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 from the 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 ;19 ;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. ;20 ;Formulation example 1 (emulsion formulation) ;ingredients wt% ;compound of general formula (1) 5 ;dimethyl sulfoxide 85 ;methyl isobutyl ketone 5 ;Sorpole 800 A (emulsifying agents of Toho Kagaku Co.) 5 ;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 (1) 20 ;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 (1) 20 ;lauryl sulfate 2 ;zansanth gum 2 ;21 ;hydroxy-propyl cellulose 1 ;distilled water 75 ;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 materials andproducts, and one in which industrial rawmaterials 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 field of agents for preventing adhesion of organisms, the ;22 ;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. ;A solvent, pigment and the like may be further used as 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. ;Examples of formulation when the agents for preventing adhesion of organisms of the present invention is used as an antifouling coating are given below. The present invention is not limited to ;23 ;these. ;Formulation example 4 ;ingredients wt% ;compound of general formula (1) 8 ;VYHH (vinyl type synthetic resin from UCC Co.) 7 rosin 7 ;tricresyl phosphate 3 ;talc 20 ;barium sulfate 15 ;red iron oxide 10 ;xylene 20 ;methyl isobutyl ketone 10 ;100 ;Formulation example 5 ;ingredients wt% ;compound of general formula (1) 5 ;CR-10 (chlorinated rubber resin from Asahi Denka Co.) 13 zinc white 20 ;talc 20 ;plasticizer 2 ;red iron oxide 10 ;xylene 30 ;24 ;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 to be 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. ;Examples of formulation when the agents for preventing adhesion of organisms of the present invention is used as an agent for preventing adhesion of organisms solution are given below. However, the present invention is not limited to these. ;25 ;Formulation example 6 ;ingredients wt% ;compound of general formula (1) 15 ;acrylic resin (50 % xylene solution) 50 ;xylene 35 ;100 ;Formulation example 7 ;ingredients wt% ;compound of general formula (1) 10 ;acrylic resin (50 % xylene solution) 40 ;di-tertiary nonyl pentasulfide 5 ;liquid paraffin 5 ;xylene 40 ;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 ;26 ;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 50 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°C) ;compound 2 (melting point of 92.0 to 94.0°C) ;compound 3 (melting point of 128.0 to 129.0°C) ;27 ;compound 4 (melting point of 109.0 to 110.0°C) ;compound 5 (melting point of 88.0 to 89.0°C) ;compound 6 (melting point of 52.0 to 53.0°C) ;compound 7 (melting point of 59.0 to 60.0°C) ;/ \ /^e /=\ Me \ /y~~N\ ^ compound 1 ;\ fl~N\ ^CN compound 5 \ N CN ;c°2Me ^ ^C02Pr-n compound 2 ;C°2Et C02Pr-i ;P3 CF3 ;

Claims (8)

Table 5 repellent activity against Mytilus edulis Compound amount of chemical(mg) j udgment compound 7 2.0 ++ 1.0 + copper sulfate 1.0 + 0.5 - Blank - Industrial Applicability The cyanoacrylate compound represented by the general formula (1) 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. 33 CLAIMS
1. Industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms, characterized by containing a cyanoacrylate compound of general formula (1): wherein R1 represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R2 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.
2. Industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms, characterized by containing the cyanoacrylate compound of general formula (1) as claimed in claim 1, wherein the X and Y are each independently a hydrogen atom, or trifluoromethyl group.
3. Industrial antibacterial and antifungal agents characterized by containing the cyanoacrylate compound as claimed in claim 1. X (1)
4. Algicides characterized by containing the cyanoacrylate compound as claimed in claim 1. 34
5. Agents for preventing adhesion of organisms characterized by containing the cyanoacrylate compound as claimed in claim 1.
6. Industrial antibacterial and antifungal agents characterized by containing the cyanoacrylate compound as claimed in claim 2.
7. Algicides characterized by containing the cyanoacrylate compound as claimed in claim 2.
8. Agents for preventing adhesion of organisms characterized by containing the cyanoacrylate compound as claimed in claim 2. 35 Abstract Industrial antibacterial and antifungal agents, algicides and agents for preventing adhesion of organisms, characterized by containing a cyanoacrylate compound of general formula (1): wherein R1 represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms, R2 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. X (1) 36
NZ503079A 1997-08-28 1998-08-27 Cyanoacrylate-containing antibacterial and antifungal agents, algicides and antifouling agents NZ503079A (en)

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DE10063867A1 (en) * 2000-12-21 2002-07-11 Haarmann & Reimer Gmbh Compositions for protecting human skin and hair against the damaging effects of ultraviolet radiation, comprise new or known N-substituted anilinomethylene malonic acid derivatives
PT3456717T (en) 2015-07-06 2021-05-26 Gilead Sciences Inc Tablets containing 4,6-diamino-quinoline-3-carbonitrile derivatives as cancer osaka thyroid (cot) modulators for treating cancer
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EP4126231A1 (en) 2020-03-30 2023-02-08 Gilead Sciences, Inc. Solid forms of (s)-6-(((1-(bicyclo[1.1.1]pentan-1-yl)-1h-1,2,3-triazol-4-yl)2-methyl-1-oxo-1,2- dihydroisoquinolin-5-yl)methyl)))amino)8-chloro-(neopentylamino)quinoline-3-carb onitrile a cot inhibitor compound
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CN112114002B (en) * 2020-08-07 2024-06-07 北京建筑大学 Precipitation and surface runoff water quality full-parameter online measurement system and application
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