CA2284492A1 - Fungicidal benzothiophene-2-carboxamide-s,s-dioxides for cooling lubricants - Google Patents
Fungicidal benzothiophene-2-carboxamide-s,s-dioxides for cooling lubricants Download PDFInfo
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- CA2284492A1 CA2284492A1 CA002284492A CA2284492A CA2284492A1 CA 2284492 A1 CA2284492 A1 CA 2284492A1 CA 002284492 A CA002284492 A CA 002284492A CA 2284492 A CA2284492 A CA 2284492A CA 2284492 A1 CA2284492 A1 CA 2284492A1
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- carboxamide
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to the use of N-alkyl-benzothiophene-2-carboxamide-S,S-dioxides to protect cooling lubricants from microbia l activity.
Description
Le A 32 273-Foreign countries Lin/Kr/W6/30.09.1997 F I L E, R+Pl-EN T H I S AiN~-~E~--~
T~-T TRANSt,AfIOI~
Fun~icidal benzothiophene-2-carboxamide S,S-dioxides for cutting oils The application relates to the use of benzothiophene-2-carboxamide S,S-dioxides, preferably N-cyclohexylbenzothiopen-2-carboxamide S,S-dioxide, as fungicide in S cutting oils.
Benzothiophene-2-carboxamide S,S-dioxides (BCDs), a process for their preparation and their fungicidal action are known (DE-A-41 15 184). Their activity against phytotoxic fungi and dermatophytes is described especially. In addition, it is stated that BCDs are suitable for the protection of industrial materials against microbial change or destruction. Industrial materials mentioned are, inter alia, coatings. It has now surprisingly been found that N-alkyl-BCDs are not only active against the moulds usually growing on coatings, but also have an outstanding action against the other types of fungal and yeast populations in cutting oils. Furthermore, BCDs offer the advantage over other fungicides employed in this use that, even with relatively long service times, no unwanted discoloration phenomena occur. The low application rates necessary to control fungal and yeast growth in addition permit an economic procedure and thus represent a contribution to increasing environmental safety and safety at work.
The application therefore relates to the use of N-alkyl-benzothiophene-2-carboxamide S,S-dioxides, preferably N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide, for the protection of cutting fluid emulsions against infections by fungi and yeasts.
Preference is given to N-alkyl compounds in which alkyl represents methyl, ethyl, n- or isopropyl, n-, isobutyl, s- or t-butyl, n- or isopentyl, n- or isohexyl, n- or isoheptyl, n- or isooctyl, n- or isononyl, n- or isodecyl, n- or isododecyl, n-or isooctadecyl, allyl, n- or isobutenyl, n- or isopentenyl, n- or isohexenyl, propargyl, n- or isobutinyl, n- or isopentinyl, n- or isohexinyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, Le A 32 273-Foreign countries cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl; in addition cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each of which is optionally monosubstituted to tetrasubstituted in the cycloalkyl moiety, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or isopropyl, chloromethyl, dichloromethyl or trifluoromethyl.
Particular preference is given to N-n-butyl-, N-n-pentyl-, N-n-hexyl-, N-cyclohexylmethyl-, N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxides.
High particular preference is given to N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide.
These compounds are distinguished by high activity and low tendency to discoloration, so that they, in contrast to the other BCDs and other commercially conventional fungicides, can also be used in cutting oils over relatively long periods of time without losses in action.
Surprisingly, the compounds demonstrate a particularly high microbicidal activity, in particular fungicidal action, in conjunction with a broad spectrum of action against moulds and yeasts relevant in cutting oils.
Examples, but without being limiting, which may be mentioned are the groups of fungi and yeasts below:
Aspergillus, such as Aspergillus niger, Le A 32 273-Foreign countries Candida, such as Candida albicans, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puteana, Geotrichum, such as Geotrichum candidum, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Acremonium, such as Acremonium strictum, Aureobasidium, such as Aureobasidium pullulans, I 0 Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Fusaria, such as Fusarum solani.
The application likewise relates to mixtures of N-alkyl-BCDs with at least one further microbicidal or microbiostatic active ingredient.
Owing to this active ingredient combination, the activity spectrum of the N-alkylbenzothiopen-2-carboxamide S,S-dioxides is further broadened, or particular effects are achieved. In many cases this produces synergistic effects. If the active ingredient combinations are present in certain weight ratios, the synergistic effect is demonstrated particularly markedly. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied in a relatively broad range.
Preferred mixing partners are, for example, the compounds:
N-Methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylen-isothiazolinone, 4,5-benzisothiazolinone;
Le A 32 273-Foreign countries formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono(poly)hemiformal, oxazolidines, hexahydro-s-triazines, N-methylolchloro-acetamide, paraformaldehyde, 1,6-dihydroxy-2,5-dioxohexane, N,N'-dihydroxy-methyleneurea, N-(2-hydroxypropyl)aminomethanol;
S
thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;
iodine derivatives such as diiodomethyl-p-tolylsulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl-n-butyl carbamate, 3-iodo-2-propinyl-n-hexyl carbamate, 3-iodo-2-propinyl-cyclohexyl carbamate, 3-iodo-2-propinyl-phenyl carbamate;
phenol derivatives such as 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
bromine derivatives such as 3-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrilo-propionamide, 1,2-dibromo-2,4-dicyanobutane, (3 -bromo-(3-nitrostyrene;
pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts), tetra-chloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
metal soaps such as tin naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; copper naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
dialkyldithiocarbamates such as sodium and zinc salts of dialkyldithiocarbamates, tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;
Le A 32 273-Foreign countries nitrites such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimido-carbamate;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thio-phonate methyl, thiabendazoles or their salts;
moropholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; aldimorph, fenpropidine and their arylsulphonic salts such as p-toluenesulphonic acid and p-dodecylphenylsulphonic acid;
dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, metiram, thiram, zeneb, ziram;
benzothiazoles such as 2-mercaptobenzothiazole;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamides;
boron compounds such as boric acid, boric ester, borax;
triazoles:
amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fen-chlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, Opus, paclobutrazole, penconazole, propioconazole, (~)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, tebuconazole, tetracona-zole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole;
imidazoles:
imazalil, pefurazoate, prochloraz, triflumizole.
Le A 32 273-Foreign countries High particular preference is given to mixtures of compounds of the formula (I) with N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, n-octylisothia-zolin-3-one, benzoisothiazolinone, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol(hemi)-formal, glutaraldehyde, Omadine, 1,6-dihydroxy-2,5-dioxohexane, N,N'-dihydroxymethyleneurea, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine and/or 3-iodo-2-propinyl-n-butyl carbamate.
The N-alkyl-BCDs and the active ingredient combinations according to the invention have a strong microbicidal action and can be used in practice for controlling unwanted microorganisms. The N-alkyl-BCDs and the active ingredient combinations according to the invention are suitable for the protection of industrial materials against infestation and destruction by unwanted microorganisms.
Industrial materials are, in the present context, taken to mean non-living materials which are prepared for use in industry. For example, industrial materials which are to be protected by active ingredients according to the invention against microbial change or destruction can be adhesives, sizes, paper and cardboard, textiles, leather, wood, coatings and plastics articles, cutting fluids and other materials which can be infested or decomposed by microorganisms. In the context of materials to be protected, parts or production plants, for example cutting fluid circuits, which can be impaired by growth of microorganisms, may also be mentioned.
Particular preference is given to industrial materials which comprise water or are prepared on a water basis or are processed using water, such as cutting fluids.
Preferably, the N-alkyl-BCDs are used in cutting fluids, in adhesives, sizes or in cutting fluid circuits. In this case, the long-term stability given is of particularly great commercial benefit, since in this manner, an adequate protection for many weeks is ensured by a single small dosage. Furthermore, the non-occurrence of discoloration is Le A 32 273-Foreign countries _7_ advantageous in practice, since as a result the otherwise necessary addition of complexing agents can be dispensed with. Finally, there are also ecological advantages, since compounds from the prior art contain iodine in the molecule, which iodine accumulates in the material (e.g. cutting oil) due to decomposition and then must be disposed of separately.
The N-alkyl-BCDs and the active ingredient combinations according to the invention can, depending on their respective physical and/or chemical properties, be converted into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.
These formulations are prepared in a known manner, e.g. by mixing the active ingredients with extenders, that is liquid solvents, pressurized liquefied gases and/or solid carriers, with or without the use of surfactants, that is emulsifiers and/or dispersants and/or foam-forming agents. In the case of use of water as an extender, for example, organic solvents can also be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol or their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents, such as dimethylformamide or dimethyl sulphoxide, as well as water; liquefied gaseous extenders or carriers is taken to mean those fluids which are gaseous at standard temperature and at atmospheric pressure, e.g. aerosol propellant gases, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; solid carriers which are suitable are:
e.g. natural rock flours, such as kaolins, aluminas, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earths and synthetic rock flours, such as highly disperse silicic acid, aluminium oxide and silicates; solid carriers for granules which are suitable are: for example crushed and fractionated natural rocks such as calcite, Le A 32 273-Fore~n countries _g_ marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and granules from organic materials such as sawdust, coconut shells, corn cobs and tobacco stalks; emulsifiers and/or foam-formers which are suitable are:
for example non-ionogenic and anionic emulsifiers, such as polyoxyethylene esters of fatty acids, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ether, alkyl sulphonates, alkyl sulphates, aryl sulphonates and protein hydrolysates;
dispersants which are suitable are: for example lignin sulphite liquors and methylcellulose.
In the formulations, use can be made of adhesion promoters such as carboxymethylcellulose, natural and synthetic, pulverulent, granular or latex-form polymers, such as gum arabic, polyvinyl alcohol), polyvinyl acetate), as well as natural phospholipids, such as cephalins and lecithins and synthetic phospholipids.
Other additives can be mineral oils and vegetable oils.
Use can be made of colours such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyanide blue and organic colours such as alizarin, azo and metallophthalocyanine colours and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The microbicidal compositions or concentrates used to protect industrial materials comprise the active ingredient or the active ingredient combination in a concentration of 0.1 and 95% by weight, in particular 1.0 to 60% by weight.
The use level of the active ingredient or active ingredient combinations to be used according to the invention depends on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum application rate can be determined by test series. Generally, the use levels are in the range from 0.001 to S% by weight, preferably from 0.01 to 1.0% by weight, based on the material to be protected. When the active ingredients or active ingredient combinations to be used according to the invention are incorporated into cutting fluid Le A 32 273-Foreign countries concentrates, the respective dilution factor with respect to preparation of the water-mixed cutting fluid emulsion must be taken into account.
The compositions according to the invention advantageously allow the previously available compositions to be replaced by more effective ones. The compositions according to the invention show a good stability, do not lead to discolorations and advantageously have a broad spectrum of activity.
The examples below serve to illustrate the invention. The invention is not restricted to the examples.
Le A 32 273-Foreign countries Example 1 Determination of activity in a cutting fluid emulsion The study is carried out with a mineral-oil-based cutting fluid. The concentrate is diluted with water so that a S% strength emulsion results. The active ingredients to be tested are incorporated into this formulation in the specified concentration range.
The resultant samples are then inoculated with bacteria and also a mixture of moulds and yeasts (separate solutions). After one week at room temperature, a sample is withdrawn to determine the number of surviving microorganisms. Subsequently thereto, inoculation is repeated, there is a wait of one week and further processing is carried out as described. The assay is terminated as soon as the growth of the microorganisms is no longer controlled by the amount of microbicide added in the particular case.
The surviving microorganisms are determined, for bacteria on standard plate count agar, for moulds and yeasts on malt extract agar, duplicate determinations being carried out in each case.
The microorganisms serving for the inoculation comprise the following representatives:
Bacteria Pseudomonas aeruginosa Pseudomonas fluorescens Pseudomonas oleovorans Pseudomonas rubescens Pseudomonas stutzeri Alcaligenes faecalis Citrobacter freundii Corynebacterium sp.
Le A 32 273-Foreign countries Moulds Acremonium strictum Fusarium solani Geotrichum Yeasts Rhodotorula rubra The results are shown in the table below:
Table 1 1 2 3 4 5 6 7 8 Weeks B 10~
~ S02 H~ - _ _ - _ _ according to the invention B = Bacteria; M = moulds; Y = yeasts The table reports the number of colony-forming units per ml (CFU/ml).
Active ingredient concentration: 100 ppm of N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide As Table 1 verifies, addition of the compound according to the invention, even at low concentration, leads to the active suppression of the growth of moulds and yeasts, this effect remaining over several weeks, after only one addition of active ingredient (long-term stability).
Le A 32 273-Foreign countries In contrast to the prior art (Na-Pyrion), with the invention according to the invention there is no risk of discolorations, even in the case of relatively long use.
T~-T TRANSt,AfIOI~
Fun~icidal benzothiophene-2-carboxamide S,S-dioxides for cutting oils The application relates to the use of benzothiophene-2-carboxamide S,S-dioxides, preferably N-cyclohexylbenzothiopen-2-carboxamide S,S-dioxide, as fungicide in S cutting oils.
Benzothiophene-2-carboxamide S,S-dioxides (BCDs), a process for their preparation and their fungicidal action are known (DE-A-41 15 184). Their activity against phytotoxic fungi and dermatophytes is described especially. In addition, it is stated that BCDs are suitable for the protection of industrial materials against microbial change or destruction. Industrial materials mentioned are, inter alia, coatings. It has now surprisingly been found that N-alkyl-BCDs are not only active against the moulds usually growing on coatings, but also have an outstanding action against the other types of fungal and yeast populations in cutting oils. Furthermore, BCDs offer the advantage over other fungicides employed in this use that, even with relatively long service times, no unwanted discoloration phenomena occur. The low application rates necessary to control fungal and yeast growth in addition permit an economic procedure and thus represent a contribution to increasing environmental safety and safety at work.
The application therefore relates to the use of N-alkyl-benzothiophene-2-carboxamide S,S-dioxides, preferably N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide, for the protection of cutting fluid emulsions against infections by fungi and yeasts.
Preference is given to N-alkyl compounds in which alkyl represents methyl, ethyl, n- or isopropyl, n-, isobutyl, s- or t-butyl, n- or isopentyl, n- or isohexyl, n- or isoheptyl, n- or isooctyl, n- or isononyl, n- or isodecyl, n- or isododecyl, n-or isooctadecyl, allyl, n- or isobutenyl, n- or isopentenyl, n- or isohexenyl, propargyl, n- or isobutinyl, n- or isopentinyl, n- or isohexinyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, Le A 32 273-Foreign countries cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl; in addition cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, each of which is optionally monosubstituted to tetrasubstituted in the cycloalkyl moiety, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or isopropyl, chloromethyl, dichloromethyl or trifluoromethyl.
Particular preference is given to N-n-butyl-, N-n-pentyl-, N-n-hexyl-, N-cyclohexylmethyl-, N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxides.
High particular preference is given to N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide.
These compounds are distinguished by high activity and low tendency to discoloration, so that they, in contrast to the other BCDs and other commercially conventional fungicides, can also be used in cutting oils over relatively long periods of time without losses in action.
Surprisingly, the compounds demonstrate a particularly high microbicidal activity, in particular fungicidal action, in conjunction with a broad spectrum of action against moulds and yeasts relevant in cutting oils.
Examples, but without being limiting, which may be mentioned are the groups of fungi and yeasts below:
Aspergillus, such as Aspergillus niger, Le A 32 273-Foreign countries Candida, such as Candida albicans, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puteana, Geotrichum, such as Geotrichum candidum, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Acremonium, such as Acremonium strictum, Aureobasidium, such as Aureobasidium pullulans, I 0 Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Fusaria, such as Fusarum solani.
The application likewise relates to mixtures of N-alkyl-BCDs with at least one further microbicidal or microbiostatic active ingredient.
Owing to this active ingredient combination, the activity spectrum of the N-alkylbenzothiopen-2-carboxamide S,S-dioxides is further broadened, or particular effects are achieved. In many cases this produces synergistic effects. If the active ingredient combinations are present in certain weight ratios, the synergistic effect is demonstrated particularly markedly. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied in a relatively broad range.
Preferred mixing partners are, for example, the compounds:
N-Methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylen-isothiazolinone, 4,5-benzisothiazolinone;
Le A 32 273-Foreign countries formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono(poly)hemiformal, oxazolidines, hexahydro-s-triazines, N-methylolchloro-acetamide, paraformaldehyde, 1,6-dihydroxy-2,5-dioxohexane, N,N'-dihydroxy-methyleneurea, N-(2-hydroxypropyl)aminomethanol;
S
thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;
iodine derivatives such as diiodomethyl-p-tolylsulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl-n-butyl carbamate, 3-iodo-2-propinyl-n-hexyl carbamate, 3-iodo-2-propinyl-cyclohexyl carbamate, 3-iodo-2-propinyl-phenyl carbamate;
phenol derivatives such as 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
bromine derivatives such as 3-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrilo-propionamide, 1,2-dibromo-2,4-dicyanobutane, (3 -bromo-(3-nitrostyrene;
pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts), tetra-chloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
metal soaps such as tin naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; copper naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
dialkyldithiocarbamates such as sodium and zinc salts of dialkyldithiocarbamates, tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;
Le A 32 273-Foreign countries nitrites such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimido-carbamate;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thio-phonate methyl, thiabendazoles or their salts;
moropholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; aldimorph, fenpropidine and their arylsulphonic salts such as p-toluenesulphonic acid and p-dodecylphenylsulphonic acid;
dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, metiram, thiram, zeneb, ziram;
benzothiazoles such as 2-mercaptobenzothiazole;
quinolines such as 8-hydroxyquinoline and their copper salts;
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamides;
boron compounds such as boric acid, boric ester, borax;
triazoles:
amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fen-chlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, Opus, paclobutrazole, penconazole, propioconazole, (~)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, tebuconazole, tetracona-zole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole;
imidazoles:
imazalil, pefurazoate, prochloraz, triflumizole.
Le A 32 273-Foreign countries High particular preference is given to mixtures of compounds of the formula (I) with N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, n-octylisothia-zolin-3-one, benzoisothiazolinone, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol(hemi)-formal, glutaraldehyde, Omadine, 1,6-dihydroxy-2,5-dioxohexane, N,N'-dihydroxymethyleneurea, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine and/or 3-iodo-2-propinyl-n-butyl carbamate.
The N-alkyl-BCDs and the active ingredient combinations according to the invention have a strong microbicidal action and can be used in practice for controlling unwanted microorganisms. The N-alkyl-BCDs and the active ingredient combinations according to the invention are suitable for the protection of industrial materials against infestation and destruction by unwanted microorganisms.
Industrial materials are, in the present context, taken to mean non-living materials which are prepared for use in industry. For example, industrial materials which are to be protected by active ingredients according to the invention against microbial change or destruction can be adhesives, sizes, paper and cardboard, textiles, leather, wood, coatings and plastics articles, cutting fluids and other materials which can be infested or decomposed by microorganisms. In the context of materials to be protected, parts or production plants, for example cutting fluid circuits, which can be impaired by growth of microorganisms, may also be mentioned.
Particular preference is given to industrial materials which comprise water or are prepared on a water basis or are processed using water, such as cutting fluids.
Preferably, the N-alkyl-BCDs are used in cutting fluids, in adhesives, sizes or in cutting fluid circuits. In this case, the long-term stability given is of particularly great commercial benefit, since in this manner, an adequate protection for many weeks is ensured by a single small dosage. Furthermore, the non-occurrence of discoloration is Le A 32 273-Foreign countries _7_ advantageous in practice, since as a result the otherwise necessary addition of complexing agents can be dispensed with. Finally, there are also ecological advantages, since compounds from the prior art contain iodine in the molecule, which iodine accumulates in the material (e.g. cutting oil) due to decomposition and then must be disposed of separately.
The N-alkyl-BCDs and the active ingredient combinations according to the invention can, depending on their respective physical and/or chemical properties, be converted into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances.
These formulations are prepared in a known manner, e.g. by mixing the active ingredients with extenders, that is liquid solvents, pressurized liquefied gases and/or solid carriers, with or without the use of surfactants, that is emulsifiers and/or dispersants and/or foam-forming agents. In the case of use of water as an extender, for example, organic solvents can also be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol or their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents, such as dimethylformamide or dimethyl sulphoxide, as well as water; liquefied gaseous extenders or carriers is taken to mean those fluids which are gaseous at standard temperature and at atmospheric pressure, e.g. aerosol propellant gases, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; solid carriers which are suitable are:
e.g. natural rock flours, such as kaolins, aluminas, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earths and synthetic rock flours, such as highly disperse silicic acid, aluminium oxide and silicates; solid carriers for granules which are suitable are: for example crushed and fractionated natural rocks such as calcite, Le A 32 273-Fore~n countries _g_ marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours and granules from organic materials such as sawdust, coconut shells, corn cobs and tobacco stalks; emulsifiers and/or foam-formers which are suitable are:
for example non-ionogenic and anionic emulsifiers, such as polyoxyethylene esters of fatty acids, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ether, alkyl sulphonates, alkyl sulphates, aryl sulphonates and protein hydrolysates;
dispersants which are suitable are: for example lignin sulphite liquors and methylcellulose.
In the formulations, use can be made of adhesion promoters such as carboxymethylcellulose, natural and synthetic, pulverulent, granular or latex-form polymers, such as gum arabic, polyvinyl alcohol), polyvinyl acetate), as well as natural phospholipids, such as cephalins and lecithins and synthetic phospholipids.
Other additives can be mineral oils and vegetable oils.
Use can be made of colours such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyanide blue and organic colours such as alizarin, azo and metallophthalocyanine colours and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The microbicidal compositions or concentrates used to protect industrial materials comprise the active ingredient or the active ingredient combination in a concentration of 0.1 and 95% by weight, in particular 1.0 to 60% by weight.
The use level of the active ingredient or active ingredient combinations to be used according to the invention depends on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum application rate can be determined by test series. Generally, the use levels are in the range from 0.001 to S% by weight, preferably from 0.01 to 1.0% by weight, based on the material to be protected. When the active ingredients or active ingredient combinations to be used according to the invention are incorporated into cutting fluid Le A 32 273-Foreign countries concentrates, the respective dilution factor with respect to preparation of the water-mixed cutting fluid emulsion must be taken into account.
The compositions according to the invention advantageously allow the previously available compositions to be replaced by more effective ones. The compositions according to the invention show a good stability, do not lead to discolorations and advantageously have a broad spectrum of activity.
The examples below serve to illustrate the invention. The invention is not restricted to the examples.
Le A 32 273-Foreign countries Example 1 Determination of activity in a cutting fluid emulsion The study is carried out with a mineral-oil-based cutting fluid. The concentrate is diluted with water so that a S% strength emulsion results. The active ingredients to be tested are incorporated into this formulation in the specified concentration range.
The resultant samples are then inoculated with bacteria and also a mixture of moulds and yeasts (separate solutions). After one week at room temperature, a sample is withdrawn to determine the number of surviving microorganisms. Subsequently thereto, inoculation is repeated, there is a wait of one week and further processing is carried out as described. The assay is terminated as soon as the growth of the microorganisms is no longer controlled by the amount of microbicide added in the particular case.
The surviving microorganisms are determined, for bacteria on standard plate count agar, for moulds and yeasts on malt extract agar, duplicate determinations being carried out in each case.
The microorganisms serving for the inoculation comprise the following representatives:
Bacteria Pseudomonas aeruginosa Pseudomonas fluorescens Pseudomonas oleovorans Pseudomonas rubescens Pseudomonas stutzeri Alcaligenes faecalis Citrobacter freundii Corynebacterium sp.
Le A 32 273-Foreign countries Moulds Acremonium strictum Fusarium solani Geotrichum Yeasts Rhodotorula rubra The results are shown in the table below:
Table 1 1 2 3 4 5 6 7 8 Weeks B 10~
~ S02 H~ - _ _ - _ _ according to the invention B = Bacteria; M = moulds; Y = yeasts The table reports the number of colony-forming units per ml (CFU/ml).
Active ingredient concentration: 100 ppm of N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide As Table 1 verifies, addition of the compound according to the invention, even at low concentration, leads to the active suppression of the growth of moulds and yeasts, this effect remaining over several weeks, after only one addition of active ingredient (long-term stability).
Le A 32 273-Foreign countries In contrast to the prior art (Na-Pyrion), with the invention according to the invention there is no risk of discolorations, even in the case of relatively long use.
Claims (6)
1. The use of N-alkyl-benzothiophene-2-carboxamide S,S-dioxides for the protection of cutting oils against microbial attack.
2. The use of compounds according to Claim 1 in which alkyl represents methyl, ethyl, n- or isopropyl, n-, isobutyl, s- or t-butyl, n- or isopentyl, n- or isohexyl, n- or isoheptyl, n- or isooctyl, n- or isononyl, n- or isodecyl, n-or isododecyl, n- or isooctadecyl, allyl, n- or isobutenyl, n- or isopentenyl, n-or isohexenyl, propargyl, n- or isobutinyl, n- or isopentinyl, n- or isohexinyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl; in addition cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclo-hexylpropyl, each of which is optionally monosubstituted to tetrasubstituted in the cycloalkyl moiety, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, n- or isopropyl, chloromethyl, dichloromethyl or trifluoromethyl.
3. The use of N-cyclohexyl-benzothiophene-2-carboxamide S,S-dioxide in cutting fluids.
4. Process for the protection of cutting fluids against microbial attack, characterized in that cutting fluids are admixed with N-alkyl-benzothiophene-2-carboxamide S,S-dioxide.
5. Cutting fluids comprising N-alkyl-benzothiophene-2-carboxamide S,S-dioxides.
6. Cutting fluids according to Claim 5, additionally comprising at least one further microbicidal or microbiostic active ingredient.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19709875.4 | 1997-03-11 | ||
| DE19709875A DE19709875A1 (en) | 1997-03-11 | 1997-03-11 | Fungicidal benzothiophene-2-carboxamide-S, S-dioxide for cooling lubricants |
| PCT/EP1998/001094 WO1998039968A1 (en) | 1997-03-11 | 1998-02-26 | Fungicidal benzothiophene-2-carboxamide-s,s-dioxides for cooling lubricants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2284492A1 true CA2284492A1 (en) | 1998-09-17 |
Family
ID=7822898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002284492A Abandoned CA2284492A1 (en) | 1997-03-11 | 1998-02-26 | Fungicidal benzothiophene-2-carboxamide-s,s-dioxides for cooling lubricants |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0969721A1 (en) |
| JP (1) | JP2001519840A (en) |
| AU (1) | AU6725798A (en) |
| CA (1) | CA2284492A1 (en) |
| DE (1) | DE19709875A1 (en) |
| WO (1) | WO1998039968A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5571795B2 (en) * | 2009-10-16 | 2014-08-13 | ダウ グローバル テクノロジーズ エルエルシー | Aqueous cutting fluid for use with diamond wire saws |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU761471A1 (en) * | 1978-11-14 | 1980-09-07 | Inst Khim Im V I Nikitina An T | 1-thiaindane-1,1-dioxide-2(3)-carboxylic acid amide as antimicrobic additive to petroleum oils |
| SU1409592A1 (en) * | 1986-10-29 | 1988-07-15 | Научно-производственное объединение по геологофизическим методам повышения нефтеотдачи пластов | Method of preventing growth of microorganisms |
| ZA894985B (en) * | 1988-11-04 | 1990-04-25 | Buckman Labor Inc | A synergistic combination for use in controlling fungal or bacterial growth in synthetic metalworking fluids |
| ZA918514B (en) * | 1990-10-31 | 1992-11-25 | Buckman Labor Inc | Synergistic combinations of idopropargyl compounds with hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine in controlling fungal and bacterial growth in metalworking fluids |
| DE4115184A1 (en) * | 1991-05-09 | 1992-11-12 | Bayer Ag | BENZOTHIOPHEN-2-CARBOXAMID-S, S-DIOXIDE |
| DE4328074A1 (en) * | 1993-08-20 | 1995-02-23 | Bayer Ag | Mold-resistant emulsion paints |
-
1997
- 1997-03-11 DE DE19709875A patent/DE19709875A1/en not_active Withdrawn
-
1998
- 1998-02-26 WO PCT/EP1998/001094 patent/WO1998039968A1/en not_active Application Discontinuation
- 1998-02-26 AU AU67257/98A patent/AU6725798A/en not_active Abandoned
- 1998-02-26 JP JP53913898A patent/JP2001519840A/en active Pending
- 1998-02-26 CA CA002284492A patent/CA2284492A1/en not_active Abandoned
- 1998-02-26 EP EP98912404A patent/EP0969721A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0969721A1 (en) | 2000-01-12 |
| AU6725798A (en) | 1998-09-29 |
| WO1998039968A1 (en) | 1998-09-17 |
| DE19709875A1 (en) | 1998-09-17 |
| JP2001519840A (en) | 2001-10-23 |
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