CA2041348A1 - Composition and use - Google Patents
Composition and useInfo
- Publication number
- CA2041348A1 CA2041348A1 CA 2041348 CA2041348A CA2041348A1 CA 2041348 A1 CA2041348 A1 CA 2041348A1 CA 2041348 CA2041348 CA 2041348 CA 2041348 A CA2041348 A CA 2041348A CA 2041348 A1 CA2041348 A1 CA 2041348A1
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- Canada
- Prior art keywords
- composition
- component
- carbon atoms
- isothiazolin
- medium
- Prior art date
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Abstract
ABSTRACT
"COMPOSITION AND USE"
A composition which contains a 4,5-polymethylene-4 -isothiazolin-3-one, and a defined isothiazolinone which is different from the 4,5-polymethylene-4-isothiazolin-3-one and which can be a 4,5 optionally halogenated N-alkyl isothiazolin-3-one. The compositions exhibit anti-microbial activity and certain combinations are surprisingly effective against bacteria.
"COMPOSITION AND USE"
A composition which contains a 4,5-polymethylene-4 -isothiazolin-3-one, and a defined isothiazolinone which is different from the 4,5-polymethylene-4-isothiazolin-3-one and which can be a 4,5 optionally halogenated N-alkyl isothiazolin-3-one. The compositions exhibit anti-microbial activity and certain combinations are surprisingly effective against bacteria.
Description
3 ~ ~
COMPOSITION APID USE
The present invention relates to compositions which are useful as industrial biocides.
Industrial biocides are useful to prevent industrial spoilage, in particular that caused hy bacteria and fungi.
Industrial biocides find application in the preservation of paints, latices, adhesives, leather, wood, metal working fluids and cooling water.
One class of compound which can be used as an industrial biocide is based on the isothiaæolinone structure. There are many disclosures of isothiazolinone derivatives which are stated to have useful biocidal properties. US Patent 3761488 discloses isothiazolinGne deriva~ives in which alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl groups, which may optionally be substituted, are attached to the nitrogen atom and the 4 and 5 positions are unsubstituted or are substituted with halogen or lower alkyl groups. US Patent 4165318 discloses a solution of an isothia~olin-3-one in a polar organic solvent, wherein the solution also contains a stabilising amount of formaldehyde. Stabilisation of similar compounds is also claimed in US Patent 4,067,878 where the stabilising compound is a nitrite or nitrate of a metal cation.
British Patent Specification 2087388 discloses 4,5-polymethylene-4-isothia~olin-3-ones and derivatives thereof in which the polymethylene chain has three or four carbon atoms.
Compounds and compositions of the foregoing types, and related compounds of the same general type, are effective to a varying degree, depending on the particular compound or composition, against a range of bacteria and/or fungi. However, to reduce the cost of using these compounds it is desirable to improve their effectiveness as antimicrobial materials.
~ , " . '' , 3 ~ ~
COMPOSITION APID USE
The present invention relates to compositions which are useful as industrial biocides.
Industrial biocides are useful to prevent industrial spoilage, in particular that caused hy bacteria and fungi.
Industrial biocides find application in the preservation of paints, latices, adhesives, leather, wood, metal working fluids and cooling water.
One class of compound which can be used as an industrial biocide is based on the isothiaæolinone structure. There are many disclosures of isothiazolinone derivatives which are stated to have useful biocidal properties. US Patent 3761488 discloses isothiazolinGne deriva~ives in which alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl groups, which may optionally be substituted, are attached to the nitrogen atom and the 4 and 5 positions are unsubstituted or are substituted with halogen or lower alkyl groups. US Patent 4165318 discloses a solution of an isothia~olin-3-one in a polar organic solvent, wherein the solution also contains a stabilising amount of formaldehyde. Stabilisation of similar compounds is also claimed in US Patent 4,067,878 where the stabilising compound is a nitrite or nitrate of a metal cation.
British Patent Specification 2087388 discloses 4,5-polymethylene-4-isothia~olin-3-ones and derivatives thereof in which the polymethylene chain has three or four carbon atoms.
Compounds and compositions of the foregoing types, and related compounds of the same general type, are effective to a varying degree, depending on the particular compound or composition, against a range of bacteria and/or fungi. However, to reduce the cost of using these compounds it is desirable to improve their effectiveness as antimicrobial materials.
~ , " . '' , 3 ~ ~
Compositions have been proposed which contain more than one compound which has antimicrobial properties. In general such compositions show an aggregate of the properties of the co~pounds present in the composition. Typically such compositions contain one compound which e~hibits useful antibacterial properties together with a different compGund which exhibits useful antifungal properties.
We have now found that certain compositions possess surprisingly useful antimicrobial properties, especially antibacterial properties.
Thus, according to the present invention there is provided a composition which comprises (a) at least one 4,5 polymethylene-4-isothiazolin-3-one or a derivative thereof, and (b) at least one isothiazolin-3-one derivative which does not lS contain a fused ring attached to the isothiazole ring.
The 4,5 polymethylene-4-isothia~olin-3-one derivative which is component a) of the composition is typically z compound of the general formula I.
- R \ / O\
\ 3 ) ~ N - R
~-Rl \S/
wherein:
Rl and R2 taken together represent A polymethylene chain, having 3 or 4 carbon a~oms or a polymethylene chain having 3 or 4 carbon atoms s~bstituted by at least one lower alkyl rad:Lcal having from 1 to 4 carbon atoms;
We have now found that certain compositions possess surprisingly useful antimicrobial properties, especially antibacterial properties.
Thus, according to the present invention there is provided a composition which comprises (a) at least one 4,5 polymethylene-4-isothiazolin-3-one or a derivative thereof, and (b) at least one isothiazolin-3-one derivative which does not lS contain a fused ring attached to the isothiazole ring.
The 4,5 polymethylene-4-isothia~olin-3-one derivative which is component a) of the composition is typically z compound of the general formula I.
- R \ / O\
\ 3 ) ~ N - R
~-Rl \S/
wherein:
Rl and R2 taken together represent A polymethylene chain, having 3 or 4 carbon a~oms or a polymethylene chain having 3 or 4 carbon atoms s~bstituted by at least one lower alkyl rad:Lcal having from 1 to 4 carbon atoms;
3 ~ $
3_ S 35718 R represents hydrogen; a linear or branched alkyl group having from 1 to 12 carbon atoms; a linear or branched alkyl group having from 1 to 3 carbon atoms substituted by one or more hydroxyl groups; an alk~nyl group having from 3 to 6 carbon atoms; a radical of the formula (R5)m (C~IR4) wherein:
; n is 0 or 1;
m is 1 or 2;
R4 represents hydrogen or a lower alkyl group; and R5 represents hydrogen, lower alkyl, nitro, trifluoromethyl or halogen, preferably chlorine, bromine or iodine; cyclo alkyl having from 3 to 6 carbon atoms; and a radical of formula o _ C - NHR
wherein R6 represents hydrogen, linear or branched alkyl having from 1 to 12 carbon atoms or a radical of the formula (R5)~
-(CEIR4) ~
as defined above, and their salts with a mineral or organic Acid.
:
3 ~ ~
~ S 35718 In a preferred embodiment of the invention the 4,5-polymethylene-4-isothiazolin-3-one can be represented by the general formula II
(cH2~t C82 ) f \ N - R3 II
\ CH \ S /
wherein t is l or 2 and R3 is as defined above. These compounds are, thus, derivatives of 4,5-trimethylene or 4,5-tetramethylene-4-isothia701in-3--ones.
R3, in formulae I and II, may be a linear or branched alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl or dodecyl.
When R3 represents alkyl substituted by one or more hydroxyl groups, this includes, for instance, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl and l,2 dihydroxy propyl.
As an example of alkenyl as represented by R3, ~here may be mentioned allyl.
When K3 represents a radical of formula (RS)m -tCHR4)n ~
this can be, for example, phenyl, chlorophenyl, 2,4-dichlorophenyl, benzyl, 4-chlorob~nzyl or 2,4-dichlorobenzyl.
- ' ~ ' When R3 represents cycloalkyl havirlg from 3 to 6 carbon atoms, this can be, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Finally, when R3 represents a radical of formula o Il 6 - C-NHR
it can be carbomoyl, N-methyl carbamoyl, N-ethylcarbamoyl, N-isopropyl carbamoyl, N-propyl carbamoyl, N-phenyl carbamoyl, N-cyclohexyl carbamoyl, N-butyl carbamoyl or N-octyl carba~oyl.
The tenm lower alkyl represented by R4 above includes linear or branched alkyl chains containing up to 4 carbon atoms such as methyl, ethyl, isopropyl, butyl and tertiary butyl.
As specific examples of compounds which may be used as component (a) of the composition of the present invention, there may be mentlonsd 2-methyl-4,5-trimethylene isothiazolin-3-one. (formula II, in which t is 1 and R3 is methyl), and 4,5-trimethylene lsothiazolin-3-one tformula II, in which t is 1 and R3 is hydrogen).
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Component bj of the composition is an isothiazolin-3-one of general formula III
~ / III
S
wherein Y is a hydrogen atom, an alkyl, substitutsd alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl group;
:. . .
.: . . . .
, R7 is hydrogen, halogen or an alkyl group; and R8 is hydrogen, halogen or an alkyl group.
When Y is alkyl, it is preferably an alkyl group containing from 1 to 18 carbon atoms and especially from 1 to 4 carbon atoms and particularly a methyl group.
When Y is cycloalkyl, it is preferably a cycloalkyl group containing from 3 to 12 carbon atoms and especially fro~ 3 to 8 carbon atoms and particularly a cyclohexyl group.
When Y is alkyl or aralkyl, it preferably contains up to 10 carbon atoms. The aryl groups, themselves, may also carry substituents such as halogen, particularly chlorine, or alkyl or alkoxy groups containing up to 4 carbon atoms such as methyl and methoxy.
When R andlor R8 is halogen, it is particularly chlorine or bromine, and when R7 andlor R3 is alkyl it is particularly an alkyl group containing from 1 to 4 carbon atoms and especially methyl.
Particularly important within this group of compounds are those in which Y represents a linear or branched alkyl group containing up to 8 carbon atoms and where R7 and R8 represent independently hydrogen or chlorine. Thus, as specific examples of compounds which may be used as componen~ ~b) of the composition of the present invention, there may be mentioned 2~methyl isothiazolin-3-one ~formula III, in which Y is methyl, R7 and R~ are both hydrogen), 5-chloro-2-methyl -lsothia7,01in-3-one ~formula III, in which Y is methyl, R7 is chlorine and R8 is hydrogen) and 4,5 dichloro-2-methyl -isothiazolin-3-one ~formula III, in which Y is methyl, R7 and R8 are both chlorine). Such compounds may represent component b) ln the comyosition of the present invention as individual chemical compounds or they may be preseDt in combination.
: . : - ,.- ~, , : ~
3_ S 35718 R represents hydrogen; a linear or branched alkyl group having from 1 to 12 carbon atoms; a linear or branched alkyl group having from 1 to 3 carbon atoms substituted by one or more hydroxyl groups; an alk~nyl group having from 3 to 6 carbon atoms; a radical of the formula (R5)m (C~IR4) wherein:
; n is 0 or 1;
m is 1 or 2;
R4 represents hydrogen or a lower alkyl group; and R5 represents hydrogen, lower alkyl, nitro, trifluoromethyl or halogen, preferably chlorine, bromine or iodine; cyclo alkyl having from 3 to 6 carbon atoms; and a radical of formula o _ C - NHR
wherein R6 represents hydrogen, linear or branched alkyl having from 1 to 12 carbon atoms or a radical of the formula (R5)~
-(CEIR4) ~
as defined above, and their salts with a mineral or organic Acid.
:
3 ~ ~
~ S 35718 In a preferred embodiment of the invention the 4,5-polymethylene-4-isothiazolin-3-one can be represented by the general formula II
(cH2~t C82 ) f \ N - R3 II
\ CH \ S /
wherein t is l or 2 and R3 is as defined above. These compounds are, thus, derivatives of 4,5-trimethylene or 4,5-tetramethylene-4-isothia701in-3--ones.
R3, in formulae I and II, may be a linear or branched alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl or dodecyl.
When R3 represents alkyl substituted by one or more hydroxyl groups, this includes, for instance, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl and l,2 dihydroxy propyl.
As an example of alkenyl as represented by R3, ~here may be mentioned allyl.
When K3 represents a radical of formula (RS)m -tCHR4)n ~
this can be, for example, phenyl, chlorophenyl, 2,4-dichlorophenyl, benzyl, 4-chlorob~nzyl or 2,4-dichlorobenzyl.
- ' ~ ' When R3 represents cycloalkyl havirlg from 3 to 6 carbon atoms, this can be, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Finally, when R3 represents a radical of formula o Il 6 - C-NHR
it can be carbomoyl, N-methyl carbamoyl, N-ethylcarbamoyl, N-isopropyl carbamoyl, N-propyl carbamoyl, N-phenyl carbamoyl, N-cyclohexyl carbamoyl, N-butyl carbamoyl or N-octyl carba~oyl.
The tenm lower alkyl represented by R4 above includes linear or branched alkyl chains containing up to 4 carbon atoms such as methyl, ethyl, isopropyl, butyl and tertiary butyl.
As specific examples of compounds which may be used as component (a) of the composition of the present invention, there may be mentlonsd 2-methyl-4,5-trimethylene isothiazolin-3-one. (formula II, in which t is 1 and R3 is methyl), and 4,5-trimethylene lsothiazolin-3-one tformula II, in which t is 1 and R3 is hydrogen).
~;:
Component bj of the composition is an isothiazolin-3-one of general formula III
~ / III
S
wherein Y is a hydrogen atom, an alkyl, substitutsd alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl group;
:. . .
.: . . . .
, R7 is hydrogen, halogen or an alkyl group; and R8 is hydrogen, halogen or an alkyl group.
When Y is alkyl, it is preferably an alkyl group containing from 1 to 18 carbon atoms and especially from 1 to 4 carbon atoms and particularly a methyl group.
When Y is cycloalkyl, it is preferably a cycloalkyl group containing from 3 to 12 carbon atoms and especially fro~ 3 to 8 carbon atoms and particularly a cyclohexyl group.
When Y is alkyl or aralkyl, it preferably contains up to 10 carbon atoms. The aryl groups, themselves, may also carry substituents such as halogen, particularly chlorine, or alkyl or alkoxy groups containing up to 4 carbon atoms such as methyl and methoxy.
When R andlor R8 is halogen, it is particularly chlorine or bromine, and when R7 andlor R3 is alkyl it is particularly an alkyl group containing from 1 to 4 carbon atoms and especially methyl.
Particularly important within this group of compounds are those in which Y represents a linear or branched alkyl group containing up to 8 carbon atoms and where R7 and R8 represent independently hydrogen or chlorine. Thus, as specific examples of compounds which may be used as componen~ ~b) of the composition of the present invention, there may be mentioned 2~methyl isothiazolin-3-one ~formula III, in which Y is methyl, R7 and R~ are both hydrogen), 5-chloro-2-methyl -lsothia7,01in-3-one ~formula III, in which Y is methyl, R7 is chlorine and R8 is hydrogen) and 4,5 dichloro-2-methyl -isothiazolin-3-one ~formula III, in which Y is methyl, R7 and R8 are both chlorine). Such compounds may represent component b) ln the comyosition of the present invention as individual chemical compounds or they may be preseDt in combination.
: . : - ,.- ~, , : ~
A particularly useful combination has been found to be one comprising ~-methyl-l~,5-trimethylene-4-iso~hiazolin-3-one together with at least one of 2-methyl isothiazolin-3-one, S-chloro-~-methyl isothiazolin-3-one and 4,5-dichloro-~-methyl isothia~olin-3-one.
In various types of applications, it is ~requently necessary or convenient to formulate the isothiazolin-3-one as represented by formula III in solution, especially using water or polar organic solvents such as alcohols. While such formulation has no effect on the stability or function of isothiazolin-3-ones as anti-microbial agents if used relatively quickly, extanded storage of the formulated solutions, especially at elevated temperature, may result in chemical decomposition of the isothiazolin-3-one, thus leading to reduced biocidal effectiveness. Consequently, it is common to stabilise such formulations by incorporating nitrite or nitrate salts of metals. It is also possible to stabilise such compounds in the presence of formaldehyde or compounds which release formaldehyde.
When isothizolin-3-ones of the afore-mentioned structures as represented by formulae I and III are used in aqueous solution, their solubility may be improved by forming their salts with strong organic and/or inorganic acids such as hydrochloric acid, sulphuric acid, succinic and citric acids.
The relative proportions of the components o the composltion can vary and compositions having useful properties can be obtained which contain from one part by weight o~ component (a) or component (b) and correspondingly up to 1000 parts by weight of component (b) or component (a). The preferred proportions are dependent on the compouncls used as component (a) and component (b), and also ~he particular system in which the mixture ls to be used.
In general the composition contains at least l part by weight of one component and not more than 100 parts by weight of the other component.
Particularly preferred compositions are those were the ratio of component (a) to component (h) is be~ween 1:10 and 10:1 and preferably between 1:5 and S:l such as, Eor ex~mple, 1:1.
, `
In various types of applications, it is ~requently necessary or convenient to formulate the isothiazolin-3-one as represented by formula III in solution, especially using water or polar organic solvents such as alcohols. While such formulation has no effect on the stability or function of isothiazolin-3-ones as anti-microbial agents if used relatively quickly, extanded storage of the formulated solutions, especially at elevated temperature, may result in chemical decomposition of the isothiazolin-3-one, thus leading to reduced biocidal effectiveness. Consequently, it is common to stabilise such formulations by incorporating nitrite or nitrate salts of metals. It is also possible to stabilise such compounds in the presence of formaldehyde or compounds which release formaldehyde.
When isothizolin-3-ones of the afore-mentioned structures as represented by formulae I and III are used in aqueous solution, their solubility may be improved by forming their salts with strong organic and/or inorganic acids such as hydrochloric acid, sulphuric acid, succinic and citric acids.
The relative proportions of the components o the composltion can vary and compositions having useful properties can be obtained which contain from one part by weight o~ component (a) or component (b) and correspondingly up to 1000 parts by weight of component (b) or component (a). The preferred proportions are dependent on the compouncls used as component (a) and component (b), and also ~he particular system in which the mixture ls to be used.
In general the composition contains at least l part by weight of one component and not more than 100 parts by weight of the other component.
Particularly preferred compositions are those were the ratio of component (a) to component (h) is be~ween 1:10 and 10:1 and preferably between 1:5 and S:l such as, Eor ex~mple, 1:1.
, `
The compositions of the present invention have antimicrobial properties. We have found that compositions in accordance with the present invention are especially active against bacteria. Furthermore, compositions in accordance with the presen~
invention are such that the sum of the fractional inhibitory concentration (FIC) for all the components of the composition is less than one and, with preferred compositions is less than 0.7.
Especially preferred compositions are those in which the sum of the FIC for all the components of the composition is not more than 0.6.
The FIC is the ratio of the concentration of an individual component to the minimum inhibitory concentration of that component. It will be appreciated that if the value of the sum of the FIC for all the components of the composition is less than one, the composition is synergistic, the extent of synergy being indicated by the amount by which the 9um of the E~'IC is below one. We have found that some compositions in accordance with the present invention are such that the sum of the FIC is less than 0.6.
The compositions of the present invention have antimicrobial properties and are suitable for use as industrial bioc~des. They exhibit good wet state preservation and hence may be used as a cutting fluid preservative and also in cooling water applications.
They may be used to preserve industrially important formulations, especially aqueous based formulations, which are used for coloration, such as dyestuffs and printing inks. They may also be used in the a~rochemical industries to preserve formulations such as herbicide and pesticide flowables.
Still further important appllcations of the compositions of the present invention include their use in hydrocarbon fluids such as diesel fuels. They may also be incorporated into adhesives in order to inhiblt microbial spoilage.
The preservation of wood and leather is yet another important application of the compositions.
Especially important is the use of the composition of the present invention in paints, particularly in aqueous based latices.
2~3~
_g_ S 35718 A particularly preferred use of ~he compositions of the present invention is for the preservation of poly vinyl acrylate and particularly acrylic latices, espPcially those whose p~ is above 7, and more especially those containing ammonia or amines.
The materials which are component (a) and component (b) of the composition of the present invention are soluble in many polar solvents, although the solubility is dependent on the nature of the particular compounds which are present in the composition. Ho~ever, many of the compounds are soluble in water, alcohols, ethers, ~etones and other polar solvents or mixtures thereof.
The compositions of the present invention may be used alone as an antimicrobial material but may also be used in, or on, a suitable carrier material.
Thus, as a further aspect of the present invention there is provided a biocide composition comprising a carrier and an effective amount of a composition of components (a) and (b) in accordance with the invention.
The carrier is typically a material which shows little, if any, antimicrobial activity and may be, or include~ a material which is susceptible to the growth of micro-organisms, particularly bacteria. The carrier is preferably a liquid medium and the biocide composition may be a solution, suspension or emulsion of the composition of components (a~ and (b) ln a liquid carrier. The carrier may be water, ln which one or both oE components (a) and (b) are soluble, or may be a liquid such as acetic acid, N,N-dimethyl-formamide, propylene glycol, dimethyl sulphoxide or N-methyl-2-pyrrolidone in which at least one, and preferably both, o componerlts (a) and (b) are soluble. Alternatively, a mix~ure of liquids may be used, one being a solvent for component (a) and component (b) and the other being a non-solvent Eor both components, snd using such a mixture the composition typically comprises sn emulsion or droplets of a solution of components (a) and (b) in the solvent therefor dispersed ln ~he non-solvent. If a suspension or emulsion is used, this conveniently contAins a surface active agent - '.: .`~. ' ' '~
:
.
2 ~ 3 l~ ~
which is effective to maintain the non-continuous phase as a suspension or emulsion. Any surface active agent known for use in biocide compositions may be used in such a system, for example alkylene oxide adducts of fatty alcohols, alkyl phenols and amines such as ethylene diamine.
Whereas it is advantageous in using the composition of the present invention to add component (a) and component (b) simultaneously, it will be appreciated that in certain circumstances it may be beneficial to add cornponent (a) and component (b) sequentially.
The amount of the composition which is present in the biocide composition may be just sufficient to have an antimicrobial effect or the composition may be present in a substantially greater proportion. It will be appreciated that the biocide composition may be provided as a concentrated solution which is subsequently diluted for use as an anti~icrobial material. The higher concentrations of the biocide composition are useful for example in the bulk transportation of the composition. Thus, the amount of the composition of components (a) and (b) which is present in the biocide composition is typically in the range from 0.00001% up to 30 by weight of the biocide composition.
The composition of the present invention is especially effective in providing anti-bacterial activity. Thus, the compositions can be used for the treatment of various media to inhibit the growth of micro-organisms.
As a furthar aspect of the present invention there is provided a method for inhlbiting the growth o micro-organisms on, or in, a medium which comprises treating the medium with a composition of components (a) and (b) as hereinbefore defined.
, ' 2 ~ L~
~ S 35718 The composition can be used in conditions in which micro-organisms grow and cause problems. Systems in which micro-organisms cause problems include liquid, particularly aqueous, systems such as coollng water liquors~ paper mill liquors, metal working fluids, geological drilling lubricants, polymer emulsions and surface coating compositions such as paints, varn~shes and lacquers and also solid materials such as wood and leather. The composition of thP present invention can be included in such materials to provide an anti-microbial effect. The amount of the composition is l¢ typically in the ran8e from 0.00001 up to lOZ, preferably 0.00002 up to 5z and especially 0.00002 to 1% by weight of the composition relative to the system to which it is added. In many cases, microbial inhibition has been obtained with between 0.00002 and O.OlZ
by weight of the composition.
lS Components (a) and (b) of the composition of the present invention may be the only antimicrobial compounds or may be used together with ~urther compounds having antimicrobial characteristics.
The composition may contain more than one compound which is component (a) together with one or more compound which is component (b). Alternatively, a composition of components (a) and (b~ in accordance with the present invention may be used together with one or more known antimicrobial compounds. The use of a mixture of anti-microbial compounds can provide a co~position having a broader anti-microbial spectrum and hence one which is more generally effective than the components thereof. The known antimicrobial may be one possessing anti-bacterial, antl-fungal, anti-algal or other antimicrobial characteristic. The mixture o the composition of the present invention with other antimicrobial compounds typically contains from 1 to 9gZ by weight, relative to the weight of total antimicrobially active compounds, of the composition of components (a) and (b), and particularly from 40 to 60Z by weight of the composition of components (a) and (b).
.'.-: ,: ' ~ ' ' .
-12- ~34~
As examples of known antimicrobial compounds which may be used, together with the composition of the present invention, there may be mentioned quaternary ammonium compounds such as diPthyldodecylbenzyl ammonium chloride; dimethyloctadecyl-(dimethylbenzyl)ammonium chloride; dimethyldidecylammonium chl.oride;
dimethyldidodecylammonium chloride; trimethy-tetradecylammonium chloride; benzyldimethyl(Cl2-C18 alkyl)ammonium chloride;
dichlorobenzyldimethyldodecylammonium chloride; hexadecylpyridinium chloride; hexadecylpyridinium bromide; hexadecyltrimethylammonium bromide; dodecylpyridinium chloride; dodecylpyridini~m bisulphate;
benzyldodecyl-bi~(beta-hydroxyethyljammonium chloride; dodecyl-benzyltrimethylammonium chloride; benzyldimethyl(C12-C18 alkyl~
ammonium chloride; dodecyl.dimethylethyl ammonium ethylsulphate;
dodecyldimethyl-(l-naphthylmethyl)ammoni~ chloride; hexadecyl-dL~ethylbenzyl ammonium chloride; dodecyldimethylbenzyl ammlonium chloride and l-(3-chloroallyl)-3,5,7-triaza l-azonia-adamantane chloride; urea derivatives such as 1,3-bis(hydroxymethyl)-5,5-dimethylhydan~oin; bis(hydroxymethyl)urea; tetrakis(hydroxy-methyl)acetylene diurea; l-(hydroxymethyl)-5,5-dime~hylhydantoin and imidazolidinyl urea; amino compounds such as 1,3-bis~2-ethyl-hexyl)-S-methyl-5-aminohexahydropyrimidine; hexamethylene tetra amine; 1,3-bis(4-aminophenoxy)propane; and 2-[(hydroxymethyl)-amino]ethanol; imidazole derivatives such as 1[2-(2,4 dichloro-phenyl)-2-(2-propenyloxy)ethyl~ -imidazole; 2-(methoxycarbonyl-amino)-benzimidazole; nitrile compounds such as 2,4,5,6-tetra-chloroisophthalodinitrile and 1,2-dibromo-2,4-dicyanobutane;
thiocyanate derivatives such as methylene bis thiocyanate; tin compounds or complexes such as tributyl~in-oxide, chlorlde, naphthoate, benzoate or 2-hydroxybenzoate; thiaæole derivatives such as 2--(thiocyanomethylthio)-benzthiazole; and mercaptobenzthiazole;
nitro compounds such as tris(hydroxymethyl)nitromethane; 5-bromo-S-nitro-1,3-dioxane and 2-bromo-2-nitropropane-1,3-diol; aldehydes and derivatives such as gluteraldehyde ~pentanedial) p-chlorophenyl-3-iodopropargyl formaldehyde and g:Lyoxal; amides such as chloracetamide; ~,N-bis(hydroxymethyl)chloracetamide;
N-hydroxymethyl-chloracetamide and dithio-2,2-bis(benzmethyl amide);
.
3 l~ ~
guanidine derivatives such as poly hexamethylene biguanide and 1,6 hexamet~ylene-bis[5-(4-chlorophenyl)biguanide]; thiones such as 3,5-dimethyltet~ahydro-1,3,5-2EI-thiodiazine-2-thione; triazine derivatives such as hexahydrotriazine and 1,3,5-tri-(hydroxyethyl)-1,3,5-hexahydrotriazine; oxazolidine and derivatives thereof such as bis-oxazolidine; furan and derivatives thereof such as 2,5-dlhydro-2,5-dialkoxy-2,5-dialkylfuran; carboxylic acids and the salts and esters thereof such as sorbic acid and the salts thereof and 4-hydroxybenzoic acid and the salts and esters thereof; phenol and derivatives thereof such as 5-chloro-2-(2,4-dichloro-phenoxy)phenol; thio-bis(4-chlorophenol) and 2-phenylphenol;
sulphone derivatives such as diiodomethyl-paratolyl sulphone, 2,3,5,6 ~etrachloro-4-(methylsulphonyl) pyridine and hexachlorodimethyl sulphone.
Further aspects of ~he present invention are described in the following illustrative exa~tples.
In the following examples, compositions in accordance with the present invention were subjected to evaluation of the antmticrobial properties especially anti-bacterial properties~ of the compositions. The evaluation was effected, under sterile conditions throughout, as &etailed below.
Microbiolo~ical evaluation The materials, or mixture of materials, to be tested were added to a mltrient broth in amounts to give a clc~ired concentration of the added material. The added materials were added at concentrations from zero to above the minimum inhlbitory concentration of the particular material In the mixtures, the concentrations of each material were varied in a systematic fashion to give a matrlx of mixtures o~ different relative proportions ancl different total concentrations.
.
, ~ ~ .
s~
The effect on ~he inhibition of growth of bacteria was investigated by inoculating each sample of broth with sufficient of the test micro-organism to give about lO5 cells cm~3. The mixture was incubated at 30C for 48 hours. At the end of the test period the presence of turbidity in the broth indicated that growth of the test micro-organism had occurred. A lack of turbidity was indicative that no growth had occurred. The results were used to draw an isobologram from which the sum of the fractional inhibitory concentration for a mixture can be determined.
Example 1 The microbiological evaluation as described was carried out using the bacterium, Escherichla coli. The composition tested was a mixture of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 5-chloro-2-methyl-isothiazolin-3-one.
An isobologram was drawn using concentrations of 0, 0.2, 0.5, 0.7, 0.9, l.l, l.4, l,6, l.8 and 2 microgram cm 3 of the trimethylene-isothiazolinone and 0, 0.2, 0.5, 0.7, 0.9, l.l, l.~, 1.6, l.8 and 2 microgr~m cm~3 of the chloro isothiazolinone.
From the results obtained, it was found that the lowest sum of the fractional inhibitory concentration was 0.54 which was obtained with a mixture of 0.2 microgram cm~3 of the 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 0.2 microgram cm 3 of the S-chloro-2-methyl-isothiazolin 3~one. This may be contrasted with the minimum inhibitory concentrations (MIC) for the two individual compounds against the ~amo micro-organism which were found to be 1.4 microgram cm~3 and 0.5 mlcrogram cm~3 respectively.
~ , . ~ .
invention are such that the sum of the fractional inhibitory concentration (FIC) for all the components of the composition is less than one and, with preferred compositions is less than 0.7.
Especially preferred compositions are those in which the sum of the FIC for all the components of the composition is not more than 0.6.
The FIC is the ratio of the concentration of an individual component to the minimum inhibitory concentration of that component. It will be appreciated that if the value of the sum of the FIC for all the components of the composition is less than one, the composition is synergistic, the extent of synergy being indicated by the amount by which the 9um of the E~'IC is below one. We have found that some compositions in accordance with the present invention are such that the sum of the FIC is less than 0.6.
The compositions of the present invention have antimicrobial properties and are suitable for use as industrial bioc~des. They exhibit good wet state preservation and hence may be used as a cutting fluid preservative and also in cooling water applications.
They may be used to preserve industrially important formulations, especially aqueous based formulations, which are used for coloration, such as dyestuffs and printing inks. They may also be used in the a~rochemical industries to preserve formulations such as herbicide and pesticide flowables.
Still further important appllcations of the compositions of the present invention include their use in hydrocarbon fluids such as diesel fuels. They may also be incorporated into adhesives in order to inhiblt microbial spoilage.
The preservation of wood and leather is yet another important application of the compositions.
Especially important is the use of the composition of the present invention in paints, particularly in aqueous based latices.
2~3~
_g_ S 35718 A particularly preferred use of ~he compositions of the present invention is for the preservation of poly vinyl acrylate and particularly acrylic latices, espPcially those whose p~ is above 7, and more especially those containing ammonia or amines.
The materials which are component (a) and component (b) of the composition of the present invention are soluble in many polar solvents, although the solubility is dependent on the nature of the particular compounds which are present in the composition. Ho~ever, many of the compounds are soluble in water, alcohols, ethers, ~etones and other polar solvents or mixtures thereof.
The compositions of the present invention may be used alone as an antimicrobial material but may also be used in, or on, a suitable carrier material.
Thus, as a further aspect of the present invention there is provided a biocide composition comprising a carrier and an effective amount of a composition of components (a) and (b) in accordance with the invention.
The carrier is typically a material which shows little, if any, antimicrobial activity and may be, or include~ a material which is susceptible to the growth of micro-organisms, particularly bacteria. The carrier is preferably a liquid medium and the biocide composition may be a solution, suspension or emulsion of the composition of components (a~ and (b) ln a liquid carrier. The carrier may be water, ln which one or both oE components (a) and (b) are soluble, or may be a liquid such as acetic acid, N,N-dimethyl-formamide, propylene glycol, dimethyl sulphoxide or N-methyl-2-pyrrolidone in which at least one, and preferably both, o componerlts (a) and (b) are soluble. Alternatively, a mix~ure of liquids may be used, one being a solvent for component (a) and component (b) and the other being a non-solvent Eor both components, snd using such a mixture the composition typically comprises sn emulsion or droplets of a solution of components (a) and (b) in the solvent therefor dispersed ln ~he non-solvent. If a suspension or emulsion is used, this conveniently contAins a surface active agent - '.: .`~. ' ' '~
:
.
2 ~ 3 l~ ~
which is effective to maintain the non-continuous phase as a suspension or emulsion. Any surface active agent known for use in biocide compositions may be used in such a system, for example alkylene oxide adducts of fatty alcohols, alkyl phenols and amines such as ethylene diamine.
Whereas it is advantageous in using the composition of the present invention to add component (a) and component (b) simultaneously, it will be appreciated that in certain circumstances it may be beneficial to add cornponent (a) and component (b) sequentially.
The amount of the composition which is present in the biocide composition may be just sufficient to have an antimicrobial effect or the composition may be present in a substantially greater proportion. It will be appreciated that the biocide composition may be provided as a concentrated solution which is subsequently diluted for use as an anti~icrobial material. The higher concentrations of the biocide composition are useful for example in the bulk transportation of the composition. Thus, the amount of the composition of components (a) and (b) which is present in the biocide composition is typically in the range from 0.00001% up to 30 by weight of the biocide composition.
The composition of the present invention is especially effective in providing anti-bacterial activity. Thus, the compositions can be used for the treatment of various media to inhibit the growth of micro-organisms.
As a furthar aspect of the present invention there is provided a method for inhlbiting the growth o micro-organisms on, or in, a medium which comprises treating the medium with a composition of components (a) and (b) as hereinbefore defined.
, ' 2 ~ L~
~ S 35718 The composition can be used in conditions in which micro-organisms grow and cause problems. Systems in which micro-organisms cause problems include liquid, particularly aqueous, systems such as coollng water liquors~ paper mill liquors, metal working fluids, geological drilling lubricants, polymer emulsions and surface coating compositions such as paints, varn~shes and lacquers and also solid materials such as wood and leather. The composition of thP present invention can be included in such materials to provide an anti-microbial effect. The amount of the composition is l¢ typically in the ran8e from 0.00001 up to lOZ, preferably 0.00002 up to 5z and especially 0.00002 to 1% by weight of the composition relative to the system to which it is added. In many cases, microbial inhibition has been obtained with between 0.00002 and O.OlZ
by weight of the composition.
lS Components (a) and (b) of the composition of the present invention may be the only antimicrobial compounds or may be used together with ~urther compounds having antimicrobial characteristics.
The composition may contain more than one compound which is component (a) together with one or more compound which is component (b). Alternatively, a composition of components (a) and (b~ in accordance with the present invention may be used together with one or more known antimicrobial compounds. The use of a mixture of anti-microbial compounds can provide a co~position having a broader anti-microbial spectrum and hence one which is more generally effective than the components thereof. The known antimicrobial may be one possessing anti-bacterial, antl-fungal, anti-algal or other antimicrobial characteristic. The mixture o the composition of the present invention with other antimicrobial compounds typically contains from 1 to 9gZ by weight, relative to the weight of total antimicrobially active compounds, of the composition of components (a) and (b), and particularly from 40 to 60Z by weight of the composition of components (a) and (b).
.'.-: ,: ' ~ ' ' .
-12- ~34~
As examples of known antimicrobial compounds which may be used, together with the composition of the present invention, there may be mentioned quaternary ammonium compounds such as diPthyldodecylbenzyl ammonium chloride; dimethyloctadecyl-(dimethylbenzyl)ammonium chloride; dimethyldidecylammonium chl.oride;
dimethyldidodecylammonium chloride; trimethy-tetradecylammonium chloride; benzyldimethyl(Cl2-C18 alkyl)ammonium chloride;
dichlorobenzyldimethyldodecylammonium chloride; hexadecylpyridinium chloride; hexadecylpyridinium bromide; hexadecyltrimethylammonium bromide; dodecylpyridinium chloride; dodecylpyridini~m bisulphate;
benzyldodecyl-bi~(beta-hydroxyethyljammonium chloride; dodecyl-benzyltrimethylammonium chloride; benzyldimethyl(C12-C18 alkyl~
ammonium chloride; dodecyl.dimethylethyl ammonium ethylsulphate;
dodecyldimethyl-(l-naphthylmethyl)ammoni~ chloride; hexadecyl-dL~ethylbenzyl ammonium chloride; dodecyldimethylbenzyl ammlonium chloride and l-(3-chloroallyl)-3,5,7-triaza l-azonia-adamantane chloride; urea derivatives such as 1,3-bis(hydroxymethyl)-5,5-dimethylhydan~oin; bis(hydroxymethyl)urea; tetrakis(hydroxy-methyl)acetylene diurea; l-(hydroxymethyl)-5,5-dime~hylhydantoin and imidazolidinyl urea; amino compounds such as 1,3-bis~2-ethyl-hexyl)-S-methyl-5-aminohexahydropyrimidine; hexamethylene tetra amine; 1,3-bis(4-aminophenoxy)propane; and 2-[(hydroxymethyl)-amino]ethanol; imidazole derivatives such as 1[2-(2,4 dichloro-phenyl)-2-(2-propenyloxy)ethyl~ -imidazole; 2-(methoxycarbonyl-amino)-benzimidazole; nitrile compounds such as 2,4,5,6-tetra-chloroisophthalodinitrile and 1,2-dibromo-2,4-dicyanobutane;
thiocyanate derivatives such as methylene bis thiocyanate; tin compounds or complexes such as tributyl~in-oxide, chlorlde, naphthoate, benzoate or 2-hydroxybenzoate; thiaæole derivatives such as 2--(thiocyanomethylthio)-benzthiazole; and mercaptobenzthiazole;
nitro compounds such as tris(hydroxymethyl)nitromethane; 5-bromo-S-nitro-1,3-dioxane and 2-bromo-2-nitropropane-1,3-diol; aldehydes and derivatives such as gluteraldehyde ~pentanedial) p-chlorophenyl-3-iodopropargyl formaldehyde and g:Lyoxal; amides such as chloracetamide; ~,N-bis(hydroxymethyl)chloracetamide;
N-hydroxymethyl-chloracetamide and dithio-2,2-bis(benzmethyl amide);
.
3 l~ ~
guanidine derivatives such as poly hexamethylene biguanide and 1,6 hexamet~ylene-bis[5-(4-chlorophenyl)biguanide]; thiones such as 3,5-dimethyltet~ahydro-1,3,5-2EI-thiodiazine-2-thione; triazine derivatives such as hexahydrotriazine and 1,3,5-tri-(hydroxyethyl)-1,3,5-hexahydrotriazine; oxazolidine and derivatives thereof such as bis-oxazolidine; furan and derivatives thereof such as 2,5-dlhydro-2,5-dialkoxy-2,5-dialkylfuran; carboxylic acids and the salts and esters thereof such as sorbic acid and the salts thereof and 4-hydroxybenzoic acid and the salts and esters thereof; phenol and derivatives thereof such as 5-chloro-2-(2,4-dichloro-phenoxy)phenol; thio-bis(4-chlorophenol) and 2-phenylphenol;
sulphone derivatives such as diiodomethyl-paratolyl sulphone, 2,3,5,6 ~etrachloro-4-(methylsulphonyl) pyridine and hexachlorodimethyl sulphone.
Further aspects of ~he present invention are described in the following illustrative exa~tples.
In the following examples, compositions in accordance with the present invention were subjected to evaluation of the antmticrobial properties especially anti-bacterial properties~ of the compositions. The evaluation was effected, under sterile conditions throughout, as &etailed below.
Microbiolo~ical evaluation The materials, or mixture of materials, to be tested were added to a mltrient broth in amounts to give a clc~ired concentration of the added material. The added materials were added at concentrations from zero to above the minimum inhlbitory concentration of the particular material In the mixtures, the concentrations of each material were varied in a systematic fashion to give a matrlx of mixtures o~ different relative proportions ancl different total concentrations.
.
, ~ ~ .
s~
The effect on ~he inhibition of growth of bacteria was investigated by inoculating each sample of broth with sufficient of the test micro-organism to give about lO5 cells cm~3. The mixture was incubated at 30C for 48 hours. At the end of the test period the presence of turbidity in the broth indicated that growth of the test micro-organism had occurred. A lack of turbidity was indicative that no growth had occurred. The results were used to draw an isobologram from which the sum of the fractional inhibitory concentration for a mixture can be determined.
Example 1 The microbiological evaluation as described was carried out using the bacterium, Escherichla coli. The composition tested was a mixture of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 5-chloro-2-methyl-isothiazolin-3-one.
An isobologram was drawn using concentrations of 0, 0.2, 0.5, 0.7, 0.9, l.l, l.4, l,6, l.8 and 2 microgram cm 3 of the trimethylene-isothiazolinone and 0, 0.2, 0.5, 0.7, 0.9, l.l, l.~, 1.6, l.8 and 2 microgr~m cm~3 of the chloro isothiazolinone.
From the results obtained, it was found that the lowest sum of the fractional inhibitory concentration was 0.54 which was obtained with a mixture of 0.2 microgram cm~3 of the 2-methyl-4,5-trimethylene-4-isothiazolin-3-one and 0.2 microgram cm 3 of the S-chloro-2-methyl-isothiazolin 3~one. This may be contrasted with the minimum inhibitory concentrations (MIC) for the two individual compounds against the ~amo micro-organism which were found to be 1.4 microgram cm~3 and 0.5 mlcrogram cm~3 respectively.
~ , . ~ .
Claims (26)
1. A composition which comprises a) at least one 4,5-polymethylene-4-isothiazolin-3-one or a derivative thereof, and b) at least one isothiazolin-3-one derivative which cloes not contain a fused ring attached to the isothiazoline ring.
2. A composition as claimed in claim 1 wherein a) is at least one compound of the general formula:
wherein R1 and R2 together represent a polymethylene chain having 3 or 4 carbon atoms, or a polymethylene chain having 3 or 4 carbon atoms substituted by a lower alkyl radical having from 1 to 4 carbon atoms;
R3 represents hydrogen, linear or branched alkyl having up to 12 carbon atoms, linear or branched alkyl having up to 3 carbon atoms substituted by at least one hydroxyl group, an alkenyl group having from 3 to 6 carbon atoms, a radical of the formula wherein n is 0 or 1;
m is 1 or 2;
R4 represents hydrogen or alkyl having from 1 to 4 carbon atoms; and R5 represents hydrogen, alkyl having from 1 to 4 carbon atoms, nitro, trifluoromethyl or halogen, cycloalkyl having from 3 to 6 carbon atoms, a radical of formula wherein R6 represents hydrogen, linear or branched alkyl having up to 12 carbon atoms or a radical of formula as defined above, or a mineral or organic salt thereof.
wherein R1 and R2 together represent a polymethylene chain having 3 or 4 carbon atoms, or a polymethylene chain having 3 or 4 carbon atoms substituted by a lower alkyl radical having from 1 to 4 carbon atoms;
R3 represents hydrogen, linear or branched alkyl having up to 12 carbon atoms, linear or branched alkyl having up to 3 carbon atoms substituted by at least one hydroxyl group, an alkenyl group having from 3 to 6 carbon atoms, a radical of the formula wherein n is 0 or 1;
m is 1 or 2;
R4 represents hydrogen or alkyl having from 1 to 4 carbon atoms; and R5 represents hydrogen, alkyl having from 1 to 4 carbon atoms, nitro, trifluoromethyl or halogen, cycloalkyl having from 3 to 6 carbon atoms, a radical of formula wherein R6 represents hydrogen, linear or branched alkyl having up to 12 carbon atoms or a radical of formula as defined above, or a mineral or organic salt thereof.
3. A composition as claimed in claim 2 wherein a) is at least wherein t is 1 or 2.
4. A composition as clalmed in claim 3 wherein t is 1 and R3 is either hydrogen or alkyl.
5. A composition as claimed in any one of claims 1 to 4 wherein component a) is either 4,5-trimethylene-4-isothiazolln-3-one or 2-methyl 4,5-trimethylene-4-isothiazolin-3-one.
6. A composition as claimed in any one of claims 1 to 5 where component b) is at least one compound of general formula wherein Y is a hydrogen atom, an alkyl, substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl group; and R7 is hydrogen, halogen or an alkyl group; and R8 is hydrogen, halogen or an alkyl group.
7. A composition as claimed in claim 6 wherein Y is an alkyl group containing from 1 to 18 carbon atoms.
8. A composition as claimed in claims 6 or 7 wherein Y is nn alkyl group containing from 1 to 4 carbon atoms.
9. A composltion as claimed in any one of claims 6 to 8 wherein R7 and/or R8 is independently chlorine, bromine or alkyl containing from 1l to 4 carbon atoms.
10. A composition as claimed in any one of claims 1 to 9 wherein component (b) is selected from 2-methyl isothiazolin-3-one, 5-chloro-2-methyl isothiazolin-3-one and 4,5 dichloro-2-methyl isothiazolin-3-one either alone or in combination.
11. A composition as claimed in any one of claLms 1 to 10 which comprises 2-methyl-4,5-trimethylene-4-isothiazolin-3-one together with at least one of 2-methyl isothiazolin-3-one, 5-chloro-2-methyl isothiazolin-3-one and 4,5-dichloro-2-methyl isothiazolin-3-one.
12. A composition as claimed in any one of claims 1 to 11 which contains from one part by weight of component (a) or of component (h) and correspondingly up to 1000 parts by weight of component (b) or of component (a).
13. A composition as claimed in claim 12 which contains at least one part by weight of one component, or mixture of components, and not more than 100 parts by weight of the other component or mixture of components.
14. A composition as claim in any one of claims 12 and 13 which contains between 1 and 10 parts which is component (a) and between 10 and 1 parts which is component (b).
15. A composition as claimed in any one of claims 12 to 14 which contains between 1 and 5 parts of component (a) and between 5 and 1 parts which is component (b).
16. A composition as claimed in any one of claims 1 to 15 wherein the sum of the fractional inhibitory concentration of the components is less than 0.7.
17. A composition as claimed in any one of claims 1 to 16 which additionally includes a carrier.
18. A medium which is susceptible to attack by micro-organisms and which contains from 0.00001 to 10% by weight of the medium of a composition us claimed in any one of claims 1 to 16.
19. A medium as claimed in claim 18 which contains from 0.00002 to 1% by weight of the medium of the composition.
20. A medium as claimed in either claim 18 or claim 19 which contains from 0.00002 to 0.01% by weight of the medium of the composition.
21. A medium as claimed in any one of claims 18 to 20 which is selected from a cooling water system, a paper mill liquor, a metal working fluid, a geological drilling lubricant, a polymer emulsion, a paint, a lacquer, a varnish, a hydrocarbon fluid, an adhesive, a dyestuff or ink formulation, an agrochemical formulation, leather or wood.
22. A paint medium as claimed in claim 21 which is an acrylic latex.
23. A method for inhibiting the growth of micro-organisms on, or in, a medium, which comprises treating the medium with a composition as claimed in any one of claims 1 to 17.
24. A method for inhibiting the growth of micro-organisms on, or in, a medium, which comprises treating the medium with component (a) and component (b) sequentially, wherein a) is at least one 4,5-polymethylene-4-isothiazolin-3-one or a derivative thereof, and b) is at least one isothiazolin-3-one which does not contain a fused ring attached to the isothiazoline ring.
25. A method as claimed in either claim 23 or claim 24 wherein the medium which is treated is a cooling water system, a paper mill liquor, a metal working fluid, a geological drilling lubricant, a polymer emulsion, a paint, a lacquer, a varnish, a hydrocarbon fluid, an adhesive, a dyestuff or ink formulation, an agrochemical formulation, leather or wood.
26. A composition as claimed in claim 1 and substantially as hereinbefore described with reference to the Example.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909009530A GB9009530D0 (en) | 1990-04-27 | 1990-04-27 | Composition and use |
| GB9009530.8 | 1990-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2041348A1 true CA2041348A1 (en) | 1991-10-28 |
Family
ID=10675120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2041348 Abandoned CA2041348A1 (en) | 1990-04-27 | 1991-04-26 | Composition and use |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2041348A1 (en) |
| GB (1) | GB9009530D0 (en) |
-
1990
- 1990-04-27 GB GB909009530A patent/GB9009530D0/en active Pending
-
1991
- 1991-04-26 CA CA 2041348 patent/CA2041348A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| GB9009530D0 (en) | 1990-06-20 |
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