DK151868B

DK151868B - PROCEDURE FOR COMBATING GROWTH OF BACTERIA AND ALGES IN WATER IN SWIMMING POOLS

Info

Publication number: DK151868B
Application number: DK704473A
Authority: DK
Inventors: Graham Carter; Anthony John Hinton
Original assignee: Ici Ltd
Priority date: 1973-12-21
Filing date: 1973-12-21
Publication date: 1988-01-11
Also published as: DK151868C; DK704473A

Description

iin

DK 151868 BDK 151868 B

Den foreliggende opfindelse angår en fremgangsmåde til bekæmp-ning af vækst af bakterier og alger i vand i svømmebassiner.The present invention relates to a method for controlling the growth of bacteria and algae in water in swimming pools.

Vandet i svømmebassiner recirkuleres til stadighed, og frisk vand tilsættes normalt kun for at opretholde det ønskede rum- 5 fang. Selv om vandet i reglen filtreres kontinuerligt for at holde det fri for suspenderet stof, bliver det til stadighed udsat for infektion med bakterier og alger, og behandling for at bekæmpe denne infektion er nødvendig af hygiejniske grun- 10 de*The water in swimming pools is constantly recycled, and fresh water is usually added only to maintain the desired volume. Although the water is usually filtered continuously to keep it free of suspended matter, it is constantly exposed to bacteria and algae infection, and treatment to combat this infection is required for hygienic reasons *

Det vigtigste desinfektionsmiddel, der anvendes i svømmebassiner i øjeblikket, er chlor, som er effektivt, men som lider af den ulempe, at det forårsager irritation af øjnene og endvidere må tilsættes hyppigt for at vedligeholde en effektiv i n koncentration.The most important disinfectant currently used in swimming pools is chlorine, which is effective, but suffers from the disadvantage of causing eye irritation and must be added frequently to maintain an effective concentration.

Ozoniseret luft er også blevet anvendt som desinfektionsmiddel, men her igen er hyppig eller kontinuerlig dosering nødvendig, og berøring med høje koncentrationer på det sted, hvor 20 den ozoniserede luft blæses ind i bassinet, er ubehagelig og kan forårsage hovedpine.Ozonized air has also been used as a disinfectant, but here again frequent or continuous dosing is required, and high concentration contact at the point where the ozonated air is blown into the basin is uncomfortable and can cause headaches.

Det har nu vist sig, at vækst af bakterier og alger i svømmebassiner kan bekæmpes i længere tid ved tilsætning af visse 25 biguanidforbindelser.It has now been found that bacteria and algae growth in swimming pools can be combated for a longer time by the addition of certain 25 biguanide compounds.

Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at der til vandet i en mængde, som giver en koncentration fra 1 til 200 ppm, sættes et lineært polymert biguanid eller et salt deraf, som i sin frie baseform har en gentagen polymer enhed 30 , , repræsenteret ved formlen -X-NH-C-NH-C-NH-Y-NH-C-NH-C-NH-The process according to the invention is characterized in that a linear polymeric biguanide or a salt thereof, which has a repeating polymeric unit 30, represented by a repeating polymer unit 30, is added to the water in an amount giving a concentration from 1 to 200 ppm. the formula -X-NH-C-NH-C-NH-Y-NH-C-NH-C-NH-

II «I ti IIII «I ti II

NH NH NH NHNH NH NH NH

3g hvor X og Y er brodannende grupper, hvori det samlede antal carbonatomer tilsammen, der er direkte indskudt mellem parrene af nitrogenatomer forbundne med X og Y, er mere end 9 og mindre end 17.3g where X and Y are bridging groups in which the total number of carbon atoms directly interposed between the pairs of nitrogen atoms linked to X and Y is more than 9 and less than 17.

22

DK 151868 BDK 151868 B

De brodannende grupper X og Y kan bestå af polymethylenkæder, der eventuelt er afbrudt af heteroatomer, f.eks. oxygen svovl eller nitrogen. X og Y kan også indeholde cykliske kerner, der kan være mættet eller umættet, i hvilket tilfælde antallet af 5 carbonatomer, der er direkte indskudt mellem parrene af nitrogenatomer, der er forbundne med X og Y, beregnes som indbefattende den del af den cykliske gruppe eller grupper, som er den korteste. Antallet af carbonatomer, der er direkte indskudt mellem nitrogenatomerne i gruppen 10The bridging groups X and Y may consist of polymethylene chains optionally interrupted by heteroatoms, e.g. oxygen sulfur or nitrogen. X and Y may also contain cyclic nuclei which may be saturated or unsaturated, in which case the number of 5 carbon atoms directly interposed between the pairs of nitrogen atoms linked to X and Y is calculated as including that portion of the cyclic group. or groups that are the shortest. The number of carbon atoms directly interposed between the nitrogen atoms in group 10

RR

-nh-ch2-o o-ch2-nh- 15 er således 4 og ikke 8.Thus, -nh-ch2-o o-ch2-nh-15 is 4 and not 8.

Det foretrukne polymere biguanid til brug ifølge opfindelsen er poly(hexamethylenbiguanid), hvori X og Y begge repræsenterer -{CH2)g-gruppen. Forbindelsen anvendes fortrinsvis i form 20 af sit hydrochloridsalt, der bekvemt anvendes som en 20% w/w vandig opløsning (dvs. 100 vægtdele af opløsningen indeholder 20 vægtdele af det aktive middel).The preferred polymeric biguanide for use in the invention is poly (hexamethylene biguanide) wherein X and Y both represent the - (CH 2) g group. The compound is preferably used in the form 20 of its hydrochloride salt, which is conveniently used as a 20% w / w aqueous solution (i.e., 100 parts by weight of the solution contains 20 parts by weight of the active agent).

Polymere biguanider kan fremstilles ved reaktion af et bisdi-25 cyandiamid med formlenPolymeric biguanides can be prepared by the reaction of a bisdiacyanamide of the formula

CN-NH-C-NH-X-NH-C-NH-CNCN-NH-C-NH-X-NH-C-NH-CN

ti titi ti

NH NHNH NH

med en diamin H2N-Y-NH2, hvor X og Y har den ovenfor anførte 30 betydning, eller ved reaktion mellem et diaminsalt af dicyan-imid med formlen + + (H3N-X-NH3)(N(CN)2)2 35 og en diamin H2N-Y-NH2, hvor X og Y har den ovenfor anførte betydning. Disse fremstillingsmetoder er beskrevet i de engelske patenter nr. 702.268 og 1.152.243, og ethvert af de polymere biguanider beskrevet deri kan anvendes ifølge opfindelsen .with a diamine H2N-Y-NH2 wherein X and Y are as defined above, or by reaction of a diamine salt of dicyanimide of formula + + (H3N-X-NH3) (N (CN) 2) and a diamine H2N-Y-NH2 wherein X and Y are as defined above. These methods of preparation are described in British Patents Nos. 702,268 and 1,152,243, and any of the polymeric biguanides disclosed therein may be used in accordance with the invention.

DK 151868 BDK 151868 B

33

De polymere kæder er afsluttet enten med en aminohydrochlorid-gruppe eller med en -NH-C-NH-CN-gruppe, og de afsluttende grup- itThe polymer chains are terminated either with an amino hydrochloride group or with a -NH-C-NH-CN group and the final group

NHNH

5 per kan være ens eller forskellige på hver polymer-kæde.5 per can be the same or different on each polymer chain.

En lille mængde af en primær amin R-NH2# hvor R repræsenterer en alkylgruppe indeholdende fra 1 til 18 carbonatomer, kan være indeholdt i diaminen H2N-Y-NH2 ved fremstillingen af polymere biguanider som ovenfor beskrevet. Den primære monoamin 50 virker som kædeafsluttende middel, og den ene eller begge enderne af de polymere biguanid polymerkæder kan derfor være afsluttet med en -NHR-gruppe. Brugen af disse kædeafsluttede polymere biguanider ligger også indenfor den foreliggende opfindelses rammer.A small amount of a primary amine R-NH 2 # wherein R represents an alkyl group containing from 1 to 18 carbon atoms may be contained in the diamine H2 N-Y-NH 2 in the preparation of polymeric biguanides as described above. The primary monoamine 50 acts as a chain terminating agent and therefore one or both ends of the polymeric biguanide polymer chains may be terminated by an -NHR group. The use of these chain-terminated polymeric biguanides is also within the scope of the present invention.

1515

Det vil forstås, at ved begge de ovenfor beskrevne fremgangsmåder fås de polymere biguanider som blandinger af polymere, hvori de polymere kæder har forskellige længder, idet antallet af enkelte biguanidenheder, dvs.It will be appreciated that in both of the methods described above, the polymeric biguanides are obtained as mixtures of polymers in which the polymeric chains have different lengths, the number of single biguanide units, i.e.

20 -X-NH-C-NH-C-NH--X-NH-C-NH-C-NH-

II IIII II

NH NHNH NH

og -Y-NH-C-NH-C-NH- .and -Y-NH-C-NH-C-NH-.

II ItII It

25 NH NH25 NH NH

tilsammen er fra 3 til ca. 80.the total is from 3 to approx. 80th

Hvor det drejer sig om det foretrukne poly(hexamethylenbigua-nid) med formlen 30 --(CH2)6-NH-C-NH-C-NH--In the case of the preferred poly (hexamethylene biguanide) of the formula 30 - (CH 2) 6-NH-C-NH-C-NH--

II IIII II

NH NHNH NH

n er værdien af n i intervallet fra 6 til 10, og gennemsnitsmo- 35 lekylvægten af den polymere blanding er fra ca. 1100 til ca. 1800,n is the value of n in the range of 6 to 10, and the average molecular weight of the polymeric mixture is from ca. 1100 to approx. 1800,

Det er kendt fra britisk patent nr. 702.268, at polymere biguanider har kraftige ant ibakterie11e og antifungale egenskaber.It is known from British Patent No. 702,268 that polymeric biguanides have potent anti-bacterial and anti-fungal properties.

44

DK 151868 BDK 151868 B

Det er imidlertid ikke kendt herfra, at forbindelserne har nogen virkning mod alger. Det er endvidere kendt fra britisk patent nr. 1.167.249, at de særlige biguanider, som dette patent angår, er nyttige som baktericider. De eksempler på or-5 ganismer, som patentet nævner, er enten bakterier eller svampe, og der er ingen omtale af alger. Overraskende har det vist sig, at en enkelt behandling af vandet i et svømmebassin med det polymere biguanid, således at der fås en koncentration i det ovenfor definerede interval, kan være effektiv til at be-10 kæmpe væksten af bakterier og alger i en hel sæsom på op til 9 måneder eller endog længere.However, it is not known from here that the compounds have any effect on algae. It is further known from British Patent No. 1,167,249 that the particular biguanides to which this patent relates are useful as bactericides. The examples of organisms mentioned by the patent are either bacteria or fungi and there is no mention of algae. Surprisingly, it has been found that a single treatment of the water in a pool with the polymeric biguanide, so as to obtain a concentration in the above defined range, can be effective in combating the growth of bacteria and algae in a whole season. up to 9 months or even longer.

Under normale omstændigheder har en koncentration på 10-12 dele pr. million af det polymere biguanidsalt vist sig at være 1δ effektiv, men det vil forstås, at det afhænger af antallet af personer, der anvender svømmebassinet, hvor længe en effektiv koncentration vedligeholdes. Gennem en periode på flere måneder kan et meget anvendt bassin kræve en anden eller endog en tredie dosering med det polymere biguanid for at opretholde koncentrationen på det ovenfor definerede effektive niveau. Koncentrationen skal fortrinsvis ikke være mindre end ca. 4 dele pr. million.Under normal circumstances, a concentration of 10-12 parts per million of the polymeric biguanide salt was found to be 1δ effective, but it will be understood that depending on the number of people using the swimming pool, how long an effective concentration is maintained. Over a period of several months, a widely used basin may require a second or even a third dosage of the polymeric biguanide to maintain the concentration at the effective level defined above. The concentration should preferably not be less than about. 4 parts per million.

Da Iangtidsbekæmpning af bakterievækst og algevækst i vand i svømmebassiner let opnås ifølge opfindelsen, undgås nødvendig- 2 5 heden af at skaffe kostbart anlæg til konstant afmåling af regulerede mængder af chlor i vandet. Det er blot nødvendigt at opløse det polymere biguanid i vandet og sikre en ensartet koncentration i det nævnte interval. I de meget lave koncentrationer, der har vist sig at være effektive, har de polymere 30 biguamder endvidere ingen irriterende virkning på øjnene og ingen uheldig lugt eller smag.Since long-term control of bacterial growth and algae growth in water in swimming pools is readily achieved according to the invention, the necessity of providing expensive systems for constant measurement of controlled amounts of chlorine in the water is avoided. It is only necessary to dissolve the polymeric biguanide in the water and ensure a uniform concentration during the said interval. Furthermore, at the very low concentrations that have been shown to be effective, the polymeric 30 bigamids have no irritating effect on the eyes and no unpleasant odor or taste.

Opfindelsen illustreres af følgende eksempler, hvori delene og procenterne er efter vægt, medmindre andet er anført.The invention is illustrated by the following examples in which the parts and percentages are by weight, unless otherwise stated.

3535

Eksempel 1 5Example 1 5

DK 151868BDK 151868B

Et udendørs svømmebassin med et overf ladeareal på 50 m2 og en kapacitet på 61.000 liter blev behandlet med poly(hexamethy-5 lenbiguanid)hydrochlorid i form af en 20% w/w vandig opløsning, således at der fremkom en koncentration i vandet på 10 dele pr. million dele af den aktive bestanddel. Et forsøg blev udført i løbet af 12 måneder fra september til den følgende september. Iagttagelser for at spore algevækst og bestemmelser 1Q af visse patogene bakterier blev udført fra maj til september, i hvilket tidsrum bassinet blev anvendt af 237 personer. Vandets temperatur varierede fra 21 til 27eC. I midten af juni var mængden af polymer biguanid i vandet faldet til 2 dele pr. million dele, og en anden dosering på 8 dele pr. million 15 dele blev tilføjet for at bringe koncentrationen op på det oprindelige niveau af 10 dele pr. million dele.An outdoor swimming pool with a surface area of 50 m2 and a capacity of 61,000 liters was treated with poly (hexamethylene biguanide) hydrochloride in the form of a 20% w / w aqueous solution, resulting in a concentration of 10 parts in the water. per. million parts of the active ingredient. A trial was conducted over 12 months from September to the following September. Observations to track algae growth and determinations 1Q of certain pathogenic bacteria were conducted from May to September, during which time the basin was used by 237 individuals. The temperature of the water ranged from 21 to 27 ° C. By mid-June, the amount of polymer biguanide in the water had dropped to 2 parts per second. million and another dosage of 8 parts per million 15 parts were added to bring the concentration to the original level of 10 parts per million parts.

Under forsøgets forløb blev ikke iagttaget nogen algevækst, og der blev ikke sporet nogen koliforme bakterier (herunder E.During the course of the experiment, no algae growth was observed and no coliform bacteria (including E.

C o 1 i) eller stafylokokker (herunder Staph, aureus) i 100 ml ? o vand, som blev udtaget som prøve ugentlig.C o 1 i) or staphylococci (including Staph, aureus) in 100 ml? o water sampled weekly.

Ovenstående resultater viser, at en koncentration på 10 dele pr. million dele af poly(hexamethylenbiguanid)hydrochlorid tilfredssti Ilende bekæmpede formeringen af alger og visse 25 bakterielle patogener i forsøgsperioden.The above results show that a concentration of 10 parts per million parts of poly (hexamethylene biguanide) hydrochloride satisfactorily The misery fought the propagation of algae and certain 25 bacterial pathogens during the experimental period.

Eksempel 2Example 2

Et indendørs svømmebassin med et overfladeareal på 50 m2 og en kapacitet på 68.000 liter blev behandlet med po!y(hexamethy- 3 0 * lenbiguanid)hydrochlorid i form af en 20% w/w vandig opløsning til dannelse af en koncentration i vandet på 10 dele pr. million dele af den aktive bestanddel.An indoor swimming pool with a surface area of 50 m2 and a capacity of 68,000 liters was treated with poly (hexamethylene-30 * biguanide) hydrochloride in the form of a 20% w / w aqueous solution to give a water concentration of 10 parts per million parts of the active ingredient.

Et forsøg blev udført i en periode på 3 måneder fra maj til 35 august, hvorunder vandets temperatur varierede fra 17 til 28°C, og bassinet blev anvendt af 420 personer. Under forsøget blev ikke iagttaget nogen algevækst, og der blev ikke sporet nogen koliforme bakterier (herunder E. coli) eller stafylokokker (herunder Staph, aureus).An experiment was conducted for a period of 3 months from May to August 35, during which the water temperature ranged from 17 to 28 ° C and the basin was used by 420 people. No algae growth was observed during the experiment and no coliform bacteria (including E. coli) or staphylococci (including Staph, aureus) were detected.

66

DK 151868BDK 151868B

Laboratorieafprøvning af antibakteriel virkning og virkning mod alger 1) Sammenligning i laboratoriet af antialgevirkningen af poly-5 (hexamethylenbiguanid)hydrochlorid med andre biocider.Laboratory testing of antibacterial and anti-algae activity 1) Comparison in the laboratory of the anti-aliasing effect of poly-5 (hexamethylene biguanide) hydrochloride with other biocides.

Der blev fremstillet et podemateriale, som bestod af en blandet kultur af alger fra et køletårnsslim i et medium af uorganiske salte med følgende sammensætning (g/1): ammoniumnitrat 3, dikaliumhydrogenphosphat 1, kaliumchlorid 0,25.An inoculum was prepared which consisted of a mixed culture of algae from a cooling tower slime in a medium of inorganic salts of the following composition (g / 1): ammonium nitrate 3, dipotassium hydrogen phosphate 1, potassium chloride 0.25.

1010

Poly(hexamethylenbiguanid)hydrochlorid blev sammenlignet med et kvaternart ammoniumbiocid (lauryldimethylbenzylammonium-chlorid) med 1,2-benzisothiazolin-3-on og med methylenbisthio-cyanat. Ovennævnte biocider blev sat til 100 ml medium af uor-15 ganiske salte i Petri skåle til dannelse af følgende koncentrationer (som aktiv bestanddel): 1, 5, 10, 50 og 100 dele pr. million dele. 1 ml af algepodematerialet blev sat til hver af Petri skålene, og disse blev inkuberet ved stuetemperatur (ca. 20°C) i 2 uger under konstant kunstig belysning. Petri skålene 20 blev så undersøgt for algevækst, hvorefter hver variant fik et andet algepodemateriale, før den blev inkuberet i en periode på yderligere 4 uger. Tilstedeværelsen eller fraværelsen af algevækst blev til slut opnoteret som følger: 2t. Minimal hæmningskoncentration (p.p.m. aktiv bestanddel) efter: Biocid 2 uger 6 ugerPoly (hexamethylene biguanide) hydrochloride was compared with a quaternary ammonium biocide (lauryldimethylbenzylammonium chloride) with 1,2-benzisothiazolin-3-one and with methylene bisthiocyanate. The above biocides were added to 100 ml of medium of inorganic salts in Petri dishes to give the following concentrations (as active ingredient): 1, 5, 10, 50 and 100 parts per ml. million parts. 1 ml of the algae seed material was added to each of the Petri dishes, and these were incubated at room temperature (about 20 ° C) for 2 weeks under constant artificial lighting. The Petri dishes 20 were then examined for algae growth, after which each variant received a different algae seed material before being incubated for a further 4 weeks. The presence or absence of algae growth was finally recorded as follows: 2h. Minimum inhibitory concentration (active ingredient) after: Biocide 2 weeks 6 weeks

Poly(hexamethylenbigua- nid)hydrochlorid 1 5 30 Kvaternært ammoniumbiocid 1 5 1,2-benzisothiazolin-3-on 50 100 methylenbisthiocyanat 50 100Poly (hexamethylene biguanide) hydrochloride 1 5 30 Quaternary ammonium biocide 1 5 1,2-benzisothiazolin-3-one 50 100 methylene bisthiocyanate 50 100

Poly(hexamethylenbiguanid)hydrochlorid og det kvaternære ammoniumbiocid er derfor tilnærmelsesvis ækvivalent og meget mere 35 effektive til undertrykkelse af algevækst end de øvrige to biocider. Det kvaternære ammoniumbiocid er imidlertid ikke egnet til brug i svømmebassiner, fordi det er stærkt overfladeaktivt og forårsager skumning.Poly (hexamethylene biguanide) hydrochloride and the quaternary ammonium biocide are therefore approximately equivalent and much more effective in suppressing algae growth than the other two biocides. However, the quaternary ammonium biocide is not suitable for use in swimming pools because it is highly surfactant and causes foaming.

77

DK 15186 8 BDK 15186 8 B

2. Et polymert biguanid blev fremstillet ved reaktion af hexa-methylendiaminsaltet af dicyanimid med 4,41-diaminodicyklohe-xylmethanhydrochlorid på den måde, der er beskrevet i det engelske patent nr. 1.152.243.2. A polymeric biguanide was prepared by reaction of the hexa-methylenediamine salt of dicyanimide with 4,41-diaminodicyclohexylmethane hydrochloride in the manner described in British Patent No. 1,152,243.

55

Dette materiale blev afprøvet for antibakteriel virkning i laboratoriet på følgende måde:This material was tested for antibacterial action in the laboratory as follows:

En 1 ml suspension af en natgammel kultur af E. coli blev overført til en portion på 10 ml af den biocide opløsning.A 1 ml suspension of a night-old culture of E. coli was transferred to a 10 ml aliquot of the biocidal solution.

1 o * Efter en berøringstid på 3 minutter blev 1 ml af opløsningen overført til 10 ml af en "AntrypoV'-opløsning. "Antrypol" har strukturformlen 15 r—*~C0M—y— S03Wa /j—rc-COMH -/ \ Γ\ CO--NH / ^==/«a05S—^ \After a touch time of 3 minutes, 1 ml of the solution was transferred to 10 ml of an "AntrypoV 'solution." Antrypol "has the structural formula 15 r - * ~ C0M-y— S03Wa / j-rc-COMH - / \ CO \ CO - NH / ^ == / «a05S— ^ \

SsO-JIa 20 ' 3· hvorved biocidet neutraliseres. De overlevende bakterieceller bestemmes så ved fortyndindstællemetoden.SsO-JIa 20 '3 · whereby the biocide is neutralized. The surviving bacterial cells are then determined by the dilute counting method.

2 52 5

Der fremkom følgende resultater, idet forsøget blev udført dobbelt (poly(hexamethylenbiguanid)hydrochlorid blev også afprøvet til sammenligning).The following results were obtained as the experiment was carried out double (poly (hexamethylene biguanide) hydrochloride was also tested for comparison).

30 35 830 35 8

DK 151868BDK 151868B

Overlevende (celler/ml) efter 3 minutters berøringstidSurvivors (cells / ml) after 3 minutes of touch time

Behandl i na l 2Treat in na l 2

Poly(hexamethy1enbiguanid)- 5 hydrochlorid, 200 p.p.m. 2,2 x 103 2,0 x 103Poly (hexamethylene biguanide) - hydrochloride, 200 p.p.m. 2.2 x 103 2.0 x 103

Poly(hexamethylen/dicyklo-hexylmethanbi guanid)- hydrochlorid, 200 p.p.m. <10 <10Poly (hexamethylene / dicyclohexylmethane bi guanide) hydrochloride, 200 p.p.m. <10 <10

Kontrol (intet biocid) 4,3 x 108 3,7 x 108 10Control (no biocide) 4.3 x 108 3.7 x 108 10

Det vil således ses af ovenstående, at poly(hexamethylen/di-cyklohexylmethanbiguanid)hydrochlorid er endnu mere effektivt end poly(hexamethylenbiguanid)hydrochlorid som baktericid. Forbindelsen er også en effektiv inhibitor for algevækst. Det oprindelige tal på <108 celler/ml ved denne prøve er naturligvis langt større end nogen tænkelig koncentration i vand i svømmebassin, hvor 500 eller flere celler/ml ville blive betragtet som en uønsket forureningsgrad, og reduktionen af bak-terietallet med en faktor på 108, hvor det drejer sig om poly-20 (hexamethylenbiguanid)hydrochlorid, og en næsten fuldstændig dræbning i tilfældet med poly(hexamethylen/dicyklohexylméthan-biguanid)hydrochloridkoncentrationer på 200 dele pr. million dele på kun 3 minutter illustrerer, hvor effektive disse forbindelser er som baktericider.Thus, it will be seen from the above that poly (hexamethylene / di-cyclohexylmethane biguanide) hydrochloride is even more effective than poly (hexamethylene biguanide) hydrochloride as a bactericide. The compound is also an effective inhibitor of algae growth. The initial figure of <108 cells / ml in this sample is, of course, far greater than any conceivable concentration in swimming pool water, where 500 or more cells / ml would be considered an undesirable degree of pollution, and the reduction of the bacterial number by a factor of 108, in the case of poly-20 (hexamethylene biguanide) hydrochloride, and a near complete killing in the case of poly (hexamethylene / dicyclohexylmethane-biguanide) hydrochloride concentrations of 200 parts per million. million parts in just 3 minutes illustrates how effective these compounds are as bactericides.

2R2R

3. Et poly(hexamethylenbiguanid)hydroch1orid med endestillet hexadecyl blev fremstillet ved reaktion af hexamethylensaltet af dicyanimid med en blanding af hexamethylendiaminhydrochlo-rid og hexadecylaminhydrochlorid på den måde, der er beskrevet i engelsk patent nr. 1.152.243. Hexamethylendiaminhydrochlo- 3 0 ridet og hexadecylaminhydrochloridet blev anvendt i det molære forhold 90:10.3. A poly (hexamethylene biguanide) hydrochloride with terminal hexadecyl was prepared by reacting the hexamethylene salt of dicyanimide with a mixture of hexamethylenediamine hydrochloride and hexadecylamine hydrochloride in the manner described in English Patent No. 1,152,243. The hexamethylenediamine hydrochloride and the hexadecylamine hydrochloride were used in the 90:10 molar ratio.

Dette materiale med endestillet alkyl blev afprøvet for anti-bakteriel virkning i laboratoriet på den ovenfor under 3) be-35 skrevne fremgangsmåde.This terminated alkyl material was tested for anti-bacterial action in the laboratory in the method described above.

Der fremkom følgende resultater, idet der igen er anvendt poly (hexamethylenbiguanid)hydrochlorid som sammenligning: 9The following results were obtained, again using poly (hexamethylene biguanide) hydrochloride for comparison: 9

DK 151868BDK 151868B

Overlevende celler efter 3 minutters berøringstidSurviving cells after 3 minutes of touch time

Behandling _(celler/ml)_Treatment _ (cells / ml) _

Poly(hexamethylenbiguanid) 200 ppm 104 5 hydrochlorid med endestillet 100 ppm 105 hexadecyl 50 ppm 10$Poly (hexamethylene biguanide) 200 ppm 104 hydrochloride with terminal 100 ppm 105 hexadecyl 50 ppm 10 $

Poly(hexamethylenbiguanid) 200 ppm lol hydrochlorid 100 ppm 103 50 ppm 103Poly (hexamethylene biguanide) 200 ppm lol hydrochloride 100 ppm 103 50 ppm 103

Kontrol (intet biocid) - 108Control (no biocide) - 108

Hexadecylforbindelsen ses at være noget mindre effektiv som baktericid end poly(hexamethylenbiguanid)hydrochlorid, men 15 virkningen af begge materialer er meget tilfredsstillende udtrykt ved reduktionen i antallet af celler, der overlever efter kun 3 minutters berøring med den oprindelige massive koncentration af E. coli bakterier. Materialet med endestillet hexadecyl blev også afprøvet for virkning mod alger ved føl- 20 gende metode:The hexadecyl compound is seen to be somewhat less effective as a bactericide than poly (hexamethylene biguanide) hydrochloride, but the effect of both materials is very satisfactorily expressed by the reduction in the number of cells surviving after only 3 minutes of contact with the initial massive concentration of E. coli bacteria. . The final hexadecyl material was also tested for action against algae by the following method:

En suspension af en blandet kultur af alger isoleret fra et industrielt køletårn blev overført til opløsninger af forsøgsbiocidet i destilleret vand i koncentrationer på 10, 25, 50 og oc. 100 dele pr. million dele i en berøringsperiode på 7 dage.A suspension of a mixed culture of algae isolated from an industrial cooling tower was transferred to solutions of the test biocide in distilled water at concentrations of 10, 25, 50 and oc. 100 parts per million parts in a 7 day touch period.

ww

Efter denne tid blev opløsningerne indeholdende algerne filtreret gennem en mi 11iporemembran. Membranen med de indesluttede alger blev overført til et algevækstmedium (mineralsalte og jordbundsekstrakt) og inkuberet under kunstigt lys i 7 30 dage. Membranen blev så undersøgt for tilstedeværelse eller fraværelse af udvikling af grønfarvning. En grøn farve viser, at biocidet ikke dræber algepodematerialet i den anvendte koncentration, hvorimod mangel på farve viser, at biocidet faktisk dræber algepodematerialet.After this time, the solutions containing the algae were filtered through an 11-pore membrane. The membrane with the enclosed algae was transferred to an algae growth medium (mineral salts and soil extract) and incubated under artificial light for 7 30 days. The membrane was then examined for the presence or absence of green dye development. A green color indicates that the biocide does not kill the algal graft material at the concentration used, whereas a lack of color indicates that the biocide actually kills the algal graft material.

3 53 5

De fremkomne resultater er følgende:The results obtained are as follows:

Claims

20 The conditions prevailing in this test are far stricter than those that would occur in water in a swimming pool, due to the massive initial concentration of algae. A much lower concentration (i.e., 4-12 ppm) of a polymeric biguanide is effective under actual conditions in swimming pools to combat algae. 4. a further laboratory experiment showed that with a concentration of 10 parts per million of poly (hexamethylene biguanide) hydrochloride became an initial number of 105 bacterial cells per 3Q ml (E. coli or Staph, faecalis) reduced to zero after 30 seconds of touch time. This bacterial concentration is much higher than one would find in water in a swimming pool. Claims.

A method for controlling the growth of bacteria and algae in water in swimming pools, characterized in that a linear polymeric biguanide or a salt thereof is added to the water in an amount giving a concentration of 1 200 ppm. which in its free base form has a repeating polymeric unit represented by the formula K-X-NH-C-NH-C-NH-Y-NH-C-NH-C-NH- w II II II II NH NH NH NH where X and Y represents bridging groups in which the total number of carbon atoms together directly interposed between the pairs of nitrogen atoms linked to X and Y is more than 10 and less than 17.

Process according to claim 1, characterized in that the polymeric chains of the polymeric biguanide are terminated at one or both ends of the group -NHR, wherein R represents an alkyl group containing from 1 to 18 carbon atoms.

Process according to claim 1 or 2, characterized in that the polymeric biguanide is poly (hexamethylene biguanide) hydrochloride.

Process according to claim 3, characterized in that the average molecular weight of the poly (hexamethylene biguanide) hydrochloride is from 1100 to 1800.

Process according to claims 1-4, characterized in that the polymeric biguanide or salt thereof is used in an amount giving a concentration of from 4 to 12 ppm. 3 0 35