DK152324B - GERMICID MEDICINE BASED ON STABILIZED H202 AND APPLICATION - Google Patents
GERMICID MEDICINE BASED ON STABILIZED H202 AND APPLICATION Download PDFInfo
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- DK152324B DK152324B DK287377A DK287377A DK152324B DK 152324 B DK152324 B DK 152324B DK 287377 A DK287377 A DK 287377A DK 287377 A DK287377 A DK 287377A DK 152324 B DK152324 B DK 152324B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Description
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Den foreliggende opfindelse angår et germicidt middel på basis af stabiliseret til anvendelse til cir kuleret industribrugsvand og vandige systemer i papirfabrikker, hvor der fremstilles pakningsmateriale til pak-5 ning af næringsmidler. Opfindelsen angår også anvendelsen af dette germicide middel i en koncentration, der svarer til 0,01-2 ml af en 35%'s vandig E^i^-opløsning pr. liter af det medium, der .skal behandles.'The present invention relates to a stabilized germicidal agent for use in circulated industrial water and aqueous systems in paper mills, where packing material is prepared for packing foodstuffs. The invention also relates to the use of this germicidal agent at a concentration corresponding to 0.01-2 ml of a 35% aqueous E liters of the medium to be treated. '
Vand, som indtil for nylig altid har været et i 10 overflod tilstedeværende og billigt naturstof, er mere og mere - navnlig for industriens vedkommende - blevet til et værdifuldt og dyrt "driftsmateriale", som ikke længere står til rådighed i vilkårlig mængde. I nogen tid har man derfor såvel på det kommunale område som i industrien be-15 stræbt sig på at begrænse forbruget af friskvand i videst muligt omfang og således rense og genanvende brugsvandet og altså - eventuelt under indskydning af ét eller flere regenereringstrin - føre vandet i kredsløb. Typiske eksempler herpå er kølevandskredsløb i de forskellige indu-20 strigrene og cirkulationsanlæg i badeanstalter.Water, which until recently has always been one of 10 abundant and inexpensive natural substances, has increasingly - especially for industry - become a valuable and expensive "operating material" which is no longer available in any quantity. For some time, therefore, efforts have been made in both the municipal and industrial sectors to limit the consumption of fresh water to the greatest extent possible and thus purify and recycle the used water and thus - possibly during the pushing of one or more regeneration steps - to carry the water into orbit. Typical examples of this are cooling water circuits in the various inductors and circulation systems in bathing facilities.
Som eksempel kan nævnes de lukkede kredsløbssystemer i papirfabrikker, hvor det mekanisk, f.eks. ved filtrering eller presning fraskilte vand anvendes på ny. Det brugsvand, der føres i kredsløb, beriges i almindelighed 25 med forureninger, som udgør næringsstoffer for mikroorganismer af forskellige arter. Netop ved papirfabrikker udgør den i det frafiltrerede eller afpressede vand tilstedeværende cellulose et særdeles godt næringssubstrat for alger, svampe og andre mikroorganismer, hvis adgang, også 30 til lukkede brugsvandsystemer, næppe kan forhindres. Denne mikroorganismeflora ytrer sig ved dannelsen af slim eller ved fremkomsten af skimmelkulturer, som på forskellige steder i kredsløbssystemet kan give anledning til betydelige afbræk eller forstyrrelser.As an example, the closed circuit systems in paper mills where it is mechanically, e.g. By filtration or pressing, separated water is reused. The circulating tap water is generally enriched with contaminants which are nutrients for microorganisms of various species. Precisely in paper mills, the cellulose present in the filtered or extruded water constitutes a very good nutrient substrate for algae, fungi and other microorganisms whose access, including 30 to closed domestic water systems, can hardly be prevented. This microorganism flora manifests itself in the formation of mucus or in the emergence of mold cultures, which at different places in the circulatory system can give rise to significant disruptions or disturbances.
35 Det er kendt, at man i videst muligt omfang kan 235 It is known that you can as far as possible 2
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hindre opræden af mikroorganismer i vand og vandafløb af enhver art ved tilsætning af et egnet germicidt middel.prevent the creation of microorganisms in water and water drains of any kind by the addition of a suitable germicidal agent.
Det er også kendt hertil at anvende sådanne germicider, der er virksomme uden at efterlade følgeprodukter, eller 5 i alt fald uden at efterlade stoffer med generende eller endog toksiske eller korrosionsfremmende egenskaber.It is also known to use such germicides which are effective without leaving follow-on products, or at least without leaving substances with both a nuisance or even toxic or corrosion-promoting properties.
Et sådant kendt germicid, som uden dannelse af nogen form for remanenser forbruges fuldstændigt, er hydro-genperoxid, der sønderdeles til oxygen og vand. Hydrogen-10 peroxid er ikke blot baktericidt, desodoriserende, oxiderende og antiphlogistisk virksomt, men også fungistatisk og fungicidt virksomt, jfr. f.eks. Dermatologische Wochen-schrift, 152, 1105 (1966).One such known germicide which is completely consumed without the formation of any residue is hydrogen peroxide which decomposes to oxygen and water. Hydrogen peroxide is not only bactericidal, deodorizing, oxidizing and antiphlogistically active, but also fungistatic and fungicidal, cf. eg. Dermatological Weeks Journal, 152, 1105 (1966).
Hydrogenperoxid er imidlertid ikke universelt anven-15 deligt som germicidt middel og navnlig ikke egnet til kontinuerlig behandling af bestemte former for brugsvand, eftersom forskellige mikroorganismer i løbet af forholdsvis kort tid er i stand til at danne resistente stammer, som ikke længere angribes af hydrogenperoxid.However, hydrogen peroxide is not universally useful as a germicidal agent and is not particularly suitable for the continuous treatment of certain types of domestic water, since in a relatively short time various microorganisms are able to form resistant strains which are no longer attacked by hydrogen peroxide.
20 Fra DE-offentliggørelsesskrift nr. 2.228.011 kendes der en biologisk rensningsmetode, ved hvilken spildevandet behandles med Ή.2®2' ^er dækker det for den samlede aerob--bakterielle rensning nødvendige oxygenbehov og samtidig hindrer udviklingen af tråddannede bakterier. Her udnyt-25 tes altså netop ^0^s selektive virkning, på basis af hvilken bestemte mikroorganismer dræbes totalt, idet dog samtidig vækstbetingelserne for andre mikroorganismer optimeres .20 From DE Publication No. 2,228,011, a biological purification method is known, in which the wastewater is treated with Ή.2®2 '^ which covers the oxygen demand necessary for the total aerobic-bacterial purification and at the same time prevents the development of filamentous bacteria. Thus, the selective effect of ^ 0 0 is utilized here, on the basis of which certain microorganisms are totally killed, while at the same time optimizing the growth conditions for other microorganisms.
For at holde vandige systemer fuldstændigt mikro-30 organismefri er det således også allerede blevet foreslået at anvende hydrogenperoxid sammen med organiske forbindelser som germicidt middel. Fra DE-offentliggørelsesskrift nr. 2.221.047 kendes der f.eks. en fremgangsmåde til fremstilling af en rense- og steriliseringsopløsning til en 35 blød kontaktlinse, ved hvilken fremgangsmåde hydrogenper-Thus, in order to keep aqueous systems completely microorganism-free, it has also already been proposed to use hydrogen peroxide with organic compounds as germicidal agent. From DE-Publication No. 2,221,047, for example, a process for preparing a cleaning and sterilizing solution for a soft contact lens, wherein
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oxidet eller vandopløselige, ikke-toksiske peroxider sammen med phenylkviksølv(II)salte, især. sammen med natrium-ethylmercurithiosalicylat, anvendes i form af en vandig isotonisk opløsning. Heller ikke dette kendte middel er 5 universelt anvendeligt, især på grund af toksiciteten af kviksølvet, der ikke blot forbyder anvendelsen af et sådant middel i badeanstalter og lignende, men også i industrien, f.eks. i papirindustrien, når papiret er bestemt til indpakning af levnedsmidler, eller i den farmaceuti-10 ske industri, eller på andre områder, hvor der f.eks. ved brud på kredsløbssystemet er mulighed for, at materialer, der er bestemt til forbrug eller brug af mennesker, kommer i berøring med toksiske stoffer.the oxide or water-soluble, non-toxic peroxides together with phenyl mercury (II) salts, in particular. together with sodium ethyl mercurithiosalicylate, is used in the form of an aqueous isotonic solution. Nor is this known agent universally applicable, especially because of the toxicity of the mercury, which prohibits not only the use of such an agent in bathing establishments and the like, but also in industry, e.g. in the paper industry, when the paper is intended for food packaging, or in the pharmaceutical industry, or in other areas where e.g. In case of a breach of the circulatory system, it is possible for materials intended for human consumption or use to come into contact with toxic substances.
Der foreligger altså et behov for et yderligere 15 germicidt middel, som udviser et bredere virkningsspektrum end det, som hydrogenperoxid alene udviser.Thus, there is a need for an additional 15 germicidal agent which exhibits a broader spectrum of action than that of hydrogen peroxide alone.
Formålet med opfindelsen er at opfylde dette behov og at tilvejebringe et germicidt middel til vandige systemer på basis af hvilket middel er universelt anven- 20 deligt, virksomt dræber mikroorganismer af alle arter, ikke efterlader nogen generende eller korrosionsfremkaldende følgeprodukter og hverken selv er toksisk eller frembringer toksiske sønderdelingsprodukter.The object of the invention is to meet this need and to provide a germicidal agent for aqueous systems on the basis of which it is universally applicable, effectively kills microorganisms of all species, leaves no nuisance or corrosion-inducing by-products, and is neither toxic nor self-producing. toxic decomposition products.
Dette formål opnås ifølge opfindelsen ved hjælp af 25 .et germicidt middel af den allerede omtalte art, hvilket middel er ejendommeligt ved, at det indeholder 0,1-5 vægt% p-hydroxybenzoesyre eller et af dens salte eller en alkyl-ester deraf med 1-4 carbonatomer og/eller mindst én med H2O2 ikke under sønderdeling reagerende nitrogen-hetero-30 cyclisk aromatisk forbindelse med mindst én hydroxy- og/-eller mindst én carboxygruppe eller salte eller alkyleste-re deraf med 1-4 carbonatomer og/eller en amidosulfonsyre med den almene formel I^NSOgH, i hvilken R betyder hydrogen eller en alkylgruppe med 1-6 carbonatomer, eller et 35 salt deraf, som synergistisk virksomt stof eller synergi-This object is achieved according to the invention by means of a germicidal agent of the kind already mentioned, which is characterized in that it contains 0.1-5% by weight of p-hydroxybenzoic acid or one of its salts or an alkyl ester thereof with 1-4 carbon atoms and / or at least one with H 2 O 2 not decomposing nitrogen heterocyclic aromatic compound with at least one hydroxy and / or at least one carboxy group or salts or alkyl esters thereof with 1-4 carbon atoms and / or an amidosulfonic acid of the general formula I NSOgH in which R is hydrogen or an alkyl group of 1-6 carbon atoms, or a salt thereof, as a synergistically active substance or
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stisk virksom blanding af stoffer, samt eventuelt en korrosionsinhibitor .a highly active mixture of substances, and possibly a corrosion inhibitor.
Det har overraskende vist sig, at midlet ifølge opfindelsen udviser en synergistisk effekt, dvs. at virk-5 ningen af komponenterne hydrogenperoxid og aromatisk forbindelse og/eller amidosulfonsyre tilsammen er væsentligt kraftigere end den rent additive virkning af komponenterne ved i øvrigt samme sammensætning. En ved den praktiske anvendelse væsentlig fordel ved det her omhandlede middel 10 består i, at stabiliteten af hydrogenperoxidet ikke generes af det germicidt virksomme tilsætningsstof eller de germicidt virksomme tilsætningsstoffer, således at germi-cidets opbevaringsstabilitet og dermed dets økonomiske anvendelse ikke påvirkes i uønsket retning. En yderligere 15 væsen.tlig fordel ved midlet ifølge opfindelsen består i, at de efter vandbehandlingen tilbageblivende stoffer, som ikke således som hydrogenperoxidet selv forbruges fuldstændigt ved kemisk reaktion, praktisk taget ikke udviser nogen for den menneskelige organisme betænkelige egenska-20 ber. Dette er især vigtigt ved anvendelsen af midlet f.eks. til desinfektion af vand fra svømmebassiner eller - på det industrielle område - ved anvendelsen i papirfabrikker, hvor der fremstilles materialer til indpakning af levnedsmidler. De sammen med som synergistisk virksomme stof- 25 fer anvendelige p-hydroxybenzoesyre-ethylestere og -propyl-estere er således fysiologisk set fuldstændigt risikofri og er derfor også under betegnelsen "PHB-estere" tilladt som konserveringsstoffer til lévnedsmidler.Surprisingly, it has been found that the agent according to the invention exhibits a synergistic effect, ie. that the action of the components hydrogen peroxide and aromatic compound and / or amidosulfonic acid together is substantially more powerful than the purely additive effect of the components in otherwise the same composition. An important advantage of the present invention in the practical application of the present invention 10 is that the stability of the hydrogen peroxide is not disturbed by the germicidal active additive or the germicidal active additives, so that the storage stability of the germicide and thus its economic use is not adversely affected. A further substantial advantage of the agent according to the invention consists in the fact that the residual substances after the water treatment, which, such as the hydrogen peroxide itself, are not completely consumed by chemical reaction, have practically no properties contemplated by the human organism. This is especially important when using the agent e.g. for the disinfection of water from swimming pools or - in the industrial area - when used in paper mills where food packaging materials are manufactured. Thus, the p-hydroxybenzoic acid esters and propyl esters useful as synergistically active substances are physiologically completely completely risk-free and are therefore also permitted under the term "PHB esters" as preservatives for foodstuffs.
En foretrukken udføreisesfom for midlet ifølge 30 opfindelsen består i, at det indeholder det eller de synergistisk virksomme stoffer i fom af vandige, eventuelt mineralsure opløsninger. Tilsætningen af en ringe mængde af en mineralsyre har den fordel, at et eventuelt indhold af virksomt stof med forholdsvis ringe opløselighed i vand 35 uden videre kan bringes i opløsning.A preferred embodiment of the agent according to the invention consists in containing the synergistically active substance (s) in the form of aqueous, optionally mineral acid solutions. The addition of a small amount of a mineral acid has the advantage that any content of active substance with relatively poor solubility in water 35 can be dissolved without delay.
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Yderligere fordelagtige udførelsesformer for det her omhandlede middel består i, at det som aromatisk ni-trogen-heterocyclisk forbindelse indeholder en sådan med kun ét ringnitrogenatom, og at det som aromatisk nitro-5 gen-heterocyclisk forbindelse indeholder en hydroxyquino-lin og/eller en pyridindicarboxylsyre.Further advantageous embodiments of the present invention are that it contains as an aromatic nitrogen heterocyclic compound having only one ring nitrogen atom and that as an aromatic nitrogen 5 heterocyclic compound contains a hydroxyquinoline and / or a pyridinedicarboxylic.
Foretrukne er sådanne germicide midler, der som aromatisk nitrogenholdig forbindelse indeholder 8-hydroxy-quinolin og/eller dipicolinsyre.Preferred are such germicidal agents which, as an aromatic nitrogen-containing compound, contain 8-hydroxyquinoline and / or dipicolinic acid.
10 Det germicide middel ifølge opfindelsen indeholder hydrogenperoxid fortrinsvis i form af en i handelen sædvanlig, vandig og stabiliseret opløsning. De gængse -stabiliseringsmidler, f.eks. natriumpyrophosphat, har ingen skadelig indflydelse på hverken den synergistiske 15 effekt eller på egenskaberne af de enkelte i det omhandlede middel indeholdte bestanddele.The germicidal agent of the invention preferably contains hydrogen peroxide in the form of a commercially available, aqueous and stabilized solution. The usual stabilizers, e.g. sodium pyrophosphate, has no detrimental effect on either the synergistic effect or on the properties of the individual components contained in the subject matter.
Det allerede omtalte formål opnås endvidere ved anvendelse af det her omhandlede germicide middel i en koncentration, der svarer til 0,01 til 2 ml af en 35%'s 20 vandig H202-opløsning pr. liter af det medium, der skal behandles.The object already mentioned is further achieved by using the germicidal agent in question at a concentration corresponding to 0.01 to 2 ml of a 35% 20 aqueous H2 O2 solution per ml. liters of the medium to be treated.
Til det omhandlede germicide middel kan der om ønsket sættes en korrosionsinhibitor, f.eks. ammoniumnitrat, når der i ledningssystemet forefindes korrosions-25 tilbøjelige eller for korrosion udsatte dele såsom arma turer, pumper og forbindelsesstykker af enhver art, uden at der hervéd sker nogen forringelse af den synergistiske effekt mellem hydrogenperoxidet og den organiske forbindelse.To the germicidal agent, a corrosion inhibitor, e.g. ammonium nitrate when there are corrosion-prone or corrosion-prone parts such as fittings, pumps and connectors of any kind in the piping system, without impairing the synergistic effect between the hydrogen peroxide and the organic compound.
30 Tilsætningen af midlet ifølge opfindelsen til det vandige medium, der skal gøres mikroorganismefrit, sker ved hjælp af gængse apparaturer, f.eks. ved hjælp af kontinuerligt eller trinvist arbejdende doseringsanordninger, der består af et overfor hydrogenperoxid bestandigt mate-35 riale.The addition of the agent of the invention to the aqueous medium to be rendered microorganism-free is effected by conventional apparatus, e.g. by means of continuous or stepwise dosing devices consisting of a hydrogen peroxide resistant material.
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Opfindelsen belyses nærmere i de følgende eksempler og den følgende forsøgsbeskrivelse.The invention is illustrated in more detail in the following examples and the following experimental description.
De følgende eksempler 1-7 illustrerer virksomme germicide midler ifølge opfindelsen. De fremstilles ved •5 blanding af 35 vægtl's vandig hydrogenperoxidopløsning med de angivne synergistisk virksomme stoffer i hver gang de angivne forhold og kan på denne form uden risiko og uden at miste deres virkning opbevares og anvendes på et vilkårligt tidspunkt efter fremstillingen.The following Examples 1-7 illustrate active germicidal agents of the invention. They are prepared by admixing 35 wt. Aqueous hydrogen peroxide solution with the indicated synergistically active substances in each of the conditions stated and can, in this form, be stored and used at any time after manufacture without any risk and without effect.
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Eksempel 1 35 vægt% H2O2 2 vægt% ammonium-amidosulfonat Rest vand.Example 1 35% by weight H2O2 2% by weight ammonium amidosulfonate Residual water.
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Eksempel 2 35 vægt% ^2^2 1,5 g p-hydroxybenzoesyre-ethylester pr. liter Rest vand.EXAMPLE 2 35% w / w 2 1.5 g of p-hydroxybenzoic acid ethyl ester liters Remaining water.
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Eksempel 3 35 vægt% H2O2 0,5 vægt% dipicolinsyre Rest vand.Example 3 35% by weight H2O2 0.5% by weight dipicolinic acid Residual water.
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Eksempel 4 35 vægt% H2O2 2 vægt% ammonium-amidosulfonat 0,5 g natriumpyrophosphat pr. liter 30 Rest vand.Example 4 35 wt% H 2 O 2 2 wt% ammonium amidosulfonate 0.5 g sodium pyrophosphate per liters 30 Remaining water.
Eksempel 5 35 vægt% 1^0 2 2 vægtf ammonium-amidosulfonat 35 0,25 vægt% dipicolinsyreExample 5 35% w / w 2% w / w ammonium amidosulfonate 0.25% w / w dipicolinic acid
Rest vand.Residual water.
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Eksempel 6 35 vægt% H202 2 vægt% 8-hydroxyquino1in 0,25 vægt% dipicolinsyre 5 Svovlsyre tilsættes til fuldstændig opløsning af hydroxyquinolinet *Example 6 35 wt% H 2 O 2 2 wt% 8-hydroxyquino1in 0.25 wt% dipicolinic acid 5 Sulfuric acid is added to complete solution of the hydroxyquinoline *
Rest vand.Residual water.
Eksempel 7 10 35 vægt% H202 2 vægt% 8-hydroxyquinolin 1,5 g p-hydroxybenzoesyre-ethylester pr. liter Svovlsyre tilsættes til fuldstændig opløsning af hydroxyquinolinet.Example 7 35 wt% H 2 O 2 2 wt% 8-hydroxyquinoline 1.5 g p-hydroxybenzoic acid ethyl ester per Liter of sulfuric acid is added to complete dissolution of the hydroxyquinoline.
15 Rest vand.15 Remaining water.
Ved hjælp af de i det følgende beskrevne forsøg bestemmes den germicide virkning af midlet ifølge opfindelsen ifølge eksemplerne 1-7.By means of the experiments described below, the germicidal effect of the agent according to the invention according to Examples 1-7 is determined.
20 Til koncentrering af cellulose-sønderdelende mikro20 For concentration of cellulose decomposing micro
organismer sættes der til en Dubo's saltopløsning, bestående af 0,5 g NaN03, 1 g K2HP04, 0,5 g MgS04, 7 H20, 0,5 g KC1, 0,01 g FeS04, 7 H20 og 1 liter destilleret vand, 5 g cellulosepulver, 0,1 g gærekstrakt og 5 g humusjord, og 25 der beluftes i flere uger. Der fremstilles herefter forsøgsportioner, som indeholder Dubo's saltopløsningen og 10% koncentreret cellulose-sønderdelende mikroorganisme-substrat. Til disse forsøgsportioner sættes der 0,25 ml pr. liter, henholdsvis 0,05 ml pr. liter af det germicide 30 middel ifølge eksemplerne 1-7, og der inkuberes ved 15°Corganisms are added to a Dubo's saline solution, consisting of 0.5 g NaNO 3, 1 g K2 HPO4, 0.5 g MgSO4, 7 H2 O, 0.5 g KCl, 0.01 g FeSO4, 7 H2 O and 1 liter of distilled water, 5 g cellulose powder, 0.1 g yeast extract and 5 g humus soil, and 25 aerated for several weeks. Test portions are then prepared containing the Dubo's saline solution and 10% concentrated cellulose decomposing microorganism substrate. To these test portions 0.25 ml per ml is added. liter, 0.05 ml per liter, respectively. liter of the germicidal agent of Examples 1-7 and incubated at 15 ° C
og beluftes let. Ved forsøgets begyndelse samt efter 1 dag, 7, 14 og 20 dage bestemmes det totale mikroorganismeantal på PC-agar (10 dage ved 22°C som dyrkningsbetingelser).and lightly aerated. At the beginning of the experiment and after 1 day, 7, 14 and 20 days, the total microorganism count on PC agar is determined (10 days at 22 ° C as culture conditions).
Desuden udføres der blindforsøg, altså uden tilsætning af 35 et germicidt middel, til bestemmelse af de i forsøgspor-In addition, blank tests, i.e. without the addition of a germicidal agent, are performed to determine the test results.
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tionerne oprindeligt indeholdte totale mikroorganismeantal.the tions originally contained total microorganism counts.
Til sammenligning og til tydeliggørelse af den med midlet ifølge opfindelsen opnåede synergistiske effekt behandles de samme forsøgsportioner under de samme betingelser uden 5 hydrogenperoxid, altså kun med de organiske bestanddele ifølge eksemplerne 1-7 (inklusive Na2H2P207 og HØO^), og til slut bestemmes, ligeledes til sammeligningsformål, den germicide virkning af 35 vægt%'s Højopløsning i gængs handelsleveringsform alene, altså uden tilsætning af flere 10 virksomme stoffer.For comparison, and to clarify the synergistic effect of the agent obtained by the invention, the same test portions are treated under the same conditions without hydrogen peroxide, i.e. only with the organic constituents of Examples 1-7 (including Na 2 H 2 P 2 O 7 and H 2 O 3), and finally determined, likewise, for purposes of comparison, the germicidal effect of 35 wt.% of High Resolution in conventional commercial delivery form alone, that is, without the addition of more than 10 active substances.
Resultaterne fremgår af de følgende tabeller I og II. Der er hver gang angivet antallet af de i 1 ml af forsøgsportionen indeholdte levende mikroorganismer ("<10^"" betyder, at der i 0,1 ml portion ikke længere kunne findes 15 nogen levende mikroorganismer). Som germicide midler ifølge eksemplerne 1' til 7' betegnes de sammenligningsmidler, der ikke indeholdt noget H202, men hvis sammensætning i øvrigt svarede til midlerne ifølge eksemplerne 1-7.The results are shown in the following Tables I and II. Each time, the number of living microorganisms contained in 1 ml of the test portion is indicated ("<10 ^" "means that in 0.1 ml aliquot 15 no living microorganisms could be found). to 7 'are the comparative agents which do not contain any H 2 O 2, but whose composition is otherwise similar to those of Examples 1-7.
20 25 30 3520 25 30 35
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Tabel ITable I
(Koncentration af det germicide middel: 0,25 ml/~ liter prøveportion) 8 „ . . Antal levende mikroorganismer(Concentration of the germicidal agent: 0.25 ml / ~ liter sample portion) 8 ". . Number of living microorganisms
Germicidt middel Begyndelse efter 1 dag efter 7 dage efter 14 dage 7 x 104 6 x 105 5 x 106 2 x 106Germicidal agent Beginning after 1 day after 7 days after 14 days 7 x 104 6 x 105 5 x 106 2 x 106
Eks. 1 2 x 104 CIO1 ClO1 ClO1 "1' 2 x 105 4 x 105 3 x 107 5 x 105 10 4 1 1 1 " 2 2 x 10 <10 <10 10 "2' 2 x 105 2 x 106 3 x ΙΟ6 106 " 3 2 x 105 <101 <101 CIO1 3' 2 x 105 2 x 106 5 x ΙΟ5 105 " 4 5 x 105 CIO1 CIO1 CIO1 15 "4' 2 x 106 3 x 105 4 x 105 5 x 105 35% 1^02 5 x 104 2 x 102 5 x 101 5 x 102 (sammen- ligning) ___ 20Ex. 1 2 x 104 CIO1 ClO1 ClO1 "1 '2 x 105 4 x 105 3 x 107 5 x 105 10 4 1 1 1" 2 2 x 10 <10 <10 10 "2' 2 x 105 2 x 106 3 x ΙΟ6 106 "3 2 x 105 <101 <101 CIO1 3 '2 x 105 2 x 106 5 x 1055 105" 4 5 x 105 CIO1 CIO1 CIO1 15 "4' 2 x 106 3 x 105 4 x 105 5 x 105 35% 1 ^ 02 5 x 104 2 x 102 5 x 101 5 x 102 (comparison) ___ 20
Tabel IITable II
(Koncentration af det germicide middel: 0,05 ml/-liter forsøgsportion) 25 , ,„ Antal levende mikroorganismer(Concentration of the germicidal agent: 0.05 ml / liter test portion) 25, "Number of living microorganisms
Germicidt middel Begyndelse efter 1 dag efter 7 dage efter 20 dage 3- x 108 3 x 108 8 x 106 10?Germicidal agent Beginning after 1 day after 7 days after 20 days 3- x 108 3 x 108 8 x 106 10?
Eks. 5 3 x 108 2 x 103 ClO1 'CIO1 "5' 3 x 108 1 x 108 8 x 106 3 x 106 30 " 6 3 x 108 6 x 102 CIO1 CIO1 "6' 3 x 108 1 x 108 106 106 " 7 3 x 108 3 x 102 CIO1 CIO1 ”7' 3 x 108 1 x 108 3 x 107 2 x 106 35% H„0 3 x ΙΟ8 ΙΟ6 103 2 x 104 35 11 (sammenligning)_______Ex. 5 3 x 108 2 x 103 ClO1 'CIO1 "5' 3 x 108 1 x 108 8 x 106 3 x 106 30" 6 3 x 108 6 x 102 CIO1 CIO1 "6 '3 x 108 1 x 108 106 106" 7 3 x 108 3 x 102 CIO1 CIO1 ”7 '3 x 108 1 x 108 3 x 107 2 x 106 35% H„ 0 3 x ΙΟ8 ΙΟ6 103 2 x 104 35 11 (comparison) _______
DK 152324BDK 152324B
ίο 0ίο 0
Resultaterne i tabellerne I og II viser, at der ved anvendelse af det germicide middel ifølge opfindelsen i en koncentration på 0,25 ml pr. liter allerede efter 1 dag i hver gang 0,1 ml prøveopløsninger ikke mere kunne konsta- 5 teres nogen levende mikroorganismer, medens man med 35 vægt%'s hydrogenperoxidopløsning efter 1 dag endnu kunne 2 konstatere 2 x 10 levende mikroorganismer, efter 14 dage 2 endog endnu 5 x 10 mikroorganismer, og med de yderligere organiske materialer alene, altså uden tilsætning af hydro- 10 genperoxid, efter 1 dag endnu 3 x 10^ til 2 x 106 og efter 5 6 14 dage 10 til 10 levende mikroorganismer. Det fremgår heraf, at virkningen af det her omhandlede middel ikke blot, således som man skulle have ventet det, sammensættes additivt af virkningerne af H202 ^ver 9an9 yderligere 15 anvendte virksomme stof, men at der ved midlerne ifølge opfindelsen desuden optræder en ægte synergistisk effekt. Resultaterne viser desuden, at hverken tilstedeværelsen af en gængs stabilisator for H202 (eksempel 4) eller nærværelsen af ringe mængder af en mineralsyre (eksempel 6 og 7) 20 formår at indvirke skadeligt på den synergistiske effekt og på virkningen af det omhandlede middel.The results in Tables I and II show that using the germicidal agent of the invention at a concentration of 0.25 ml after 1 day in each time 0.1 ml of sample solutions no longer could any live microorganisms be found, while with 35 wt% hydrogen peroxide solution after 1 day 2 could still detect 2 x 10 living microorganisms, after 14 days 2 even another 5 x 10 microorganisms, and with the additional organic materials alone, ie without the addition of hydrogen peroxide, after 1 day another 3 x 10 5 to 2 x 106 and after 5 6 14 days 10 to 10 living microorganisms. It can be seen from this that the effect of the present invention not only, as one would have expected, is additively compounded by the effects of H202 beyond 9 further active substance used, but that the agents of the invention also have a genuine synergistic effect. . Furthermore, the results show that neither the presence of a conventional stabilizer for H 2 O 2 (Example 4) nor the presence of low amounts of a mineral acid (Examples 6 and 7) 20 can adversely affect the synergistic effect and the effect of the present agent.
De omhandlede midler er således ganske alment fremragende egnede til sterilisering og/eller desinfektion af vandige systemer, og dette ikke blot til i.kredsløb ført 25 brugsvand i industrien, men også på andre områder, f.eks. ved behandling af vand fra svømmebassiner.The agents in question are thus generally well suited for sterilizing and / or disinfecting aqueous systems, and this has not only led to industrial use water, but also in other areas, e.g. when treating water from swimming pools.
30 3530 35
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762629081 DE2629081A1 (en) | 1976-06-29 | 1976-06-29 | GERMIZIDES MEDIUM |
| DE2629081 | 1976-06-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK287377A DK287377A (en) | 1977-12-30 |
| DK152324B true DK152324B (en) | 1988-02-22 |
| DK152324C DK152324C (en) | 1988-08-15 |
Family
ID=5981700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK287377A DK152324C (en) | 1976-06-29 | 1977-06-28 | GERMICID MEDICINE BASED ON STABILIZED H202 AND APPLICATION |
Country Status (12)
| Country | Link |
|---|---|
| JP (2) | JPS533525A (en) |
| BE (1) | BE856132A (en) |
| BR (1) | BR7704208A (en) |
| CA (1) | CA1102502A (en) |
| DE (1) | DE2629081A1 (en) |
| DK (1) | DK152324C (en) |
| FI (1) | FI66722C (en) |
| FR (1) | FR2356600A1 (en) |
| GB (1) | GB1584170A (en) |
| IT (1) | IT1083432B (en) |
| NL (1) | NL7706807A (en) |
| SE (1) | SE440849B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3109070A1 (en) * | 1981-03-10 | 1982-09-30 | Bayrol Chemische Fabrik Gmbh, 8033 Planegg | METHOD FOR CHEMICAL TREATMENT AND DISinfection of WATER AND WATER SYSTEMS |
| DE3625280A1 (en) * | 1986-07-25 | 1988-02-04 | Feldmann Hagen | Purifier for drinking water plants |
| CA1321137C (en) * | 1988-08-08 | 1993-08-10 | Raymond C. Kralovic | Anti-microbial composition |
| ES2025018A6 (en) * | 1991-02-18 | 1992-03-01 | Bueno Flamarique Luis Miguel | Liquid cleaning product for dentures. |
| DE4142319A1 (en) * | 1991-12-20 | 1993-06-24 | Henkel Kgaa | wound antiseptic |
| FR2748267B1 (en) * | 1996-04-19 | 1999-04-23 | Assche Charles Jacques Van | NOVEL PROCESSES FOR BIOCIDAL TREATMENT OF INDUSTRIAL AND BATHING WATER BY APPLICATION OF SUBSTANCES INDUCING MORTALITY TO LIGHT |
| DE19837068A1 (en) | 1998-08-17 | 2000-02-24 | Bayer Ag | Water treatment composition, especially for use in cooling circuits, comprises polyaspartic acid, biocidal oxidizing agent and sulfamic acid stabilizer |
| EP2338343B1 (en) | 2002-02-12 | 2016-11-02 | Virox Technologies Inc. | Enhanced activity hydrogen peroxide disinfectant |
| US20080305182A1 (en) | 2002-11-15 | 2008-12-11 | Ramirez Jose A | Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol |
| JP4813059B2 (en) * | 2002-11-15 | 2011-11-09 | ヴィロックス テクノロジーズ インコーポレーテッド | Hydrogen peroxide disinfectant containing cyclic carboxylic acid and / or aromatic alcohol |
| AU2005244462B2 (en) | 2004-05-14 | 2010-12-16 | Virox Technologies Inc. | Hydrogen peroxide-based skin disinfectant |
| US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
| US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| BRPI0907918B1 (en) | 2008-03-28 | 2018-07-24 | Ecolab Inc. | SULFOPEROXIC CARBOXYLIC ACIDS, THEIR PREPARATION AND METHODS OF USE AS AN ANTIMICROBYANES |
| FR2979243B1 (en) | 2011-08-25 | 2013-12-20 | Arkema France | STABILIZATION OF HYDROGEN PEROXIDE IN A PACKAGING DISINFECTION COMPOSITION |
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| FR2988088B1 (en) * | 2012-03-16 | 2014-11-07 | Rhodia Operations | PROCESS FOR TREATING EFFLUENTS OF PRODUCTION OF AROMATIC COMPOUND DERIVED FROM BENZENE DIHYDROXYL |
| US9242879B2 (en) | 2012-03-30 | 2016-01-26 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| US10450535B2 (en) | 2017-10-18 | 2019-10-22 | Virox Technologies Inc. | Shelf-stable hydrogen peroxide antimicrobial compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE807122C (en) * | 1950-02-04 | 1951-06-25 | Krisp Kg Kukirol | Process for the production of highly effective bactericidal and disinfecting agents |
| GB669612A (en) * | 1950-02-24 | 1952-04-02 | Ethan Allan Brown | Improvements in or relating to antiseptics of the peroxide type |
| CH310644A (en) * | 1950-08-16 | 1955-10-31 | Mueller Otto | Process for the production of an agent which kills germs and microorganisms. |
| FR1347436A (en) * | 1963-02-05 | 1963-12-27 | Heilmittelwerke Wien Gmbh | Process for obtaining germ-free liquids and disinfection products |
| NL173919C (en) * | 1970-05-29 | 1984-04-02 | Henkel Kgaa | METHOD FOR DISINFECTING MEDICAL DEVICES AND INSTRUMENTS. |
| DE2235539A1 (en) * | 1972-07-20 | 1974-02-07 | Degussa | PROCEDURES FOR DISINICIATING AND DEALGING OF WATERS AND WATER SYSTEMS |
| ZA74799B (en) * | 1973-03-21 | 1974-12-24 | American Cyanamid Co | Substituted halotriazine derivatives as peroxygen bleach activators |
| US3948795A (en) * | 1973-12-21 | 1976-04-06 | Tokai Denka Kogyo Kabushiki Kaisha | Method of low-temperature activation of peroxides |
-
1976
- 1976-06-29 DE DE19762629081 patent/DE2629081A1/en active Granted
-
1977
- 1977-06-07 CA CA280,024A patent/CA1102502A/en not_active Expired
- 1977-06-15 IT IT6839477A patent/IT1083432B/en active
- 1977-06-20 SE SE7707117A patent/SE440849B/en not_active IP Right Cessation
- 1977-06-21 NL NL7706807A patent/NL7706807A/en not_active Application Discontinuation
- 1977-06-27 BE BE1008226A patent/BE856132A/en not_active IP Right Cessation
- 1977-06-27 FR FR7719898A patent/FR2356600A1/en active Granted
- 1977-06-28 BR BR7704208A patent/BR7704208A/en unknown
- 1977-06-28 DK DK287377A patent/DK152324C/en not_active IP Right Cessation
- 1977-06-28 FI FI772018A patent/FI66722C/en not_active IP Right Cessation
- 1977-06-29 JP JP7770677A patent/JPS533525A/en active Pending
- 1977-06-29 GB GB2716577A patent/GB1584170A/en not_active Expired
-
1985
- 1985-10-11 JP JP60225015A patent/JPS61218505A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FI66722C (en) | 1984-12-10 |
| BR7704208A (en) | 1978-03-21 |
| DE2629081A1 (en) | 1978-01-12 |
| FI66722B (en) | 1984-08-31 |
| GB1584170A (en) | 1981-02-11 |
| JPS61218505A (en) | 1986-09-29 |
| SE7707117L (en) | 1977-12-30 |
| JPS533525A (en) | 1978-01-13 |
| DK287377A (en) | 1977-12-30 |
| NL7706807A (en) | 1978-01-02 |
| DK152324C (en) | 1988-08-15 |
| BE856132A (en) | 1977-12-27 |
| JPS6332326B2 (en) | 1988-06-29 |
| DE2629081C2 (en) | 1987-01-15 |
| CA1102502A (en) | 1981-06-09 |
| SE440849B (en) | 1985-08-26 |
| FR2356600B1 (en) | 1982-06-04 |
| FI772018A (en) | 1977-12-30 |
| IT1083432B (en) | 1985-05-21 |
| FR2356600A1 (en) | 1978-01-27 |
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