SE178789C1 - - Google Patents

Description

Uppfinnare: E Model, 3 Bindler och R Zinkernagel Prioritet begard feat den 8 september 1958 och den 18 augusti 1959 (Schweiz) Foreliggande uppfinning avser ett forfarande for skydd av organiska material av alla slag mot mikroorganismer under anvandning av ett mikroorganismadande medel, samt sjalva medlet och ett enligt forfarandet skyddat material. Inventors: E Model, 3 Bindler and R Zinkernagel Priority begard feat September 8, 1958 and August 18, 1959 (Switzerland) The present invention relates to a process for protecting organic materials of all kinds against microorganisms using a microorganism-feeding agent, and the agent itself and a material protected according to the procedure.

Det har visat sig, att man kan skydda organiska material av alla slag mot mikroorganismer, cm man behandlar dessa material med en verksam amneskombination, som bestar av minst ett mikroorganismcloclande verksamt amne tillhorande en klass av foreningar med den allmanna formeln A R1—N N—R 2 \(I) NH• och minst ett mikroorganismclodande amne tillInirande en klass av foreningar med den allmanna formeln 4 /\/NH\ I (Hal). IC=0(II) 7 I dessa formler betecknar Ri en lipofil grupp av 10-14 kolatomer eller en lipofil grupp innehallande aralifatisk rest, R, vate eller en alifatisk grupp med 1-4 kolatomer. A en genom a, .- eller a, y-kolatomer fOrenad alifatisk eller en genom a, fl-kolatomer forenad cykloalifatisk rest, Hal en halogenatom och n 0, 1, 2, 3 eller 4. R1 betecknar exempelvis en. dekyl-, dodekyl-, tetradekylgrupp eller en 4-dodekylbensylgrupp. Flireningar med den allmanna formeln I, van i R1 betecknar en dodekyl- eller tetradekylgrupp, arc att foredraga. It has been found that one can protect organic materials of all kinds against microorganisms by treating these materials with an active compound combination, which consists of at least one microorganism-cleaving active substance belonging to a class of compounds of the general formula A R1-NN-R 2 \ (I) NH • and at least one microorganism clodding substance forming a class of compounds of the general formula 4 / \ / NH \ I (Hal). IC = 0 (II) 7 In these formulas, R 1 represents a lipophilic group of 10-14 carbon atoms or a lipophilic group containing araliphatic radical, R, vate or an aliphatic group having 1-4 carbon atoms. A is an aliphatic aliphatic compound represented by α, eller or α, γ-carbon atoms or a cycloaliphatic radical united by α, β-carbon atoms, Hal has a halogen atom and n has 0, 1, 2, 3 or 4. R 1 represents, for example, a. decyl, dodecyl, tetradecyl group or a 4-dodecylbenzyl group. Flirins of the general formula I, used in R1 represent a dodecyl or tetradecyl group, are preferred.

R, betecknar exempelvis en metyl-, etyl-, n-propyl-, isopropyl- eller en n-butylgrupp; fbreningar med den allmanna formeln I, van i R, betecknar vate, aro emellertid att fOredraga. Som vid a, kolatomerna forenade alkylenrester A ifragakomma exempelvis 1,2-etylen-, 1,2-propylen-, 1,2- eller 2,3-butylenresten, som analogt bundna cykloalkylenrester exempelvis 1,2-cyklohexylenresten eller 3- eller 4-mety1-1,2-cyklohexylresten. Som vid a,y-kolatomerna bundna alkylenrester A kunna exempelvis namnas 1,3-propylen-, 1,3-butylen-, 1,3- eller 2,4-pentylenresten. Sadana foreningar med den allmanna formeln I, van i A betecknar en 1,2-etylenrest, arc att foredraga. Hal betecknar i den allmanna formeln II forctradesvis klor eller brom. Vad den fungicida verkan betraffar, har sadana amnessammanstallningar visat sig vara bast lampade, i vilka som verksamma amnen med formeln II inga 5,6-diklor-2,3-dihydrobensoxazol-2-on eller 4,5,7-triklor-2,3-dihydrobensoxazol-2-on. R 1 represents, for example, a methyl, ethyl, n-propyl, isopropyl or an n-butyl group; compounds of the general formula I, van i R, denote vate, however, are to be preferred. As in the case of a, the carbon atoms combined alkylene radicals A are used, for example, 1,2-ethylene, 1,2-propylene, 1,2- or 2,3-butylene radical, as analogously bound cycloalkylene radicals, for example 1,2-cyclohexylene radical or 3- or 4 -methyl-1,2,2-cyclohexyl radical. As alkylene radicals A bonded to the α, γ carbon atoms, for example, the 1,3-propylene, 1,3-butylene, 1,3- or 2,4-pentylene radical can be mentioned. Such compounds of the general formula I, used in A, represent a 1,2-ethylene residue, which is to be preferred. Hal in the general formula II preferably denotes chlorine or bromine. As far as the fungicidal action is concerned, such compound formulations have been found to be highly lamped, in which as active substances of the formula II no 5,6-dichloro-2,3-dihydrobenzoxazol-2-one or 4,5,7-trichloro-2, 3-dihydrobenzoxazol-2-one.

De verksanuna substanserna med formel I kunna anvandas som sadana eller i form av sina salter med syror, exempelvis som hydroklorider eller hydrobromider, eventuellt aven under tillsats av attiksyra. Viktforhallandet verksamt amne med formeln I till verksamt amne med formeln II ut- lampligen 1: 1 till 4: 1. The active substances of formula I can be used as such or in the form of their salts with acids, for example as hydrochlorides or hydrobromides, optionally also with the addition of acetic acid. The weight ratio of active substance of formula I to active substance of formula II is approximately 1: 1 to 4: 1.

Den fungicida verkan av 2,3-dihydrobensoxazol-2-oner ãr visserligen kand (jamfor Virtanen, Acta Chemica Scandinavica, 12, (1958) 124-128, Nr. 1). ii.vensâ är den fungicida och baktericida verkan av vissa dialkylerade 2-imino-1,3-di-Nheteroeykler kand. Verksamma amnessammanstallningar enligt foreliggande uppf inning visa dock, isynnerhet i ovan angivna viktforhallanden, en fungicid verkan, som overtraffar summan av de fungicida verkningarna hos de enskilda komponenterna. Tack vane denna synergistiska effekt uppnar man ett onskat resultat med en betydligt mindre koncentration av den verksamma 2— — amnessammanstaningen i bararmaterialet an vid anvandning av de enskilda komponenterna. De baktericida och algicida egenskaperna hos de definitionsenliga 2-imino-1,3-N-heterocyklerna bibehallas helt i de verksamma amneskombinationerna enligt uppfinningen. HSr och i det foljande taIas om »fungicith eller »baktericid» verkan aven for det fall det eventuellt endast är fraga om »fungistatisk» eller »bakteriostatisk» verkan. The fungicidal action of 2,3-dihydrobenzoxazol-2-ones is admittedly well known (cf. Virtanen, Acta Chemica Scandinavica, 12, (1958) 124-128, No. 1). ii.vensâ is the fungicidal and bactericidal action of certain dialkylated 2-imino-1,3-di-Nheteroeykler kand. However, active amnesic compositions according to the present invention show, in particular in the above weight ratios, a fungicidal effect, which exceeds the sum of the fungicidal effects of the individual components. Due to this synergistic effect, a desired result is obtained with a much smaller concentration of the active compound in the bar material than in the use of the individual components. The bactericidal and algicidal properties of the 2-imino-1,3-N-heterocycles defined by definition are fully maintained in the active amnesic combinations of the invention. HSr and hereinafter referred to as "fungicite or" bactericidal "action even in the case where it may only be a question of" fungistatic "or" bacteriostatic "effect.

En ytterligare vardefull egenskap hos de verksamma amnessammanstallningarna Sr deras goda vattenloslighet resp. dispergerbarhet. Detta Sr overraskande, emedan de uppfinningsenligt anvandbara 2,3-dihydro-bensoxazol-2-onerna enbart for sig aro svarhisliga i vatten. Det Sr en stor for-del hos de verksamma amnessammanstallningarna enligt uppfinningen, att de aro anvandbara som vattenhaltiga eller organisk-vattenhaltiga losningar. Som organiska losningsmedel ifragakomma I forsta hand sadana som aro blandbara med vatten, exempelvis etanol eller etylenglykolmonometyl- eller etyleter. De verksamma vattenhaltiga eller vattenhaltigt-organiska amneslosningarna enligt uppfinningen hro latt applicerbara pa organiska material, framforallt pa textiHer, exempelvis p5 textilier av ylle, siden, bomull eller av acetylcellulosa, polyamid-, polyakrylnitril- eller polyesterfibrer, varvid de ph fibrer, vilka icke sjalva aro utsatta for mikrobiskt angrepp, verka som skydd for angripbara klister och mjukningsmedel. An additional valuable property of the active amnesic compositions Sr their good water solubility resp. dispersibility. This is surprising, since the 2,3-dihydro-benzoxazol-2-ones usable according to the invention alone are black in water. It is a great advantage of the active amnesic compositions according to the invention that they are useful as aqueous or organic-aqueous solutions. Suitable organic solvents are primarily those which are miscible with water, for example ethanol or ethylene glycol monomethyl or ethyl ether. The active aqueous or aqueous-organic bead solutions according to the invention are readily applicable to organic materials, in particular to textiles, for example to textiles of wool, silk, cotton or of acetylcellulose, polyamide, polyacrylonitrile or polyester fibers, the ph fibers which are not themselves aro exposed to microbial attack, act as protection against attackable adhesives and plasticizers.

Den basta verkan erhalles genom impregnering med sadana amnessammanstallningar, vilka lanehalla de ovan definierade verksamma amnena i viktfOrhallandet 2: 1 till 3: 1. Koncetrationen av den verksamma hmnessammanstallningen i losningen uppgar med fordel till minst 0,5 promille. Som losningsmedel Sr vatten att foredraga. Det genom impregneringen med de uppfinningsenliga amnessammanstallningarna erhallna skyddet av ovan anforda material omfattar exempelvis skydd mot Fusarium oxysporum, Aspergillus niger, Ctenomyces interdigitalis, Penicillium expansum, Stachybotris atra, Chaetonium globosum on mot vissa bakterier on alger. The best effect is obtained by impregnation with such amnesic compositions, which contain the active ingredients defined above in the weight ratio 2: 1 to 3: 1. The concentration of the active amnesic composition in the solution advantageously amounts to at least 0.5 per mille. As a solvent Sr water is preferred. The protection of the above-mentioned materials obtained by the impregnation with the amnesic compositions according to the invention includes, for example, protection against Fusarium oxysporum, Aspergillus niger, Ctenomyces interdigitalis, Penicillium expansum, Stachybotris atra, Chaetonium globosum and against certain bacteria and algae.

De verksamma amneskombinationerna enligt uppfinningen kunna icke endast anvandas i form av deras vattenhaltiga eller vattenhaltigt-organiska losningar, utan Oven blandade med andra inerta barare eller fyllmaterial, exempelvis med rengoringsmedel, kosmetiska eller medicinska preparat, med andra biocida eller med insekticida medel o.s.v. och narmare bestamt i pulverform, som hisningar eller som dispersioner. Da de icke endast aro losliga i alkoholer, utan Oven i andra organiska losningsmedel, sasom exempelvis i alifatiska eller aromatiska klorerade eller oklorerade kolvaten, sasom bensen, toluen, klorbensen eller dikloretylen, lampa sig Oven for anvandning i torrengoringsmedel samt for framstallning av s.k. »Sprays* for rumsdesinfektion. (I dessa fall anvander man komponenten I lampligen i form av dess fria bas). Man kan dessutom inblanda dem pappersbehandlingsbad eller tryckfortjockningar av starkelse eller cellulosaderivat eller anvanda dem for impregnering av tra. Men polyvinylklorid-preparat, exempelvis folier, samt hacker och malarfarger, vilka framstallts jiS kaseinbasis eller innehalla kasein, och jamval oorganiska material som exempelvis Melilotuspulver, bibringas med den uppfinningsenliga verksamma amneskombinationen ett verksamt skydd mot mikroorganismangrepp. Dessutom kunna amnessammanstallningar enligt uppfinningen Sven med framgang anvandas for skydd av fotterna mot svampangrepp, t. ex. genom behandling av skodon, av inlaggssulor eller av strumpor fOr tillintetgorande av infektionshardar eller for profylax. Den baktericida och algicida verkan av sammanstallningarna enligt uppfinningen stracker sig exempelvis till stafylokocker, coli-, paratyfusoch enteritisbakterier. Dessa mangsidiga egenskaper hos de nya fungicida och baktericida medlen mojliggOra en anpassning av anvandningsformen efter de foreliggande forhallandena. SOlunda kan man exempelvis vid sarbehandling anvanda saval dessa verksamma amneskombinaHoner innehalland.e salvor, puder och fOrbandsmaterial, som Oven tvattvatskor i form av vattenhaltiga eller vattenhaltigt-alkoholiska losningar av dessa medel. :Men for desinfektion av instrument, verktyg och installationstillbehor aro de uppfinningsenliga medlen lampliga. Slutligen ma Sven namnas anvandningen i kosmetiska preparat. The active amnesic combinations according to the invention can be used not only in the form of their aqueous or aqueous-organic solutions, but also mixed with other inert carriers or fillers, for example with detergents, cosmetic or medicinal preparations, with other biocides or with insecticides and so on. and more specifically in powder form, as elevators or as dispersions. Since they are not only soluble in alcohols, but also in other organic solvents, such as, for example, aliphatic or aromatic chlorinated or chlorinated hydrocarbons, such as benzene, toluene, chlorobenzene or dichloroethylene, they are also suitable for use in dry cleaners and for the preparation of so-called »Sprays * for room disinfection. (In these cases, component I is suitably used in the form of its free base). They can also be mixed with paper treatment baths or pressure thickeners of starch or cellulose derivatives or used for impregnating wood. However, polyvinyl chloride preparations, for example foils, as well as hacker and paint paints, which are made from a casein-based or casein-containing material, and from inorganic materials such as Melilotus powder, are provided with the active amine combination according to the invention as an effective protection against microorganism attack. In addition, amnesia compositions according to the invention can be successfully used to protect the feet from fungal infestation, e.g. by treating footwear, insoles or socks for the destruction of infectious cures or for the prophylaxis. The bactericidal and algicidal action of the compositions according to the invention extends, for example, to staphylococci, coli, paratyphoid and enteritis bacteria. These multifaceted properties of the new fungicidal and bactericidal agents make it possible to adapt the form of use to the present conditions. Thus, for example, in the case of special treatment, these active amnesic combinations containing ointments, powders and dressings may be used, as well as wash water shoes in the form of aqueous or aqueous-alcoholic solutions of these agents. : But for disinfection of instruments, tools and installation accessories, the means according to the invention are suitable. Finally, Sven must mention the use in cosmetic preparations.

Foljande tabeller askadliggiira den synergistiska verkan i verksamma amneskombinationer enligt foreliggande uppfinning. Talen ange granskoncentrationen ay verkan i delar per miljon. The following tables illustrate the synergistic effect in active amnesic combinations of the present invention. The figures indicate the concentration concentration ay effect in parts per million.

Tabell 1. Table 1.

Komponenternas verkan mot mikroorganIsmer. The action of the components against microorganisms.

Verkan mot Fusarium Asper- oxy-gillus sporum niger CI \ 0 \ I 111 IC=0300300 Cl 0 21C=O100300 Ij Cl/y Cl CEL—CH, iI 3 C,21-1—NNH3001000 c NH • HC1 NrAmnen — —a CH2—CH2 4 C12H—N N—C2F193001000 \ c = NH • HC1 CH2—CH, C14l-129—NNH10001000 C/ NH • HC1 Tabell 2. Action against Fusarium Asper- oxy-gillus sporum niger CI \ 0 \ I 111 IC = 0300300 Cl 0 21C = O100300 Ij Cl / y Cl CEL — CH, iI 3 C, 21-1 — NNH3001000 c NH • HC1 NrAmnen - —a CH2 — CH2 4 C12H — NN — C2F193001000 \ c = NH • HCl CH2 — CH, C141-129 — NNH10001000 C / NH • HCl Table 2.

Verkan av uppfinningsenliga verksamma amnesblandningar i viktforhallandet 2: 1 pa samma mikroorganismer. Effect of active amnesic mixtures according to the invention in the weight ratio 2: 1 on the same microorganisms.

Blanduingar; av nr fran tabell Verkan mot FusariumAspergillus oxysporumniger 3 + 1 100 3 + 2 4 + 1 100 300 + 1 100 100 4 -I- 2 100 + 2 Foljande exempel 5.skadliggora narmare uppfinningen. De begransa dock pa intet satt densamma. I dessa exempel beteekna, forsavitt icke annat angives, delar viktdelar. Temperaturerna angivas i Celsiusgrader. Viktdelar forhalla sig till volymdelar som kilogram till liter. Med werksamt forstas i exemplen den definitionsenliga verksamma amneskombinationen. Mixtures; of no. from table Action against FusariumAspergillus oxysporumniger 3 + 1 100 3 + 2 4 + 1 100 300 + 1 100 100 4 -I- 2 100 + 2 The following examples 5.had harming the invention. However, they do not limit themselves in any way. In these examples, parts, unless otherwise indicated, denote parts by weight. The temperatures are given in degrees Celsius. Weight parts relate to volume parts such as kilograms to liters. In the examples, effective means the effective combination of amnes combinations.

Exempel 1. Man loser 30 delar 1-dodeky1-2- imino-imidazolidin-hydroklorld och 15 delar 5,6- diklor-2,3-dihydrobensoxazol-2-on i 55 delar etylenglykolmonometyleter och framstaller av denna stamlosning genom utspadning med hett vatten ett behandlingsbad, som pa 1 000 delar innehaller 1 del verksamt amne. Med hjalp av attiksyra installes pa ett pH-varde av 4,5. Med detta behandlingsbad behandlas bomullskalika. i badforhallandet 1: 20 20 minuter vid 60°. Darph. avcentrifugeras materialet och torkas. Det pa sa salt behandlade materialet dr skyddat mot mogelflacksbildning (Stockfleckenbildung) och forruttnelse, vilket framgar ay tabell 3. Kontrollproven utfordes pa foljande sdtt. a) Mogelflacksprov. Cirkelformade vavnadsutskarningar med en diameter av 9 cm placeras i petriskalar pa ett agarnaringssubstrat och ympas med en suspension av en sporblandning av Penicillium expansum, Stachybotrys atra och Aspergillus niger, vilken blandning innehaller 40 000 sporer per ml. De slutna petriskalarna odlas 10 dagar vid 28° C och darpa raknas antalet svampkolonier. Example 1. 30 parts of 1-dodecyl-2-imino-imidazolidine hydrochloride and 15 parts of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one are dissolved in 55 parts of ethylene glycol monomethyl ether and this stock solution is prepared by diluting with hot water. a treatment bath, which in 1,000 parts contains 1 part of active substance. With the help of attic acid is installed at a pH value of 4.5. This treatment bath treats cotton scales. in the bath ratio 1:20 20 minutes at 60 °. Darph. centrifuge the material and dry. The material so treated with salt is protected against mold staining (Stockfleckenbildung) and decay, as shown in Table 3. The control samples are challenged in the following way. a) Mogelflacksprov. Circular 9 cm diameter circular tissue incisions are placed in petri dishes on an agar ring substrate and inoculated with a suspension of a spore mixture of Penicillium expansum, Stachybotrys atra and Aspergillus niger, which mixture contains 40,000 spores per ml. The closed petri dishes are grown for 10 days at 28 ° C and the number of fungal colonies is shaved.

Forruttnelseprov. Cirkelformade vavnadsutskdrningar med en diameter av 3,8 cm placeras i petriskalar pa ett agarndringssubstrat, som ympats med 0,5 ml ay en sporsuspension av Chetonium globosum, vilken innehaller cirka 700 000 sporer per ml. Man odlar 10 dagar mid 28', avbryter darph. mikroorganismutvecklingen med en alkoholisk tymollosning, skoljer vavnadsutskarningarna och torkar dem. Darpa undersokes i en halstotningsapparat enligt R. Burgess (Microorganismus and Textiles: The Journal of Applied Bacteriology 17, 241 (1954)) pa halstotningshallfasthet. Decay test. Circular tissue sections with a diameter of 3.8 cm are placed in petri dishes on an agaring substrate, inoculated with 0.5 ml of a spore suspension of Chetonium globosum, which contains about 700,000 spores per ml. You grow 10 days mid 28 ', interrupts darph. microorganism development with an alcoholic thymol solution, rinses the tissue excisions and dries them. Darpa is examined in a cervical spine according to R. Burgess (Microorganism and Textiles: The Journal of Applied Bacteriology 17, 241 (1954)) on cervical spine resistance.

Jordnedgravningsprov. Cirkelformade vavnadsutskarningar med en diameter air 3,8 cm nedgravas 14 dagar i en jordblandning, som her en fuktighetshalt av 30 procent och en temperatur av 28°, och som framstallts av 50 procent kompostjord, 30 procent kogOdsel och 20 procent sand. Darpa skoljas vavnaderna och torkas. Nu provas de i halstotningsapparat enligt Burgess pA hallfasthet. 'lid forruttnelse- och jordnedgravningsprov anvandes ett genomsnittsvarde av 10 prover. Hallfastheten anges i procent av den ursprungliga vavnadshallfastheten. Resultatet ay dessa undersokningar har sammanstallts i tabell 3. Soil burial test. Circular tissue cuts with a diameter of 3.8 cm in air are buried for 14 days in a soil mixture, which here has a moisture content of 30 percent and a temperature of 28 °, and which is produced from 50 percent compost soil, 30 percent cow dung and 20 percent sand. Darpa rinses the tissues and dries. Now they are tested in neck throttling apparatus according to Burgess pA half strength. A mean value of 10 samples was used in the decay and soil burial samples. The half strength is stated as a percentage of the original fabric half strength. The results of these studies have been compiled in Table 3.

Exempel 2. Man loser 60 delar 1-tetradecy1-2- iminoimidazolidin-hydroklorid och 30 delar 4,5,7- triklor-2,3-dihydrobensoxazol-2-on1110 delar etylenglykolmonometyleter och framstaller darav genom utspadning med hett vatten ett behandlingsbad, som per 1 000 delar innehaller 1 del verksamt amine. Med delta behandlingsbad be-handles bomullskalika ph. sett som beskrivits exempel 1. Det impregnerade materialet ar skyddat mot mogelflackar och forruttnelse, sasom framgar av exempel 3. Kontrollprov utfOrdes pa i exempel 1 beskrivet satt. Example 2. 60 parts of 1-tetradecyl-2-iminoimidazolidine hydrochloride and 30 parts of 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one1110 parts of ethylene glycol monomethyl ether are dissolved and a treatment bath is prepared therefrom by dilution with hot water. per 1,000 parts contains 1 part of active amine. With delta treatment bath, cotton calica ph. as described in Example 1. The impregnated material is protected against mold flakes and rot, as shown in Example 3. Control tests were performed in the manner described in Example 1.

Exempel 3. 30 delar 1-dodeky1-3-buty1-2-iminoimidazolidin-hydroklorid och 15 delar 4,5,7- triklor-2,3-dihydrobensoxazol-2-on loses i 55 delar etylenglykolmonometyleter. Deane losning utspades med kokande vatten ph. salt, att man erhaller ett behandlingsbad, som pa 1 000 delar innehaller 0,5 delar verksamt am.ne. Darmed behandlas bomullskalika pa sa satt som beskrivits i exempel 1. Det impregnerade materialet dr skyddat mot mogelflacksbildning och forruttnelse. Det underkastades i exempel 1 beskrivet mogelfIdeks-, forruttnelse- och jordnedgravningsprov. Resultatet framgar ay tabell 3. Example 3. 30 parts of 1-dodecyl-3-butyl-2-iminoimidazolidine hydrochloride and 15 parts of 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one are dissolved in 55 parts of ethylene glycol monomethyl ether. Deane solution was diluted with boiling water ph. salt, to obtain a treatment bath, which in 1,000 parts contains 0.5 parts of effective am.ne. This treats cotton scales in the manner described in Example 1. The impregnated material is protected against mold buildup and decay. It was subjected to the mold index, decay and soil burial tests described in Example 1. The result is shown in Table 3.

Exempel 4. 30 delar 1-dodeky1-2-iminoimidazolidin-hydroklorid och 15 delar 2,3-dihydrobensoxazol-2-on losas i 55 delar etylalkohol. Ay denna stamlosning framstaller man genom utspadning med vatten ett behandlingsbad, corn pa 1 000 delar innehaller 1 del verksam substans. Med delta bad behandlas bomullskalika pA satt som beskrivits i exempel 1. Det pa sh salt framstallda materialet dr skyddat mot mogelflacksbildning och forruttnelse. Resultaten av kontrollproven framgh ay tabell 3. Anvander man i stallet fOr ovan anforda stamlosning en sadan, corn inne- — — hailer 25 delar 1-dodeky1-2-iminolmidazolidinhydrobromid och 25 delar 2,3-dihydro-bensoxazol2-on losta i 50 delar isopropylalkohol och forfar sasom ovan angivits, sd erhdller man lika goda resultat. Example 4. 30 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride and 15 parts of 2,3-dihydrobenzoxazol-2-one are dissolved in 55 parts of ethyl alcohol. In this stock solution, a treatment bath is prepared by diluting with water, corn of 1,000 parts containing 1 part of active substance. With delta baths, cotton scales are treated in the manner described in Example 1. The material produced on salt is protected against mold formation and decay. The results of the control tests are shown in Table 3. If in the stable above the stock solution is used, such a mixture contains 25 parts of 1-dodecyl-2-iminolmidazolidine hydrobromide and 25 parts of 2,3-dihydro-benzoxazol2-one solution in 50 parts. isopropyl alcohol and forfar as indicated above, so as to obtain equally good results.

Exempel 5. Man loser 30 delar 1-tetradeky1-2- irninohnidazolidin-hydroklorid och 15 delar 5,6- diklor-dihydrobensoxazol-2-on i 55 delar etylenglykolmonoetyleter och atspader denna stamlosning med hett vatten pa sa satt, att ett behandlingsbad erhalles, som pd. 1 000 delar innehaller 0,5 delar verksam substans. I denna lOsning behandlas bomullskalika, sasom beskrivits i exempel 1. Det pa sa satt behandlade materialet Or skyddat mot mogelflacksbildning och fOrruttnelse. Det underkastades mogelflacks-, forruttnelse- och jordnedgrdvningsprov, sasom beskrivits i exempel 1. Resultaten framga av tabell 3. Anvander man i stallet fOr 30 delar 1-tetradeky1-2-iminoimidazolidin-hydroklorid 30 delar 1-dodeky1-2-iminohexahydro-pyrimidin-hydroklorid och forfar sasom ovan angivits, sa. erhAller man lika goda resultat. Example 5. Dissolve 30 parts of 1-tetradecyl-2-triminohnidazolidine hydrochloride and 15 parts of 5,6-dichloro-dihydrobenzoxazol-2-one in 55 parts of ethylene glycol monoethyl ether and dilute this stock solution with hot water so as to obtain a treatment bath. as pd. 1,000 parts contain 0.5 parts of active substance. In this solution, cotton scale is treated as described in Example 1. The material thus treated is protected against mold buildup and decay. It was subjected to mold flattening, decay and soil degradation tests as described in Example 1. The results are shown in Table 3. If 30 parts of 1-tetradecyl-2-iminoimidazolidine hydrochloride are used instead of 30 parts of 1-dodecyl-2-iminohexahydro-pyrimidine hydrochloride and forfar as indicated above, said. you get equally good results.

Exempel 6. 30 delar 1-dodeky1-2-iminoimidazolidin-hydroklorid och 15 delar 5-klor-2,3-dihydrobensoxazol losas i 55 delar etylenglykolmonometyleter. Av stamlosningen framstaller man genom utspadning med hett vatten ett behandlingsbad, som per liter innehaller 2 g verksam substans. Med detta behandlingsbad behandIas bomullskalilth, sasom beskrivits i exempel 1. Det pa sa salt behandlade materialet Or skyddat mot mogelflacksbildning och fOrruttnelse, sasom framgar av exempel 3. Provningen skedde p0 sat som utforligt beskrivits i exempel 1. Anyander man i stallet f6r den ovan beskrivna stamlosningen en sadan, som innelialler 40 delar dodeky1-2-iminoimidazoIidin-hydroklorid och 10 delar 5,6-diklor-2,3-dihydrobensoxazol-2-on i 50 delar etylenglykolmonometyleter, eller 40 delar 1-deky1-2-iminoimidazolidin-hydroklorid och 10 delar 5,6-diklor-2,3-dihydrobensoxazol-2-on i 50 delar etylenglykolmonoetyleter, och forfar sasom ovan angivits, sh. erhailer man lika goda resultat. Example 6. 30 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride and 15 parts of 5-chloro-2,3-dihydrobenzoxazole are dissolved in 55 parts of ethylene glycol monomethyl ether. From the stock solution, a treatment bath is prepared by diluting with hot water, which contains 2 g of active substance per liter. This treatment bath is treated with cotton scale, as described in Example 1. The salt-treated material is protected against mold build-up and decay, as shown in Example 3. The test was carried out in the manner described in detail in Example 1. Instead of the one described above. the stock solution is one containing 40 parts of dodecyl-2-iminoimidazolidine hydrochloride and 10 parts of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one in 50 parts of ethylene glycol monomethyl ether, or 40 parts of 1-decyl-2-iminoimidazolidine hydrochloride and 10 parts of 5,6-dichloro-2,3-dihydrobenzoxazol-2-one in 50 parts of ethylene glycol monoethyl ether, and forfar as indicated above, sh. you get equally good results.

Exempel 7. Man loser 30 delar 1-dodeky1-2- iminoimidazolidin-hydroklorid och 15 delar 4,5,7- triklor-2,3-dihydrobensoxazol-2-on i 55 delar etyllenglykolmonoetyleter och franastaller &ray ge- nom utspadning med hett vatten ett behandlings- bad, som pa 1 000 delar innehaller 0,5 delar verksam substans. Med detta behandlingsbad behand- las bomullskalika sasom i exempel 1. Det p0 sa. satt behandlade materialet Or skyddat mot mogelflacksbildning och forruttnelse. Resultaten fram- ga av tabell 3. Anvander man i stallet for ovan beskrivna stamlosning en sadan, som innehaller 30 delar 1-(4'-dodekylbensyl)-2-iminoimidazolidin- hydroklorid och 15 delar 5,6-diklor-2,5-dihydrobesoxazol-2-on 16sta i 55 delar etylenglykolmonometyleter, och arbetar ph ovan angivet satt vi-dare, sa erhAller man lika goda resultat. Example 7. 30 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride and 15 parts of 4,5,7-trichloro-2,3-dihydrobenzoxazol-2-one are dissolved in 55 parts of ethylene glycol monoethyl ether and franastaller & ray by dilution with hot water. a treatment bath, which in 1,000 parts contains 0.5 parts of active substance. With this treatment bath, cotton scales are treated as in Example 1. It p0 sa. treated material Or protected against mold buildup and decay. The results are shown in Table 3. Instead of the stock solution described above, use one containing 30 parts of 1- (4'-dodecylbenzyl) -2-iminoimidazolidine hydrochloride and 15 parts of 5,6-dichloro-2,5- dihydrobesoxazol-2-one 16sta in 55 parts ethylene glycol monomethyl ether, and working ph above indicated continued, so you get equally good results.

Exempel 8. Man loser 30 delar 1-dodeky1-2- imino -4,5-tetrametylen-imidazolidin - h3rdroklorid och 15 delar 5,6-diklor-2,3-dihydro-bensoxazol on i 55 delar etylenglykolmonometyleter och framstaller av denna stamlOsning genom utspadning med hett vatten ett behandlingsbad, som pa 1 000 delar innehiller 1 del verksam substans. Med detta behandlingsbad behandlas bomullskalika. sasom i exempel 1. Det p0 sa. satt behandlade materialet Or skyddat mot mogelflacksbildning och fOrruttnelse. Det underkastas enligt exempel 1 mogelflacksprov, forruttnelseprov och jordnedgravningsprov. Resultaten framga av tabell 3. Example 8. 30 parts of 1-dodecyl-2-imino-4,5-tetramethylene-imidazolidine hydrochloride and 15 parts of 5,6-dichloro-2,3-dihydro-benzoxazolone are dissolved in 55 parts of ethylene glycol monomethyl ether and preparations of this stock solution are prepared. by dilution with hot water a treatment bath, which in 1,000 parts contains 1 part of active substance. This treatment bath treats cotton scales. as in Example 1. That p0 said. The treated material is protected against mold formation and decay. According to Example 1, it is subjected to mold flake tests, decay tests and soil burial tests. The results are shown in Table 3.

Exempel 9. Man loser 20 delar 1-dodeky1-2- imino-imidazolidin-hydroldorid och 10 delar 4,5,- 6,7-tetraklor-2,3-dihydro-bensoxazol-2-on i 45 delar etylenglykohnonometyleter och framstaller av denna stamlosning genom utspadning med hett vatten ett behandlingsbad, som pft 1 000 delar innehaller 2 delar verksam substans. I detta behandlingsbad infores bomullskalika 10 sekunder vid 25°, avpressas till en viktokning av 77 procent och kalltorkas. Det pa sa aft behandlade materialet Or skyddat mot mogelflacksbildning och forruttnelse. Det underkastas mogelfla.cks-, forruttnelse- och jordnedgravningsprov, sasom beskrivits i exempel 1. Resultaten framga. av tabell 3. Example 9. 20 parts of 1-dodecyl-2-imino-imidazolidine hydrolide and 10 parts of 4,5, - 6,7-tetrachloro-2,3-dihydro-benzoxazol-2-one are dissolved in 45 parts of ethylene glycol monomethyl ether and preparations of this stock solution by dilution with hot water a treatment bath, which pft 1,000 parts contains 2 parts of active substance. In this treatment bath, cotton scale is introduced for 10 seconds at 25 °, squeezed to a weight gain of 77 percent and cold dried. The material thus treated is protected against mold buildup and decay. It is subjected to mold flakes, decay and soil burial tests, as described in Example 1. The results are apparent. of table 3.

Exempel 10. Man framstaller en »Spray» av 2 delar 5,6-diklor-2,3-dihydro-bensoxazol-2-on, 2 delar 1-dodeky1-2-iminoimidazolidin-hydroklorid, 5 delar dioktylftalat, 25 delar etylenglykolmonoetyleter och 66 delar av en i huvudsak av alifatiska kolvaten bestaende blandning med kokpunkten 150-180°. Darmed besprutas en yllemuslin, vars kvadratmetervikt uppgar till cirka 8g, p0 sa. satt, att per inz pasprutas 20 g »Spray. Yllemuslinen far torka i luft. Det pa sa salt behandlade materialet underkastas mi5gelflacksprov sasom beskrivits i exempel 1. Nagon vdxt av mikroorganismkolonier erhalles icke. Anvandes I stallet for yllemuslin bomullskalika vid ovan beskrivna behandling, sa. undertryckes all vaxt av mikroorganismkolonier. Example 10. A "Spray" is prepared of 2 parts of 5,6-dichloro-2,3-dihydro-benzoxazol-2-one, 2 parts of 1-dodecyl-2-iminoimidazolidine hydrochloride, 5 parts of dioctyl phthalate, 25 parts of ethylene glycol monoethyl ether and 66 parts of a mixture consisting essentially of aliphatic carbonates with a boiling point of 150-180 °. Thereby a woolly muslin is sprayed, whose square meter weight amounts to about 8g, p0 sa. true, that 20 g »Spray is injected per inch. The woolly muslin is allowed to dry in air. The salt-treated material is subjected to powdery mildew testing as described in Example 1. No growth of microorganism colonies is obtained. Used in the place of wool muslin cotton calico in the treatment described above, said. all growth is suppressed by microorganism colonies.

Tabell 3. Table 3.

Resultaten av kontrallproven i exemplen. The results of the control tests in the examples.

Mogelflacksprov Halt be-Antal syamp- Ehand-kolonier x-. ern-Peibad Penieil- Stachy- Asper- glitter lium ex- botrysgums pansumatraniger For-Jord- rutt- nedgrav nelse-nings- prov.prov. Mogelflacksprov Halt be-Antal syamp- Ehand-kolonier x-. ern-Peibad Penieil- Stachy- Asper- glitter lium ex- botrysgums pansumatraniger For-Jord- rutt- nedgrav nelse-nings- prov.prov.

Halsttit- Halstot- nings-flings- hdllfast- hallfast- hethet 11 0 0 0 91 % 100 % 21 0 0 0 100%90% 30,0 0 0 93% 99% 41 0 0 0 88 % 100 % 0,0 0 0 90% 92% 62 0 0 0 100 % 100 % 70,0 0 0 89% 90% 81 0 0 0 98% 89% 92 0 0 0 97% 98% Blind- fors& 0 co co co %0% — —Halsttit- Halstot- nings-flings- hdllfast- hallfast- hethet 11 0 0 0 91% 100% 21 0 0 0 100% 90% 30.0 0 0 93% 99% 41 0 0 0 88% 100% 0.0 0 0 90% 92% 62 0 0 0 100% 100% 70,0 0 0 89% 90% 81 0 0 0 98% 89% 92 0 0 0 97% 98% Blind- fors & 0 co co co% 0% - -

Claims (8)

Patentansprak:Patent claim: 1. Forfarande for skydd av organiska material av alla slag mot mikroorganismer, kdnnetecknat av att materialen fOrsattas med en amneskombination, som bestar av minst ett mikroorganismdodande verksamt arnne tillhorande en klass av foreningar med den allmanna formeln A / 111—N N—R, (I) NH van i R, betecknar en lipofil grupp av 10-14 kolatomer eller en lipofil grupp innehallande aralifatisk rest, R, betecknar vale eller en alifatisk grupp med 1-4 kolatomer och A betecknar en genom a,3- eller a,-kolatomer forenad alifatisk eller en genom a,fl-kolatomer forenad cykloalifatisk rest, och av minst ett mikroorganismdodande verksamt dime tillhorande en klass av foreningar med den allmanna formeln 4 NH 5 / (Hal). n C=(II) 6'\\ 0 / van i Hal betecknar halogen och n betecknar 0,1,2,3 eller 4, varvid viktforhallandet verksamt amne med formeln I till verksamt amne med formeln II tapir 1:1 till 4:1.1. A process for the protection of organic materials of all kinds against micro-organisms, characterized in that the materials are represented by a combination of amnesis, consisting of at least one micro-organism-killing active substance belonging to a class of compounds of the general formula A / 111 — NN-R, (I ) NH van in R, denotes a lipophilic group of 10-14 carbon atoms or a lipophilic group containing araliphatic residue, R, denotes vale or an aliphatic group having 1-4 carbon atoms and A denotes one by a, 3- or a, carbon atoms united aliphatic or a cycloaliphatic radical united by α, β-carbon atoms, and of at least one microorganism-killing active dime belonging to a class of compounds of the general formula 4 NH 5 / (Hal). n C = (II) 6 '\\ 0 / van i Hal represents halogen and n represents 0,1,2,3 or 4, the weight ratio of active substance of formula I to active substance of formula II tapir 1: 1 to 4: 1. 2. Forfarande enligt patentanspraket 1, kannetecknat darav, att viktforhallandet verksamt am-no med formeln I till verksamt amne med formeln II utgor 2: 1 till 3: 1.2. A process according to claim 1, characterized in that the weight ratio of active compound of formula I to active substance of formula II is 2: 1 to 3: 1. 3. Forfarande enligt patentanspraket 1 eller 2, kannetecknat darav, att som bararmaterial for de verksamma amnena anvandes vatten.3. A method according to claim 1 or 2, characterized in that water is used as the carrier material for the active substances. 4. Forfarande enligt nagot av patentanspraken 1-3, kannetecknat darav, att A betecknar en 1,2-etylenrest.4. A process according to any one of claims 1-3, characterized in that A represents a 1,2-ethylene residue. 5. Forfarande enligt nagot av patentanspraken 1-4, kannetecknat &ray, att H1 betecknar en alifatisk kolvaterest med 12-14 kolatomer och R, betecknar vate.5. A process according to any one of claims 1-4, characterized in that H1 represents an aliphatic carbonate residue having 12-14 carbon atoms and R represents hydrogen. 6. Forfarande enligt nagot av patentanspraken 1-5, kannetecknat ddrav, att som verksamt amne med formeln II anvandes 5,6-diklor-2,3-dihydro-bensoxazol-2-on eller 4,5,7-triklor-2,3-dihydro-bensoxazol-2-on.6. A process according to any one of claims 1-5, characterized in that 5,6-dichloro-2,3-dihydro-benzoxazol-2-one or 4,5,7-trichloro-2 is used as active ingredient of formula II. 3-dihydro-benzoxazol-2-one. 7. Mikroorganismdodande medel for utforande av sattet enligt patentanspraket 1, kannetecknat av en halt av en amneskombination, som bestar av minst ett mikroorganismdodande verksamt amne tillhorande klassen av foreningar med den allmanna formeln A / RN—R 2 / 5. NH och av minst ett mikroorganismdodande amne tillhorande klassen av threningar med den all-manna formeln ,\4NH 1 \\(/ C=O 6. (Hal). 61 / \ 0 van iR„ A, Hal och n ha den i patentanspra- ket 1 angivna betydelsen.A microorganism-killing agent for carrying out the kit according to claim 1, characterized by a content of an amnesic combination, which consists of at least one microorganism-killing active substance belonging to the class of compounds of the general formula A / RN-R 2 / 5. NH and of at least one microorganism-killing substance belonging to the class of exercises of the general formula, \ 4NH 1 \\ (/ C = O 6. (Hal). 61 / \ 0 van iR „A, Hal and n have the meaning given in patent claim 1 . 8. Ett enligt nagot av patentanspraken 1-6 skyddat material. Anfiirda publikationer: Stockholm 1962. Kungl. Boktr. P. A. Norstedt & Saner. 6200898. A material protected according to any of claims 1-6. Listed publications: Stockholm 1962. Kungl. Boktr. P. A. Norstedt & Saner. 620089