WO2012041910A1

WO2012041910A1 - Solution made of guanidinium compounds, method using said solution, and use thereof

Info

Publication number: WO2012041910A1
Application number: PCT/EP2011/066872
Authority: WO
Inventors: Sebastian Oberwalder
Original assignee: Elektra Management S.R.O.; Schark, Christopher
Priority date: 2010-10-01
Filing date: 2011-09-28
Publication date: 2012-04-05
Also published as: EP2621281A1

Abstract

The invention relates to a solution containing (a) one or more polymeric guanidinium compounds having the formula (A), where R₁and R₂ independently of each other are H, an organic radical or [-C(=NH)-NHR₃], where R₃ is a hydrocarbon group, X^-= anion and n ≥ 2, (b) one or more surfactants, surface active substances, film-forming agents, layer-forming agents, detergents and/or wetting agents, (c) one or more solvents, and optionally (d) one or more disinfecting agents, and to the use thereof.

Description

Solution of guanidinium compounds, methods using this solution and their use

I. Field of the Invention The invention relates to solutions of guanidinium compounds and to a method using this solution and to the use thereof, in particular solutions for killing microorganisms, for preventing renewed growth of microorganisms and for eliminating odors. II. Background of the Invention

The efficient killing of microorganisms and the prevention of microbial growth are of high or growing importance in a number of areas. This starts with normal household hygiene and goes beyond the cleanliness of public facilities such as public buildings and transport facilities to areas with specific hygiene requirements, such as hospitals, medical practices, care facilities, laboratories and military facilities. The type of hygiene requirement ranges from purely preventive measures for preventing or slowing down the relocation of microorganisms after cleaning, to conservation measures, for example in the food sector, to (special) decontamination, for example to remove mold from buildings or from ( highly) pathogenic germs in hospitals and laboratories.

For the purposes mentioned, a variety of different substances are known, which will be summarized below under the terms "preservatives" and "biocides", depending on whether the main purpose of these funds is the Prevention of colonization by microorganisms is preservative or its destruction (= biocide). The known substances differ in many ways, especially in their uses and effects or undesirable effects. Thus, the way in which the application is used or the (security) measures to be taken care of is very different, as well as in which areas a secure application is possible at all. Furthermore, individual substances are effective faster or slower, in lesser or greater amounts or for a shorter or longer period, for killing or preserving against different microorganisms or different groups of microorganisms. In addition, in particular compounds which kill quickly or against a variety of microorganisms often have in addition to the desired effects and undesirable effects, such as from a certain amount for higher organisms are toxic or incompatible, burns the skin or at least corrosion of all materials Cause damage, contaminate waters or are generally hazardous to the environment.

Among the compounds with the best efficiency profile, defined here as the ratio of the desired activity against microorganisms in comparison to the undesirable side effects such as toxicity, corrosion and environmental compatibility and the ease of use include polymeric guanidine or guanidinium compounds (both terms are hereinafter used as interchangeable), probably the most common representative of which is polyhexamethylene biguanidinium chloride (hereinafter: PHMB, by: Arch Chemical Inc.).

Since these basically very efficient polymeric guanidinium compounds have gaps in their efficacy profile, for example, to kill germs often require longer periods of time (eg PHMB requires at a concentration of 100 ppm for about 30 minutes to a 99.99% reduction of Pseudomonas aeruginosa (NCTC 10662)), there is a need to combine polymeric guanidinium compounds with other preservatives or biocides. In US 2010/0055196 a combination of - among other possible biocides - PHMB with at least one acid and possibly other disinfectants such as, inter alia, quaternary ammonium compounds described as surfactants.

In US 2002/0071874 is generally the possibility of a combination of guanidines - without specifying them in more detail - as a (therapeutically) effective component with a solubility enhancer and another preservative described.

US 2004/0191284 describes an ophthalmic solution consisting of a surfactant, an oil and a chlorite, which may also contain a biguanidine as further disinfectant. No. 7,575,673 describes a system for water treatment in which other biocides can be used in addition to polymeric biguanidines as disinfectants.

Finally, US 2007/0048344 describes the possibility of combining PHMB with another biocide, and optionally an anti-static agent or fluoropolymer.

III. DESCRIPTION OF THE INVENTION a) Object of the invention

The object of the invention is therefore to provide a solution of a guanidinium compound, which is particularly long-lasting efficacy against microorganisms, and to provide a method using this solution and their use. Solution of the task

According to the invention, this object is solved by the features of claims 1, 10 and 16. Preferred developments can be found in the dependent claims.

According to the invention, a solution containing

(a) one or more polymeric guanidinium compound (s) having the formula (A)

⁺ NH ₂ X ^"

C (A)

/ \

R ₂ HN NH-Ri where R 1 and R ₂ independently of one another are H, an organic radical or [-C (NHNH) -NHR ₃ ], in which R _{3 is} a hydrocarbon radical,

X ^" = anion and

n> 2, are,

(b) one or more surfactants, surface-active substances, film formers, layer formers, detergents and / or wetting agents,

(c) one or more solvents, and optionally

(d) one or more disinfectants are provided. Advantage of this solution according to the invention is the particularly good efficiency profile, defined here as the ratio of the desired to the undesirable effects. The solution according to the invention is also particularly suitable for

Odor removal, In addition, according to the invention, the use of acids verzieh et forgiven that are even considered harmful. Avoiding acids avoids massive undesirable effects, such as the corrosion of (metal) surfaces or the skin of persons entrusted with the use of this solution. Thus, the present invention already quite generally differs from the prior art in that instead of polymeric biguanidines, in particular PHMB, it is also possible to use polymeric (mono) guanidines, in particular polyhexamethyleneguanidine (chloride) (hereinafter: PHMG). In this context, it should be noted that the possibility of using polymeric mono-guanidines by no means follows logically from the use of polymeric biguanidines. For example, the manufacturing process and the availability of polymeric guanidines and polymeric biguanidines are completely different. Similarly, completely different derivatives of the individual polymers are available: While available on the market biguanidines are as far as visible only in their chloride form, polymeric (mono) guanidines are also available as hydroxide or phosphate form, which brings significant advantages hirisichtlich their corrosion behavior. Finally, the efficacy of polymeric (mono) guanidines and polymeric biguanidines also varies. Thus, it is known with regard to the effectiveness of the polymeric biguanidines that they act primarily by immobilization of microorganisms and the destruction of their cell walls, and thus may have a cytostatic effect with respect to polymeric (mono) guanidines. This leads, inter alia, to different bacterial profiles, such as in particular different killing times and minimal inhibitory concentrations, as shown in Table 1 below. Table 1

Paulus, Wilfried: Microbicides for the Protection of Materials: A Handbook, 1993, p. 396 Table 122 Test on 2x10 ⁶ CFU jin broth coated glass test specimens

For the purposes of the invention, it has been found to be sufficient if the individual components (one or more guanidinium compound (s), one or more surfactants, film formers, layer formers, surface-active substances, detergents and / or wetting agents, for simplicity's sake referred to as "film former", unless otherwise stated), solvent and optionally one or more disinfectants) are sprayed in succession and the mixture directly on eg the surface of the object to be treated (surface, etc.) mixed as a solution, the order without Influence on the intended effect.

Also, the successive delivery of the components of the solution according to the invention in the environment (indoor air or in closed systems) and the there mixing is suitable as sufficient for the method steps described later.

According to the invention, the radicals R 1, R ₂ and R ₃ in the formula A are independently of one another aliphatic or aromatic, branched or unbranched hydrocarbon radicals having 1 to 40 carbon atoms and X ^"is an acid radical _{In this case, 2} and R ₃ have been found to be 2- (2-ethoxy) ethoxyethylene, ethylenediamine, triethyleneglycol diamine, hexamethylenediamine and various (poly) oxyalkylenediamines.

By specific selection of the corresponding radicals, it is possible to obtain the desired properties in a simple manner.

According to the invention, the solution contains 0.00001 to 15% by weight of the one or more polymeric guanidinium compound (s), 0.0001 to 15% by weight of one or more film formers, 55 to 99.99% by weight. a solvent and optionally 0.00001 to 15% by weight of one or more disinfectants. Solutions have been found to be particularly effective, from 0.001 to 2 parts by weight of one or more polymeric guanidinium compound, 0.01 to 2 wt .-% of one or more film formers, 94 to 99.9% by weight of a solvent and optionally from 0.001 to 2% by weight of one or more disinfectants, in particular of stabilized chlorine dioxide.

Preferred radicals X ^'are the radicals hydroxide, phosphate, fluoride, bromide, iodide, acetate, diphosphate, sulfate, nitrate, thiocyanate, thiosulfate, carbonate, maleate, fumarate, tartrate, mesylate, gluconate or toluenesulfonate, in particular

Hydroxide, phosphate, diphosphate, acetate and carbonate are preferred. With the selection of the corresponding radicals according to the invention, the corrosivity in comparison with the economically most prevalent radical, chloride, can be considerably reduced, in particular with low additional costs. This improves both the ease of use and the range of applications. Regardless of the lower corrosivity increased by the preferred ions, the environmental compatibility of the product or its degradation products. Particularly useful guanidinium compounds which can be used in the present invention are compounds selected from the group consisting of polyhexamethylene biguanide, polyhexamethylene guanidinium chloride, polytriethylene glycol di-guanuanidinium chloride, oligo- (2- (2-ethoxy) ethoxy-ethylguanidinium chloride), polyoxy; alkylguanidinium hydroxide, polytriethylene glycol diamine guanidinium hydroxide, oligo- (2- (2-ethoxy) ethoxyethylguanidine dinium hydroxide), polyoxyalkylene guanidine diamine phosphate, polytriethylene glycol diamine guanidinium phosphate or oligo (2- (2-ethoxy) ethoxyethyl guanidinium phosphate). Particularly preferred are polyhexamethylene biguanidine hydroxide, polyhexamethylene guanidinium hydroxide, polyhexamethylene biguanidine phosphate or polyhexamethylene guanidinium phosphate. These compounds are commercially available from Arch Chemical Inc. or Innova Solutions GmbH, Friedrichshafen, Germany.

The hydroxide or 'phosphate derivatives of the abovementioned compounds can also be obtained by Ibnentausch of the chloride derivatives.

The same also applies to the derivatives of the surfactants, surface-active substances, film formers, layer formers, detergents and / or wetting agents used, where the one or more surfactants is a cationic, nonionic and / or amphoteric surfactant. The surfactants according to the invention, surface-active substances, film formers, layer formers, detergents and / or wetting agents are generally added in a molar ratio of surfactant / surfactants, surface-active substances, film formers, layer formers, detergents and / or wetting agents to the guanidinium compounds or compounds used a molar ratio of 0.001: 1 to 10: 1 used. Particularly preferred is a molar ratio of 0.1: 1 to 5: 1, particularly preferably a ratio of 0.7: 1 to 1, 3: 1. This selection according to the invention allows - as detailed below - in particular a better surface distribution with reduced duration of use and improved Nachreinigungsmöglichkeiten.

to be required. Also may be required to produce a homogeneous solution, the use of several different solvents.

In addition, if appropriate, the solution according to the invention may contain one or more disinfectants. Biocides are preferably used or tenside or an oxidizing action preservatives, such as stabilized chlorine dioxide, _benzyl-2- Ci-i8 alkyldimethylchlorid, didecyl dimethyl ammonium chloride, N-alkyl (C ₁ i ₄ _2-) -N-ethylbehzyl-N, N-dimethyl ammonium chloride. The addition of these additional disinfectants and / or biocides is usually in from 0.00001 to 15% by weight, preferably from 0.001 to 2% by weight. It has been found to be particularly effective if chlorine dioxide is added to the solution as a disinfectant. Particularly preferred is stabilized chlorine dioxide, which is commercially available from Dow Chemical Michigan, USA. Peroxodisulfates, preferably sodium peroxodisulfate, ammonium peroxodisulfate or potassium peroxodisulfate are particularly preferred as stabilizers of the chlorine dioxide. The influence of the stabilizers means that the chlorine dioxide in the solution or in its precursors remains storable for longer, which considerably simplifies the logistics required for distribution or generally increases the economic efficiency of the application. |

(Stabilized) chlorine dioxide is preferred over other disinfectants in that, unlike other disinfectants, it has a very low corrosive effect. In addition, chlorine dioxide is highly efficient at destroying spores, bacteria and viruses, requiring very little contact time, in particular. Furthermore, chlorine dioxide is biofilm-destructive. This property is advantageous because often only insufficient biofilm destruction and, consequently, rapid repopulation of the infested objects, rooms, etc. with germs occurs due to other disinfectants, as well as by low-concentration polymeric guanidines. The extensive biofilm destruction caused by chlorine dioxide not only slows down any repopulation, but also reduces the effect that repopulation is often predominantly due to particularly undesirable pathogens, because these are beneficial to uninhabited biofilms Find nutrient conditions. Instead, the resettlement of a biofilm-free area is often more uniform due to different types of bacteria, creating a fundamentally preferred bioenvironment. According to the invention, the (stabilized) chlorine dioxide is introduced in from 0.01 ppm to 3000 ppm into the ready-to-use solution. Particularly preferred ranges are from 0.1 ppm to 1000 ppm, in particular from 0.01 ppm to 300 ppm, very particularly preferably from 0.1 ppm to 150 ppm. In addition, the! Solution far less corrosive than similar known solutions. This is due, inter alia, to lower use concentrations due to the synergistic or enhanced effectiveness. In addition, the corrosion properties; significantly improved by the extensive use of hydroxide or phosphate derivatives instead of chloride derivatives of the compounds used. Likewise, the corrosion properties can possibly be improved by ion exchange of the solution or its feed chemicals from chloride derivatives to hydroxide derivatives in a manner known per se. Finally, depending on the embodiment, the pH of the solution used is from 4 to 10. Particularly preferred is a pH of from 5 to 9, particularly preferably from 5.5 to 8.5. The pH value according to the invention makes it possible to achieve increased human compatibility, in particular increased skin tolerance, and generally lower corrosiveness.

In addition, the solution according to the invention may contain corrosion inhibitors as a further constituent. The anticorrosion agents for the purposes of the invention in particular the corrosion inhibitors from the group consisting of triazo compounds, triethanolamine and their compounds, aminocarboxylates, neutralized carboxylic acid compounds, bisethanols, (alkyl) phosphoric esters and / or poly / / orthophosphates have been shown. Preferred corrosion inhibitors include triazo compounds such as benzotriazole, tolutriazole, triethanolamines, and the like Compounds such as triethanolamine dinonylnaphthalenesulfonate, amine carboxylates, neutralized carboxylic acid compounds such as amine neutralized alkylsulfonamidocarboxylic acids, bisethanols such as 2,2 '- [[(5-methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol; 2,2 '- [[(4-Methyl-1H-benzotriazol-1-yl) methyl] imino] - bisethanol, (alkyl) phosphoric acid ester.

Likewise preferred are poly- / orthophosphates which, in addition to their suitability for inhibiting corrosion when used in water-carrying systems, have the advantage of hardness stabilization, thereby preventing undesirable scale precipitations. Likewise, the formation of protective films on the treated surfaces is desired. Finally, it has been shown that these substances have no effect on the smell, taste, hygiene and digestibility of drinking water, and thus are generally classified as harmless in the application.

Usually, these anti-corrosive agents are used in concentrations of 0.0001 to 5% by weight, preferably in concentrations of 0.01 to 1% by weight. The solution according to the invention has largely surprising advantages over known solutions of guanidine compounds and is usually used for killing bacteria, viruses, fungi and / or other microorganisms for the reduction or elimination of perceptible odors for preservation, as an additive and / or for surface treatment ,

Surprisingly, the mixture according to the invention is not only suitable for killing microorganisms, but also outstanding for odor neutralization. This is by no means self-evident, since many known disinfection solutions themselves often cause a smell that is often perceived as unpleasant. It is particularly surprising that odors are greatly reduced or; neutralized by bioactivity but by completely independent sources such as burning smell, smoke, tobacco smoke or kitchen fumes. The effect This is done by actual odor reduction, so not by covering the possibly perceived as disturbing smell with the inherent odor of the mixture. Rather, the lyiischung appears to be more or less odor-free for the human sense of smell, depending on the concentration of use, and does not leave any perceptible odor in the long term.

In addition, a significantly faster onset of action is achieved by the combination of the polymeric guanidinium compounds used according to the invention with in particular oxidatively acting preservatives or biocides, without significantly adversely affecting the known long-term effect of polymeric guanidinium compounds, as shown in Table 2 below.

Table 2

In addition, the combination of polymeric guanidines with oxidative preservatives or biocides generally leads to a better profile of action. For example, combinations of polymeric guanidines and oxidative preservatives or biocides are effective Surprisingly, not only as expected in the short and long term, but also mutually enhancing and synergistic, which is in no way obvious. Enhancement of action is defined here in that the effect of the combination of two or more active ingredients is greater than would be expected by pure addition of their known modes of action, ie, for example, a combination of less than half the known minimum inhibitory concentration (minimum MIC) of two active ingredients is sufficient to achieve an inhibitory effect. Synergetic effect is here defined to the effect that the effect of the combination of two or more active ingredients has a greater spectrum of activity than the respective individual substances.

Neither the basic effect enhancement nor the synergistic effect are self-evident, and certainly not the fact that this enhancement of action and synergetic effect occurs in all investigated guanidine derivatives and oxidative preservatives or biocides.

The use according to the invention of surfactants, surface-active agents, film formers, layering agents detergents and / or wetting agents (hereinafter referred to as "film formers" for simplification purposes, unless stated otherwise) leads, in addition to the already described reduced corrosivity, to a better applicability of the composition It is known that polymeric guanidinium compounds have disadvantageous properties for many applications in that, after evaporation of the solvent used, they remain as a sticky residue on the treated surfaces and thereby promote re-fouling of these surfaces These can be applied without the addition of a surfactant, resulting in visually unsightly and extremely difficult to remove impurities to surface damage a much better surface distribution of the substances used, whereby impurities are at least less visible. Also, some of the film formers used themselves leave residues, which combine in an advantageous manner with the applied polymeric guanidines. So can be formed by the use of fatty alcohols, a waxy film, which is no longer sticky, but effectively counteracts a renewed contamination by dust particles, for example. In addition, the inclusion of film formers or the residues caused by these often protects against certain forms of surface damage, especially corrosion.

The often desired long-term effect, however, is promoted by the use of film formers. For example, the long-term effect on wall surfaces has already been fundamentally improved, since the uniform distribution better prevents the formation of inactive areas or offers better protection against accidental removal by stripping or similar mechanical impairments. Likewise, the residues of the film formers result in the formation of a mixed layer of the polymeric guanidines and the film formers (and possibly the other constituents of the solution), as already described above. This mixed layer now represents a more or less permanent biocidal or preservative protective layer depending on the selected film former (s). In particular, the use of high molecular weight film formers leads to relatively long-term to permanent surface coatings, which in turn depend on the film former used have high specific or general resistance to chemicals and / or solvents and / or mechanical stresses and / or deposits or deposits of other substances and dirt particles and / or other impairments.

In the overall result, the addition of surfactants, surface-active agents, film formers, layer formers, detergents and / or wetting agents to the polymeric guanidinium compounds thus leads to very substantial application advantages.

In particular, the solution according to the invention is suitable for application in the spray process and thus leads to a spray disinfection, in particular in the compressed air / cold mist process. According to the invention it has been found that at Use of the solution! Advantageously, when spraying the solution, a device under positive pressure with at least one spray nozzle is used, wherein the solution in the form of a mixture or aerosol from the solution and a gas is applied.

Although the use of polymeric guanidines for spray disinfection is known.

The problem with this application, however, is often that the spray nozzles used stick together after a very short time, and thus in reusable or refillable sprayers cleaning is required, or disposable and disposable sprayers only part of the spray solution contained in the can or device can actually be applied. The mixture according to the invention now offers the application advantage that this gluing of the j spray nozzles in the test over several months with four different reusable spray devices (Innova Solutions) could no longer be determined. Likewise, a sticking in a total of 100 hand spray bottles over a period of over 3 months was not observed. Finally, refillable hand spray bottles whose spray nozzles were partially adhered by the use of a solution of 99.5% by weight of water with 0.5% by weight of PHMG, thus yielding only insufficient dispersion performance, were replenished by the use of a spray solution Solution 2 according to the following Production Example 1 was again cleaned to such an extent that again a dispersion performance comparable with new spray nozzles was achieved.

Another surprising application advantage of the solution according to the invention in comparison with the subsequent atomization of polymeric guanidines is the residence time of the cold mist - also referred to as mist life - in a treated container or room. While this mist life with the use of pure polymeric guanidines depending on the concentration relatively long can be surprisingly significantly shortened in the inventive solution, ι

This lower fog life is advantageous because this shortened cleaning cycle times and thus a lower time and personnel costs for cleaning personnel is possible. In particular, this reduction of the Nebelyerweildauer from when applied in areas where as immediate as possible reusability should be given, e.g. in the medical field in the disinfection of operating rooms, which should be unusable due to any need for space use for emergencies only as briefly as possible due to cleaning measures.

In addition, the surprising effect of shortened fogging times can be exploited to the effect that influencing the fogging times is made possible by the concrete composition of the solution according to the invention.

In general, for the reasons mentioned above, a short mist life will be preferable. In individual cases, however, despite the fundamental advantages of the shortened fog periods, such a shortening may not be desirable, but rather a stabilization of the fog. This could be the case, for example, if the main purpose of the disinfection measure is the air purification itself, or if in a space permanently filled with the aerosol ("cloud chamber") changing bodies are disinfected by introducing and removing these bodies into the cloud chamber For this purpose, the use of a high proportion of polymeric guanidinium compounds and a small proportion of film formers is preferred, since surprisingly the mist life can be controlled via the amount of film former, and thus a reduction in this proportion surprisingly leads to a sometimes considerable extension of the fog lives. As already stated above, the inclusion of film formers, regardless of their influence on the fog lives to general considerable application advantages, such as the formation of a long-term or permanent protective layer, the use of the inventive solution in comparison to the mere spraying or misting of

Guanidine compounds, chlorine dioxide solutions or any known

Combinations appear highly advantageous.

Because of the unwanted change in the fog lifetime in each case, however, the ratio between film formers and polymeric guanidines, such as PHMB, has to be determined separately, with no appreciable changes in the application behavior at a MoH ratio of less than 0.001 mol of film former per 1 mol of PHMB is expected. Conversely, a molar ratio of more than 5 moles of film-forming agent per one (1) mole of polymeric guanidine no longer leads to a significant increase in the application advantages such as (re) cleaning options, surface protection or fog lives. In general, a ratio of about 0.1 mole of film former per 1 mole Polyhexamethylenbiguanidin already leads to a greatly improved (Nach-) cleaning ability and significantly improved surface protection with still relatively little influence on the fog lives, while at a ratio of one (1) mol Filmbildner per one (1) mol Polyhexamethylenbiguanidin already bebbachten a significant reduction in fog life with excellent (Nach-) cleaning ability or surface protection.

The surprising possibility of influencing the mist life by the change in the film former content opens up the potentially extremely advantageous possibility of faster elimination of an already built fog. If, for example, a cold mist with a rather long residence time is introduced into a room, and if this room unexpectedly becomes fog-free again before the (calculated) end of the fog period - for example because of a surprising need for another use or because of an accident during the execution of the disinfection measure the in itself relatively stable Fog - in addition to other removal measures such as airing - be eliminated much faster by the additional nebulization of a pure film-forming solution.

Due to the enhancement of the effect of the inventive solution, there are also application advantages due to the lower demand

Disinfectant for performing a spray disinfection. In addition to a lower environmental impact, this is expressed above all in further shortened periods of use, which have a significant cost-saving effect, in particular due to the likewise saved working hours and faster reusability. For example, the same or a better disinfecting effect as with about 1, 35 l of a 0.2% PHMG solution can be achieved with one liter of the solution 4 according to preparation example 1 described below, whereby u.a. shorten the application times by approx. 25%. This is particularly important in the disinfection of large objects, such as

Industrial halls, whereby then the working time and the due to the disinfection measure: conditional inability to use can be reduced by several hours. The particularly broad effectiveness, the combination of immediate with long-term effect, the reduced corrosivity and the surprising ability to remove odor are particularly advantageous when used for spray disinfection. When using the solution for spray disinfection, the following method is particularly preferred:

Since spray disinfection is only a supplement and not a substitute for normal surface cleaning, pre-cleaning of visible or presumably soiled and not only biologically contaminated surfaces is preferred. Due to the biofilm destructive effect of the oxidative disinfectant preferably used in addition to the polymeric guanidines is a On the other hand, pre-cleaning in the case of only biologically contaminated surfaces is dispensable.

For pre-cleaning, standard cleaning measures such as wiping cleaning will generally suffice. In closed systems, rinsing with compressed air and / or water are also preferred for pre-cleaning. In water-bearing systems, a pre-cleaning by compressed air / water mixtures is preferred, in piping and hose systems in particular by the use of diiirch compressed air accelerated water units, which is also referred to as "Druckpulsverfahren'l. For larger water-bearing or water-resistant containers and for outdoor use on vehicles, buildings, etc., the use of high pressure washers is also preferred.

The spray disinfection can in principle be carried out with all suitable devices. Preferably, the use is with at least one spray nozzle and at least one compressed air or propellant gas source, e.g. the use of hand pump spray bottles, pump spray containers, compressed air spray cans, propellant spray cans, compressed air nozzle spray systems, compressor nozzle spray systems, vacuum turbine nozzle spray systems, or ultrasonic nozzle spray systems.

Particularly preferred is! the use of cold mist spray devices, through which in a single device, an aerosol of compressed air and the inventive solution with droplet sizes of preferably <50 microns, more preferably <1 0 microns, generated and sprayed. These devices are commercially available from Innova Solutions GmbH.

When used for spray disinfection, preference is given to the use of water as solvent or carrier medium, in particular water purified by nanofiltration or distillation and demineralized water. This is due to the fact that other solvents often used, such as alcohols, have considerable disadvantages for use, such as an increased flammability, which, for example, in cold fogging; ranging from industrial halls to the risk of explosion could. The demineralization of the water proves to be advantageous in terms of any application residues (limescale, etc.).

The mixing of the individual components of the solution can also be done by several leads or a two-chamber cartridge only directly in the nebulization. Likewise, the solution can be prepared by simultaneous or timely successive nebulization of the individual components only on the treated surface. The mixing can also be done in front of the nozzle before nebulization or by two nozzles, but also by applying one after the other.

Normally the spray disinfection will take place under normal pressure. In closed systems, however, it may be expedient to carry out the spray disinfection under overpressure / overpressure.

A spray disinfection under vacuum ventilation is particularly preferred in the disinfection or decontamination of (potentially) with biological

Hazardous substances contaminated rooms, such as biotechnical laboratories. Spray over-pressure spray disinfection is preferred in at least partially flexible closed systems, such as systems containing tubing. Here, the overpressure in the system ensures better wetting of all surfaces inside the system. To generate the overpressure, the pressure of the spray system in combination with one or more counterpressure countervalves (s) at the one or more outlet points of the closed system is generally sufficient. An application example may be the disinfection of fiber hoses as air conditioning exhaust systems. Here already the hose itself represents the overpressure counter-valve, whereby; In the case of spray disinfection with positive pressure ventilation, optimum disinfection of the entire outlet system can be achieved. Basically, no post-cleaning is required after spray disinfection. In individual cases, however, different post-treatment steps may be required. If rapid reuse of a treated room or closed system is intended, flushing the system with compressed air or ventilating the room may be appropriate. Likewise, alternatively or additionally, an accelerated mist degradation by post-fogging with film-forming solutions - as described above - be useful. In water-bearing systems, a rinse with a water / compressed air mixture, preferably in idesinfizierter form gem. the German law for the order of the water household (WHG) and the German drinking water regulation (TrinkwV), expediently. It has according to the invention; shown to be advantageous when the solution used for post-purification is composed of water and / or surfactants and / or further film formers, with particular amphoteric surfactants such as benzyl-Ci2-i 8-alkyldimethylchlorid, Didecyldimethylammoniumchlorid, N-alkyl (ci2-i4) - N-ethylbenzyl-N, N-dimethylammonium chloride, benzyl-C-i2-i8-alkyldimethyl- hydroxide, Didecyldimethylammoniumhydroxid and N-alkyl (Ci _2- i ₄ ) -N-ethylbenzyl- Ν, Ν-dimethylammonium hydroxide are advantageous. According to the invention, water and surfactants are used in a ratio of from 90 to 99.9999% by weight of water and from 0.0001 to 10% by weight of surfactants. Particularly preferred is the

Use of 99 to 99.99% by weight of water and 0.01 to 1% by weight of surfactants.

In addition, the solution according to the invention is particularly suitable for use as a preservative due to the induction immediate disinfection with subsequent long-term effect. Here comes the first

Preservation by admixture in appropriate concentration into consideration.

In addition, the mixture according to the invention is also particularly suitable for use as a means for dip-disinfecting or dip-preserving. Here, the body to be preserved in a bath with the

is neutralized by the solution of any odor residues of the

Achieved manufacturing process

Due to the already described surprising suitability of the mixture according to the invention for odor removal, use for the purpose of odor removal or odor reduction is also preferred, be it in combination within the scope of a simultaneous (spray) disinfection, or independently of other hygiene measures. Preferred applications are in the human and veterinary field, as well as in personal hygiene, for example odor removal and disinfection in hospital kitchens, odor removal and disinfection on farms, pet odor removal, odor removal and personal care disinfection, e.g. as a shoe spray, mouthwash or deodorant.

The invention is based on the following manufacturing

Application examples explained in more detail.

Example 1: General example for the preparation of the solution according to the invention

The mixture of the solution according to the invention is carried out according to the general manufacturing or laboratory standards, e.g. by mixing in suitable glass laboratory vessels using magnetic stirrers at atmospheric pressure and room temperature (about 20 ° C), wherein the chemicals used are preferably j already used as solutions in the solvent used. Depending on the solvent used, the mixture can also be carried out in a further temperature range, with water at approximately from 1 to 40 ° C., with temperatures close to or just below 20 ° C. being preferred. Temperatures higher than 40 ° G should be avoided, in particular when using chlorine dioxide as a further disinfectant, but can only be used with the exclusive use of polymeric guanidines and film formers in the

Individual case permissible or expedient. The mixture under lower or Overpressure is basically possible, but usually brings no benefits. In case of use! of certain other disinfectants, such as in particular chlorine dioxide, the mixture under negative pressure is disadvantageous or to be avoided.

With regard to the mixing process, there are usually no special requirements. In particular, it does not matter in what order the components of the solution J are joined together. Likewise, no minimum mixing time is usually required. Only a complete and thorough mixing must be ensured, which in the case of laboratory preparation of the following solutions 1 to 5 in total amounts of about 1 I under atmospheric pressure at room temperature usually after using a Magneticührvorrichtung with medium stirring intensity for a period of about 1 min is guaranteed.

Special processing steps, such as distillation, etc. are not required.

As a safety precaution in the preparation of laboratory preparations, the use of protective gloves, protective clothing and goggles is recommended. Depending on the further disinfectant or film former used, further safety measures may be required according to the product-specific safety data sheet.

According to the general production example, a solution 1 consisting of

0.4% PHMB (polyhexamethylene biguanidinium chloride)

0, 1%, benzyl-Ci _2- i ₈ - ^ alkyldimethyl chloride (CAS: 68391-01 -5, Bayer AG, Leverkusen, Germany)

0, 1%, didecyldimethylammonium chloride (CAS: 7173-51 -5, Akzo Nobel Surface Chemistry AB, Sweden)

0, 1% N-alkyl (C ₁₂ -i ₄ ) -N-ethylbenzyl-N, N-dimethylammonium chloride (CAS: 85409-23-0, Lonza AG, Basel Switzerland)

Made 99.8% demineralized water (H ₂ 0). According to the general production example, a solution 5 consisting of

0.08% PHMG (polyhexamethyleneguanidinium chloride)

0.08% PHMB (polyhexamethylene biguanidinium chloride)

0.04% benzyl-Ci2-i8-alkyldimethylchloride

0.04% didecyldimethylammonium chloride

0.04% N-alkyl (Ci _2- i ₄ ) -N-ethylbenzyl-N, N-dimethylammonium chloride

0.02% chlorine dioxide (CI0 ₂ )

Made 99.7% demineralized water (H ₂ 0).

According to the general production example, a solution 6 consisting of

30.0% PHMB (polyhexamethylene biguanidinium chloride)

5.0% didecyldimethylammonium chloride

65.0% butanediol produced. Notwithstanding the general preparation example, in addition to the mixture, a distillation process for the separation of the water contained in the solution may be required if I is to be added to the PHMB used in aqueous solution. Here, in particular, the mixture with a 20% aqueous solution with subsequent vacuum drying in a suitable device (eg Rotavapor) is preferred. If the PHMB used is already dissolved in butanediol, this step can be dispensed with. If the mixing of the feed chemicals from original materials, so is a prolonged Stirring over a period of at least 240 min required, preferably at a temperature between 20 and 40 ° C.

Example 2: Use of the Odor Removal Solution According to the Invention

5 test persons took a passenger car, which was driven over a mileage of more than 100,000 km by a heavy smoker, without appropriate interior cleaning took place. 5 out of 5 test persons have noticed a strong smell of tobacco smoke or a subjectively "smell like an ashtray".

Thereafter, 300 ml of the solution 1 according to Preparation Example 1 using a "Car" cold mist compressed air device from Innova Solutions GmbH in the interior of the car with closed doors and windows sprayed or fogged, the ventilation system of the vehicle at the stage recirculation 5 minutes after the mist has been completely introduced, the ventilation system is switched off.

The fog has time to settle overnight. The windows and doors remain closed, additional ventilation or other additional measures do not take place. The following morning, the windows of the car are opened and the ventilation system of the vehicle is switched on for 5 min at the highest level with the highest heat output in order to eliminate any moisture residues. Then the windows are closed again. One hour (1 h) after switching off the ventilation system and closing the windows, the same 5 test persons take the car: again. 5 out of 5 people notice a significant reduction in odor. 4 out of 5 people perceive the car as virtually odor-free, without being able to identify a specific residual odor. A person still takes a hard-to-define, very weak one possibly smoky smell true, but "not at all to compare with the smell of the day before and at least many times less".

Example 3: Use of the solution according to the invention for the removal of burning smell

There was a fire damage in a building. After completion of the structural renovation work for 5 out of 5 people still a typical fire smell was clearly noticeable. In the attic, this smell was particularly noticeable. On an attic floor area of about 60 m ² with a volume of about 120 m ³ then about 3 I of the solution 2 were nebulized according to Preparation Example 1 with a standard cold fogger from Innova Solutions. The nebulization time was about 50 minutes, the further exposure time / mist life was 20 minutes. Thereafter, the room was ventilated by means of a strong fan and the process of atomization repeated again. After another fogging time of 50 minutes and an exposure time of 20 minutes, the room was again ventilated by means of a powerful ventilator. Immediately after completion of the ventilation, no burning smell was noticeable for 5 out of 5 people.

Example 4 Cold Nebulization of the Solution According to the Invention (Reduction of Mist Life)

In the case of cold fogging of 25 l of a 0.5% PHMG solution with a standard room fogging cold fogger manufactured by Innova Solutions in a room about 22 ° C. warm and about 200 m ² with a volume of about 800 m ³ is to be expected with a detectable residence time of the nebula in the air of about 330 minutes, if no ventilation of the nebulized space takes place. Repeated tests were performed with a deviation of +/- 30 min, followed by a further +/- 30 min, unless otherwise specified. Instead of the 0.5% PHMG solution, the same amount of a solution 1 according to Example 1 is atomized. This shortens the detectable mist residence time to about 150 minutes. Due to this lower fogging time a shorter cleaning cycle time and thus less time and personnel costs for cleaning personnel is possible. Particularly advantageous is this reduction in the mist residence time when used in areas where an immediate as possible reusability should be given, eg in the medical field in the disinfection of operating rooms, which due to any need for space use for emergencies only as briefly as possible due to cleaning measures unusable should be. Example 5 Cold Nebulization of the Solution According to the Invention (Variation of Mist Life)

By admixing in each case 0.01% of the film formers used instead of 0.1% of the film formers in solution 1 according to preparation example 1, an extension of the detectable mist life in accordance with example 4 is achieved from about 150 minutes to about 300 minutes.

As already explained above, the adding of film formers leads regardless of their impact on the fog ^■ times to general application advantages. This decision is always to be made in a balance of benefits, even if any desired maximum fogging times are thus slightly shortened. Because of this in some cases, however, undesirable mode of action is the relationship between film formers and polymeric guanidines, such as PHMB set separately for the respective applications, usually with a molar ratio of less than 0.001 mol film former per 1 mol PHMB no: noticeable changes in the application behavior is to be expected. At the other end, there is also a molar ratio of more than 5 moles of film former per one; (1) Mol polymeric guanidine no longer to a significant increase in application benefits such as cleaning options or fog lives. In general, a ratio of about 0.1 mole of film former per 1 mole of polyhexamethylene biguanide already leads to a greatly improved

Cleaning possibility still relatively little influence

Mist life while at a ratio of one (1) mole of film former per one (1) mole Polyhexamethylenbiguanidin already a significant reduction in fog life is observed with excellent cleaning ability.

Example 6: Cold fogging of the solution according to the invention (subsequent shortening of the idle time)

Thus, for example, in the above-mentioned application example 5 by subsequent nebulization of 10 l of a 1% film-forming agent solution after completion of nebulisation of the 0.5% PHMG solution, the mist life without any other

Additional measures approx. 330 min in the initial example are shortened to only approx. 180 min.

Example 7: Reduction of the agents used in the solution according to the invention and shortening of the application times

In an approximately 22 ° C and about 25 m ² large room with a volume of about 65 m ³ , 1, 35 I of a 0.2% PHMG solution with a standard room fogging cold fogger from Innova Solutions nebulized , In this room there are 6 glass test strips placed at different locations, each containing 3 x 1x10 ⁴ colony forming units (hereinafter abbreviated KBE) of the fungus strains of Candida albicans and Aspergillus niger and with 3 x 1x10 ⁴ CFU of bacterial strains Staphylococcus aureus and Pseudomonas aeruginosa were inoculated. All test strips showed at least a log 3 reduction of the bacteria and fungi on them after an exposure time of 30 min, on average a reduction of log 3.3 (bacteria: 3.36 / fungi: 3.23).

On the control strip a colonization of 1x10 ⁴ cfu / ml was still detected.

The results are summarized in Tables 3 and 4.

In the same room, instead of the PHMG solution, one liter (1 l) of a solution 4 according to general preparation example 1 was now atomised. Also in this room were 6 placed at different locations glass test strips, which were inoculated with 3 x 1x10 ⁴ CFU of the fungus strains Candida albicans or Aspergillus niger and 3 x with 1x10 ⁴ CFU of the bacterial strains Staphylokoccus aureus or Pseudomonas aeruginosa. In all test strips, more than one log 3 reduction of the bacteria and fungi found on them could be detected after an exposure time of 30 min, on average a reduction of log 4.0 (bacteria: 4, 0 / fungi: 4.0).

The results are summarized in Tables 5 and 6 below.

On the Kontrollstreifeh again a colonization of 1x10 ⁴ CFU / ml was found.

Table 5

Table 6

Disinfection experiments with "mushroom mixture"

Example 8: Cleaning of hose lines

For the disinfection of hose lines, such. As fire hoses, about 25 m C-Sehlauchauch connected to a mist-generating device with a suitable outlet, such as a hose disinfecting the company Innova Solutions. However, all aerosol or mist generators that are able to be connected to a hose opening in a targeted manner and to generate a slight overpressure in the hose are suitable. At the other end of the hose, an overpressure control valve is attached, with which an overpressure of at least 0.1 bar, preferably over 0.3 bar, is generated in the hose in order to preclude sticking of individual hose parts / hose walls. Now a gem with a solution 4. Production example 1 enriched aerosol produced and introduced with an overpressure of at least the pressure of the control valve plus 0.1 bar in the hose. This is preferably done via a compressor, but can also be done by compressed air such as compressed air bottles. Due to the control valve at the other end creates a controlled overpressure in the hose and the aerosol is now distributed evenly in the hose. After an exposure time of about 10 minutes, the hose is disinfected. A post-cleaning is usually

Preservation of food by dip preservation

In a 100 liter container, 500 ml of the solution 1 according to general preparation example 1 are diluted with 49.5 liters of demineralized water. Two plastic sausages are mixed with 50 ml of a solution of Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli at a concentration of

1x10 ⁴ cfu / ml coated with a teflon spoon. Thereafter, the prepared sausages for about 30 min at a temperature of 35 ° C dried (incubated). One of the sausages prepared in this way is then completely immersed in the container with the prepared solution for about 30 seconds. Thereafter, both sausages are dried for a further 30 minutes at a temperature of 35 ° C (incubated). By pressing in each case 2 Petri dishes with a nutrient solution in each case at two places, a replica pattern of the surfaces of both sausages is subsequently taken. These samples are incubated for a further 24 h at a temperature of 35 ° C and excluding the bacterial concentration in the dishes determined.

The samples of the sausage submerged in the solution have an average concentration of 2 cfu. In the samples of untreated sausage, on the other hand, there are on average about 1x10 ² CFU, ie the CFU is significantly reduced.

Example 11: Preservation of food by spraying

Instead of immersion for preservation purposes, it is also possible to spray disinfect the bodies or surfaces to be preserved, preferably by the cold mist method described above. The concentration corresponds in this case preferably to the undiluted solution used for dip disinfection, although in individual cases deviating concentrations may be expedient.

According to this method, the sausage was treated not by immersion but by spraying with the undiluted solution 1 according to General Production Example 1, thus showing that the treated sausage average of 0 cfu the untreated sausage: on average 1x10 ² cfu had.

Example 12: Dilution of the solution as an additive

The effectiveness as an additive was demonstrated by the addition of the solutions to a polyester resin (PE-Hafe). For example, in each case 50 g of a polyester resin with 0.05, 0.1 and 0.25 ml of a solution 6 gem. to the general preparation example 1 or 0.05 ml of a 35% solution of PHMG in butanediol (BDÖ). It was found that the solution 6 was much easier or faster with the polyester resin bring in a homogeneous mixture. Thereafter, the respective mixtures were mixed with 50 ml of Staphylococcus aureus, J Pseudomonas aeruginosa or Escherichia coli in a concentration of 1 × 10 ⁴ CFU / ml of a germinated solution. After further thorough mixing, 1 (one) ml of this mixture was applied to glass plates provided with nutrient medium (TSB) and incubated at 35 ° C. for 24 h. Thereafter, the nucleating units on the samples were determined (see Table 8).

Table 8

The above Table 8 shows that when using the solutions according to the invention, the CFU is significantly reduced and goes to zero. Example 13: Use of the surface treatment solution

On a 5x5 cm cotton fabric, a thin layer of the solution of the invention is applied by misting 50 ml of a solution 2 according to General Preparation Example 1 in a 1000 liter container in which the fabric is suspended.

The tissue treated in this way is evenly coated with 1 ml of a bacteria mixture containing 10 ⁶ CFU of bacteria per ml by means of a teflon spoon. After a reaction time of 5 [10 or 30 min, the samples were rinsed with 100 ml of a saline solution! and immediately determines the bacteria in the rinse solution.

The results are summarized in Table 9.

Table 9

Bacterium / log reduction Log reduction Log reduction Contact time after 5 min: after 10 min: after 30 min:

Calculate Calculate / Calculate Equal / Equal with Control Equal to Accumulate with Control

Staphylococcus 3.7 (3, 66) 4 (3.9) 4 (3.85)

aureus

Pseudomonas 3.25 (: 3.21) 4 (3.9) 4 (3.85)

aeruginosa

Escherichia coli 4 (3.96) 4 (3.9) 4 (3.85)

Control KBE 3.96 \ 3.9 3.85

after rinsing

of untreated tissue

(Log) Table 9 above shows that surfaces treated with the solution according to the invention, tissue, etc., even after treatment, still have the growth of microorganism-inhibiting properties. This leads to a longer-term sterility or germ reduction on treated surfaces, tissues, etc., which is advantageous, inter alia, for their use in the medical or medical sector.

Claims

1. containing solution

(a) one or more polymeric guanidinium compound (s) having the formula (A)

wherein Ri and R _{2 are} independently H, an organic radical or [-C (= NH) -NHR 3], wherein R _{3 is} a hydrocarbon, X ^" = anion and

n> 2, are,

(b) one or more surfactants, surfactants,

Film formers, layer formers, detergents and / or wetting agents,

(c) one or more solvents, and optionally

(d) one or more disinfectants.

2. Solution according to claim 1,

characterized in that

the radicals Ri, R ₂ and R ₃ in the formula (A) independently of one another are aliphatic or aromatic, branched or unbranched hydrocarbon radicals having 1 to 40 carbon atoms and X ^"is an acid radical.

3. Solution according to one of claims 1 or 2,

characterized in that

Component (b) is a cationic, nonionic and / or amphoteric surfactant, a fatty alcohol, a fatty alcohol sulfate, a polyakohol glycol, a polyolefin, a polyhaloolefin, polyvinylpyrrolidone and / or a fluorosurfactant.

4. Solution according to one of the preceding claims,

characterized in that

the solution center! (c) water is.

5. Solution according to one of the preceding claims,

characterized in that

the molar ratio of the component (b) to the guanidinium compound (a) is from 0.001: 1 to 10: 1.

6. Solution according to one of the preceding claims 1 to 5,

characterized in that

the further disinfectant (d) is selected from the group consisting of oxidative or surfactant disinfectants.

7. Solution according to claim 6,

characterized in that

the disinfectant is chlorine dioxide.

8. Solution according to one of the preceding claims 1 to 7,

characterized in that

the solution additionally contains a corrosion inhibitor.

9. Solution according to one of the preceding claims 1 to 8,

characterized in that

the pH of the solution is between 4 and 10.

10. A method for killing bacteria, viruses, fungi and / or other microorganisms, for reducing or eliminating perceptible odors, for preserving and / or for surface treatment,

characterized in that

a solution according to any one of claims 1 to 9 is used.

11. The method according to claim 10,

characterized in that

the solution is applied by spraying.

12. The method according to claim 0,

characterized in that

the solution is applied in the form of a mixture or aerosol from the solution and a gas.

13. The method according to claim 11 or 12,

characterized in that

for spraying the solution, a device under positive pressure with at least one spray nozzle is used.

14. The method according to any one of claims 11, 12 or 13,

characterized in that

by using a cold mist generating device more than 80% of the particles of the solution <50 pm, preferably more than 90% of the particles of the solution <10 pm.

15. The method according to any one of claims 10 to 14,

characterized in that

the solution contains less than 0.3% chlorine dioxide.

16. Use of a solution according to claims 1 to 10 as an additive in plastics, paints, lacquers, detergents and cleaners, cosmetics, lubricants, paper, cardboard, building materials of all kinds, natural and synthetic polymers.