WO2012010700A1

WO2012010700A1 - Prevention of bacterial adhesion

Info

Publication number: WO2012010700A1
Application number: PCT/EP2011/062666
Authority: WO
Inventors: Birgit Veith; Mirko Weide; Francesca Corbellini; Brigitte Giesen; Stefan Stumpe; Roland Breves; Paula Barreleiro; Stefan Karsten; Dirk Bockmühl; Frank Meier
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2010-07-23
Filing date: 2011-07-22
Publication date: 2012-01-26
Also published as: DE102010038340A1

Abstract

In a method for preventing the adhesion of microorganisms on hard surfaces by the semi-permanent modification thereof during the cleaning process, a cleaning agent is employed which contains surface-active polymers. Said cleaning agent is used accordingly to prevent the bacterial colonization of hard surfaces.

Description

"Prevention of bacterial adhesion"

The invention relates to a method for preventing the adhesion of microorganisms on hard surfaces by their semi-permanent modification during the cleaning process with a cleaning agent.

The bacterial colonization of hard surfaces leads to the formation of biofilms, in particular in the case of at least partially water-rinsed surfaces, for example in toilets and bathrooms. The biofilm is the gelatinous protective layer that is collectively released by the adhering microbes and envelops them. At the same time, this mucus is the reason why bacteria living under real conditions, as well as other biofilm-producing microorganisms, are much more resistant to - even biocide-containing - cleaning agents than laboratory cultures, usually from individual free-floating bacteria, so-called.

planktonic cells. Biofilms lead to massive in technical systems

Impairments and can cause persistent infections in medicine, which are largely resistant to conventional antibiotics. In the household, the biofilm-induced impairments are both hygienic and aesthetic. In addition, they can also have an unpleasant odor, and finally they can clog pipes and other flow systems even in strong severity.

Biofilms can be removed mechanically, but this is associated with a not inconsiderable expenditure of time and effort and also does not or only partially succeed in biofilms in less accessible places. The control of biofilms by biocides is only possible to a limited extent because the mucus matrix, which mainly consists of polysaccharides, protects the cells against the action of the biocides (so-called pseudoresistance). To achieve an effect at all, the biocides would therefore have to be used in much higher doses than would be the case for a

comparable amount of unassociated existing bacteria would be needed. The use of biocides in the home, however, is unfavorable from an ecological point of view, so that the efforts are more likely to provide detergents with only low concentrations or completely without biocides. So far, however, this has not been reconciled with the desire for as complete a removal as possible of bacterial biofilms - and thus optimal hygiene. It would therefore be desirable to prevent the bacterial colonization of hard surfaces as far as possible.

It has now been shown that certain surface-active polymers are able to modify surfaces in such a way that both the formation of biofilms is avoided and the easier removal of soils is made possible. A first subject of the invention is therefore a method of preventing the adhesion of microorganisms to hard surfaces by their semi-permanent modification during the cleaning process with a cleaning agent containing surface-active polymers.

Another object is the use of a detergent containing surfactant polymers to prevent the bacterial colonization of hard surfaces.

For the purposes of this application, "surface-active polymer" means that the polymer modifies a hard surface to which it is applied

Surface properties, so that in the case of the surface-active polymers of the invention, the adhesion of microorganisms and contaminants is inhibited.

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1 101 17th Street, NW, Suite 300, Washington, DC 20036, USA, and contains more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical names, including its distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, for example, polymer ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 bis 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, the oxo alcohols obtainable, for example, by Roelen's oxo synthesis or derivatives thereof having preferably 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, most preferably 1 1 to 15 carbon atoms, for example 9 to 1 1, 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

The agent used in the method according to the invention contains one or more

surface-active polymers. These may be, in particular, amphoteric polymers, generally copolymers. Preferred copolymers are based on acrylate or

Methacrylate, in particular terpolymers are preferred. Furthermore, it is preferred that the polymer has a pH of 0 to 1 1, preferably 2 to 8 and is soluble in aqueous systems

Suitable polymers are preferably composed of the following monomers:

a) cationic monomers of the formula (I),

wherein and R _{4 are} each H or linear or branched C 1 -C ₄ -alkyl,

R ₂ and R _{3 are} each linear or branched CC ₆ alkyl or hydroxyalkyl, n and m are integers from 1 to 3 and

X- stand for a counterion,

anionic monomers, preferably selected from the group consisting of C ₃ -C ₈ - carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids and anhydrides or salts thereof,

A substituted of the formula

where RT is H or CH ₃ ,

R _{2 is} H or CrCz-alkyl and

R ₃ and R _{4 are} each H or C Cs-alkyl.

Preferred cationic monomers a) are diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate,

Diallyldimethylammonium phosphate, di (methylallyl) dimethylammonium chloride,

Di (ethylallyl) dimethylammonium chloride, diallyldi (.beta.-hydroxyethyl) ammonium chloride and

Diallyldiethylammonium. As monomer b) C ₃ -C ₈ carboxylic acids, sulfonic, sulfuric, phosphonic and phosphoric acids and their anhydrides and water-soluble salts are preferred, with at least monounsaturated compounds being particularly preferred.

Examples of suitable C ₃ -C ₈ -carboxylic acids or anhydrides are acrylic acid (AA), methacrylic acid (MA), ethacrylic acid, dimethylacrylic acid, maleic acid, maleic anhydride,

Succinic anhydride, methylenemalonic acid, crotonic acid, fumaric acid, itaconic acid,

Sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid,

Aconitic acid, phenylacrylic acid, vinylbenzoic acid and mesaconic acid.

Suitable sulfonic and sulfuric acid monomers include sulfoethyl methacrylate,

Sulfopropyl acrylate, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS),

Ethylene sulfonic acid, vinyl sulfuric acid, 4-vinylphenylsulfuric acid, 2-methyl-2-propene-1-sulfonic acid and 2-propene-1-sulfonic acid.

Suitable phosphonic or phosphoric acid containing monomers include ethylene phosphonic acid, vinyl phosphonic acid, divinyl phosphonic acid, allyl phosphonic acid, methallyl phosphonic acid, methacrylamidomethane phosphonic acid, 2-arylamido-2-methylpropane phosphonic acid, 3-phosphonopropyl acrylate and 3-phosphonopropyl methacrylate.

Particularly preferred monomers of type b) are acrylic acid, methacrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). The monomers b) can be used as free acids or in the form of their salts. Suitable salts include alkali and alkaline earth metal salts and ammonium salts.

The (meth) acrylamides of the formula II which can be used as monomers c) include

in particular N, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-methylethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-methylpropyl (meth) acrylamide , N, N-ethylpropyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-methylbutyl (meth) acrylamide, N, N-ethylbutyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide , N, N-Propylbutyl (meth) acrylamide, N, N-dipentyl (meth) acrylamide, N, N-methylpentyl (meth) acrylamide, N, N-ethylpentyl (meth) acrylamide, N, N-propylpentyl (meth) acrylamide , N, N-butylpentyl (meth) acrylamide, N, N-dihexyl (meth) acrylamide, N, N-methylhexyl (meth) acrylamide, N, N-ethylhexyl (meth) acrylamide, N, N-propylhexyl (meth) acrylamide , N, N-butylhexyl (meth) acrylamide, N, N-pentylhexyl (meth) acrylamide, N, N-diheptyl (meth) acrylamide, N, N-methylheptyl (meth) acrylamide, N, N-ethylheptyl (meth) acrylamide , N, N-Propylheptyl (meth) acrylamide, N, N-butylheptyl (meth) acrylamide, N, N-pentylheptyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N, N-methyloctyl (meth) acrylamide , N, N-ethyloctyl (meth) acrylamide, N, N-Propyloct yl (meth) acrylamide, N, N-butyl octyl (meth) acrylamide, N, N-pentyloctyl (meth) acrylamide and N, N-heptyloctyl (meth) acrylamide, Particularly preferred is a terpolymer of diallyldimethylammonium chloride (DADMAC), acrylic acid and acrylamide or an acrylamide derivative, especially N, N-dimethylacrylamide. The surface-active polymer is contained in amounts of 0.01 to 2 wt .-%, preferably 0.05 to 1, 5 wt .-%, in particular 0.1 to 1 wt .-%.

The cleaning agent used in the process according to the invention preferably contains one or more surfactants, preferably selected from the group of nonionic and / or anionic surfactants.

Nonionic surfactants in the invention may be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers. Another important class of nonionic surfactants which can be used according to the invention are the polyol surfactants, in particular the glycerides, such as alkyl polyglycosides and fatty acid glucamides. Particularly preferred are the alkyl polyglycosides, in particular the

Alkyl polyglucosides, and especially the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers).

Preferred fatty alcohol alkoxylates are alkoxylated, unbranched or branched, saturated or unsaturated C ₈ with ethylene oxide (EO) and / or propylene oxide (PO). ₂₂ -alcohols having a degree of alkoxylation up to 30, preferably ethoxylated C ₂ -22-fatty alcohols with a

Degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C ₆ . _8- fatty alcohol ethoxylates with 25 EO.

Alkylpolyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, wherein, depending on the nature of the preparation, a mixture of monoalkylated, oligomeric or polymeric sugars is obtained. Preferred alkyl polyglycosides are the alkyl polyglucosides, the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ - to C ₈ -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1, 1 to 3, more preferably 1, 1 to 1, 7, is, for example, C ₈ . _0- alkyl-1 .5-glucoside (DP of 1, 5).

Suitable anionic surfactants in the cleaning agent according to the invention are aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also useful in the present invention are alkylbenzenesulfonates, fatty acid cyanamides, sulfosuccinates

(Sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-C ₈ -C ₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (Fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates, and α-sulfo fatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glyceryl disulfate. Preferred in the context of the present invention are the fatty alcohol sulfates and / or

Fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols. As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the

Reaction conditions, a complex mixture of addition products of different degrees of ethoxylation. Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.

Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO. Both

Alkylbenzenesulfonates are particularly preferred those having about 12 carbon atoms in the alkyl moiety, such as linear sodium C10-13 alkyl benzene sulfonate. Preferred olefin sulfonates have a

Carbon chain length of 14 to 16 on.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali metal or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic.

Depending on the field of use, the cleaning agent used in the process according to the invention may have an acidic or an alkaline pH. In this case, acidic cleaning agents have a pH of less than 7, preferably 1 to 5, more preferably 2 to 4, alkaline cleaning agents have a pH of 8 or more, preferably 9 to 13, particularly preferably 10 to 12.5.

Acidically formulated cleaning agents used in the process according to the invention may furthermore comprise one or more acids and / or salts thereof. Suitable acids are in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and

Mixtures thereof. In addition, however, the inorganic acids hydrochloric acid,

Sulfuric acid, phosphoric acid and nitric acid or amidosulfonic acid or mixtures thereof are used. The acids and / or their salts are particularly preferably selected from the group comprising citric acid, formic acid, acetic acid, malic acid, lactic acid, sulfamic acid, hydrochloric acid, phosphoric acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-%. The agent used in the process of the invention may further contain thickening agents. Suitable such viscosity regulators are, for example, organic natural thickeners (agar-agar, carrageenan, xanthan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethylcellulose and others Cellulose ethers, hydroxyethyl and propyl cellulose and the like, core flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas).

Thickeners based on carbohydrates are preferably used here. Polysaccharides, especially heteropolysaccharides, are used as such in particular. Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures. Other

Polysaccharide thickeners such as starches or cellulose derivatives may alternatively, but preferably in addition to a polysaccharide gum be used, for example starches

of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl,

Hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. The content of thickener is usually not more than 8 wt .-%.

In agents used in the process according to the invention, one or more water-soluble or water-miscible organic solvents can be used. Suitable solvents are for example, saturated or unsaturated, preferably saturated, branched or unbranched C ^ o-hydrocarbons, preferably C ₂ -i ₅ hydrocarbons, with at least one hydroxy group and optionally one or more ether functions CO- C, ie the carbon atom chain interrupting oxygen atoms. Preferred solvents are - optionally unilaterally with a C ^ alkanol etherified - C ₂ - ₆ alkylene glycols and poly C ₂ - ₃ -alkylene glycol having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well as the C ^ Alcohols, preferably ethanol, n-propanol or iso-propanol, especially ethanol. But also aromatic group-containing solvents can be suitably used in the composition according to the invention, such as ethylene glycol monophenyl ether (monophenyl glycol, phenoxyethanol).

Exemplary solvents are the following INCI compounds: alcohol (ethanol), buteth-3, butoxy diglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, Dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, Hexanediol, 1, 2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyl diol, isopropyl alcohol (isopropanol), 3-methoxybutanol, methoxy diglycol, methoxyethanol, methoxy isopropanol, methoxymethyl butanol, methoxy PEG-10, methylal, methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 Methyl Ether, Pentylene Glycol, Phenoxyethanol, PPG-7, PPG-2 Buteth-3, PPG-2 Butyl Ether, PPG-3 Butyl Ether, PPG-2 Methyl Ether, PPG-3 Methyl Ether, PPG-2 Propyl Ether, Propanediol, Propyl Alcohol (n-Propanol), Propylene Glycol, Propylene Glycol Butyl Ethers, propylene glycol, propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

The agent used in the method according to the invention may contain one or more perfumes, preferably in an amount of 0.01 to 1 wt .-%, in particular 0.02 to 0.8 wt .-%, particularly preferably 0.05 to 0.5 wt .-%, most preferably 0.1 to 0.3 wt .-%, and / or one or more dyes (INCI Colorants), preferably in an amount of 0.0001 to 0.1% by weight, in particular 0, 0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contain.

Bleaching agents may also be used in the process of the invention

Detergents are added. Suitable bleaching agents include peroxides, percarbonates, peracids and / or perborates, particularly preferred is hydrogen peroxide (H ₂ 0 ₂ ). Furthermore, chlorine bleaches can be used, in particular sodium hypochlorite.

The agent used in the method of the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the composition according to the invention in any form established according to the prior art. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes may be encapsulated, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

In addition, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, depending in each case on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, in particular derivatives with aromatic groups, for example substituted ones Phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₂ , such as succinic acid, others

Dicarboxylic acids or salts of said acids; end-capped

Fatty acid; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known in the art. Combinations of stabilizers are preferably used, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or

Combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

In addition, the agent used in the process according to the invention can be further customary

Hard surface cleaning ingredients, preferably selected from the group consisting of abrasives, UV stabilizers, corrosion inhibitors, cleaning enhancers, antistatics, pearlescing agents, builders, opacifiers, skin protection agents, fillers and mixtures thereof. On the other hand, it is preferably free of biocides, acids and bleaching agents not being considered as biocides for the purposes of this invention.

Various cleaning agents for hard surfaces are suitable for use in processes according to the invention or for use according to the invention. Depending on the application, it may be about liquid or gel toilet cleaners, bathroom cleaners or all-purpose cleaners or solid, powdered detergent or detergent medium additives. Solid, pulverulent, gel-like or liquid, optionally sprayable machine cleaning and care agents can also be used in processes according to the invention.

Another object of the invention is a cleaning agent for use in a

inventive method or for use according to the invention, containing

surface-active polymers which causes a biofilm reduction of at least 40%, preferably 60%, in the WC reactor. The toilet reactor is a device which adjusts the rinsing cycles of a conventional flush toilet. To determine the biofilm reduction pretreated ceramic tiles are clamped in this device, with different

Media flushed, inoculated with biofilm builders and incubated. Subsequently, the

semi-automatic controlled rinses. For evaluation, the biofilm residues are stained on the dried tiles, the evaluation is carried out by means of a graphics program. embodiments

Different compositions were formulated with two different terpolymers A and B and investigated for their properties in terms of purification and biofilm reduction. Terpolymer A was a slightly crosslinked polymer of acrylamide, DADMAC and acrylic acid (75.6 / 20 / 4.4 wt .-%), terpolymer B consisted of Ν, Ν-dimethylacrylamide, DADMAC and

Acrylic acid (75.6 / 20 / 4.4% by weight).

First, the preventive effect on biofilm reduction was investigated. For this purpose, in a so-called WC reactor, which simulates the rinsing cycles of a conventional flush toilet, pretreated ceramic tiles with TBY medium 1: 50 (aqueous solution of tryptone, yeast extract and sodium chloride) was rinsed. For this purpose, the tiles were immersed for three minutes in 15 to 20 ml of polymer solution of defined concentration, briefly rinsed with water and dried at 60 ° C for two hours. The polymer solutions were prepared either with water or with a commercial WC cleaner formulation. Subsequently, the tiles were clamped in the reactor. The reactor was filled with 680 ml of medium, inoculated with a germ mixture of the biofilm generators Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1982 and Xanthomonas campestris DSMZ 1526 and incubated overnight.

The semi-automatic rinses were then taken with 680 ml of medium in 20 minutes, 15 times in each case on the first two days after incubation. After these 30 rinses, the tiles were removed from the reactor, dried and remaining biofilms stained with 6 ml of 0.01% safranine O solution for 15 minutes. The excess staining solution was filtered off with suction, unbound dye with redist. Rinse off water and dry the tiles. Now the colored surfaces were scanned and with the help of a

Graphics program (Corel Draw Paint 9) evaluated after a zero value for an untreated surface was subtracted from the detected color intensity. The reference values were biofilm-loaded tiles which had been treated with water or toilet cleaner without polymer addition and had been set to 0% biofilm reduction.

The result is shown in the following table:

Polymer Concentration Solvent for Polymer Biofilm Reduction [%]

Polymer A Polymer B

1% water 78 72

0.25% water 82 70

1% toilet cleaner 74 65

0.25% WC cleaner 60 70 The adhesion of bacteria was also determined by another comparative test. For this purpose, the test surfaces (stainless steel coupons) were immersed in the agent to be tested and then covered with a suspension of Pseudomonas aeruginosa and incubated for one hour. After rinsing off the non-adherent cells, the bacteria adhering to the surface were removed mechanically by means of glass beads, determining the "colony forming units" (CFU) and comparing them with the reference sample (polymer-free agent)

Carried out in triplicate, a bath cleaner, which was optionally 1 wt .-% was investigated.

Terpolymer B contained. Compared with the respective reference value of 100% adhesion

(polymer-free), the steel coupons treated with polymer B in water exhibited 81% adhesion, and the coupons treated with polymer B in bath cleaner even as low as 68%. The treatment with the polymer thus leads to a reduction in the number of adhering bacteria by 20 to 30%, both in water and in the bath cleaner.

By means of a test, the "easy to clean" properties of agents containing one of the polymers were tested, using white glazed tiles with polymer-containing

Provided detergent and rinsed after five minutes exposure time with demineralized water and dried to constant weight. They were then stained with black stained calcium stearate, dried at 180 ° C for one hour and wiped with a Sheen Wet Abrasion Scrub Tester under defined conditions. After 10, 20, 30, 40 and 50 strokes, a visual assessment was made. The results are shown in the following table:

By means of a similar test bath cleaners of the following composition were tested:

All quantities are in wt .-% active. The pH of these agents is 2.5. A test stain was prepared as follows: 85% by weight of ethanol were introduced and 5% by weight of finely divided calcium stearate were stirred in. Subsequently, 9.8 wt .-% of water and added to 0.2 wt .-% Special Black 4, the suspension is for 10 minutes in an ultrasonic bath for three minutes and at 5000 U / min homogenized with a Turrax ^® stirrer.

To perform the wipe test, white tiles (15x15 cm, Villeroy & Boch) were first cleaned with an abrasive, rinsed with water, wiped with ethanol, and rinsed again with demineralized water. Subsequently, the tiles were pretreated with the appropriate agent. For this purpose, 2 ml of the product were placed on a cloth (kitchen paper, 1 × 13 cm) and applied with the aid of the cloth on one side of a tile. Subsequently, the tiles were rinsed with 500 ml of demineralized water, dried for four hours at 120 ° C in a ventilated drying oven and weighed after cooling. Using airbrush, the test soil was applied to the tiles from a distance of 20 cm, dried for 30 minutes and then the tiles were weighed to ensure that the

Order amount of soiling was 100 to 120 mg, and optionally further

Apply test dirt. The tiles were then placed horizontally for one hour at 180 ° C in the ventilated drying oven to melt the calcium stearate, and then cooled in the oven with the door open. In a re-path, the weight difference to the treated tile had to be 20 to 60 mg.

After at least 24 hours storage at room temperature, the wipe test was finally performed. While the polymer-free bath cleaner had no cleaning effect even after 100 wiping movements, polymer B in particular showed a very good cleaning effect even after 30 wiping movements.

For comparison, wipe tests were also carried out in which instead of the terpolymer A or B, the commercially available polymer Mirapol Surf-S 500 (ex Rhodia) was used. Both with 0.25 wt.% And with 1 wt.% Active, only a minimal cleaning effect was observed after 30 wiping motions.

A bleach-containing cleaner of the following composition was also subjected to a washing test:

pH = 12.5 The polymer-free cleaner showed no cleaning effect even after 100 wiping movements. In contrast, polymer B in particular showed a very good cleaning effect after only 30 wiping movements.

For comparison, wipe tests were also carried out in which instead of the terpolymer A or B, the commercially available polymer Mirapol Surf-S 500 (ex Rhodia) was used. Both with 0.25 wt.% And with 1 wt.% Active, only a minimal cleaning effect was observed after 30 wiping motions

Another acid bath cleaner (pH 3.6) was formulated as follows:

In addition, optionally 0.25 wt .-% polymer were included.

Again, the polymer-free cleaner showed no cleaning effect after 50 wiping movements, while the agent with polymer A after only 10 wiping movements a good

Had cleaning effect. A comparison agent with 0.25 wt.% Mirapol Surf-S 1 10 required 20 strokes for a good cleaning performance.

Further cleaning agents which can be used in the process according to the invention can be taken from the following exemplary formulations in which all quantities are in% by weight of active substance:

Bleach-containing detergency booster / machine cleaner in powder form

pH = 1 1, 5 Bleach-containing pretreatment agent / machine care agent, spray

pH = 6.5

Claims

claims

1 . A method for preventing the adhesion of microorganisms on hard surfaces by their semi-permanent modification during the cleaning process with a cleaning agent containing surface-active polymers.

2. Use of a detergent containing surfactant polymers to prevent bacterial colonization of hard surfaces.

3. The method according to claim 1 or use according to claim 2, wherein the

Detergent has a pH of less than 7, preferably 1 to 5, particularly preferably 2 to 4.

4. The method according to claim 1 or use according to claim 2, wherein the

Detergent has a pH of 8 or more, preferably 9 to 13, particularly preferably 10 to 12.5.

5. A method or use according to claim 3, wherein the cleaning agent contains one or more acids and / or salts thereof, preferably selected from the group comprising citric acid, formic acid, acetic acid, malic acid, lactic acid,

Amidosulfonic acid, hydrochloric acid, phosphoric acid, their salts and mixtures thereof.

6. A method or use according to any one of the preceding claims, wherein the cleaning agent contains one or more surfactants, preferably selected from the group of nonionic and / or anionic surfactants.

A method or use according to any one of the preceding claims, wherein the detergent contains a thickening agent, preferably a carbohydrate-based thickener.

8. A method or use according to any one of the preceding claims, wherein the cleaning agent is free of biocides.

A method or use according to any one of the preceding claims, wherein the surface-active polymer is preferably a copolymer.

10. A method or use according to claim 7, wherein the copolymer is preferably a terpolymer, more preferably a terpolymer of acrylic acid,

Diallyldimethylammonium chloride (DADMAC) and acrylamide or an acrylamide derivative, among which Ν, Ν-dimethylacrylamide is preferred.

1 1. Method or use according to one of the preceding claims, wherein the surface-active polymer in an amount of 0.01 to 2 wt .-%, preferably 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 1 wt. % is included.

12. A method or use according to any one of the preceding claims, wherein the cleaning agent contains one or more conventional ingredients of hard surface cleaners, preferably selected from the group consisting of solvents, abrasives, UV stabilizers, corrosion inhibitors, cleaning enhancers, antistatic agents, perfumes, dyes, Pearlescing agents, enzymes, builders, opacifiers, skin protection agents and mixtures thereof.

13. Cleaning agent for use in a method or for use according to one of the preceding claims, containing surface-active polymers, characterized in that it causes a biofilm reduction of at least 40%, preferably 60% in the toilet reactor.