EP2430138A1

EP2430138A1 - Probiotic cleaner for hard surfaces

Info

Publication number: EP2430138A1
Application number: EP10714455A
Authority: EP
Inventors: Dirk Bockmühl; Cornelius Bessler; Rainer Simmering
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-05-12
Filing date: 2010-04-21
Publication date: 2012-03-21
Also published as: DE102009003027A1; WO2010130541A1

Abstract

The invention relates to a cleaner for hard surfaces, especially a sanitary cleaner which contains microorganisms for the decomposition and/or removal of inorganic stains and/or residues and to the use thereof for cleaning and/or finishing hard surfaces, especially for cleaning and/or finishing ceramic surfaces in and around toilets and urinals.

Description

"Probiotic cleaner for hard surfaces"

The invention relates to a cleaner for hard surfaces, in particular a sanitary cleaner containing microorganisms for degradation and / or removal of inorganic stains and / or residues and its use for cleaning and / or finishing hard surfaces, in particular for cleaning and / or equipment of ceramics Surfaces in the toilet area.

Hard surface cleaners, and in particular sanitary cleaners, have, inter alia, the task of removing inorganic residues, in particular lime, from surfaces. For this purpose, these cleaners usually contain larger amounts of acids.

Surprisingly, it has now been found according to the invention that effective removal of inorganic residues can also be effected by adding to these cleaners microorganisms which produce acids.

An advantage of using such microorganisms is that the cleaner itself must be added lower amounts of acids, and on the other hand after the application of the microorganisms on the surface at the site of application itself, the desired acids can be produced. Another advantage of the use of such microorganisms in cleaners is that due to the colonization of microorganisms on the surface to be treated the settlement of undesirable microorganisms can be suppressed, on the one hand due to the competitive displacement of undesirable microorganisms, on the other hand due to the creation of an acidic environment in which unwanted microorganisms are not viable.

In WO 97/25865 cleaners are already disclosed which may contain microorganisms. The microorganisms described therein are bacilli which are capable of producing extracellular enzymes, in particular proteases, amylases or lipases, or antibiotics. As a result, the degradation of organic soils is to be made possible or the settlement of unwanted microorganisms can be suppressed. However, the use of microorganisms for the purpose of degrading inorganic soiling is not disclosed in WO 97/25865.

A first subject of the present invention is therefore a hard surface cleaner, characterized in that it contains microorganisms for the removal of inorganic stains and / or residues and / or for effecting a probiotic effect on the surface to be treated. The present invention therefore furthermore also relates to the use of a cleaner according to the invention for cleaning and / or finishing hard surfaces.

The subject matter of the present invention is therefore likewise a method for cleaning and / or finishing hard surfaces, characterized in that in at least one method step an inventive cleaner is used.

The present invention therefore furthermore also relates to the use of a cleaner according to the invention for removing inorganic stains and / or residues, in particular hard surfaces.

The subject matter of the present invention is therefore likewise a process for the removal of inorganic stains and / or residues, in particular of hard surfaces, characterized in that a cleaner according to the invention is used in at least one of the process steps.

The present invention therefore also relates to the use of a cleaner according to the invention, in particular on a hard surface, for suppressing the growth of undesired microorganisms, in particular for suppressing the growth of pathogenic and / or biofilm-forming microorganisms.

The present invention therefore also provides a process for suppressing the growth of undesired microorganisms, in particular for suppressing the growth of pathogenic and / or biofilm-forming microorganisms, in particular on a hard surface, characterized in that in at least one of the process steps, a cleaner according to the invention is used.

The subject of the present invention is therefore likewise the use of a cleaner according to the invention for effecting a probiotic effect on a hard surface. By effecting a probiotic effect, it is to be understood that due to the microorganisms contained in the cleaner, the growth and / or survivability of undesirable pathogenic and / or biofilm-forming microorganisms present on the surface to be treated is inhibited, preferably by competitive displacement unwanted microorganisms by the microorganisms contained in the cleaner and / or due to the acid production by the microorganisms contained in the cleaner.

The subject of the present invention is therefore likewise a method for effecting a probiotic effect on a hard surface, characterized in that in at least one of the method steps a cleaner according to the invention is used. According to the invention, the inorganic stains or residues are preferably carbon black or inorganic salts, in particular sparingly soluble carbonate, sulfate or phosphate salts, more preferably urine stone or lime.

The microorganisms to be used according to the invention are preferably acid-producing, especially organic acid-producing, microorganisms, the organic acid preferably being selected from lactic acid, acetic acid, citric acid, oxalic acid, succinic acid, fumaric acid, malic acid, propionic acid and formic acid, more preferably aus Lactic acid and acetic acid.

In a preferred embodiment, bacteria are used which can form lactic acid via homo- or heterofermentative lactic acid fermentation. The bacteria here are preferably selected from the family of Lactobacteriaceae or from the family of Bacillaceae. The lactic acid bacteria are particularly preferably selected from the genera Lactococcus, Lactobacillus, Leuconostoc, Streptococcus, Bacillus, Actinomyces, Bifidobacterium, Caseobacter, Propionibacterium, Sporolactobacillus and Coryneform bacteria.

In a further preferred embodiment, bacteria are used which can form fatty acids and acetic acid by incomplete oxidation of the corresponding alcohols or by oxidation of sugar molecules. The acetic acid bacteria are particularly preferably selected from the genera Acetobacter, Acetomonas, Glucobacter and Gluconacetobacter.

For example, clostridia and enterobacteria are also suitable for the production of acetic acid, with clostridia producing acetic acid from carbon monoxide, while enterobacteria produce acetic acid in the course of a mixed acid fermentation. Enterobacteria are also suitable for the production of formic acid.

For the production of succinic acid Zygomyceten and Propionibakterien are suitable. Zygomycetes are also suitable for the production of fumaric acid and malic acid. Propionibakterien are also suitable for the production of propionic acid.

For example, Aspergilli are suitable for the production of citric acid and oxalic acid.

The microorganisms are used according to the invention in a preferred embodiment in the form of a suspension and / or in the form of a cell disruption and / or in inactivated form.

In a further preferred embodiment, the microorganisms are used in the form of a lyophilisate. In a further preferred embodiment, spore-forming bacteria are used. As spore-forming lactic acid bacteria Lactobacillus sporogenes or Alicyclobacillus are preferably used.

In a further preferred embodiment, the microorganisms are used in encapsulated form. Polysaccharides, in particular alginate, carrageenan, gelatin, starch, chitosan or gellan gum are suitable as material for encapsulating the microorganisms. Reference is made in particular to Kailasapathy (Curr Issues Intest Microbiol. (2002) 3: 39-48). The production of the encapsulated microorganisms can be carried out, for example, by spray drying or extrusion.

In a preferred embodiment, the cleaners according to the invention comprise a substrate which is suitable for the particular microorganism and which can be metabolically converted by the microorganism to the corresponding organic acid.

The microorganisms are in inventive cleaners, optionally in the form of a cell disruption and / or in lyophilized form, preferably in an amount of 0.001 to 10 wt .-%, preferably in an amount of 0.1 to 5 wt .-%, based on the dry matter of the microorganisms used.

The hard surface to be treated according to the invention may in particular be a ceramic, glass, metal or plastic surface. In a preferred embodiment, the surface to be treated is a ceramic surface.

Embodiments of the present invention include all of the prior art and / or all expedient dosage forms of the detergents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.

The cleaner according to the invention in a preferred embodiment is a bath and / or sanitary and / or toilet cleaner.

The pH of a cleaner according to the invention is preferably from 1 to 8, particularly preferably from 1 to 5, in particular from 1 to 3 or from 3 to 5.

In the following, preferred embodiments according to the invention will be further explained. 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 may be listed after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" may also be given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , is published. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as 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.

surfactants

The cleaning formulation according to the invention preferably contains one or more surface-active substances, preferably those based on renewable raw materials. Suitable surface-active substances for the compositions according to the invention are, in particular, anionic, nonionic, cationic or amphoteric surfactants, preferably anionic and nonionic surfactants. With regard to surfactants which can be used according to the invention, reference is made in particular to published patent application WO2008 / 101909.

Suitable anionic surfactants are preferably C ₈ -C ₁₈ -Alkylbenzolsu If ₈ -C ₁₈ are ₈ -C onate, in particular about 12 carbon atoms in the alkyl moiety, C ₈ -C ₂ o-alkane sulfonates, C ₁₈ -Monoalkylsulfate, C - alkylpolyglycolethersulfates with 2 to 6 ethylene oxide units (EO) in the ether portion and sulfosuccinic mono- and di-C ₈ -C ₁₈ alkyl esters. Furthermore, C ₈ -C ₁₈ -α-olefinsulfonates, sulfonated C ₈ -C ₁₈ -fatty acids, in particular dodecylbenzenesulfonate, C ₈ -C ₂₂ - Carbonsäureamidethersulfate, C ₈ -C ₁₈ -Alkylpolyglykolethercarboxylate, C ₈ -C ₁₈ -N-Acyltauride , C ₈ -C ₁₈ -N sarcosinates and C ₈ -C ₁₈ -alkyl isethionates or mixtures thereof. It is always preferred that the carbon chains are derived from natural sources, such as vegetable oils and fats.

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 acid. Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven particularly suitable.

Particularly suitable nonionic surfactants are Cs-C-is-alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), Cs-C -is-carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units. Examples of such surfactants are oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units. Also particularly preferred are surfactants based on oleochemicals such as C ₈ . ₁₈ - fatty alcohol polyglycol having in particular 2 to 8 EO, for example, C ₁₂ fatty alcohol + 7-EO ether, and C ₈ -io-alkylpolyglucosides having 1 to 2 glycoside units used.

Suitable amphoteric surfactants are, for example, betaines of the formula (R '") (R ^IV ) (R ^v ) N ⁺ CH ₂ C 00 ^- , in which R'" is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^IV and R ^{V are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl dimethylcarboxymethylbetain and C 1 -C 4 -alkylamidopropyl-dimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^VI ) (R ^V ") (R ^VI ") (R ^IX ) N ⁺ X ^" , in which R ^vι to ^Rιx for four identical or different, in particular two long, and two short-chain, alkyl radicals and X ^"are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.

In a particularly preferred embodiment, however, the surfactant component comprises only one or more anionic surfactants, preferably C ₈ -C ₁₈ -alkylsulfates and / or C ₈ -C ₁₈ -alkyl ether sulfates, and / or one or more nonionic surfactants, preferably C. ₈ . ₁₈ - fatty alcohol polyglycol ethers having 2 to 8 EO and / or C. ₈ _10- Alkylpolyglucoside with 1 to 2 glycoside units. It is further very particularly preferred that the surfactants are made from renewable raw materials.

The agent according to the invention preferably contains surfactants in amounts of from 0.1 to 50% by weight.

In a preferred embodiment according to the invention, a cleaner according to the invention contains 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt. -% surfactants. In a further preferred embodiment according to the invention, a cleaner according to the invention contains from 5 to 50% by weight, in particular from 10 to 40% by weight, of surfactants.

acids

Cleaning formulations according to the invention also contain one or more acids and / or salts thereof for enhancing the cleaning performance against lime and urine stone. The acids are preferably produced from renewable raw materials. Suitable acids are therefore 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, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or else sulfamic acid or mixtures thereof. The acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic 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 .-%.

In a preferred embodiment, a cleaner according to the invention in this case contains that acid or one of those acids which can be produced by the microorganisms contained in the cleaner.

Perfume

The agent contains one or more fragrances, preferably in an amount of 0.01 to 10 wt .-%, in particular 0.05 to 8 wt .-%, particularly preferably 0, 1 to 5 wt .-%. As a perfume component, d-limonene may be contained. Preferably, the perfume contains natural fragrance mixtures, as they are mainly accessible from plant sources. Therefore, in a particularly preferred embodiment, the perfume is a perfume of essential oils (also referred to as essential oils). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such in the context of this invention. Also suitable are Muskateller sage oil, chamomile oil, lavender oil, clove oil, balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of one of several changes Perfume perfumes during evaporation, wherein the odor impressions in top note, middle note or body and "base note" (end note or dry out) divided.

Adhesive-resistant fragrances which are advantageously usable in the perfume oils in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, Ginger Grass Oil, Guajac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calam Oil, Chamomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopaϊvabalsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lemongrass Oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli oil, Niaouli oil, Olibanum oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Star aniseed oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen l, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil and cypress oil.

But the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures in the perfume oils. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, α-bromostyrene, n -Decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole , Jasmon, camphor, Karvakrol, Karvon, p-cresolmethyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-naphthyl ketone, methyl-n nonyl acetaldehyde, methyl n-nonyl ketone, muscon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitr topol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, cyclohexyl salicylate, santalol, skatole, terpineol, thymene, Thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

Among the more volatile fragrances, which are advantageously used in the perfume oil in the context of the present invention, in particular the lower-boiling fragrances include natural or synthetic origin, which can be used alone or in mixtures. Examples for more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Other ingredients

In addition to the components mentioned so far, the composition of the invention may contain other ingredients, including other acids, salts, surfactants, film formers, thickeners, solvents, antimicrobial agents, builders, corrosion inhibitors, complexing agents, sequestering agents, electrolyte, foam inhibitors, disintegration aids, "soil release" - Soil repellents, UV absorbers, alkalis, preservatives, bleaching agents, bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers, fragrances and dyes and mixtures thereof. Overall, preferably not more than 30 wt .-% of other ingredients should be included. Particularly preferred are 0.01 to 30 wt .-%, in particular 0.2 to 15 wt .-%, further ingredients.

film formers

A preferred component of the cleaning agent according to the invention is a film former which contributes to better wetting and surface modification. All the film-forming polymers used in detergents and cleaners in the prior art can be used for this purpose, but the film former is preferably selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably having a molecular weight between 200 and 20,000,000 between 5,000 and 200,000. The film former is advantageously used in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.

thickener

Both in order to allow longer adherence of the cleaning agent to the surface to be cleaned, as well as to optimize the rheology of liquid or gel detergent, it may also be advantageous to increase the viscosity of the agent by using a thickener. Suitable for this purpose are all viscosity regulators customarily used in detergents and cleaners, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein ), organic modified natural products (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose 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, silicic acids).

Examples of polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers. Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ^® such as Polygel ^® DA, and by the company. BFGoodrich under the tradename Carbopol ^®, such as Carbopol ^® 940 (molecular weight about 4,000,000), Carbopol ^® 941 (molecular weight approximately 1,250,000) or Carbopol ^® 934 (molecular weight approximately 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C |. _4- alkanols formed esters (INCI Acrylates Copolymer), which include about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3 ), and which are obtainable for example from Messrs. Rohm & Haas under the trade names Aculyn ^® and Acusol ^® and from Evonik (Goldschmidt) under the trade name Tego ^® polymer, eg, the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of do- _30- alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C |. ₄ -alkanols formed, esters (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and which are for example available from the company. BFGoodrich under the tradename Carbopol ^®, for example hydrophobized Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates / C 10-30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473).

Further thickeners are the polysaccharides and heteropolysaccharides, in particular 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, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15x10 ⁶ and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or available from Rhodia under the trade name Rhodopol ^®.

As thickeners, it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ^® magnesium or sodium magnesium phyllosilicates from Solvay Alkali, in particular the Laponite ^® RD or Laponite ^® RDS, and the magnesium silicates Süd-Chemie, especially the Optigel ^® SH.

In a preferred embodiment, the cleaning agent according to the invention contains from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight, of a thickener, preferably a polysaccharide thickener, for example xanthan gum.

solvent

Another preferred component of agents according to the invention are solvents, in particular water-soluble organic solvents. These include, for example, lower alcohols and / or ether alcohols, which are understood as lower alcohols in the context of this invention straight-chain or branched C-ι- ₆ alcohols.

The alcohols used are in particular ethanol, isopropanol and n-propanol. As ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether,

Propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. In a preferred embodiment, however, ethanol is used as the solvent. Solvents may be included in the detergent in amounts of 0.01 to 30% by weight, preferably 0.2 to 15% by weight.

Antimicrobial agents

Disinfection and sanitation constitute a particular form of purification. In a corresponding particular embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial agents, preferably in an amount of 0.01 to 1% by weight, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0.1 to 0.3 wt .-%, most preferably 0.2 wt .-%. The terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention. While disinfection in the narrower sense of the medical practice means the killing of - in theory all - infectious germs, sanitation is to be understood as the greatest possible elimination of all - including the saprophytic - normally harmless to humans saprophytic - germs. Here, the extent of disinfection or sanitation depends on the antimicrobial effect of the applied agent, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.

For example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, it is also possible to use antimicrobial-effective essential oils which at the same time ensure scenting of the cleansing agent. However, particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite and mixtures thereof.

With regard to further antimicrobial agents which can be used according to the invention, reference is made to the published patent application WO2008 / 101909.

Builder

If desired, water-soluble and / or water-insoluble builders may be used in the cleaning agents according to the invention. Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces. Typical builders which may be present in the context of the invention are the low molecular weight ones Polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders.

With regard to further builders and / or cobuilders which can be used according to the invention and their preferred amounts used, reference is made to the publication WO2008 / 101909.

corrosion inhibitors

Suitable corrosion inhibitors (INCI Corrosion Inhibitors) are, for example, the following named according to INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphates, Nitromethanes, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

With regard to further corrosion inhibitors which can be used according to the invention, in particular also glass corrosion inhibitors, reference is made to the published patent application WO2008 / 101909.

complexing

INCI chelating agents, also called sequestrants, are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.

Suitable examples are the following according to INCI called complexing agents: Aminotri- methylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium Azacycloheptane Diphosphonates, Disodium EDTA, Disodium Pyrophosphates, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphates, Pentasodium Aminotrimethylene Phosphonates, Pentasodium Ethylenediamine Tetramethylene Phosphonates, Pentasodium Pentetates, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethyl Glycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

alkalis

In agents according to the invention, it is also possible for alkalis to be present. Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, it is also possible to use ammonia and / or alkanolamines having up to 9 C atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

preservative

Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.

bleach

According to the invention, bleaching agents can be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids and / or perborates, particularly preferred is hydrogen peroxide. Sodium hypochlorite, on the other hand, is less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline detergents.

With regard to further bleaches which can be used according to the invention and with regard to bleach activators and bleach catalysts which can be used according to the invention and with regard to their preferred amounts used, reference is made to published patent application WO2008 / 101909. enzymes

The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases, amadoriases, perhydrolases, oxidoreductases, hemicellulases 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 can be encapsulated, for example by spray drying or extrusion of 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-shelled form. 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, in each case depending on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to _C12, such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; 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.

Preference is given to using combinations of stabilizers, 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 the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

With regard to further enzymes and enzyme stabilizers which can be used according to the invention and their preferred amounts used, reference is made to the published patent application WO2008 / 101909. abrasives

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasives are preferably present in the detergents according to the invention in an amount of not more than 20% by weight, in particular in an amount of from 5 to 15% by weight.

Fragrances and dyes

As further ingredients, the agent according to the invention may finally contain one or more fragrances and / or one or more dyes (INCI Colorants). As dyes both water-soluble and oil-soluble dyes can be used, on the one hand the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the toilet ceramic should not act substantively even with prolonged exposure. The dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.

polymers

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. For the purposes of the present invention, "amphoteric polymers" also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.

With regard to inventively preferred sequestering agents, electrolytes, foam inhibitors, Disintegrationshilfsstoffe, "soil release" agents or "soil repellents" and UV absorbents and with respect to their preferred amounts used reference is made to the publication WO2008 / 101909.

A hard surface cleaner according to the invention may also contain one or more propellants (INCI propellants), usually in an amount of from 1 to 80% by weight, preferably from 1 to 5% by weight, in particular from 2 to 10% by weight, more preferably 2.5 to 8% by weight, most preferably 3 to 6% by weight.

With regard to blowing agents which can preferably be used according to the invention, reference is made to published patent application WO2008 / 101909.

A further subject of the present invention is also a product comprising a hard surface cleaner according to the invention and a spray dispenser. The product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a transparent polyethylene or polyethylene terephthalate container. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference. Triggersprühspender and pump sprayer have over compressed gas tanks the advantage that no propellant must be used. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, optionally contained enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.

According to the invention, particularly preferred bath cleaners comprise

0.5 to 12 wt .-%, preferably 1 to 10 wt .-% and in particular 2 to 8 wt .-% of organic acid and / or a salt of organic acids, preferably selected from formic acid, citric acid, lactic acid and mixtures thereof and Salts of these organic acids; 0.1 to 5 wt .-%, preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt .-%

Surfactant (s), preferably nonionic and / or anionic surfactant (s), more preferably nonionic surfactant (s), especially alkyl polyglycoside (s);

0.1 to 5 wt .-%, preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt .-%

Thickener; such as

0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-%

Microorganisms, preferably organic acid-producing microorganisms, particularly preferably lactic acid or acetic acid-producing microorganisms, in particular in the form of a cell disruption and / or in encapsulated form and / or in the form of a lyophilisate; at a pH of 1 to 6, preferably 3 to 5.

Particularly preferred WC cleaners according to the invention

0.5 to 12 wt .-%, preferably 1 to 10 wt .-% and in particular 2 to 8 wt .-% of organic acid and / or a salt of organic acids, preferably selected from

Formic acid, citric acid, lactic acid and mixtures thereof and salts of these organic acids;

0.1 to 5 wt .-%, preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt .-%

Thickener; such as

Microorganisms, preferably organic acid-producing microorganisms, particularly preferably lactic acid or acetic acid-producing microorganisms, in particular in the form of a cell disruption and / or in encapsulated form and / or in the form of a lyophilisate; at a pH of 1 to 5, preferably 1 to 3.

Claims

claims

1. hard surface cleaner, characterized in that it contains microorganisms for the removal of inorganic stains and / or residues and / or for effecting a probiotic effect on the surface to be treated.

2. Cleaner according to claim 1, characterized in that it is the microorganisms acid-producing, especially organic acid-producing microorganisms.

3. cleaner according to claim 1 or 2, characterized in that the microorganisms are selected from lactic acid or acetic acid-producing bacteria.

4. cleaner according to any one of the preceding claims, characterized in that the microorganisms are selected from bacteria of the genera Lactococcus, Lactobacillus, Leuconostoc, Streptococcus, Bacillus, Actinomyces, Bifidobacterium, Caseobacter, Propionibacterium and Sporolactobacillus and from Coryneform bacteria, Clostridium, Enterobacteriaceae, Aspergillus and Zygomycetes.

5. Cleaner according to one of the preceding claims, characterized in that it contains at least one thickener.

6. cleaner according to one of the preceding claims, characterized in that it contains at least one acid.

7. cleaner according to the preceding claim, characterized in that it contains at least one organic acid, in particular selected from the group consisting of formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures of these acids.

8. Cleaner according to one of the preceding claims, characterized in that the microorganisms are contained in encapsulated and / or lyophilized form and / or in the form of a cell disruption.

9. cleaner according to one of the preceding claims, characterized in that a metabolizable by the microorganisms substrate is included.

10. cleaner according to any one of the preceding claims, characterized in that it is a sanitary, bath or all-purpose cleaner.

11. Use of a cleaner according to any one of the preceding claims for cleaning and / or equipment hard surfaces.

12. Use according to the preceding claim for the removal of inorganic stains and / or residues, preferably selected from carbon black and inorganic salts, in particular urine scale and lime.

13. Use of a cleaner according to any one of claims 1 to 10, in particular on a hard surface, for suppressing the growth of undesirable microorganisms, in particular for suppressing the growth of pathogenic and / or biofilm-forming microorganisms, or for effecting a probiotic effect on a hard surface.

14. A method for cleaning and / or finishing hard surfaces, characterized in that in at least one method step, a cleaner is used according to one of the preceding claims.

15. A method for removing inorganic stains and / or residues of surfaces, characterized in that in at least one method step, a cleaner according to any one of the preceding claims is used.