DE102008029939A1 - Dirt-repellent detergent - Google Patents

Abstract

A hard surface cleaner comprising an alcohol ethoxylate of a straight or branched C4-8 alkyl or alkylene radical and 1 to 10 ethylene oxide units and at least one anionic and at least one other nonionic surfactant and an acrylate or methacrylate based block polymer block of quaternary ammonium compounds as well as N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) can be used for cleaning and concomitant stain resistant hard surface modification.

Description

The invention relates to a hard surface cleaner which comprises an alcohol ethoxylate of a straight-chain or branched C _4-8 -alkyl or alkylene radical and 1 to 10 ethylene oxide units and at least one anionic and at least one further nonionic surfactant and an ampholytic block copolymer on acrylate or methacrylate base with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS).

All Purpose cleaner have long been firmly established in many households. they are coming when cleaning hard surfaces are used and are able to handle a variety of, especially fatty, Remove soiling. However, it is desirable that gave the surface more positive properties become. This includes an improved water flow as well like dirt-repellent properties. These positive qualities should be concentrated as well as diluted Application can develop.

When Cleaner for hard surfaces with improved Soil removal has become aqueous compositions which is a short-chain fatty alcohol polyglycol ether, an anionic surfactant and another nonionic surfactant. Your performance, especially regarding soil release effects and the water drain on vertical surfaces, however still capable of improvement.

Accordingly One task was to use liquid all-purpose cleaners provide that at consistently good or even improved Cleaning performance an improvement of dirt-repellent properties as well as the water drainage on surfaces cleaned with them cause.

It has been shown to be the addition of an ampholytic block copolymer based on acrylate or methacrylate with blocks of quaternary Ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) a performance increase of the cleaning agent leads.

An object of this application is therefore a hard surface cleaner which is a short chain nonionic surfactant of formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ¹ is a straight or branched C _4-8 alkyl or alkenyl radical and n is a number between 1 and 10, and at least one anionic surfactant and at least one further non-ionic surfactant comprises block copolymer, and further an ampholytic on acrylate or methacrylate with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS).

To the use of such an agent could accelerate water flow to be observed on vertical surfaces, too, were already One-time pre-cleaning Soil-release effects on hydrophilic surfaces like glass and ceramics and with it a long lasting shine determine. In addition, an improved cleaning performance was compared To observe fatty soil.

A further subject of this application is accordingly the use of a hard surface cleaner which is a short chain nonionic surfactant of formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight or branched C _4-8 alkyl or alkenyl radical and n is a number between 1 and 10, and at least one anionic surfactant and at least one further nonionic surfactant, and further an acrylate or methacrylate based ampholytic block copolymer containing blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS) for the cleaning and simultaneous dirt-repellent modification of hard surfaces.

at The application may be helpful if the detergent on the surface to be cleaned by spraying is applied.

A further subject of this application is therefore a product of a cleaning agent which is a short-chain nonionic surfactant of the formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight or branched C _4-8 alkyl or alkenyl radical and n is a number between 1 and 10, and at least one anionic surfactant and at least one further nonionic surfactant, and further an acrylate or methacrylate based ampholytic block copolymer with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and a spray dispenser.

The Cleaning agent according to the invention can in a Process for cleaning and simultaneous dirt-repellent modification Hard surfaces are used. The agent can do this used both in concentrated form and diluted become.

Yet a further subject of this application is therefore a process for cleaning and simultaneous dirt-repellent modification hard surfaces, consisting of the steps applying a cleaning agent according to the invention the surface to be cleaned, if necessary by spraying, Wipe with a cloth, a sponge or another for this purpose suitable substrate to the agent on the whole Distribute the surface, if necessary leave it to act, Rinse with clear water and dry if necessary the surface with another cloth, a sponge or another substrate suitable for this purpose. This method is especially suitable for concentrated use of the cleaning agent.

Yet a further subject of this application, however, concerns the dilute Application of the agent in a process for purification and simultaneous Dirt-repellent modification of hard surfaces, consisting from the steps Preparation of a cleaning liquor by dilution a cleaning agent according to the invention Water, applying the diluted detergent the surface to be cleaned, wiping with a cloth, a Sponge or other suitable substrate for this purpose, to distribute the agent over the entire surface and let dry.

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 exclusively in Linnaeus in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997) issued by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical designations including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymeric 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.

Ampholytic block copolymer

The cleaning agent according to the invention contains an ampholytic block copolymer based on acrylate or methacrylate with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). Such polymers are already mentioned in the patent application EP 1767554 A1 and are commercially available, for example, from Cognis under the trade name Polyquart Pro.

The Inventive agent preferably contains 0.01 to 2% by weight of the ampholytic block copolymer, especially preferably 0.025 to 0.25 wt .-%.

Short-chain nonionic surfactant

The composition according to the invention comprises a nonionic surfactant of the formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight-chain or branched C _1-8 -alkyl radical or C _2-8 -alkenyl radical and n is a number between 1 and 10. These are preferably pentaethylene glycol monohexyl ethers, ie R ¹ = C ₆ -alkyl and n = 5; occasionally abbreviated as "C6E5". This nonionic surfactant is preferably used in an amount of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%, in particular 0.5 to 4 wt .-%.

anionic surfactant

The Inventive agent also contains at least one anionic surfactant, preferably in an amount of 0.1 to 30 wt .-%, preferably 0.6 to 15 wt .-%, in particular 1 to 10 wt .-%.

Suitable anionic surfactants are preferably C ₈ -C ₁₈ -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C ₈ -C ₂₀ -alkanesulfonates, C ₈ -C ₁₈ -monoalkyl sulfates, C ₈ -C ₁₈ -alkyl polyglycol ether sulfates (fatty alcohol ether sulfates) 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 , Fatty acid cyanamides, C ₈ -C ₁₈ -N sarcosinates and C ₈ -C ₁₈ -alkyl isethionates or mixtures thereof.

in the The present invention relates to fatty acids or Fatty alcohols or their derivatives - if not otherwise indicated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms. The former are in particular because of their vegetable base than on renewable resources based on ecological reasons, but without the teaching of the invention on them to restrict. In particular, for example, the oxo-alcohols obtainable by the ROELEN's oxo synthesis or their derivatives used accordingly.

fatty alcohol are products of sulfation reactions on alkoxylated alcohols. The skilled worker will generally understand alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with Alcohols, preferred in the context of the present invention, the longer-chain Alcohols. In general, n moles of ethylene oxide and one Mole of alcohol, depending on the reaction conditions complex mixture of addition products of different degrees of ethoxylation. Another embodiment is the use of mixtures the alkylene oxides preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred in the context of the present invention low ethoxylated fatty alcohols (0.5 to 4 moles EO, preferably 1 to 2.5 mol EO).

The anionic surfactants are preferably used as sodium salts, but can also be used as other alkali or alkaline earth metal salts, For example, magnesium salts, as well as in the form of ammonium or mono, Di-, tri- or tetraalkylammonium salts to be included, in the case the sulfonates also in the form of their corresponding acid, z. B. dodecylbenzenesulfonic acid.

The anionic surfactant used is preferably an alkylbenzenesulfonic acid, in particular a C _10-13 -alkylbenzenesulfonic acid.

Nonionic surfactant

The inventive agent also contains 0.1 to 30 wt .-%, preferably 0.6 to 15 wt .-%, in particular 0.8 to 5 wt .-%, of a further nonionic surfactant.

C ₈ -C ₁₈ -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), C ₈ - are especially nonionic surfactants. C ₁₈ -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 part 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. Particular preference is given to using fatty alcohol alkoxylates, preferably C _8-20 fatty alcohol polyglycol ethers having, in particular, 5 to 14 EO, for example C _12-18 fatty alcohol + 7 EO ethers. The agent should, however, be free of those nonionic surfactants derived from glycerol.

in the inventive agent is the Ratio of short chain nonionic surfactant to anionic surfactant preferably 1: 100 to 100: 1, in particular 1: 5 to 5: 1, especially preferably 1: 4 to 1: 1.5. The ratio of anionic surfactant to further nonionic surfactant is preferably 1: 100 to 100: 1, in particular 5: 1 to 1: 5, particularly preferably 3: 1 to 1: 1.

Next the said surfactants and the amphoteric copolymer, the inventive Means further, usually used in cleaning agents Contain ingredients. These are preferably selected from the group comprising further surfactants, bases, acids, Viscosity modifiers, fatty acids, solvents, other polymers, antibacterial agents, preservatives, Solubilizers, complexing agents, enzymes, dyes, Perfumes and mixtures thereof.

Other surfactants

Next the surfactant types mentioned so far, the inventive Agents also continue to contain cationic surfactants and / or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii 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 -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} 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.

bases

In agents according to the invention can continue Be included bases. As such, alkalis are preferably made the group of alkali and alkaline earth metal hydroxides and carbonates, especially sodium carbonate or sodium hydroxide used. Besides but also ammonia and / or alkanolamines with bis to 9 C-atoms in the molecule are used, preferably the ethanolamines, especially monoethanolamine.

acids

invention Detergents can still be used for reinforcement the cleaning performance against lime and urine stone a or more acids. Suitable acids especially 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 or amidosulfonic acid. In addition, but also the inorganic acids Hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof are used.

Viscosity modifiers

Around a longer adherence of the cleaning agent to the to be cleaned Surface allow, it can continue from Be beneficial, the viscosity of the agent by use to increase a thickener. For this All are commonly used in detergents and cleaners used viscosity regulators, for example organic natural thickening agents (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 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, Silicic acids).

The polyacrylic and polymethacrylic compounds include, for example, 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 Ingre The Cosmetics, Toiletry, and Fragrance Association (CTFA): carbomers), also referred to as carboxyvinyl polymers. Such polyacrylic acids are inter alia from the company. 3V Sigma under the trade name Polygel ^® , z. B. Polygel ^® DA, and from the company. BF Goodrich under the trade name Carbopol ^® available, z. Carbopol ^® 940 (molecular weight approximately 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 ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, by the company Rohm & Haas under the trade names Aculyn ^®. and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymer, z. As 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 C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 Alkanols formed, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are available, for example, from the company. BFGoodrich under the trade name Carbopol ^® , z. B. hydrophobized Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). In the international application WO 97/38076 there is listed a series of polymers derived from acrylic acid which are suitable viscosity regulators.

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, eg. B. propoxylated guar, and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. As 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. 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 2-15 × 10 ^6, and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or from Rhodia is available 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.

fatty acids

Another ingredient of cleaning agents according to the invention may be fatty acids. For the purposes of this invention, this term is taken to mean branched or unbranched, saturated or mono- or polyunsaturated carboxylic acids having preferably 6 to 22 carbon atoms. Particularly preferred are C _12-18 fatty acids.

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 _1-6 alcohols.

When Alcohols are especially ethanol, isopropanol and n-propanol used. As ether alcohols are sufficiently water-soluble Compounds with up to 10 C 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. In a preferred embodiment however, ethanol is used as the solvent.

Other polymers

The composition of the invention may further comprise one or more additional polymers. These may include, for example, polymers which increase the critical micelle concentration (cmc) by interaction with the surfactants, in particular anionic surfactants, and thereby positively influence the cleaning performance. These polymers include, for example, high molecular weight polyethylene glycols (PEG having a molecular weight of over 400,000), but also derivatives of polyvinylpyrrolidone (PVP derivatives) such as PVP-K15 (ISP Corp). Polymers with builder properties can also have a positive effect on the cleaning performance. For this example, polyacrylic acids or polyacrylates are expected, such as Sokalan (R) types from BASF (Sokalan PA 15/20/25/30 CL), also acrylic acid-maleic anhydride copolymers such as Acusol 448 or Acusol 460 N (both Rohm & Haas) Maleic acid-olefin copolymer sodium salt, e.g. B. Sokalan CP 9 (BASF) or nitrogen-containing polymers, as described for example in the application DE 101 60 993 are described. The latter group includes, inter alia, alkoxylated polyvinylamines, alkoxylated, acylated or alkylated polyaminoamides and polyurethane ureas having tertiary amino groups.

In addition, it is also possible to use other polymers which raise and modify surfaces, for example by imparting hydrophilic properties or by modifying the wetting behavior on hydrophobic surfaces. Among these are, for example, those known as "soil-release polymers" amphiphilic and nonionic oligoesters, which are obtainable by polycondensation of dicarboxylic acids, polyols and alkylene oxides and in the applications DE 100 43 604 such as WO 02/18474 (Sasol). Also suitable for surface modification may be polyethersiloxanes, ie copolymers of polymethylsiloxanes and ethylene or propylene oxide units, or further polysiloxane derivatives such as Tegopren (R) 6922 and 6924 (Degussa-Goldschmidt), which also improve the liquid flow. In addition, film-forming polymers such as the acrylic copolymer Primal (R) NT 2624 (Rohm & Haas) or the acrylic resin Wokamer (R) C3303 (Worlee) and waxes, for example polyethylene waxes, such as poly (R) WE 1, can be used for surface modification.

Antibacterial agents

A special form of cleaning provide disinfection and sanitation In a corresponding particular embodiment The invention therefore comprises a cleaning agent or more antimicrobial agents, preferably in an amount from 0.01 to 1 wt .-%, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0.1 to 0.3 wt .-%, extremely preferably 0.2% by weight.

The terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning in the teaching of the invention, the example of KH Wallhäußer in "Practice of Sterilization, Disinfection - Conservation: Germ Identification - Plant Hygiene" (5th edition - Stuttgart, New York: Thieme, 1995) is reproduced. 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, as described, for example, by KH Wallhäußer in "Practice of sterilization, disinfection - preservation: germ identification tion - occupational hygiene "(5th edition - Stuttgart, New York: Thieme, 1995) describes. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning 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.

preservatives

preservative can also be used in the invention Be included means. As such, essentially the substances mentioned in the antimicrobial agents used become.

solubilizers

The agents according to the invention can be used in addition the substances already mentioned continue to be solubilizers, so-called hydrotropes. Here are all common Usable for this purpose in detergents, preferably sodium cumene sulphonate or sodium xylene sulphonate.

complexing

complexing (INCI chelating agents), also called sequestering agents, are ingredients, to complex and inactivate the metal ions, their adverse effects on stability or to prevent the appearance of the agents, such as cloudiness. On the one hand, it is important, with many ingredients incompatible calcium and magnesium ions of water hardness to complex. The complexation of the ions of heavy metals On the other hand, like iron or copper, the oxidative retards Decomposition of the finished product. In addition, the support Complexing agent the cleaning action.

Suitable For example, the following are named according to INCI Complexing agents: aminotrimethylene, phosphonic acid, beta-alanines Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine 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 Phosphonate, Pentasodium Pentetates, pentasodium triphosphates, pentetic acid, phytic acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphates, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonates, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene phosphonates, Sodium dihydroxyethyl glycinates, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphates, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium trimetaphosphates, TEA-EDTA, TEA polyphosphates, tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronates, tetrapotassium pyrophosphates, tetrasodium EDTA, tetrasodium Etidronates, Tetrasodium pyrophosphates, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and trisodium phosphates.

enzymes

The Agent may also contain enzymes, preferably proteases, lipases, Amylases, hydrolases and / or cellulases. You can do that Composition according to the invention in each of the state the technique established form be added. These include in the case of liquid or gelled agents in particular Solutions of the enzymes, preferably as possible concentrated, low in water and / or added with stabilizers. alternative For example, the enzymes can be encapsulated 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 as enclosed in a solidified gel or in such of the core-shell type, in which an enzyme-containing core with a water, Covered air and / or chemical impermeable protective layer is. In superimposed layers may additionally other active substances, for example stabilizers, emulsifiers, Pigments, bleaches or dyes are applied. such Capsules are prepared by methods known per se, for example by Shaking or rolling granulation or in fluid-bed processes applied. Advantageously, such granules, for example by applying polymeric film former, low dust and due to the Coating storage stable.

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.

Dyes and perfumes

The The agent according to the invention can finally all customary in detergents and cleaners fragrance and Dyes contain.

embodiments

It were a cleaning agent according to the invention E and a polymer-free comparison means V prepared. Subsequently on the one hand, the cleaning performance on PVC according to the Test method of the IPP (Industrial Association Cleaning and Cleaning Agents) for general purpose cleaners and on the other hand, the antisoiling effect tested against calcium carbonate.

The following table shows the investigated compositions. The quantities are in% by weight. e V Sodium-lin. alkylbenzenesulfonate 2.92 2.92 C12-18 fatty alcohol ethoxylate 7 EO 1.00 1.00 C4-8 fatty alcohol ethoxylate 5 EO 1.00 1.00 Polyquart Pro 0.11 - C _12-18 sodium soap 0.44 0.44 sodium citrate 0.49 0.49 sodium 0.20 0.20 Perfume 1.10 1.10 Dyes yellow and blue 0,006 0,006 ethanol 1.86 1.86 Demineralised water ad 100 ad 100

Examination of cleaning performance according to IPP test method:

The cleaning performance was based on the IPP test method for general purpose cleaners ( Quality standard of the industry association Cleaning and cleaning agents e. V :, SÖFW-Journal 16; 1982 ) determined test conditions. For this purpose, two different types of dirt (for diluted and undiluted cleaner) were produced according to the IPP method. The dirt was applied by brushing by means of Lackierflachpinsels in a uniform layer (25.6 g / m ² ) on the adhesive coated with white PVC film carrier strip on a surface of 30.0 × 20.8 cm with a template and after at least 1 h and cleaned for a maximum of 1.5 h exposure time. To determine the cleaning performance, the initial value of the unsmottled and soiled strip was first determined with a colorimeter, whereby in each case an average value was formed from ten measured values.

The test strips were then placed in a Sheen Wet Abrasion Scrub Tester Ref. 903 / PG and sponged with a sponge (viscous sponge, wet / fine-pored type Z14700, natural color, from Spontex) onto which the concentrated composition (6 ml) or a dilute solution (15 ml solution prepared by diluting 12 ml of the agent with 1 liter of water) was wiped off. The number of strokes was adjusted to 10 double strokes according to the IPP method. The aftertreatment was done with running cold water immediately after the cleaning. Each product was tested in total in seven parallel tests, each time claiming a different track of the multi-track wiper. The cleaning performance was measured with a colorimeter and then calculated. The metrological parameter for the assessment of soiling and soil removal was the L * value in the paint system CIELAB (1976) used. In this color system L * describes the brightness (L * = 100: "ideal white", L * = 0: "ideal black), a * the red / green value and b * the yellow / blue value. These color values were measured with a spectrophotometer (X-Rite SP78 Seeher Spectral Photometer) with illuminant D65 and the angle of the normal observer of 10 ° without gloss component, the measuring window having a diameter of 16 mm. For each sample, 10 measurements were taken, with the measurement points selected randomly over the entire measurement area. Finally, a statistical evaluation was carried out.

For The diluted cleaner E was able to do so from the seven test strips an average of 64.98% cleaning can be determined polymer-free comparison agent V achieved a value of 61.93%. In concentrated use, the differences between inventive Means and comparison means more apparent: The cleaning performance E here was 71.15%, while Composition V was only 63.95%.

Investigating the soil release / easy-to-clean effect

For this test was fine crystalline precipitated calcium carbonate (Calcite and / or aragonite) used in the precipitation reaction of calcium chloride solution with ammonium carbonate solution arises, as a by-product ammonium chloride is formed. The two Starting materials were each in a 10% aqueous Solution used and with an airbrush on a 30 × 30 cm large matt black tile to even Assignment of the surface applied. Subsequently The tile was dried, rinsed with 800 ml of tap water and finally an optical evaluation by a panel subjected by five people.

in the The framework of this experiment were both completely untreated Tiles used as well as those previously with the comparison means V or treated with the agent E according to the invention were. It was found that the untreated tile has the calcium carbonate layer was completely present even after rinsing. Also, the pretreated with the comparison means V tile still showed heavy pollution (75%) while those with the Tile E treated according to the invention only still had a slight contamination.

Of Other indicated with the agent according to the invention cleaned vertical surfaces a greatly accelerated Water drain on. So was an E cleaned tile on which in vertical position a defined amount of water was applied, dry after 20 seconds, while a tile cleaned with V still had strong traces of wetness.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• EP 1767554 A1 [0015]
• WO 97/38076 [0034]
• - DE 10160993 [0040]
• - DE 10043604 [0041]
• WO 02/18474 [0041]

Cited non-patent literature

• - International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997) [0014]
• - "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Plant Hygiene" (5th Edition - Stuttgart, New York: Thieme, 1995) [0043]
• - "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Plant Hygiene" (5th Edition - Stuttgart, New York: Thieme, 1995) [0044]
• - Quality standard of the industry association Cleaning and cleaning agents e. V :, SÖFW-Journal 16; 1982 [0054]
• CIELAB (1976) [0055]

Claims (10)

Hard surface cleaner comprising a. a short-chain nonionic surfactant of the formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight or branched C _4-8 alkyl or alkenyl radical and n is a number between 1 and 10, b. at least one anionic surfactant and c. at least one further nonionic surfactant, characterized in that it further comprises an ampholytic block copolymer based on acrylate or methacrylate with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). Cleaning agent according to claim 1, characterized in that it preferably 0.01 to 2 wt .-% of the ampholytic block copolymer, more preferably 0.025 to 0.25 wt .-%. Cleaning agent according to one of Claims 1 and 2, characterized in that the short-chain nonionic Surfactant is preferably contained in amounts of 0.1 to 10 wt .-%. Cleaning agent according to one of Claims 1 to 3, characterized in that the at least one anionic surfactant preferably in amounts of 0.1 to 30 wt .-% is. Cleaning agent according to one of Claims 1 to 4, characterized in that the at least one further nonionic surfactant preferably in amounts of from 0.1 to 30 wt .-% is included. Cleaning agent according to one of preceding claims, characterized in that it other, usually used in cleaning agents Contains ingredients, preferably selected from the group comprising further surfactants, bases, acids, Viscosity modifiers, fatty acids, solvents, other polymers, antibacterial agents, preservatives, Solubilizers, complexing agents, enzymes, dyes, Perfumes and mixtures thereof. Product of a cleaning agent according to a of the preceding claims and a spray dispenser. Use of a cleaning agent according to a of claims 1 to 6 for cleaning and simultaneous dirt-repellent modification of hard surfaces. Process for cleaning and simultaneous dirt-repellent Modification of hard surfaces, consisting of the steps a) Applying a cleaning agent according to a of claims 1 to 6 on the surface to be cleaned, optionally by spraying, b) Wipe with a cloth, one Sponge or another suitable for this purpose Substrate to the agent on the entire surface too to distribute, c) If necessary, leave it to act, d) Rinse off with clear water and e) optionally dry rubbing the surface with another cloth, a sponge or another for this suitable substrate. Process for cleaning and simultaneous dirt-repellent Modification of hard surfaces, consisting of the steps a) Preparation of a cleaning liquor by dilution of a Cleaning agent according to one of claims 1 to 6 with water, b) Apply the diluted detergent on the surface to be cleaned, c) wipe with a Cloth, a sponge or another for this purpose suitable substrate to the agent on the entire surface to distribute, d) Allow to dry.