EP2300583A1

EP2300583A1 - Dirt-repelling cleanser

Info

Publication number: EP2300583A1
Application number: EP09769103A
Authority: EP
Inventors: Erik BRÜCKNER; Patrick Markiefka; Stefan Karsten
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2008-06-26
Filing date: 2009-06-03
Publication date: 2011-03-30
Also published as: DE102008029939A1; WO2009156254A1

Abstract

A cleanser for hard surfaces, comprising an alcohol ethoxylate made up of a straight-chained or branched C_4-8-alkyl or alkyl radical and 1 to 10 ethylene oxide units and at least one anionic and at least one other non-ionic surfactant as well as an ampholytic acrylate- or methacrylate-based block copolymer with blocks of quaternary ammonium compounds and of N-isopropyl acrylamide and optionally 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS), can be used for cleaning and simultaneously modifying hard surfaces so that they repel dirt.

Description

Dirt-repellent cleaning agent

The invention relates to a hard surface cleaner comprising an alcohol ethoxylate of straight 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 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).

All-purpose cleaners have long been firmly established in many households. They are used in the cleaning of hard surfaces and are able to remove a variety of, especially greasy, soiling. However, it is desirable that the surface be given further positive properties. This includes an improved water drain as well as dirt-repellent properties. These beneficial properties should be able to develop in both concentrated and dilute applications.

As hard surface cleaners with improved soil release, aqueous compositions containing a short chain fatty alcohol polyglycol ether, an anionic surfactant, and another nonionic surfactant have been found to be useful. However, their performance, in particular with regard to soil release effects and water drainage on vertical surfaces, can still be improved.

Accordingly, it has been an object to provide liquid all-purpose cleaners which, with consistently good or even improved cleaning performance, improve the soil release properties as well as the water drainage on surfaces cleaned with them.

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

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) where R ^{1 is} a straight-chain 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 comprises 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) contains.

After the use of such an agent, an accelerated water flow could be observed on vertical surfaces, even with a single pre-cleaning Soil-release effects on hydrophilic surfaces such as glass and ceramic and associated with a long-lasting gloss to determine. In addition, an improved cleaning performance against grease contamination was observed.

A further subject of this application is accordingly the use of a hard surface cleaner which is a short chain nonionic surfactant of the formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) where 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 comprises an ampholytic block copolymer based on acrylate or methacrylate with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally containing 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) for the cleaning and simultaneous dirt-repellent modification of hard surfaces.

In use, it may be helpful if the cleaning agent is applied to the surface to be cleaned by spraying.

A further subject of this application is therefore a product from a detergent which is a short-chain nonionic surfactant of the formula I, R ¹ O (CH ₂ CH ₂ O) _n -H (I) where R ^{1 is} a straight-chain 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 comprises an ampholytic block copolymer based on acrylate or methacrylate with blocks of quaternary ammonium compounds and of N-isopropylacrylamide and optionally containing 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and a spray dispenser.

The cleaning agent according to the invention can be used in a process for cleaning and simultaneously dirt-repellent modification of hard surfaces. The agent can be used both in concentrated form and diluted.

Yet another subject of this application is therefore a process for the cleaning and simultaneous dirt-repellent modification of hard surfaces, consisting of the steps of applying a cleaning agent according to the invention to the surface to be cleaned, optionally by spraying, wiping with a cloth, a sponge or other suitable substrate for this purpose to distribute the agent over the entire surface, optionally, rinsing with clear water and optionally dry rubbing 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 another subject of this application relates to the dilute use of the agent in a process for cleaning and simultaneous dirt-repellent modification of hard surfaces, consisting of the steps of preparing a cleaning liquor by diluting a cleaning agent according to the invention with water, applying the diluted cleaning agent to the surface to be cleaned, Wipe with a cloth, sponge or other suitable substrate for this purpose to spread the agent over the entire surface and allow to 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 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), The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , which publishes more than 9,000 INCI names and references to more than 37,000 trade names and technical names, 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 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.

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 described in patent application EP 1767554 A1 and are for example, from the company Cognis under the trade name Polyquart Pro commercially available.

The agent according to the invention preferably contains 0.01 to 2% by weight of the ampholytic block copolymer, more preferably 0.025 to 0.25% by weight.

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) where R ^{1 is} a straight-chain or branched C _1-8 -alkyl radical or C ₂ . ₈ alkenyl 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; 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. -% used.

anionic surfactant

The composition according to the invention further 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 .-%.

(Fatty alcohol) alkyl polyglycol ether sulfates - The anionic surfactants are preferably C ₈ -C, ₈ -C ₈ -C ₈ -C ₁₈ alkyl benzene sulfonates are suitable, in particular ₁₈ to about 12 carbon atoms in the alkyl part, C ₂₀ alkanesulfonates, C ₁₈ -Monoalkylsulfate, C with 2 to 6 ethylene oxide units (EO) in the ether portion and sulfosuccinic mono- and di-C ₈ -C ₁₈ alkyl esters. Further, also C ₈ - C ₈ -α-olefin sulfonates, sulfonated C ₈ -C ₈ fatty acids, especially dodecyl benzene sulfonate, C ₈ -C ₂₂ - Carbonsäureamidethersulfate, C ₈ -C ₁₈ -Alkylpolyglykolethercarboxylate, C ₈ -C ₁₈ -N-acyl taurides , Fatty acid cyanamides, C ₈ -C ₁₈ -N sarcosinates and C ₈ -C ₁₈ -alkyl isethionates or mixtures thereof.

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. The former are particularly preferred because of 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 or their derivatives, which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly. 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, preferably the longer-chain alcohols for the purposes of the present invention. As a rule, n moles of ethylene oxide and one mole of alcohol give rise, depending on the reaction conditions, to a complex mixture of addition products of different degrees of ethoxylation. Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. For the purposes of the present invention, very particular preference is given to lower ethoxylated fatty alcohols (0.5 to 4 mol of EO, preferably 1 to 2.5 mol of EO).

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali 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.

The anionic surfactant used is preferably an alkylbenzenesulfonic acid, in particular a C ₁₀ -i ₃ -alkylbenzenesulfonic acid

Nonionic surfactant

The agent according to the invention likewise contains 0.1 to 30% by weight, preferably 0.6 to 15% by weight, in particular 0.8 to 5% by weight, of a further nonionic surfactant.

Particularly suitable nonionic surfactants are 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), 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. Particularly preferred are fatty alcohol alkoxylates, preferably C ₈ - ₂ o-fatty alcohol polyglycol ethers having, in particular 5 to 14 EO, for example C ₂ -i ₈ fatty alcohol + 7 EO ether, are used. The agent should, however, be free of those nonionic surfactants derived from glycerol.

In the composition according to the invention, the ratio of short-chain nonionic surfactant to anionic surfactant is preferably 1: 100 to 100: 1, in particular 1: 5 to 5: 1, particularly 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. In addition to the surfactants mentioned and the amphoteric copolymer, the composition according to the invention may contain further ingredients usually used in cleaning agents. These are preferably selected from the group comprising other surfactants, bases, acids, viscosity modifiers, fatty acids, solvents, other polymers, antibacterial agents, preservatives, solubilizers, complexing agents, enzymes, dyes, fragrances and mixtures thereof.

Other surfactants

In addition to the previously mentioned types of surfactant, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R '") (R ^IV ) (R ^V ) N ⁺ CH ₂ COO ^- , in which R ¹ " 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 _O -C ₈ alkyl and C ₁ dimethylcarboxymethylbetain rC ₁₇ -Alkylamidopropyl-dimethylcarboxymet.hylbet.ain.

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.

bases

In compositions according to the invention, it is furthermore possible for bases to be present. As such, alkalis from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide, are preferably used. 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.

acids

Detergents according to the invention may further contain one or more acids for enhancing the cleaning performance against lime and urine stone. 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 or amidosulfonic acid. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof. Viscosity modifiers

In order to enable a longer adherence of the cleaning agent to the surface to be cleaned, it may also be advantageous to increase the viscosity of the agent by using a thickening agent. 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 (carboxymethyl cellulose 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, silicas).

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 Degussa (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, which are crosslinked with an allyl ether of sucrose or of pentaerythritol copolymers of C-ιo- ₃₀ alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with CI_ ₄ - Alkanols formed, esters (INCI Acrylates / C 10-30 alkyl acrylate crosspolymer) include and which are available, for example, from the company BFGoodrich under the trade name Carbopol ^® , eg the hydrophobized Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates / C 10 -30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). In the international application WO 97/38076 lists a number 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, 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.

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 -i ₈ -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-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.

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, eg Sokalan CP 9 (BASF) or nitrogen-containing polymers, as described for example in the application DE 10160993. Among the latter group include u.a. 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, the amphiphilic and nonionic oligoesters which are also known as "soil-release polymers" and are obtainable by polycondensation of dicarboxylic acids, polyols and alkylene oxides and are described in the applications DE 10043604 and 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 particular form of cleaning is disinfection and sanitation. In a corresponding particular embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial active ingredients, 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 in the context of the teaching of the invention, for example, by KH Wallhäußer in "Practice of sterilization, disinfection - Conservation: germ identification - company hygiene" (5th ed. - Stuttgart, New York : Thieme, 1995). 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 "Praxis der Sterilisation, Desinfektion - Konservierung: Keimidentifizierung - Betriebshygiene" (5th edition - Stuttgart; New York: Thieme, 1995). 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

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

In addition to the substances already mentioned, the compositions according to the invention can also contain solubilizers, so-called hydrotropes. In this case, it is possible to use all substances customarily used for this purpose in cleaning compositions, preferably sodium cumene sulphonate or sodium xylene sulphonate.

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: aminotrimethylene, phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrates, diammonium EDTA, diethylenetriamines pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, 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, S orodium dihydroxyethylglycinate, sodium EDTMP, sodium glutamate, sodium gluconate, sodium glycereth-1 polyphosphate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydimethylglycinophenolsulfonate, sodium trimetaphosphate, TEA-EDTA, TEA polyphosphate, tetrahydroxyethyl ethylene diamine, tetrahydroxypropyl ethylene diamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate. enzymes

The agent 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 can 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, 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 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, 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

Finally, the composition according to the invention can contain all scents and dyes customary in detergents and cleaners. embodiments

An inventive cleaning agent E and a polymer-free comparative agent V were prepared. Subsequently, on the one hand, the cleaning performance was tested for PVC according to the test method of IPP (industrial cleaning and cleaning agents) for all-purpose cleaner and on the other hand, the antisoiling effect against calcium carbonate tested.

The following table shows the investigated compositions. The quantities are in% by weight.

Examination of cleaning performance according to IPP test method:

The cleaning performance was determined in accordance with the test conditions specified in the IPP test method for all-purpose cleaners (quality standard of the Industrieverband Putz- und Reinigungsmittel eV :, SÖFW-Journal 16, 1982). 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 adhered with white PVC film carrier strip on a surface of 30.0 x 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 an automatic multi-track wiper (Sheen Wet Abrasion Scrub Tester ref. 903 / PG) and washed with a sponge (viscous sponge, damp / fine-pored Art. Z14700; Spongex), to which the concentrated composition (6 ml) or a dilute solution (15 ml solution prepared by diluting 12 ml of the product with 1 liter of water) is 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. As a metrological parameter for the assessment of soiling and soil removal, the L * value in the color system according to CIELAB (1976) was 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 Spectrophotometer (X-Rite SP78 Speher Spectral Photometer) with illuminant D65 and the angle of the normal observer of 10 ° without gloss, measured with a diameter of 16 mm, 10 measurements were taken per sample with the measuring points over the entire measuring surface Finally, a statistical evaluation was carried out.

For the diluted detergent E, an average value of 64.98% of the seven test strips could be determined; the polymer-free comparison medium V achieved a value of 61.93%. With concentrated use, the differences between the composition of the invention and comparison means were more apparent: the cleaning performance of E was 71, 15%, and that of composition V was only 63.95%.

Investigating the soil release / easy-to-clean effect

For this test, finely crystalline precipitated calcium carbonate (calcite and / or aragonite) was used, which is formed during the precipitation reaction of calcium chloride solution with ammonium carbonate solution, the by-product ammonium chloride being formed. The two starting materials were each used in a 10% aqueous solution and applied with an airbrush on a 30 x 30 cm matte black tile to geichmäßigen occupation of the surface. Subsequently, the tile was dried, rinsed with 800 ml of tap water and finally subjected to optical evaluation by a panel of five persons. As part of this experiment, both completely untreated tiles were used as well as those which were previously treated with the comparison means V or with the agent E according to the invention. It was found that with the untreated tile the calcium carbonate layer was completely present even after rinsing. The tile pretreated with the comparison agent V still had a high level of contamination (75%), whereas the tile treated with the agent E according to the invention had only slight soiling. Furthermore, vertical surfaces cleaned with the agent according to the invention had a greatly accelerated water drainage. For example, a tile cleaned with E, to which a defined amount of water was applied in a vertical position, appeared to be dry after only 20 seconds, whereas a tile cleaned with V still had strong traces of wetness.

Claims

claims

A 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) where R ^{1 is} a straight-chain 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 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).

2. Cleaning agent according to claim 1, characterized in that it preferably contains 0.01 to 2 wt .-% of the ampholytic block copolymer, more preferably 0.025 to 0.25 wt .-%.

3. 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 .-%.

4. Cleaning agent according to one of claims 1 to 3, characterized in that the at least one anionic surfactant is preferably contained in amounts of 0.1 to 30 wt .-%.

5. Cleaning agent according to one of claims 1 to 4, characterized in that the at least one further nonionic surfactant is preferably contained in amounts of 0.1 to 30 wt .-%.

6. cleaning agent according to any one of the preceding claims, characterized in that it contains further, usually used in cleaning ingredients, preferably selected from the group comprising other surfactants, bases, acids, viscosity modifiers, fatty acids, solvents, other polymers, antibacterial agents, preservatives, Solubilizers, complexing agents, enzymes, dyes, fragrances and mixtures thereof.

7. Product of a cleaning agent according to one of the preceding claims and a spray dispenser.

8. Use of a cleaning agent according to any one of claims 1 to 6 for the cleaning and simultaneous dirt-repellent modification of hard surfaces.

9. A method for cleaning and simultaneously dirt-repellent modification of hard surfaces, consisting of the steps a) applying a cleaning agent according to any one of claims 1 to 6 on the surface to be cleaned, optionally by spraying, b) wiping with a cloth, a sponge or another c) optionally applying, d) rinsing with clear water and e) optionally rubbing the surface dry with another cloth, a sponge or another substrate suitable for this purpose.

10. A method for cleaning and simultaneously dirt-repellent modification of hard surfaces, comprising the steps a) Preparation of a cleaning liquor by diluting a cleaning agent according to one of claims 1 to 6 with water, b) applying the diluted cleaning agent to the surface to be cleaned, c) wiping with a cloth, a sponge or other suitable substrate for this purpose to distribute the agent over the entire surface, d) allow to dry.