WO2006021329A1

WO2006021329A1 - Cleaning agent with reduced residues and faster drying action

Info

Publication number: WO2006021329A1
Application number: PCT/EP2005/008780
Authority: WO
Inventors: Michael Dreja; Stefan Karsten; Ryszard Katowicz; Patrick Markiefka
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-08-23
Filing date: 2005-08-12
Publication date: 2006-03-02
Also published as: DE102004040847A1

Abstract

The invention relates to a liquid aqueous cleaning agent for hard surfaces. Said cleaning agent can be formulated with between 0.1 and 10 wt. % of a short-chain non-ionic surfactant of formula R1O(CH2CH2O)n-H, wherein R1 represents a straight-chain or branched C1-8 alkyl radical or C2-8 alkenyl radical, and n represents a number between 1 and 10, between 0.1 and 30 wt. % of an anionic surfactant, and between 0.1 and 30 wt. % of a non-ionic surfactant, said cleaning agent being free of magnesium sulphate and other salts of multivalent cations. The short-chain non-ionic surfactant is used to increase the cleaning performance or accelerate the dirt dissolution and/or to reduce the residues and/or to improve the wetting behaviour, and is used accordingly in methods for increasing the cleaning performance or accelerating the dirt dissolution and/or reducing residues and/or improving the wetting behaviour by means of cleaning agents containing anion surfactants.

Description

"Detergent with reduced residue behavior and faster drying"

The invention relates to a hard surface cleaner comprising an alcohol ethoxylate of a C _1-8 straight or branched alkyl radical or C _2-8 alkylene radical and from 1 to 10 ethylene oxide units and an anionic and another nonionic surfactant and free of magnesium sulfate and other salts of polyvalent cations.

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. In order to develop their good cleaning performance, however, such general-purpose cleaners generally require levels of anionic surfactants and / or nonionic surfactants with chain lengths of C ₈ -C ₆ of at least 5%, with a ratio of anionic surfactant to nonionic surfactant generally being between 3: 1 and 1: 1 is selected; Occasionally, an exclusively non-ionic detergent is described in the prior art. These cleaning agents have in common that they have a good cleaning performance, but at usual application concentrations show only a moderate residue behavior and moderate wetting behavior. The wetting behavior can be increased according to the prior art only by the addition of further raw materials, such as short-chain anionic surfactants (eg octyl sulfate), by hydrotrope (xylene sulfonate etc.) or by adding special surfactants or polymers (polysiloxane, polyacrylate copolymers) ,

Accordingly, it was an object to improve the residue behavior and the wetting behavior of anionic surfactant-containing all-purpose cleaners with consistently good or even improved cleaning performance. Surprisingly, it has been found that the cleaning performance of anionic surfactant-based cleaners by addition of 0.1 to 10 wt .-% of a short-chain alcohol ethoxylate, ie a nonionic surfactant of a straight-chain or branched C _1-8 alkyl or C _2-8 alkylene radical and 1 up to 10 ethylene oxide units, can be significantly increased. The combination with long-chain nonionic surfactants, ie those with a chain length of C ₈ -C _{2 O} , has proven to be particularly favorable. At the same time, the total content of surfactant can be reduced, so that the residue behavior is also improved. In addition, by adding the short-chain alcohol ethoxylate wetting behavior of the cleaner, even at application concentration (eg dilution 12ml / l), significantly improved, without the addition of other additives.

The use of short-chain nonionic surfactants in hard surface cleaners is described in the prior art. Thus, WO 03/080781 A1 (Colgate-Palmolive) claims a cleaning composition of an anionic surfactant, an alkoxylated nonionic surfactant, a short-chain amphiphile, a fatty acid, magnesium sulfate, a preservative, a sodium imino succinate and water and optionally a water-insoluble hydrocarbon, essential oil or perfume. This microemulsion should remove grease and have a good residue behavior. However, the good cleaning performance is attributed to the presence of magnesium sulfate or other salts of polyvalent cations, especially in soft water. Similar compositions are also described in WO 00/29528 A2 and US 6,057,279 (also Colgate-Palmolive). However, compositions without the addition of such salts are not described in the cited documents.

The subject of the present application is accordingly a liquid aqueous cleaning agent for hard surfaces, comprising

(a) 0.1 to 10% by weight of 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 radical and n is a number between 1 and 10,

(b) 0.1 to 30% by weight of an anionic surfactant and

(c) 0.1 to 30% by weight of a nonionic surfactant, the agent being free of magnesium sulfate and other polyvalent cation salts.

An advantage of this agent is the very good cleaning performance on hard surfaces combined with excellent residue freedom through the use of lower total surfactant amount, the residue behavior and the cleaning performance is improved, especially when using hard water. Furthermore, the center according to the invention also has a good wetting behavior on all hard surfaces. Further advantages are the improved drying behavior (drainage) on hard surfaces and the faster dirt removal kinetics compared to the cleaner without the short-chain nonionic surfactant. The short-chain nonionic surfactant used causes compared to anionic surfactant-containing agents that do not contain this short-chain surfactant, an increase in Reinigungs¬ performance, among other things also against dried greasy soil, which is equivalent to accelerating the soil release, as well as an improvement of the residue and wetting behavior.

Accordingly, the invention further relates to the use of 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 Ci _-8 alkyl, or C _2-8 alkenyl group and n is a number between 1 and 10, containing anionic surfactants in a Cleaning agent for hard surfaces to increase the cleaning performance or acceleration of the soil release and / or to improve the residue behavior and / or to improve the wetting behavior.

Other subjects of the invention are also processes for increasing the cleaning performance or accelerating the soil release and / or improving the residue behavior and / or improving the wetting behavior of an anionic surfactant-containing cleaning agent for hard surfaces by adding 0.1 to 10 wt .-% of a nonionic Surfactants of the formula I ₁

R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight or branched C-) _-8- alkyl radical or C _2-8 alkenyl radical and n is a number between 1 and 10.

In addition to the surfactant combination mentioned, the composition according to the invention may contain further ingredients customary in hard surface cleaners. These include, for example, other surfactants, bases, acids, viscosity modifiers, surface modifiers, fatty acids, solvents, antibacterial agents, preservatives, solubilizers, opacifiers, complexing agents, polymers, enzymes, dyes and fragrances.

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.

Short-chain nonionic surfactant

The composition according to the invention comprises 0.1 to 10% by weight, preferably 0.2 to 5% by weight.

%, in particular 0.5 to 4 wt .-% of 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".

anionic surfactant

The inventive composition further contains 0.1 to 30 wt .-%, preferably 0.6 to

15 wt .-%, in particular 1 to 10 wt .-%, of an anionic surfactant.

Suitable anionic surfactants are preferably C ₈ -C ₁₈ -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C ₈ -C ₂ 0-alkanesulfonates, C ₈ -C ₈ -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 part and sulfosuccinic mono- and di-C ₈ -C ₁₈ - alkyl esters. Can furthermore also C ₈ -C ₁₈ -α-olefinsulfonates, 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 in the context of the present invention, the longer-chain alcohols. 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 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 Dode- cylbenzenesulfonic acid.

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

Nonionic surfactant

The agent according to the invention 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.

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), C ₈ -C ₁₈ carboxylic acid polyglycol esters with 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides with 12 to mention 18 carbon atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides having 14 to 20 carbon atoms and long-chain alkylpolyglycosides having 8 to 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 wer¬ the fatty alcohol alkoxylates, C _8-2 o-fatty alcohol polyglycol ethers preferably having from 5 to 14 EO insbesonde¬ re, for example, C _2-18 fatty alcohol + 7 EO ether 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 surfactant combination mentioned, 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, antibacterial agents, preservatives, solubilizers, opacifiers, complexing agents, polymers, 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 ^iπ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO-, in which R ^{iπ is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups with 8 to 25, preferably 10 to 21, carbon atoms mean atoms ¬ and R ^IV and R ^v are identical or different alkyl radicals having 1 to 3 Koh¬ lenstoffatomen, especially C ₁₀ -C ₈ alkyl-dimethylcarboxymethylbetain and Cn-C ^ -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 for four identical or different, in particular two long and two short chain, alkyl radicals and X ^' for an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkylbenzyl-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 furthermore contain one or more acids in order to enhance the cleaning performance with respect to 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 make it possible for the cleaning agent to adhere to the surface to be cleaned for a longer time, it may furthermore be advantageous to increase the viscosity of the composition 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 (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and the like, remainder 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 montmorillonite, zeolites, silicas).

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 Ingredients of The Cosmetic, Toiletry, and Fragrance Association (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 _1-4 alkanols formed esters (INCI acrylates copolymer), including about 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 are available from Degussa (Goldschmidt) under the trade name Tego ^® polymer obtainable, for example the anionic nicht¬ associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® (crosslinked) 33, 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 Ci _O. ₃ o-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) and which are available, for example, from the company. BF Goodrich under the trade name Carbopol ^® , eg the hydrophobic Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI acrylates / C 10-30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473). 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, alternatively, but preferably in addition to a polysaccharide are used, for example, starches of various origin and starch derivatives, such as hydroxyethyl starch, starch phosphate esters or starch acetates, or Carboxymethyicellulose or her 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, the conditions of Xanthomonas campestris and some other species under aerobic Bedin¬ is produced with a molecular weight of 2-15x10 ⁶ and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® is available or 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, these are to be understood to mean branched or unbranched, saturated or mono- or polyunsaturated carboxylic acids having preferably 6 to 22 carbon atoms. Particularly preferred are Ci _2- 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 Ci _-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.

antibacterial agents

A special form of cleaning is disinfection and sanitation. In a corresponding particular embodiment of the invention, this contains Cleaning agent therefore one or more antimicrobial agents, preferably in an amount of 0.01 to 1 wt .-%, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, especially 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 far as possible elimination of all - even saprophytic germs normally harmless to humans. 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, 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.

opacifiers

In agents according to the invention, clouding agents may furthermore be present. As such, it is possible to use all substances conventionally used in detergents for this purpose, for example polymers such as the styrene-acrylic copolymers available under the trade name Acusol® (Rohm & Haas), or soap-like pearlescing agents, for example Cutina® (Cognis).

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 are, for example, the following according to INCI designated complexing agents: aminotrimethylene, 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 Diphosphonate, 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, Sodium Dihydroxyethyl Glycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenol Sulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphate, Tetrahydroxyethyl Ethyle nediamine, tetrahydroxypropyl, ethylenediamine, tetrapotassium etidronate, tetrapotassium pyrophosphate, tetrasodium EDTA, tetra-sodium etidronate, tetrasodium pyrophosphate, tripotassium EDTA, trisodium dicarboxymethyl alaninate, trisodium EDTA, trisodium HEDTA, trisodium NTA and trisodium phosphates.

polymers

The agent according to the invention can furthermore contain one or more polymers.

Polymers can fulfill several functions in detergents. Thus, for example, polymers which increase the critical micelle concentration (cmc) by interaction with the surfactants, in particular anionic surfactants, can 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, eg Sokalan CP 9 (BASF) or nitrogen-containing polymers, as described for example in the application DE 10160993. The latter group includes alkoxylated polyvinylamines, alkoxylated, acylated or alkylated polyaminoamides and polyurethane ureas having tertiary amino groups.

Other polymers attract and modify surfaces, for example by imparting hydrophilic properties or by altering 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® 6922 and 6924 (Degussa-Goldschmidt), which also improve the liquid flow. Further surface-modifying polymers are amphoteric polymers, in particular copolymers of acrylic or methacrylic acid and quaternary ammonium compounds such as MAPTAC or DADMAC, or also copolymers with AMPS (2-acrylamido-2-methylpropanesulfonic acid). In addition, film-forming polymers such as the acrylic copolymer Primal (R) NT 2624 (Rohm & Haas) or the acrylate resin Wokamer (R) C3303 (Worlee) and waxes, for example polyethylene waxes, such as poly (R) WE 1, may be used for surface modification.

In a preferred embodiment, the agent according to the invention is free of such surface-modifying polymers which change the wetting behavior and contains at most those polymers which directly influence the cleaning performance.

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 may be encapsulated, for example, by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleaches or dyes auf¬ brought. 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 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 ₁₂ , 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; as well as 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.

PH value

The agent according to the invention may have a pH of 1 to 14. The pH is preferably 5.5 to 12. In order to set the desired pH, it is possible, for example, to add to the composition the abovementioned acids and bases. The invention furthermore relates to the use of the 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 d _-8- alkyl radical or C _2-8 -alkenyl radical and n is a number between 1 and 10, in an anionic surfactant-containing Cleaning agent for hard surfaces to increase the cleaning performance or acceleration of the soil release and / or to improve the residue behavior and / or to improve the wetting behavior. Accordingly, this short-chain nonionic surfactant can also be used in processes for improving the cleaning performance or the soil release, the residue and the wetting behavior by adding to an anionic surfactant-containing detergent.

Embodiment:

Three general-purpose alkaline cleaners E1-E3 according to the invention and one comparative example V1 in which instead of the short-chain nonionic surfactant an anionic surfactant (octyl sulfate) frequently used to improve the wetting behavior were prepared. The cleaning performance of these agents as well as a commercial cleaner (Mr. Proper Sea Fresh) was checked against greasy soiling.

Composition [% by weight] V1 E1 E2 E3

C ₆ -alcohol ethoxylate-5EO (eg Emulan HE 50) 0 0.8 1, 5 3

C _10-13 -alkylbenzenesulfonic acid Na salt 4 3 3 2

Octyl sulfate (e.g., Texapon 842) 3 0 0 0

C _12-18 -EO7 (eg Dehydol LT7) 1 1.5 1 1

Sodium hydroxide 1 1 0.8 0.6

Citric acid 0.5 0.5 0.5 0.5

C _12-18 fatty acid (eg Edenor K12-18) 0.5 0.5 0.5 0.5

Ethanol 5 5 5 5

Perfume 0,2 0,2 0,2 0,2

Water ad 100 ad 100 ad 100 ad 100 pH 9.3 9.3 9.3 9.3

Removal of grease dirt 62% 81% 83% 80%

Cleaning performance against grease dirt:

0.35 g of a 20:80 dilution of a greasy dirt with isopropanol (greasy soil consisting of 75% Mazola peanut oil, 23% kaolin 60609 (Fluka), 2% Spezial Schwarz 4 (Degussa )) with the aid of an airbrush gun and burned at 100 ° C for 24 hours in a heating furnace ein¬. The resulting greasy soil was smeared on the tile using a Sheen 903 PG tester (Sheen Instruments Ltd., Unit 4, St. Georges Ind. Est., Richmond Road, Kingston KT2 5 BQ, England) 5 ml cleaning liquid with 1 cloth of 1 g each weight (cloths article number 02010100, company Wecovi) wiped.We took 10 wiping movements (5 x out, 5 x back) .The dirt could only be removed with the comparison cleaner V1 to 62 Remove%, with the By contrast, cleaners E1-E3 according to the invention are removed from 80 to 83%. With a commercial cleaner (Mr. Proper sea freshness), the dirt was removed to 71%.

Claims

claims

A liquid aqueous hard surface cleaner comprising a. 0.1 to 10% by weight of a short-chain nonionic surfactant of the formula I ₁

R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ^{1 is} a straight or branched C _1-8 alkyl radical or C _2-8 alkenyl radical and n is a number between 1 and 10, b. 0.1 to 30% by weight of an anionic surfactant and c. 0.1 to 30 wt .-% of a nonionic surfactant, characterized in that the agent is free of magnesium sulfate and other salts of polyvalent cations.

2. Liquid aqueous cleaning agent according to claim 1, characterized in that the short-chain nonionic surfactant (a) is preferably pentaethylene glycol monohexyl ether, ie R ¹ = C ₆ -alkyl and n = 5.

3. Liquid aqueous cleaning agent according to any one of claims 1 and 2, characterized in that the anionic surfactant (b) is preferably an alkylbenzenesulfonic acid, in particular a C _10-13 -alkylbenzenesulfonic acid.

4. Liquid aqueous cleaning agent according to any one of claims 1 to 3, characterized in that as nonionic surfactant (c) is preferably a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, more preferably a C _8-2 o-fatty alcohol ethoxylate with 5-14 EO, for example C _{12 -18} 7EO is used.

5. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the short-chain nonionic surfactant (a) is preferably used in amounts of 0.2 to 5 wt .-%, in particular 0.5 to 4 wt .-%.

6. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the anionic surfactant (b) is preferably present in amounts of 0.6 to 15 wt .-%, in particular 1 to 10 wt .-%.

7. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the nonionic surfactant (c) is preferably used in amounts of 0.6 to 15 wt .-%, in particular 0.8 to 5 wt .-%.

8. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the ratio (a): (b) is 1: 100 to 100: 1, preferably 1: 5 to 5: 1, in particular 1: 4 to 1: 1 ; 5.

Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the ratio (b): (c) is 1: 100 to 100: 1, preferably 5: 1 to 1: 5, in particular 3: 1 to 1: 1 ,

10. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that it may contain other common in hard surface cleaning agents ingredients, auxiliaries and additives.

11. Liquid aqueous cleaning agent according to one of the preceding claims, characterized in that the further ingredients are preferably selected from the group comprising other surfactants, bases, acids, viscosity modifiers, surface modification aids, fatty acids, solvents, antibacterial agents, preservatives, solubilizers, opacifiers , Complexing agents, polymers, enzymes, dyes, fragrances and mixtures thereof.

12. Use of 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-chain or branched C _1-8 -alkyl radical or C ₂ -S -alkynyl radical and n is a number between 1 and 10 in an anionic surfactant-containing cleaning agent for hard surfaces to increase the cleaning performance or acceleration of the soil release.

13. Use of 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 _1-8 -alkyl radical or C ₂ . ₈ alkenyl radical and n is a number between 1 and 10, in an anionic surfactant-containing hard surface cleaner to improve the residue behavior.

14. Use of 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-chain or branched C _1-8 -alkyl radical or C _2-8 -alkenyl radical and n is a number between 1 and 10, in one Anionic surfactant-containing hard surface cleaner for improving wetting performance.

15. A method for increasing the cleaning performance or acceleration of the soil release by an anionic surfactant-containing cleaning agent for hard surfaces, characterized by the addition of 0.1 to 10 wt .-% of a short-chain nonionic surfactant of the formula I _1st

R ¹ O (CH ₂ CH ₂ O) _n -H (I) wherein R ¹ is a straight or branched Ci _-8 alkyl, or C. ₂ ₈ alkenyl and n is a number between 1 and 10.

16. A method for improving the residue behavior of an anionic surfactant-containing hard surface cleaner, characterized by the addition of 0.1 to 10 wt .-% of a short-chain nonionic surfactant of the formula I,

17. A method for improving the wetting behavior of an anionic surfactant-containing hard surface cleaning agent, characterized by the addition of 0.1 to 10% by weight of 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 Ci _-8 alkyl, or C _2-8 alkenyl group and n is a number between 1 and 10 communicates.