WO2005100523A1

WO2005100523A1 - Hydrophilizing cleanser for hard surfaces

Info

Publication number: WO2005100523A1
Application number: PCT/EP2005/003703
Authority: WO
Inventors: Michael Dreja; Jürgen Noglich; Ronald Menke; Petra Plantikow
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-04-16
Filing date: 2005-04-08
Publication date: 2005-10-27
Also published as: DE102004019022A1

Abstract

A cleaning agent for hard surfaces that contains at least one hydrophilizing substance can cover 33 % to 86 % of the surface with the hydrophilizing substance. The agent can be used for cleaning and/or hydrophilizing hard surfaces and can be correspondingly used in a method for hydrophilizing hard surfaces. The use of this agent leads to an improvement in liquid run-off and in the soil detaching behavior while simultaneously reducing the formation of residues, the tendency to become soiled again, the tendency to fog, and the drying time.

Description

"Hydrophilize cleaner for hard surfaces"

The subject of the present application is a hydrophilizing cleaning agent for hard surfaces, with which the surface is not completely covered. The micro-gradients of the interfacial tension resulting from this result in better dirt release behavior and / or a lower tendency to re-soiling.

In addition to the hygienic aspect, cleaning hard surfaces also has an aesthetic side. It is desirable that a cleaned surface dries as quickly and evenly as possible in order to avoid the formation of unsightly drops or stripes in the form of "noses". In spite of the thin (monomolecular) surfactant film left behind during cleaning, such “noses” can arise after cleaning, especially when using hard water, but also between cleaning processes when the surface comes into contact with water again (so-called rain effect) is the case, for example, in bathrooms or surfaces exposed to the weather such as windows etc. Water, both clean and dirty and rainwater, will wet and run off the surface immediately after cleaning, after a short exposure time (a few hours to max. 1-2 days), however, again form spherical drops on the hard surface, which drag dirt and dust with them. The surface also dries when drying, so that "dirt" is formed in the liquid drop or film by the dirt ballast. It is therefore worth striving for both the wetting of the surfaces over a longer period of time without tearing open the film, and their rapid drying, which is due in part to the wetting with a thin film. Due to the wetting, tiny dirt particles are evenly distributed instead of concentrated in the "noses", so that the surface looks optically cleaner. As a result, as well as by reducing the tendency towards re-soiling of cleaned surfaces, the consumer can also allow a longer period of time to pass between two cleaning processes without the surface appearing dirty to the viewer.

It is therefore an object of the present invention to develop a cleaner which modifies the surface to be cleaned, in particular on hard surfaces such as glass and ceramic, in such a way that the wetting behavior compared to an untreated surface area changed for a long time. This should make the surface less dirty and dry quickly; Furthermore, the surface modification should ensure that the appearance of the surface is rated by the user as "cleaner", ie in such a way that only dots and no frequent or nose-like dirt residues are formed. In addition, the additive of the cleaner should be as efficient as possible, ie the maximum Effect with minimal use of additive.

It is already known from the prior art to temporarily impart hydrophilic properties to a hard surface and thus also to improve the drying and draining behavior. Nanoparticulate silica sols, for example, are suitable as hydrophilizing agents. In addition, polymers can preferably be used, especially amphoteric polymers, which are in particular copolymers of acrylic acid and quaternary ammonium compounds.

Cleaning agents with nanoparticles (including also with silica sols) for surface modification can be found, for example, in EP 1215276 A1 (Clariant) or DE 19952383 A1 (Henkel). In these writings, no information is given about the degree of coverage of the surface, but only the general effect. US 2002/0045010 (Procter & Gamble) also claims a nanoparticle-containing agent for the hydrophilic coating of surfaces. According to the description, the coating can completely or partially cover the surface without giving more precise information.

The use of suitable amphoteric polymers in cleaning agents for hard surfaces is described, for example, in US Pat. No. 6,703,358 B1 (Rhodia). The copolymer used is composed of the following monomers: (a) quaternary ammonium compound of a given formula, preferably MAPTAC (methacrylamidopropyltrimethylammonium chloride), (b) monounsaturated C ₃ -C ₈ carboxylic acids (with ethylene grouping) and their Anhydrides and water-soluble salts, preferably acrylic acid, methacrylic acid, etc., (c) optionally neutral hydrophilic unsaturated compound, for example acrylamide, vinyl alcohol, acrylic acid-C ₄ -alkyl esters, etc. In addition to the copolymer, the composition also contains at least one Surfactant, possibly also other ingredients. The agents are used as cleaning agents for hard surfaces (hand and machine dishwashing detergents, glass and bathroom cleaners). Be through their application hydrophilizes the surfaces and thus minimizes the contact angle of the surface against water. The degree of coverage of the surface is not discussed.

Similar copolymers are used in WO 01/05921 A1 (Rhodia). Monomer (a) here is preferably DADMAC (diallyldimethylammonium chloride). These agents also impart hydrophilic properties to the treated surfaces. Again, there is no indication of the degree of coverage of the surface. Hydrophilizing agents with further amphoteric polymers, again without mentioning the degree of coverage, are also described in US Pat. No. 6,569,261 (Rhodia).

Surprisingly, it has now been found that when hydrophilizing substances such as polymers or colloidal silica sol are added to cleaning agents, in particular cleaning agents for hard surfaces, the complete coverage of the surface with the additive does not lead to the best result. In fact, a surface coverage of at least 33% to a maximum of 86% has proven to be optimal; a coverage level of 45% to 72% is particularly preferred. Compared to conventional cleaners, this also has the advantage that less use of raw materials is required.

The addition of the hydrophilizing substances causes the hard surface to be structured at the micrometer level. At this size level, gradients in the interfacial tension are generated which lead to an improved wetting. This is also possible if the surface has only a minimal roughness. The surface charge does not have to be increased either, it can even decrease. The only decisive factor is the sufficient number of micro gradients of the interfacial tension on the surface.

The hydrophilization of the surface through the use of these cleaning agents leads to a long-lasting wettability of the surface as a flat film. As a result, the dirt particles are evenly distributed and do not form "noses", so that the appearance of the cleaned surface is clean over a long period of time. This effect, as well as the lower tendency towards re-soiling, the improved dirt removal behavior, the quick and even drying of the surface after re-irrigation and the anti-fogging effect, can be observed over a longer period of time, for example two weeks, after application of the agent, but there is no permanent effect Surface finishing. The hydrophilization of the surface also changes its contact angle, both against water and against ethylene glycol. The untreated surface has a contact angle against water of 34 ° ± 10 °, preferably 34 ° + 5 °, after treatment with the agent according to the invention it is 10 ° + 10 °, preferably 10 ° ± 5 °. For ethylene glycol, the value changes from 8 ° + 10 °, preferably 8 ° ± 5 °, to 18 ° + 10 °, preferably 1 8 ° ± 5 °.

For degrees of coverage of 0 - 32% it was found that no change in the contact angle to the desired range can be achieved with the specified means. The reason for this behavior is assumed to be that only locally limited areas with improved wetting behavior are formed in these cases. A homogeneously wetting surface is only found for degrees of coverage greater than 32%. For degrees of coverage greater than 87%, it was found that, although surface wetting, multilayer formation and aggregation of the polymers or particles takes place on the surface, which can lead to local areas with an opaque appearance or cloudiness, which the observer / consumer perceives as unattractive ,

The decisive factor for achieving the optimal coverage level of 33 to 86% is the use concentration of polymers or nanoparticles as well as the level of specific charge, which leads to a balance of aggregation and interparticle rejection in the respective mixture with surfactants and solvents. Low degrees of coverage arise when the aggregation is too early and the repulsive forces of the same, high loads are too high, and the degree of coverage is too high when the aggregation is too late and the repulsive forces are low when the loads are unequal and low.

The cleaning agent naturally also meets the usual technical and aesthetic requirements for a cleaning agent for hard surfaces. It has a good cleaning performance compared to different types of soiling, is also suitable for spraying and is transparent in a preferred embodiment.

For the hydrophilization, the addition of certain nanoparticles or certain polymers is necessary, which accumulate on the surface during cleaning. Suitable nanoparticles are in particular colloidal silica sols, ie stable dispersions of amorphous particulate silica Si0 ₂ nm with particle sizes in the range of 1 to 100, preferably 3 nm to 50, particularly 4 to 40 nm, for example 9 nm. Examples of such suitable silica sols are Bindzil ^® 30/360, 15/500, 30 / 220, 40/200, 257/360 (Akzo), Nyacof ^® 215, 830, 1430, 2034DI and Nyacof DP5820, DP5480, DP5540 etc. (Nyacol Products), Levasif 100/30, 100F / 30, 100S / 30, 200/30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HC Starck / Bayer) or also CAB-O-SPERSE ^® PG 001, PG 002 (aqueous dispersions of CAB-O-SIL ^® , Cabot), Quartron PL-1, PL-3 (FusoCiiemical Co.), Köstrosöl 0830, 1030, 1430 (chemical plant Bad Köstritz). The silica sols used can also be surface-modified silica which has been treated with sodium aluminate (alumina-modified silica).

Particularly suitable as hydrophilizing polymers are amphoteric polymers, for example copolymers of acrylic or methacrylic acid and MAPTAC, DADMAC or another polymerizable quaternary ammonium compound. Copolymers with AMPS (2-acrylamido-2-methylpropanesulfonic acid) can also be used. Polyether siloxanes, ie copolymers of polymethylsiloxanes with ethylene oxide or propylene oxide segments, are further suitable polymers. Acrylic polymers, maleic acid copolymers and polyurethanes with PEG (polyethylene glycol) units can also be used.

Suitable polymers are, for example, under the trade names Mirapol Surf-S 100, 110, 200, 210, 400, 410, A 300, A 400 (Rhodia), Tegopren 5843 (Goldschmidt), Sokalan CP 9 (BASF) or Poiyquart Ampho 149 (Cognis ) commercially available.

The hydrophilizing substances, both when using silica and also polymers, should be used in a concentration of 0.0001 to 10%, preferably of 0.01 to 3%.

The agent according to the invention can also contain surface-active substances. Suitable surfactants for the agents according to the invention are surfactants, in particular from the classes of anionic and nonionic surfactants. The agents preferably contain anionic surfactants. The amount of anionic surfactant is usually not more than 10% by weight, preferably between 0.01 and 5% by weight, in particular between 0.01 and 1% by weight, for example 0.5% by weight. If the agents contain nonionic surfactants, their concentration is in ready-to-use agents Usually not more than 3% by weight, preferably between 0.001 and 0.3% by weight and in particular between 0.001 and 0.1% by weight. In a preferred embodiment, however, the agent according to the invention is free from nonionic surfactants. It has also proven to be particularly advantageous if the total surfactant content in the ready-to-use composition is not more than 6% by weight. If the agent is offered as a concentrate for dilution before use, the total surfactant content is preferably not more than 15% by weight, particularly preferably 1 to 12% by weight, in particular 2 to 10% by weight.

Suitable anionic surfactants are preferably C ₈ -C ₈ -alkylbenzenesulfonates, in particular with about 12 C atoms in the alkyl part, C ₈ -C ₂₀ -alkanesulfonates, C ₈ -C ₈ -monoalkyl sulfates, C ₈ -C ₁₈ -alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid mono- and di-C ₈ -C ₁₈ alkyl esters. Furthermore, C ₈ -C ₁₈ -α- olefin sulfonates, sulfonated C ₈ -C ₁₈ fatty acids, especially dodecylbenzenesulfonate, C ₈ -C ₂₂ carboxamide amide sulfates, C ₈ -C ₁₈ alkyl polyglycol ether carboxylates, C ₈ -C ₁₈ -N-acyl taurides , C ₈ -C ₁₈ N-sarcosinates and C ₈ -C ₁₈ alkyl isethionates or mixtures thereof.

The anionic surfactants are preferably used as sodium salts, but can 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 acidity, e.g. Dodecylbenzenesulfonic acid.

Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkane sulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates with 12 to 14 carbon atoms have proven to be particularly suitable.

C ₈ -C ₁₈ alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl part and 2 to 15 ethylene oxide (EO) and / or propylene oxide (PO), C, are the nonionic surfactants in particular 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 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides with 14 to 20 C atoms and long-chain alkyl polyglycosides with 8 to 14 carbon atoms in the alkyl part and 1 to 3 Glycoside units to mention. Examples of such surfactants are oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, coconut alkyl dimethylamine oxide and coconut alkyl polyglucoside with an average of 1.4 glucose units. Fatty alcohol polyglycol ethers with in particular 2 to 8 EO, for example C ₂ , are particularly preferred. ₄ -fatty alcohol + 4-EO-ether, as well as C ₈ . ₁₀ -Alkylpolyglucoside with 1 to 2 glycoside units used.

C ₈ -C ₈ alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be described by the formula I, RO- (CH ₂ CH (CH ₃ ) 0) _p (CH ₂ CH ₂ 0) _e -H, in which R ^{1 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, p is 0 or numbers from 1 to 3 and e is numbers from 1 to 20.

The C ₈ -C ₁₈ alkyl alcohol polyglycol ethers of the formula I can be obtained by addition of propylene oxide and / or ethylene oxide onto alkyl alcohols, preferably onto fatty alcohols. Typical examples are polyglycol ethers of the formula I in which R 'is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁ fatty alcohol + 1 PO + 6EO ether (p = 1, e = 6) and C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and their mixtures.

End-capped C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula I is etherified. The end-capped C ₈ -C ₁₈ alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C ₈ -C ₁₈ -Alkyl alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases. Typical examples are mixed ethers of the formula I in which R 'is an industrial fatty alcohol residue, preferably C _{12 1} coconut alkyl residue, p is 0 and e is 5 to 10, which are sealed with a butyl group.

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula II, R "0 [G] _x , in which R" for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x stands for a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x in the general formula II indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound must always be an integer and here can assume the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.6. Xylose, but especially glucose, is preferably used as the glycosidic sugar.

The alkyl or alkenyl radical R "(formula II) can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as described, for example, in In the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.

Preferably, however, the alkyl or alkenyl radical R "is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Furthermore, elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol and technical-grade gemucin alcohol, erucyl alcohol.

Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. Fatty acid polyhydroxyarnides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred. The particularly suitable compounds include lauric acid, myristic acid and palmitic acid monoethanolamides.

Agents which contain anionic and nonionic surfactant, in particular combinations of fatty alkyl sulfates and / or fatty alcohol polyglycol ether sulfates with fatty alcohol polyglycol ethers, are also particularly preferred.

In addition to the previously mentioned types of surfactants, the agent according to the invention can also contain cationic surfactants and / or amphoteric surfactants. Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R) N ⁺ CH ₂ COO ^" , in which R ^{πi is} an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms and optionally interrupted by heteroatoms or heteroatom groups R ^'v and R ^v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ alkyl-dimethylcarboxymethylbetain and C _ι C ₁ -. Alkylamidopropyl-dimethylcarboxymethylbetain the compositions contain amphoteric surfactants in quantities, based on the composition, from 0 to 10% by weight.

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 types, in particular two long and two short-chain, alkyl radicals and X ^"represent an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10% by weight.

In a particularly preferred embodiment, however, the agent contains only one or more anionic surfactants, preferably C ₈ -C ₁₈ -alkyl sulfates and / or C ₈ -C ₁₈ -alkyl ether sulfates, and / or one or more nonionic surfactants as surfactant components.

Furthermore, the cleaning agents according to the invention can contain water-soluble organic solvents, for example lower alcohols and / or ether alcohols, but preferably mixtures of different alcohols and / or ether alcohols. For the purposes of this invention, lower alcohols are straight-chain or branched d-e alcohols. The amount of organic solvent is usually not more than 50% by weight, preferably 0.1 to 30% by weight, in particular 0.5 to 15% by weight, most preferably 1 to 10% by weight.

In particular, ethanol, isopropanol and n-propanol are used as alcohols. Sufficiently water-soluble compounds with up to 10 carbon atoms in the molecule are suitable as ether alcohols. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. If alcohol and ether alcohol are used side by side, the weight ratio of the two is preferably between 1: 2 and 4: 1. On the other hand, if mixtures of two different ether alcohols, in particular ethylene glycol monobutyl ether and propylene glycol monobutyl ether, ether, the weight ratio of the two is preferably between 1: 6 and 6: 1, in particular between 1: 5 and 5: 1, for example 4: 1, the proportion of ether alcohol with fewer carbon atoms preferably being the higher of the two is.

The agents according to the invention can furthermore contain volatile alkali. As such, ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule, are used. The ethanolamines are preferred as alkanolamines, and the monoethanolamine of these in turn is preferred. The content of ammonia and / or alkanolamine is preferably 0.01 to 3% by weight, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.75% by weight.

In addition to the volatile alkali, alkaline agents can additionally contain carboxylic acid, the equivalent ratio of amine and / or ammonia to carboxylic acid preferably being between 1: 0.9 and 1: 0.1. Carboxylic acids with up to 6 carbon atoms are suitable, which may be mono-, di- or polycarboxylic acids. Depending on the equivalent weight of amine and carboxylic acid, the carboxylic acid content is preferably between 0.01 and 2.7% by weight, in particular between 0.01 and 0.9% by weight. Examples of suitable carboxylic acids are formic acid, acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which acetic acid, citric acid and lactic acid are preferably used. Acetic acid is particularly preferably used.

Acidic cleaning agents according to the invention can also contain one or more acids instead of volatile alkali. Suitable acids are in particular organic acids such as the carboxylic acids 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, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Acids selected from the group comprising amidosulfonic acid, citric acid, lactic acid and formic acid are particularly preferred. They are preferably used in amounts of 0.1 to 5% by weight, particularly preferably 0.5 to 4% by weight, in particular 1 to 3% by weight.

In addition, the acidic cleaning agents according to the invention can also contain small amounts of bases. Preferred bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium umhydroxide and especially sodium hydroxide is particularly preferred. Bases are used in the acidic agents in amounts of not more than 1.5% by weight, preferably 0.01 to 0.1% by weight.

The agent preferably has a Brookfield viscosity (model DV-II +, spindle 31, rotational frequency 20 min ^"1 , 20 ° C.) of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, extremely preferably 1 For this purpose, the agent can contain viscosity regulators The amount of viscosity regulator is usually up to 0.5% by weight, preferably 0.001 to 0.3% by weight, in particular 0.01 to 0 , 2% by weight, most preferably 0.05 to 0.15% by weight.

Suitable viscosity regulators are, 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 substances (carboxymethyl cellulose and other cellulose ethers , Hydroxyethyl and propyl cellulose and the like, core meal ether), 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).

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): Carbomer), which are 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 approx.1,250,000) or Carbopol ^® 934 (molecular weight approx.3,000,000). The following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), which are preferably formed with C 1-4 -alkanols, to which, for example, the copolymers of methacrylic acid acrylate, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) belong or of butyl acrylate and methyl (CAS 25852-37-3), and, for example, by the company Rohm & Haas under the trade names Aculyn ^® and Acusol. ^® and from the company De- gussa (Goldschmidt) are available under the trade name Tego ^® Polymer, e.g. 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 from C ₁₀ - ₃ O-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C ^ - Alkanols formed, esters (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol ^® , for example the hydrophobized 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, carragenes and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and theirs mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably 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 carboxymethyl cellulose or its sodium salt, methyl, ethyl or 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 Kelco under the trade names Keltrol ^® and Kelzan ^® or is also available from Rhodia under the trade name Rhodopol ^® .

Layered silicates can also be used as thickeners. These include, for example, the magnesium or sodium-magnesium layer silicates from Solvay Alkali available under the trade name Laponite ^® , in particular the Laponite ^® RD or Laponite ^® RDS, and the magnesium silicates from Süd-Chemie, especially the Optigel ^® SH. When choosing a suitable viscosity regulator, care must be taken to ensure that the transparent impression of the cleaning agent is retained, ie the use of the thickener should not lead to clouding of the agent.

In one embodiment, the cleaning agent according to the invention can also be formulated as a higher-viscosity liquid. The viscosity is then between 200 and 1000 mPa-s (Brookfield viscometer DV-II +, small sample adapter). In these cases, the viscosity regulator (thickener) content can be up to 2% by weight.

In addition to the components mentioned, the agents according to the invention can contain further auxiliaries and additives as are customary in such agents. These include in particular dyes, perfume oils, preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems and antistatic substances. As the Sokalan CP 9 ^®, the sodium salt can still for surface modification of polymers, particularly copolymers such as Sokalan® available from BASF ^®, a maleic acid-olefin copolymer, can be used.

The amount of such additives is usually not more than 2% by weight in the cleaning agent. The lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example, for dyes. The amount of auxiliaries is preferably between 0.01 and 1% by weight.

The pH of the agents according to the invention can be varied over a wide range, but a range from 2.5 to 12 is preferred. Glass cleaner formulations and all-purpose cleaners in particular have a pH of 6 to 11, most preferably from 7 to 10.5 and bath cleaners, in particular a pH of 2 to 5, most preferably 2.5 to 4.0.

The agents according to the invention are preferably formulated ready for use. Formulation as a concentrate to be diluted appropriately before use is also possible within the framework of the teaching according to the invention, the ingredients then being contained in the upper range of the quantity ranges indicated in each case.

The agents according to the invention can be prepared by mixing them directly from their raw materials, then mixing them and then standing the agent until there are no bubbles. The agents according to the invention are used for cleaning hard surfaces. Alkaline cleaners are particularly suitable for cleaning glass, both for windows and for mirrors and other glasses. Acidic cleaners are suitable for other hard surfaces, especially those that are occasionally or frequently flushed with dirty or clean water, for example toilets, showers, bathtubs and floors in bathrooms or kitchen surfaces. Another area of use of agents according to the invention is rinse aid for dishwashers. However, textile surfaces can also undergo hydrophilization through the use of agents according to the invention. Yet another area of application is the hydrophilization of surfaces in the automotive sector, both of car paints and car windows. The agents according to the invention can of course also be used for lacquers in general, and metal surfaces can also be hydrophilized with them.

embodiments

Alkaline and acidic detergent formulations were produced, examples E1 to E6 according to the invention and polymer-free formulations V1 and V2 acting as comparative examples. After cleaning with the various agents, surfaces were exposed to the weather for a defined period of time or sprayed with water of a defined degree of hardness in order to demonstrate the particular effectiveness of the formulations according to the invention.

a) Alkaline cleaning agents:

All figures in% by weight

Fatty alcohol sulfate: Texapon LS 35 (sodium lauryl sulfate)

Polymer: Tegoprene 5843

The specified recipes can be used as glass cleaning agents.

Window panes cleaned with cleaners E1 to E3 and V1 were exposed to the weather for two weeks. Discs which had been treated with the formulations E1, E2 or E3 according to the invention still formed a spreading, flat film even after this time when wetted with water. The residue was formed in the form of very finely divided particles, so that the pane looked clean. The pane treated with the polymer-free comparison formulation V1, on the other hand, showed the formation of drops after just two days when wetted with water, as did an untreated glass pane. The residue was formed in the form of "noses" so that the pane appeared dirty. b) acidic cleaning agents:

All figures in% by weight

Fatty alcohol sulfate: Texapon LS 35 (sodium lauryl sulfate)

Polymer: Rhodia Surf-S 110

The specified recipes can be used as bathroom cleaning agents.

Bathroom tiles cleaned with cleaners E4 to E6 and V2 were sprayed with water at 15 ° dH once a day for a week. Tiles which had been treated with the formulations E4, E5 or E6 according to the invention still formed a spreading, flat film even after this time when wetted with water. The residue was formed in the form of very finely divided particles, so that the tiles looked clean. The tiles treated with the polymer-free comparison formulation V2, on the other hand, showed the formation of drops after just two days when wetted with water, just like untreated tiles. The residue was formed in the form of "noses", so that the tiles appeared dirty.

Coverage:

The degree of coverage of a surface with surface-modifying components of the cleaning formulation can be determined using Atomic Force Microscopy (AFM). AFM images of hard surfaces at the micrometer level (1 x 1 μm, 5 x 5 μm, 10 x 10 μm) can be taken, for example, in tapping mode with a Nanoscope II microscope (Digital Instruments, Inc., Santa Barbara, CA) at a scan rate of 1 Hz can be made. From the AFM height profile recordings, the AFM phase contrast recordings or the AFM amplitude contrast recordings, the percentage coverage can be determined by surface integration in direct comparison to the untreated surface by using image processing software (e.g. Adobe Photoshop). In this way, Villeroy & Boch test tiles were examined before and after treatment with the six cleaning formulations E1 to E6 according to the invention and the two polymer-free comparative formulations V1 and V2. From the evaluation of the AFM height profile recordings, the following values for the degree of coverage on an area of 10 x 10 μm were obtained:

Claims

claims

1. Cleaning agent for hard surfaces containing at least one hydrophilizing substance, characterized in that the surface is covered with the hydrophilizing substance from 33% to 86%.

2. Cleaning agent according to claim 1, characterized in that as the hydrophilizing substance polymeric materials, preferably selected from the group comprising acrylic polymers, copolymers of acrylic or methacrylic acid and MAPTAC, DADMAC or another polymerizable quaternary ammonium compound, polyether siloxanes, maleic acid copolymers, copolymers with 2-acrylamido-2-methyl-1-propanesulfonic acid groups, polyurethanes with polyethylene glycol units and mixtures thereof, and / or colloidal silica sol are used.

3. Cleaning agent according to claim 2, characterized in that the silica sol has a particle size of 1 to 100 nm, preferably 3 to 50 nm, in particular 4 to 40 nm, for example 9 nm.

4. Cleaning agent according to one of the preceding claims, characterized in that the hydrophilizing substance is used in an amount of 0.0001 to 10 wt .-%, preferably in an amount of 0.01 to 3 wt .-%.

5. Cleaning agent according to one of the preceding claims, characterized in that the degree of coverage of the surface is 45% to 72%.

6. Cleaning agent according to one of the preceding claims, characterized in that it is transparent.

7. Cleaning agent according to one of the preceding claims, characterized in that micro gradients of the interfacial tension are generated on the surface by its application.

8. Cleaning agent according to one of the preceding claims, characterized in that the surface treated with the agent has a contact angle against water of 10 ° + 10 °, preferably 10 ° + 5 °.

9. Cleaning agent according to one of the preceding claims, characterized in that it brings about an improved dirt-removing behavior and / or less re-soiling.

10. Cleaning agent according to one of the preceding claims, characterized in that it causes a quick and uniform drying of a surface after re-irrigation.

11. Cleaning agent according to one of the preceding claims, characterized in that it has an anti-fog effect.

12. Cleaning agent according to one of the preceding claims, characterized in that it contains anionic and / or nonionic surfactants.

13. Cleaning agent according to one of the preceding claims, characterized in that it contains one or more anionic surfactants, preferably selected from the group comprising C ₈ ₈ -ι alkyl benzene sulfonates, C _{_8-20} alkane sulfonates, C. ₈ Alcohol sulfates -Fett- _18, C _{_8-18} -AlkylpoIyglykolethersulfate, sulfosuccinic acid mono- and di- C ₈ -ι ₈ alkyl and mixtures thereof, particularly preferably sodium salts of fatty alcohol sulfates.

14. Cleaning agent according to one of the preceding claims, characterized in that it contains nonionic surfactants, preferably selected from the group comprising C ₈ . ₁₈ alcohol polyglycol ethers, C _{_8-18} -Carbonsäurepolyglykolester, ethoxylated fatty acid amides, to C _14. ₂₀ amine oxides and alkyl polyglycosides and mixtures thereof.

15. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one water-soluble organic solvent, preferably selected from the group comprising lower alcohols, ether alcohols and mixtures thereof.

16. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one volatile alkali, preferably selected from the group comprising ammonia, alkanolamines with up to 9 carbon atoms and mixtures thereof.

17. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one organic acid, preferably a carboxylic acid selected from the group comprising formic acid, acetic acid, glycol

, acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid, gluconic acid and mixtures thereof or amidosulfonic acid.

18. Cleaning agent according to one of the preceding claims, characterized in that it contains one or more viscosity regulators, preferably selected from the group comprising organic natural thickeners, organic modified natural substances, organic fully synthetic thickeners and inorganic thickeners.

19. Cleaning agent according to one of the preceding claims, characterized in that it contains one or more further auxiliaries and additives customary in cleaning agents, preferably selected from the group comprising dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions, enzymes, bleaching systems and antistatic substances.

20. Cleaning agent according to one of the preceding claims, characterized in that it has a viscosity of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, most preferably 1 to 60 mPa-s (Brookfield Model DV -II +, spindle 31, 20 min ^"1 , 20 ° C).

21st Cleaning agent according to one of the preceding claims, characterized in that it has a pH of 2.5 to 12.

22. A method for hydrophilizing hard surfaces by contacting the surface with an agent according to any one of claims 1 to 21.

23. Use of an agent according to claims 1 to 21 for cleaning hard surfaces.

24. Use of an agent according to any one of claims 1 to 21 for hydrophilizing hard surfaces.

25. Use of an agent according to any one of claims 1 to 21 on hard surfaces to improve the liquid flow and dirt removal behavior while reducing the formation of residues, the tendency to re-soiling, the tendency to fogging and the drying time.