EP1171559A1

EP1171559A1 - Cleaning agent for hard surfaces

Info

Publication number: EP1171559A1
Application number: EP00920696A
Authority: EP
Inventors: Michael Elsner; Anja Hanke; Jörg KAHRE
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1999-04-22
Filing date: 2000-04-13
Publication date: 2002-01-16
Also published as: WO2000065010A1; DE19918183A1; JP2002543240A

Abstract

The invention relates to cleaning agents for hard surfaces that contain (a) cationic surfactants, (b) alkyl and/or alkenyl oligoglycosides and (c) sulfate and/or sulfonate surfactants with 4 to 10 carbon atoms in the hydrophobic residue, with the proviso that the agent has a pH ranging from 1 to 5.

Description

Detergent for hard surfaces

Field of the Invention

The invention is in the field of detergents and disinfectants and relates to preparations with an advantageous viscosity which contain combinations of selected cationic, nonionic and anionic surfactants and the use of the mixtures for the production of detergents.

State of the art

Fixed toilet blocks have long been used as cleaning agents for flush toilets, which are either hung in the cistern with the help of a device or fastened under the inside edge of the toilet. Their task is to clean the surface of the toilet during the flushing process and to mask unpleasant smells, especially by releasing fragrances. Because of their task of releasing fragrances, cleaning agents for flushing toilets are also generally referred to in the literature as fragrance washers. Usually tensides, builder substances, inorganic salts and of course fragrances and colorants are used for their production. A large number of such formulations are known from the prior art. In US 4534879 (Procter & Gamble), for example, solid cleaning agents are claimed which contain alkyl sulfates with 9 to 15 carbon atoms, alkylbenzenesulfonates and inorganic salts as the surfactant component. EP 0265979 A1 (Akzo) relates to thickened aqueous cleaning agents which contain mixtures of cationic surfactants and amine oxides together with short-chain aryl sulfonates. From EP 0014979 A1 (Henkel) toilet blocks are known which contain alkylbenzenesulfonates and alkylsulfates as well as fatty alcohol or alkylphenol ethoxylates. DE 4337032 C2 (Henkel) relates to toilet blocks containing alkyl sulfates, alkyl ether sulfates and alkyl glucosides. EP 0268967 A1 (Henkel) discloses toilet blocks which contain sodium lauryl sulfate and fatty acid monoethanolamide. The toilet blocks described are generally manufactured by casting, pressing, extruding or granulating processes, which require a high level of technical effort and are often unwanted parameters due to the temperature load (casting / extrusion process) that occurs. suffer loss of film. It also proves to be disadvantageous that the refill units, which are widespread for ecological reasons, can only be used after the piece-like body has been completely used up. A desirable, arbitrary refill, for example for a stronger release of active ingredient or in particular for more intensive fragrance development, is not possible.

From the German published patent application DE 19715872 A1 (Henkel), gel-shaped toilet cleaners with pseudoplastic properties are known, which considerably reduce the effort for the production and can be produced more cheaply due to simple technology. The problem of the individual refill possibility can also be solved by such pseudoplastic active substance preparations. These gel-type toilet cleaners contain polysaccharides, in particular xanthan gum, to adjust the pseudoplastic properties, and as surfactants, alkyl polyglycosides and, if appropriate, anionic and / or nonionic co-surfactants. However, these gel-form cleaning agents have to be manufactured with special precautions during gel formation, so that on the one hand no bubbles form and on the other hand the other ingredients can be incorporated evenly distributed in the gel.

The complex object of the present invention was therefore to provide new cleaning agents for hard surfaces, but preferably gel-shaped toilet cleaners, which have a viscosity which on the one hand enables easy application and on the other hand does not run too quickly even on inclined surfaces to ensure the longest possible exposure time. The preparations should also have an improved cleaning ability, be bactericidal and maintain their advantageous viscosity without the use of typical thickeners. Furthermore, the agents should have good initial foam behavior, allow the incorporation of a wide variety of perfume oils, even in large quantities, and ultimately have a long service life, i.e. enable a high number of toilet flushes until the detergent is completely flushed (number of flushes).

Description of the invention

The invention relates to cleaning agents for hard surfaces containing

(a) cationic surfactants, preferably esterquats and / or tetraalkylammonium compounds,

(b) alkyl and / or alkenyl oligoglycosides and

(c) sulfate and / or sulfonate surfactants with 4 to 10 carbon atoms in the hydrophobic radical,

with the proviso that the agents have a pH in the range of 1 to 5. Surprisingly, it was found that the preparations according to the invention not only have excellent cleaning performance and bactericidal activity, but also have a significantly higher viscosity than conventional agents, even without the use of thickeners, and are structurally viscous. The agents according to the invention are therefore not only characterized by ease of use and excellent drainage behavior, they also have a high foaming capacity, also allow the incorporation of larger quantities of a wide variety of perfumes and, owing to their gel-like nature, can also be used primarily from inserts, for example in water boxes in toilets (" Dosing the toilet basket ") reliably over a longer period of time. It is also possible to completely or partially dewater the aqueous preparations and compress them into blocks (" toilet stones ").

Esterquats

The term "esterquats", which form component (a1), is generally understood to mean cationic surfactants of the quaternized fatty acid triethanolamine ester salt type. These are known substances which can be obtained by the relevant methods of preparative organic chemistry. In this context See international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. From German patent DE 4308794 C1 (Henkel) a process for the preparation of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Reviews on this topic are, for example, by R.Puchta et al. in Tens.Surf.De, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993) R. Lagerman et al. in J.Am.Oil.Chem. Soc, 71, 97 (1994) and I. Shapiro in Cosm.Toil. 109, 77 (1994) appeared. The quaternized fatty acid triethanolamine ester salts follow the formula (I)

R ⁴

I [R ¹ CO- (OCH2CH ₂ ) mOCH2CH2-N ⁺ -CH2CH2θ- (CH ₂ CH2θ) nR ² ] X ^" (I)

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH2CH2θ) _q H group, m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid. Acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid as well as their technical mixtures, such as those which occur in the pressure splitting of natural fats and oils. Technical C6 / 10 fatty acids are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical Cβ / io pre-flow acid. From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R ¹ CO for an acyl radical having 6 to 10 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p is 0 and X is methyl sulfate. In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

R ⁴

I [R ¹ CO- (OCH ₂ CH2) mOCH2CH2-N ⁺ -CH2CH2θ- (CH2CH ₂ 0) nR ² ] X "(II)

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. Finally, as a further group of suitable ester quats, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) are to be mentioned,

R ⁶ 0- (CH ₂ CH ₂ 0) mOCR ¹

I I

[R -N ⁺ -CH ₂ CHCH2θ- (CH ₂ CH2θ) nR ² ] X "(III)

I.

R?

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for (I) also apply to the esterquats of the formulas (II) and (III). Tetraalkylammonium compounds

Another group of suitable cationic surfactants which are suitable as component (a2) are the tetraalkylammonium compounds, which preferably follow the formula (IV)

in which R ^{8 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms or a benzyl radical, R ⁹ and R ¹⁰ independently of one another are R ⁸ or an alkyl radical having 1 to 22 carbon atoms, R ^{11 is} an optionally hydroxyl-substituted alkyl radical with 1 to 4 carbon atoms and X represents halide, alkyl sulfate or alkyl phosphate. Typical examples are cetyltrimethylammonium chloride. Dimethyldistearylammonium chloride and benzyldistearylammonium bromide.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides which form component (b) are known nonionic surfactants which follow the formula (V)

R ¹² 0- [G] _p (V)

in which R ^{12 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (V) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization are preferred p used from 1, 1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹² can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -Cιo (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and are contaminated with a proportion of less than 6% by weight of Cι ₂ alcohol can as well as alkyl oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹² can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petrotinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as described above, and their technical mixtures. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

Sulfate and / or sulfonate surfactants

The sulfate or sulfonate surfactants are solubilizers. Typical examples of this are short-chain aryl sulfonates (component d) of the formula (VI),

R14 I

R ¹³ -Ph-S0 ₃ Y (VI)

in which R ^{13 is} a linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{14 is} hydrogen or a methyl group, Ph is a phenyl radical and Y is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are toluenesulfonate, xylene sulfonate and cumene sulfonate in the form of their sodium salts and mixtures thereof. Alternatively, short-chain alkyl sulfates (component c2) can also be used, which preferably follow the formula (VII)

R «0-S0 ₃ Y (VII)

in which R ^{15 represents} a linear or branched alkyl radical having 6 to 10, preferably 8 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the alkali salts of octyl sulfate and 2-ethylhexyl sulfate. Industrial applicability

To adjust an acidic pH, the preparations according to the invention can include mineral acids, such as Hydrochloric acid or phosphoric acid or also organic acids, e.g. Contain formic acid, adipic acid, tartaric acid or preferably citric acid. The amount used depends on the desired pH, which should be in the range from 1.5 to 3 in particular. In a preferred embodiment of the invention, the agents contain

(a) 1 to 10, preferably 2 to 5% by weight of cationic surfactants,

(b) 1 to 10, preferably 1, 5 to 4.5 wt .-% alkyl and / or alkenyl oligoglycosides and

(c) 0.1 to 2, preferably 0.5 to 1.5% by weight short chain sulfate and / or sulfonate surfactants

with the proviso that the amounts given with water and, if appropriate, further auxiliaries and additives are 100% by weight. Another object of the present invention finally relates to the use of mixtures having a pH in the range from 1 to 5

(a) cationic surfactants,

(b) alkyl and / or alkenyl oligoglycosides and

(c) Sufate and / or sulfonate surfactants with 4 to 10 carbon atoms in the hydrophobic residue

for the production of cleaning agents for hard surfaces, preferably gel-shaped toilet cleaners.

Auxiliaries and additives

The gel-form cleaning agents according to the invention can also contain co-surfactants, limescale dissolving agents, builders, perfumes, perfume solubilizers, solvents, germ-inhibiting agents, preservatives, dyes, pH regulators and the like.

Non-ionic, anionic and / or amphoteric or amphoteric surfactants may be present as co-surfactants, the proportion of which in the compositions is usually about 1 to 5 and preferably 2 to 3% by weight. Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, fatty acid (monoglyl sulfide), fatty acid monoglyl sulfate ether, Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers or mixed formals, optionally partially oxidized glucoronic acid derivatives, wheat acid, protein hydrolysis products, in particular protein hydrolysis products Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, Surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Alcohol ethoxylates, hydroxy mixed ethers, fatty acid methyl ester ethoxylates, amine oxides and / or betaines are preferably used as co-surfactants.

Descaling agents preferably include descaling acids such as citric acid, formic acid, acetic acid, lactic acid or their water-soluble salts, which can be present in an amount based on from 1 to 12% by weight, preferably from 2 to 7% by weight .

Other optional constituents of the agents according to the invention are builders, preferably water-soluble builders, since they generally have less tendency to form insoluble residues on hard surfaces. Suitable liquid, water-soluble builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as, for example, the neutral sodium salts of 1-hydroxyethane-1, 1, -diphosphonate, which are present in amounts of 0.5 to 5, preferably 1 to 2,% by weight .-% may be present. The solid or water-insoluble builder used is, in particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. Suitable substitutes or Partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x θ2x + ryH2θ, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20, and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na2Si2θ5-yH2θ are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. The preparations according to the invention can preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) Na∑O: SiÜ2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 2334899 B1, EP 0026529 A1 and DE 3526405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas

(OH) 4Si8-yAl _y (Mg _x Al4-x) θ2o montmorrilonite (OH) 4Si ₈ -yAl _y (Mg6-zLiz) θ2o hectorite (OH) 4Si ₈ -yAl _y (Mg6-z Al _z ) 0 o saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Preferred Layered silicates are used that are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or containing their salts and sugar derivatives. Terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A1 and DE 4300772 A1 are particularly preferred. Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid. The group of citrates is particularly preferred. The builders can be present in the compositions according to the invention in amounts of 0 to 5% by weight.

The hygienic effect can be enhanced by adding germ-inhibiting agents. Suitable germ inhibitors are in particular isothiazoline mixtures, sodium benzoate and / or salicylic acid. Other examples are substances with specific activity against gram-positive bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) hexane) or TCC (3 , 4,4'-trichlorocarbanilide). Numerous fragrances and essential oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil. An interesting natural antiseptic agent is the terpene alcohol farnesol (3,7,11 -trimethyl-2,6, 10-dodecatrien-1 -ol), which is present in the linden blossom oil and has a lily of the valley smell. Glycerol monolaurate has also proven itself as a bacteriostatic. The amount of these antimicrobial agents strongly depends on the effectiveness of the respective compound and can be up to 5% by weight. The germ-inhibiting agents are preferably present in amounts between 0 and 10, preferably between 0.01 and 7% by weight.

The optionally contained perfume substances are those which are common from the prior art. Mixtures of natural and synthetic fragrances are mentioned as examples. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propylate and benzylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures. The amount of the dosage depends on the desired fragrance intensity and is in the range from 0 to 15% by weight.

Perfume solubilizers which can be used in the agents according to the invention are polyol fatty acid esters, for example glycerol alkoxylated with 7 moles of ethylene oxide, which is esterified with coconut fatty acid (Cetiol HE®, Henkel KGaA) and / or hardened castor oil (Eumulgin® HRE 40 or . 60, Henkel KGaA) and / or 2-hydroxy fatty alcohol ethoxylates (Eumulgin® L,

n Henkel KGaA) may be included. The amount of the perfume solubilizers in the agents according to the invention is generally between 0 and 10, preferably between 1 and 7% by weight.

As solvents, especially for dyes and perfume oils, the agents according to the invention may contain, for example, alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and other mono- and polyhydric alcohols, and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical. The group of lower alcohols, particularly ethanol, is particularly preferred. The content of the solvents depends on the type and amount of the constituents to be dissolved and is generally in the range from 0.5 to 5% by weight.

The preferably water-soluble dyes are contained either for the coloring of the agent or for the coloring of the liquid surrounding the container. The content of water-soluble dyes is preferably below 1% by weight and serves to improve the appearance of the product. If an additional color signal is required during the flushing process, the content of water-soluble dyes can be up to 5% by weight.

Examples

Various toilet cleaners were manufactured and their cleaning performance according to the IPP standard (soiling 78/19, undiluted application) and viscosity (Brookfield, RVT viscometer, 20 ° C, spindle 1, 10 rpm, see soap-oil-fat waxes , 112, 371, 1988). The results are summarized in Table 1. Examples 1 to 6 are according to the invention, examples V1 to V3 serve for comparison. All quantities are understood as% by weight.

Table 1:

Composition of various cleaning agents

nb = not determined

Claims

claims

1. Cleaning agent for hard surfaces, containing

(a) cationic surfactants,

(b) alkyl and / or alkenyl oligoglycosides and

with the proviso that the agents have a pH in the range of 1 to 5.

2. Composition according to claim 1, characterized in that they contain esterquats of the formula (I) as component (a1),

R ⁴

I.

[R ¹ CO- (OCH2CH2) mOCH2CH2-N ⁺ .CH2CH2θ- (CH2CH ₂ 0) nR ² ] X "(I)

in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH2CH2θ) _q H group, m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate.

3. Composition according to claim 1, characterized in that they contain esterquats of the formula (II) as component (a1),

R ⁴

I [RiCO- (OCH2CH2) mOCH2CH2-N ⁺ -CH ₂ CH2θ- (CH2CH ₂ O) nR ² ] X "(II)

IR ⁵

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

4. Composition according to claim 1, characterized in that they contain as component (a1) ester quats of the formula (III),

R ⁶ O- (CH2CH ₂ 0) mOCR ¹

I I

[R ⁴ -N ⁺ -CH ₂ CHCH2θ- (CH2CH2θ) nR ² ] X- (III)

IR ⁷

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

5. Compositions according to at least one of claims 1 to 4, characterized in that they contain tetraalkylammonium compounds of the formula (IV) as component (a2),

in which R ^{8 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms or a benzyl radical, R ⁹ and R ¹⁰ independently of one another are R ⁸ or an alkyl radical having 1 to 22 carbon atoms, R ^{11 is} an optionally hydroxyl-substituted alkyl radical with 1 to 4 carbon atoms and X represents halide, alkyl sulfate or alkyl phosphate.

6. Composition according to at least one of claims 1 to 5, characterized in that they contain as component (b) alkyl and alkenyl oligoglycosides of the formula (V),

R ¹² 0- [G] _p (V)

in which R ^{12 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10.

7. Compositions according to at least one of claims 1 to 6, characterized in that they contain short-chain aryl sulfonates of the formula (VI) as component (d),

R14

IR ¹³ -Ph-S0 ₃ Y (VI) in which R ^{13 is} a linear or branched alkyl radical having 1 to 4 carbon atoms, R ^{14 is} hydrogen or a methyl group, Ph is a phenyl radical and Y is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

8. Composition according to at least one of claims 1 to 7, characterized in that they contain short-chain alkyl sulfates of the formula (VII) as component (c2),

R ⁵ O-SO ₃ Y (VII)

in which R ^{15 represents} a linear or branched alkyl radical having 6 to 10, preferably 8 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

9. Composition according to at least one of claims 1 to 8, characterized in that it

(a) 1 to 10% by weight of cationic surfactants,

(b) 1 to 10 wt .-% alkyl and / or alkenyl oligoglycosides and

(c) 0.1 to 2% by weight short chain sulfate and / or sulfonate surfactants

with the proviso that the amounts given with water and possibly other auxiliary substances and additives add up to 100% by weight.

10. Use of mixtures with a pH in the range from 1 to 5 containing

(a) cationic surfactants,

(b) alkyl and / or alkenyl oligoglycosides and

for the production of cleaning agents for hard surfaces.