WO2000065006A2

WO2000065006A2 - Cleaning agents for hard surfaces

Info

Publication number: WO2000065006A2
Application number: PCT/EP2000/003312
Authority: WO
Inventors: Jörg KAHRE; Michael Elsner; Ditmar Kischkel; Anja Hanke; Bernd Fabry
Original assignee: Cognis Deutschland Gmbh
Priority date: 1999-04-22
Filing date: 2000-04-13
Publication date: 2000-11-02
Also published as: WO2000065006A3; DE19918184A1

Abstract

The invention relates to cleaning agents for hard surfaces containing (a) alkyl and/or alkenyl oligoglycoside, (b) alkyl and/or alkenyl (ether) sulfate and/or betaine, in addition to (c) fatty alcohol polyglycol ether with restricted homologue distribution.

Description

Detergent for hard surfaces

Field of the Invention

The invention is in the field of detergents and disinfectants and relates to preparations with a special surfactant combination and special fatty alcohol polyglycol ethers and their use 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 complexity and frequently suffer undesirable perfume losses due to the temperature load (casting / extruding process) that occurs. It also proves to be disadvantageous that the widespread refill units 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 toilet cleaners, which have a viscosity which on the one hand enables easy application and on the other hand does not run too quickly on inclined surfaces in order to 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. Finally, the agents should have good initial foam behavior, allow the incorporation of a wide variety of perfume oils, even in large quantities, and also show 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) alkyl and / or alkenyl oligoglycosides,

(b) alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) Fatty alcohol polyglycol ether with a narrow homolog distribution.

Surprisingly, it was found that the preparations according to the invention not only have excellent cleaning performance and bactericidal activity, but, compared to conventional agents, also have a significantly higher viscosity without the use of thickeners and have a pseudoplastic behavior. The agents according to the invention are therefore distinguished not only due to easy application and excellent drainage behavior, they also have a high foaming capacity, allow the incorporation of larger quantities of different perfume substances and, due to their gel-like nature, can also be used primarily in water boxes in toilets ("toilet bowls") dosing reliably over a longer period of time. It is also possible to dewater the aqueous preparations in whole or in part and to compress them into blocks (“toilet blocks”).

Alkyl and / or alkenyl olefin glycosides

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

R10- [G] _P (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number 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 (I) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6 in particular, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. 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 ¹ 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 Cs-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ciδ-coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of Ci2-alcohol and Alkyl oligoglucosides based on technical Cθ / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols containing 12 to 22 preferably derive from 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.

Alkyl and / or alkenyl sulfates

Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol or oxo alcohol sulfates and which form component (b1), are to be understood as meaning the sulfation products of primary alcohols which follow the formula (II)

R2O-SO3X (II)

in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachelyl alcohol, aridyl alcohol, ela-elyl alcohol, ela-alcohol alcohol, and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts, and in particular their sodium salts. Alkyl sulfates based on Ci6 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.

Alkyl and / or alkenyl ether sulfates

Alkyl ether sulfates ("ether sulfates"), which form component (b2), are also known anionic surfactants which are prepared on an industrial scale by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention, ether sulfates which follow the formula (III) are suitable

R30- (CH ₂ CH ₂ 0) nSθ3X (III) in which R ^{3 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n represents numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostearyl alcohol Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts. The ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C12 / 14 or C12 / 18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.

Betaine

Betaines which can be considered as component (b3) are known surfactants which are predominantly prepared by carboxyalkylation, preferably carboxymethylation, of amine compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. The addition of unsaturated carboxylic acids such as acrylic acid is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.PIoog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in Tens.Surf.Det. 23, 309 (1986), R.Bilbo et al. in Soap Cosm.Chem. Spec. Apr. 46 (1990) and P.EIIis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (IV)

I.

R ⁴ -N- (CH ₂ ) _m COOY (IV)

IR ^β

R ⁴ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁶ for alkyl radicals with 1 to 4 carbon atoms, m for numbers from 1 to 6 and Y. represents an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldi methylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C 12/14 cocoalky ld i-methylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, Ci6 / 18-tallow alkyldimethylamine and their technical grade. Carboxyalkylation products of amidoamines which follow the formula (V) are also suitable,

IR ⁷ CO-NH- (CH ₂ ) _P -N- (CH2) qCOOY (V)

I.

R6

in which R ⁷ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁶ for alkyl radicals with 1 to 4 carbon atoms, p and q independently of one another for Numbers from 1 to 6 and Y represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, including caproic acid, caprylic acid, capric acid, Laurinsäu- acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic - Acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of Cβ / iβ-coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Fatty alcohol polyglycol ether with a narrow homolog distribution

Fatty alcohol polyglycol ethers with a narrow homolog distribution, especially fatty alcohol ethoxylates, which represent component (c) and are often referred to as "narrow range ethoxylates (NRE)", generally follow the general formula (VI),

in which R ^{8 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and z represents numbers from 1 to 5. Under the term narrow homolog distribution, those skilled in the art are notoriously familiar with those polyglycol ethers which have a steeper maximum and a lower proportion of free alcohol compared to conventional substances of the same average degree of ethoxylation. Overviews of this are for example by K.Dillan et al. in HAPPI May, 121 (1986), M.Cox in J.Am.Oil.Chem.Soc. 67: 599 (1990) and W. Hreczuch et al. in J.Am.Oil. Chem.Soc. 73, 73 (1996). The substances of component (c) are usually obtained by carrying out the addition of ethylene oxide to the fatty alcohols mentioned in the presence of special catalysts, preferably calcined or hydrotalcites hydrophobicized with fatty acids, as is described, for example, in German patent application DE 3817415 A1 (Henkel). Addition products of 1 or 2 moles of ethylene oxide with fatty alcohols having 12 to 18 carbon atoms are preferably used.

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 alkyl and / or alkenyl oligoglycosides,

(b) 1 to 10, preferably 2 to 5% by weight of alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) 0.1 to 15, preferably 5 to 11% by weight of fatty alcohol polyglycol ether with a narrow homolog distribution

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 containing

(a) alkyl and / or alkenyl oligoglycosides,

(b) alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) fatty alcohol polyglycol ether with a narrow homolog distribution,

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 dissolvers, builders, perfumes, perfume solubilizers, solvents, germ-inhibiting agents, preservatives, dyes, pH regulators and the like. Non-ionic, anionic, cationic and / or amphoteric or amphoteric surfactants can be present as co-surfactants, the proportion of which in the compositions is usually about 1 to 5% by weight and preferably 2 to 3% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates and ether sulfate sulfates, fatty sulfate sulfates, fatty acid sulfates, fatty acid sulfate, , mono- and dialkyl sulfosuccinamates, Sulfotriglyce- ride, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether ) phosphates. If the anionic surfactants contain polyglycol ether chains, these 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 amides, especially vegetable hydrolysis products, fatty acid-N-alkylglucose products, Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. Typical examples of cationic surfactants are esterquats and tetraalkylammonium compounds. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made, for example, to relevant reviews by J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Kataly- sators, surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Alcohol ethoxylates, hydroxy mixed ethers, fatty acid methyl ester ethoxylates and / or amine oxides 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 used in an amount of 1 to 12, preferably 2 to 7,% by weight, based on the agent.

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, can contain these small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Cβ-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 is 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 ß- and γ-sodium disilicate

Na2Si2θ5-yH2θ is preferred, β-sodium disilicate being able to be obtained, for example, by the process 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) a∑O: SiO∑ of 1: 1 to 1: 4.5, preferably 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 additionally 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 layer silicates, which belong to the group of water-swellable smectites, are e.g. those of the general formulas

(OH) ₄ Si8.yAly (Mg _x Al4-x) θ2o montmorrilonite (OH) 4Si8-yAly (Mg6-zLi _z ) 0 ₂ o hectorite (OH) ₄ Si8.yAl _y (Mg ₆ -z Al _z ) θ2o 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. Layer silicates are preferably used which 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. Further 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 optional additional perfume substances are those that 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, cumin, 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, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl and benzylsalylyl propyl allyl propylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-

Isomethyl ionone and methyl cedryl ketone, the terpene alcohols menthol, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, nerol, phenylethyl alcohol, tetrahydromyrcenol 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,

n Rose oxide, Romilllat, Irotyl and Floramat used 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 mol of ethylene oxide, which is esterified with coconut fatty acid (Cetiol HE®, Henkel KGaA) and / or hardened castor oil alkoxylated with 40 or 60 mol of ethylene oxide (Eumulgin® HRE 40 or . 60, Henkel KGaA) and / or 2-hydroxy fatty alcohol ethoxylates (Eumulgin® L, Henkel KGaA). 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 can 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 gels were produced 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 fats -Wachsen, 112, 371, 1988). The results are summarized in Table 1. Examples 1 to 4 are according to the invention, examples V1 and V2 serve for comparison. All quantities are understood as% by weight.

Table 1:

Composition of various toilet gel toilet blocks

Claims

claims

1. Cleaning agent for hard surfaces, containing

(a) alkyl and / or alkenyl oligoglycosides,

(b) alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) Fatty alcohol polyglycol ether with a narrow homolog distribution.

2. Composition according to claim 1, characterized in that they contain as component (a) alkyl and alkenyl oligoglycosides of the formula (I),

R10- [G] _P (I)

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

3. Compositions according to claims 1 and / or 2, characterized in that they contain alkyl and / or alkenyl sulfates of the formula (II) as component (b1),

R ² 0-S0 ₃ X (II)

in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

4. Composition according to at least one of claims 1 to 3, characterized in that they contain as component (b2) alkyl and / or alkenyl ether sulfates of the formula (III),

R30- (CH ₂ CH2θ) nS0 ₃ X (III)

in which R ^{3 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n represents numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

5. Compositions according to at least one of claims 1 to 4, characterized in that they contain betaines of the formula (IV) as component (b3), I

R ⁴ -N- (CH ₂ ) _m COOY (IV)

I.

R6

in which R ⁴ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁶ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.

6. Composition according to at least one of claims 1 to 5, characterized in that they contain betaines of the formula (V) as component (b3),

IR ⁷ CO-NH- (CH ₂ ) _p -N- (CH2) qCOOY (V)

I R6

in which R ⁷ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ⁶ for alkyl radicals with 1 to 4 carbon atoms, p and q independently of one another for Numbers from 1 to 6 and Y represents an alkali and / or alkaline earth metal or ammonium.

7. Compositions according to at least one of claims 1 to 6, characterized in that they contain as component (c) fatty alcohol polyglycol ethers with a narrowed homolog distribution of the formula (VI),

in which R ^{8 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and z represents numbers from 1 to 5.

8. Composition according to at least one of claims 1 to 7, characterized in that it

(a) 1 to 10% by weight of alkyl and / or alkenyl oligoglycosides,

(b) 1 to 10% by weight of alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) 0.1 to 15% by weight of fatty alcohol polyglycol ether with a narrow homolog distribution with the proviso that the amounts given with water and, if appropriate, further auxiliaries and additives are 100% by weight.

9. Composition according to at least one of claims 1 to 8, characterized in that they have a pH in the range 1 to 5.

10. Use of mixtures containing

(a) alkyl and / or alkenyl oligoglycosides,

(b) alkyl and / or alkenyl (ether) sulfates and / or betaines and

(c) Fatty alcohol polyglycol ether with a narrow homolog distribution

for the production of cleaning agents for hard surfaces.