WO2000065012A1

WO2000065012A1 - Cleaning agents for hard surfaces

Info

Publication number: WO2000065012A1
Application number: PCT/EP2000/003313
Authority: WO
Inventors: Jörg KAHRE; Ditmar Kischkel; Bernhard Guckenbiehl; Anja Hanke; Michael Elsner; 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: DE19918192A1; EP1171560A1

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) terpene alcohols.

Description

Detergent for hard surfaces

Field of the Invention

The invention is in the field of cleaning agents and disinfectants and relates to preparations with a special combination of surfactants and terpene alcohols and their use for the production of cleaning agents.

State of the art

As a cleaning agent for flush toilets have long been used toilet blocks in fixed supply form, which are either hung in the cistern with the help of a device or attached under the inner edge of the toilet. Their task is to clean the surface of the toilet during the flushing process and to mask unpleasant smells, in particular 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 as the surfactant component alkyl sulfates with 9 to 15 carbon atoms, alkylbenzenesulfonates and inorganic salts. 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 refill units, which are widespread for ecological reasons, only after complete consumption of the piece shaped body can be used. 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 geiform toilet cleaners contain polysaccharides, in particular xanthan gum, to adjust the pseudoplastic properties and, as surfactants, alkyl polyglycosides as well as optionally 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 task 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 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 rinsed (number of rinses).

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) Terpene alcohols.

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 not only characterized by easy use and excellent drainage behavior, they also have a high foaming capacity, allow the incorporation of even large amounts of different perfume substances and can be Because of its gel-like nature, especially from applications, for example, in water boxes in toilets ("toilet bowls"), it can be metered reliably over a longer period of time. It is also possible to completely or partially dewater the aqueous preparations and to form blocks ("toilet stones" ) to press.

Alkyl and / or alkenylolyl αoqlvkoside

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

R ¹ 0- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyi 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 using the unique procedures of 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 parameter, 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, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyi radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, 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 the chain length Cβ-Cio (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 can be contaminated with a proportion of less than 6% by weight of Ci2-alcohol and Alkyl oligoglucosides based on technical Cg _/ n oxo alcohols (DP = 1 to 3). The alkyl or alkenyi radical R can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryial alcohol, myristyl alcohol, cetyl alcohol, palmoieyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroseiinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyial alcohol and the technical mixtures described above can be. Alkyl oligoglucosides based on hardened C12 / 14 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)

in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyi radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali metal 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, capryial alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryial alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol alcohol, elaidyl alcohol alcohol - Leyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by 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 / ßβ-tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.

Alkyl and / or alkylene ether sulfates

Alkyl ether sulfates ("ether sulfates"), which form component (b2), are also known anionic surfactants which are prepared industrially by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol 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) nS03X (III)

in the R ³ for a linear or branched alkyl and / or alkenyi radical with 6 to 22 carbon atoms, n for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanammonium or glucammonium stands. 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 capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, .capric alcohol, lauryial alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmo leylalkohol, Stearylaikohol, isostearyl alcohol, Oleylalkohoi, Elaidylaikohol, petroselinyl, Arachylaiko- hol, Gadoleyialkohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures ^¬ Mi, in the form of their sodium and / or magnesium salts. The ether sulfates can have both a conventional and a narrowed homogeneous distribution. Especially preferred is the use of Ethersuifaten based on adducts of on average 2 to 3 moles Ethyienoxid to techni cal ^¬ C12 / 14 or C 12 / 18- Kokosfettalkohoifraktionen 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. Preferably, the starting materials with halocarboxylic acids or salts thereof, in particular ^¬ sondere condensed with sodium chloroacetate, wherein per mole of betaine mole of salt is formed. 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)

IR -N- (CH ₂ ) mCOOY (IV)

in which R ^{4 stands} for alkyl and / or alkenyi residues with 6 to 22 carbon atoms, R ^{5 stands} for hydrogen or alkyl residues with 1 to 4 carbon atoms, R ^{6 stands} for alkyl residues with 1 to 4 carbon atoms, m stands for numbers from 1 to 6 and Y. represents an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxy methyiierungsprodukte of hexylmethylamine, Hexyidimethylamin, octyldimethylamine, decyldimethylamine, dodecylmethylamine, Dodecyldimethyiamin, Dodecylethylmethylamin, Ci2 / i4-Kokosalkyldi-methylamine, styldimethylamin myristic, cetyldimethylamine, stearyldimethylamine, stearyl, Oleyidimethylamin, Ci6 / 18 as well as their technical Talgalkyidimethylamin Mixtures. Carboxyalkylation products of amidoamines which follow the formula (V) are also suitable,

IR ⁷ CO.NH- (CH2) pN- (CH ₂ ) qCOOY (V) in the 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 ⁸ 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, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and NN-diethylamino propylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of Ca / 18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Teroen alcohols

Terpene alcohols, which are component (c), are derived from hydrocarbons, which in turn can be regarded as polymerization products of isoprene. Natural tefen alcohols are usually in the form of their esters. Typical examples are menthol, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, nerol, phenylethyl alcohol, tetrahydro-myrcenol and Teφineol. Geraniol or tetrahydromyrcenol are preferably used. The particular advantage of using them is that they are primarily perfumes, but at the same time have a thickening effect.

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 te alcohols, with the proviso that the amounts given with water and possibly other 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) partial alcohols,

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 furthermore contain co-surfactants, lime-dissolving 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 these agents usually being about 1 to 5 and preferably 2 to 3% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkylethersulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, and sulfate amide monosulfonate and fatty acid amide (ether) sulfate, fatty acid amide sulfate, and fatty acid amide sulfonate, fatty acid amide sulfate, and fatty acid amide sulfate, fatty acid amide (F) 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, for example, acyl lactylates, acyl tartrates, acyl giutamates and acyl aspartates, protein (alcyl sulfate based products), alcyl sulfate oligogate products, alcyl sulfate based products, alcyl sulfate organic products, . If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homogeneous 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, in particular vegetable hydrolysis products, fatty acid-N-alkyl glucose products, fatty acid-N-alkyl glucose 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 narrowed, homogeneous distribution. 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, relevant review articles include, for example, J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, p. 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 esters and / or amine oxides are preferably used as co-surfactants.

As descaling agents, preferably descaling acids such as citric acid, formic acid, acetic acid, lactic acid or their water-soluble salts are present, which in an amount - based on the agent - from 1 to 12 wt .-%, preferably from 2 to 7 wt .-% can be used.

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, nitriiotrieslacetic 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. % can 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 Ci2-Ci8 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 layer silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline layer silicates are those in which M stands for sodium in the general formula and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na2Si2θs-yH2θ are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. As solid builders, the preparations according to the invention can preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous; it is particularly preferred that the agents 20 contain up to 50 wt .-% zeolite and / or crystalline layer 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, in particular, sodium silicate with a molar ratio (module) Na ₂ 0: SiO _∑ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5. The content of funds amorphous sodium silicates are 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. Such layer silicates 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, for example, those of the general formulas

(OH) ₄ Si8-yAly (Mg _x Al4-x) θ2o Montmoπilonit (OH) 4Si8- _y Aly (Mg6- _z Li _z ) θ2o Hectorite (OH) 4Si8-yAl _y (Mg6-z Al _z ) 0 ₂ 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 layer silicate according to the above formulas. Because of their ion-exchanging properties, the layered silicates can also 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), as long as such use is not objectionable for ecological reasons, and mixtures of 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 tepolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylalysulfonic acid or salts thereof as well as sugar derivatives. In particular, polymers are preferred which, according to the teaching of German patent applications DE 4221381 A1 and DE 4300772 A1 can be obtained. Further suitable builder substances are polyacetia, 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 polyacetas are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalic aldehyde and mixtures thereof and from polyol carboxylic 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-chloro-phenyl-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 germ-inhibiting agent is the Teφenalkohol Famesol (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, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (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, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenyethyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyipropionate, benzyl formate, benzyl formate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanols having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, α-isomethyl ionone and methylcedryiketon belong mainly to the Teφene and balms. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils too Lower volatility, which are mostly used as aroma components, are suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden tree oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyciamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandeiice, citric oil, mandolin oil, mandolinolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamylolamine lamino lolamine oil , Lavandin oil, muscatel sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evemyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone Mixtures used. 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, alkoxylated with 40 or 60 moles of ethylene oxide) , 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 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 desired during the flushing-in 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

Table 2 shows further toilet gel toilet stone formulations that have an optimized ratio of surfactants to geraniol, the co-emulsifiers and perfume oil. The transparent area of these microemulsions is thereby achieved. The result is clear, gel-like formulations as shown in Examples 7 to 9.

Table 2:

Composition of various toilet gel toilet blocks

a) Na lauryl ether sulfate b) mixture of fatty alcohol ethersulfates with emulators c) C8 / 10 alkyl polyglycoside d) oleyl cetyl alcohol 5 EO e) amidobetaine f) dimethyloctadien-1-ol, 3.7

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) Terpene alcohols.

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

R ¹ 0- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyi 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 ^∑ O-SOaX (II)

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

R ³ 0- (CH ₂ CH ₂ 0) _n S03X (III)

in which R ^{3 represents} a linear or branched alkyl and / or alkenyi radical with 6 to 22 carbon atoms, n for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanoiammonium 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 ) mCOOY (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, m for numbers from 1 to 6 and X for is an 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),

R5

I R7CO-NH- (CH2) pN- (CH2) _q COOY (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. Composition according to at least one of claims 1 to 6, characterized in that they contain as component (c) terpene alcohols which are selected from the group formed by menthol, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, Nerol, phenyethyl alcohol, tetrahydromyrcenol and terpineol.

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 terpene alcohols,

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) Terpene alcohols

for the production of cleaning agents for hard surfaces.