DE19918189A1 - Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and alkanediol - Google Patents

Abstract

Cleaning agents for flush toilet pans comprising a combination of alkyl- and/or alkenyl oligoglycoside, alkyl- and/or alkenyl (ether)sulfate and/or betaine, and alkanediol have required viscosity properties without addition of separate thickening agent. Cleaning agents for hard surfaces comprising a combination of : (a) alkyl- and/or alkenyloligoglycoside; (b) alkyl- and/or alkenyl (ether)sulfate and/or betaine; and (c) alkanediol.

Description

Field of the Invention

The invention is in the field of cleaning agents and disinfectants and relates to accessories riding with a special combination of surfactants and alkane diols and their use in the manufacture provision of cleaning agents.

State of the art

Toilet stones have long been available as a cleaning agent for flush toilets set, which is either suspended in the cistern or under the inside using a device be attached to the edge of the toilet. Your job is to use the toilet during the flushing process to be cleaned superficially and especially unpleasant smells due to the release of fragrances to cover. Because of their task of releasing fragrances, they become detergents for flush toilets in the literature also generally referred to as fragrance washer. Usually, too their manufacture tensides, builder substances, inorganic salts and of course fragrances and dyes used. A large number of such formulations are known from the prior art. In the US 4534879 (Procter & Gamble), for example, claims solid cleaning agents which are used as Surfactant component alkyl sulfates with 9 to 15 carbon atoms, alkylbenzenesulfonates and inorganic Contain 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 00149791 A1 (Henkel) toilet blocks are known, the alkylbenzenesulfonates and alkylsul fate and fatty alcohol or alkylphenol ethoxylates. Subject of DE 43 37 032 C2 (Henkel) are toilet blocks containing alkyl sulfates, alkyl ether sulfates and alkyl glucosides. In the EP 0268967 A1 (Henkel) discloses toilet blocks which contain sodium lauryl sulfate and fatty acid mo contain noethanolamide. The toilet blocks described are usually cast, pressed, Extrusion or pelletizing processes, which require a high level of technical effort and often fig due to the temperature load (casting / extrusion process) undesirable par suffer loss of film. It also proves to be disadvantageous that the spread for ecological reasons  Refill units can only be used after the piece-like body has been completely used up can. A desirable, any refill z. B. for stronger drug release or ins especially the more intensive fragrance development is not possible.

From the German patent application DE 197 15 872 A1 (Henkel) are gel-shaped toilet cleaners known pseudoplastic properties that significantly reduce the effort of production and are cheaper to produce due to simple technology. Even the problem of the individual Refillability can be solved by such pseudoplastic active ingredient preparations. This Gel-shaped toilet cleaners contain polysaccharides, especially xanthan gum, for adjustment the pseudoplastic properties, and as surfactants mandatory alkyl polyglycosides and possibly anioni and / or non-ionic co-surfactants. However, these gel detergents need to be taken under Adherence to special precautions in gel formation can be made, for one thing There are no bubbles and the other ingredients are evenly distributed in the gel can be incorporated.

The complex object of the present invention has therefore been to create new cleaning agents for hard surfaces, but preferably toilet cleaners, that have a viscosity have on the one hand easy application, on the other hand also on inclined surfaces do not run too quickly to ensure the longest possible exposure time. The preparations should also have an improved cleaning ability, be bactericidal and their beneficial Obtain viscosity without the use of typical thickeners. Finally, the funds should be one have good initial foam behavior, the incorporation of different perfume oils also in allow large quantities and also have a long service life, d. H. a high number of toilets Allow rinsing until the detergent is completely rinsed in (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) alkanediols.

Surprisingly, it was found that the preparations according to the invention do not have only one excellent cleaning performance and bactericidal effect, but compared to conventional Chen agents have a significantly higher viscosity even without the use of thickeners sen and have a structurally viscous behavior. The agents according to the invention are therefore distinguished  not only by easy use and excellent drainage behavior, they also have one high foaming capacity, allow the incorporation of larger quantities of different par foams and because of their gel-like nature they can also be used for inserts for example in water boxes of toilets ("toilet basket") reliably over a longer period of time dose. It is also possible to completely or partially dewater and to dewater the aqueous preparations Blocks ("toilet stones") to be pressed.

Alkyl and / or alkenyl oligoglycosides

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

R ¹ O- [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. Representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90103977. 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 before can assume all 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. Before preferably alkyl and / or alkenyl oligoglycosides are used with an average degree of oligomerization p of 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 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, capronic alcohol, capric alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosi de of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by technical means and with a proportion of less than 6% by weight of C ₁₂ alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ 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, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, as described above, and their technical mixtures can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Alkyl and / or alkenyl sulfates

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

R ² O-SO 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. 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, aridselyl alcohol, elaidyl alcohol , Behenyl 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 C _16/18 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 SO ₃ - 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

R ³ O- (CH ₂ CH ₂ O) _n SO ₃ X (III)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n is a number from 1 to 10 and X is an alkali metal and / or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of add-on products of on average 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capro alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol 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 on average 2 to 3 mol ethylene oxide with technical C _12/14 or C _12/18 coconut fatty _{alcohol fractions} in the form of their sodium and / or magnesium salts.

Betaine

Betaines which are suitable 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. Furthermore, the addition of unsaturated carboxylic acids such as acrylic acid is possible. Regarding the nomenclature and in particular the distinction between betaines and "real" am photensiden, reference is made to the contribution by U. Ploog 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. Ellis 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)

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 Y for is an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine methylamine, hexyldimethylamine, octyldimethylamine, Decyldi, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C methylamine _12/14 -Kokosalkyldi, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof. Carboxyalkylation products of amidoamines which follow the formula (V) are also suitable,

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 ⁶ for alkyl radicals with 1 to 4 carbon atoms, p and q independently of one another represents 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, linolenic acid, arenachic acid, gadoleic acid, gadoleic acid, gadoleic acid, gadoleic acid, galenic acid 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 C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Alkanediols

Alkanediols which are component (c) preferably follow the general formula (VI),

HO (CH ₂ ) _z OH (VI)

in which z stands for numbers from 5 to 12. Typical examples are 1,5-pentanediol, 1,6-hexanediol, 1,8- Octanediol, 1,10-decanediol and 1,12-dodecanediol and mixtures thereof.

Industrial applicability

To set an acidic pH, the preparations according to the invention can include mineral acids, such as. B. hydrochloric acid or phosphoric acid or organic acids, such as. B. 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 wt .-% alkyl and / or alkenyl (ether) sulfates and / or betaines such as
• c) 0.1 to 15, preferably 5 to 11 wt .-% alkanediols

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) alkanediols,

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

Auxiliaries and additives

The gel-form cleaning agents according to the invention can furthermore contain co-surfactants, lime-dissolving agents, Builders, perfumes, perfume solubilizers, solvents, germicides, preservatives, Contain dyes, pH regulators and the like.

Non-ionic, anionic, cationic and / or amphoteric or amphoteric can be used as co-surfactants Surfactants are included, the proportion of which is usually around 1 to 5 and preferably 2 is up to 3% by weight. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, Al kansulfonate, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sul fatty acids, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglyce ride, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, Fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and Acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable pro wheat-based products) and alkyl (ether) phosphates. If the anionic surfactants polyglycol ether chains contain, these can be a conventional, but preferably a narrowed homo have lye distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol  ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine po lyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers or mixed formals, optionally partially oxidized glucoronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolyzates (especially plant products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and Amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a con conventional, but preferably have a narrow homolog distribution. Typical examples for cationic surfactants are esterquats and tetraalkylammonium compounds. With the above Surfactants are only known compounds. Regarding structure and manufacture For example, 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. Preferred co-surfactants are alcohol ethoxylates, hydroxy mixed ethers, fatty acid methyl esters thoxylates and / or amine oxides used.

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

Other optional components of the agents according to the invention are builders, preferably water-soluble builders, since they generally tend to form less insoluble residues on hard surfaces. Suitable liquid, water-soluble builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as. B. the neutral reacting sodium salts of 1-hydroxyethane-1,1, -diphosphonate, which can be present in amounts of 0.5 to 5, preferably 1 to 2 wt .-%. As a solid or water-insoluble builder, in particular fine-crystalline, synthetic and bound water-containing zeolite such as zeolite NaA is used 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 which is still moist from its production. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ 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 O _{2x + 1.y} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 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 represents sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can 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. Agents which contain Na ₂ O: SiO _{2 in} a molar ratio (modulus) of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are particularly preferred. 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 23 34 899 B1, EP 0026529 A1 and DE 35 26 405 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 e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ 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. Usable layered 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 that 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 terpolymers, which are used as monomers acrylic acid and maleic acid or their salts, and also vinyl alcohol or vinyl alcohol derivatives or which are used as monomers acrylic acid and 2-alkylallyl sulfonic acid or containing their salts and sugar derivatives. In particular, terpolymers are preferred which he will keep according to the teaching of German patent applications DE 42 21 381 A1 and DE 43 00 772 A1. Other 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 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 a specific action 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'-trichlorocarbonilide). Numerous fragrances and essential oils also have antimicrobial eggs 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 Farriesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in linden blossom oil and a lily of the valley smell of kitchen. Glycerol monolaurate has also proven itself as a bacteriostatic. The amount of this germicide depends heavily on the effectiveness of the particular compound and can be up to 5% by weight. The germ-inhibiting agents are preferably in amounts between 0 and 10, preferably contain between 0.01 and 7 wt .-%.

The optional additional perfume substances are those from the prior art Technology common. Mixtures of natural and synthetic odors are mentioned as examples  fabrics. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang- Ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, Juniper), fruit peels (bergamot, lemon, oranges), roots (mace, angelica, celery, kar damon, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and Grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, lat ), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Farther animal raw materials are possible, such as civet and castoreum. Typical synthetic Fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethy lisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate tat, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propio nat and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, Cy clamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α- Isomethyl ionone and methyl cedryl ketone, to the terpene alcohols menthol, anethole, citronellol, eugenol, Isoeugenol, geraniol, linalool, nerol, phenylethyl alcohol, tetrahydromyrcenol and terpineol Hydrocarbons mainly include the terpenes and balms. However, Wed are preferred uses different fragrances, which together produce an appealing fragrance Essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, e.g. B. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lin denflower oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Before Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α- Hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, Indole, Hedione, Sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclover valley, lavan din oil, muscatel sage oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, Rose oxide, Romilllat, Irotyl and Floramat used alone or in mixtures. The amount of the dose tion is dependent 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 Glycerin alkoxylated with 7 moles 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 ethylene oxide (Eu mulgin® HRE 40 or 60, Henkel KGaA) and / or 2-hydroxy fatty alcohol ethoxylates (Eumulgin® L, Henkel KGaA) may be included. The amount of perfume solubilizers in the agents according to the invention is usually between 0 and 10, preferably between 1 and 7 wt .-%.

As solvents, especially for dyes and perfume oils, can be used in the invention Agents, for example alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and others  re mono- and polyhydric alcohols, and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl rest included. The group of lower alcohols is particularly preferred, very particularly Ethanol. The solvent content depends on the type and quantity of the stock to be dissolved parts and is usually in the range of 0.5 to 5 wt .-%.

The preferably water-soluble dyes are either for the coloring of the agent or for contain the coloring of the liquid surrounding the container. The content is preferably water-soluble dyes 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 Chen dyes up to 5 wt .-%.  

Examples

Various toilet gels were manufactured and their cleaning performance according to the IPP standard (An dirt 78/19, undiluted application) and viscosity (Brookfield, RVT viscometer, 20 ° C, Spindle 1, 10 rpm, cf. Soap-oil-fat waxes, 112, 371, 1988). The results are in Table 1 summarized. Examples 1 to 4 are according to the invention, Examples V1 and V2 are for comparison. All quantities are understood as% by weight.

Table 1

Composition of various toilet gel toilet blocks

Claims (12)

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) alkanediols.

2. Composition according to claim 1, characterized in that they contain as component (a) alkyl and alkylene nyloligoglycosides of the formula (I),
R ¹ O- [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 O-SO ₃ X (II)
in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is 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),
R ³ O- (CH ₂ CH ₂ O) _n SO 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, alky lammonium, 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),
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),
in which R ⁷ CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ⁵ for hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ⁶ for alkyl radicals having 1 to 4 carbon atoms, p and q independently of one another represents 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 alkanediols of the formula (VI) as component (c),
HO (CH ₂ ) _z OH (VI)
in which z stands for numbers from 5 to 12. 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 wt .-% alkyl and / or alkenyl (ether) sulfates and / or betaines and
• c) 0.1 to 15 wt .-% alkanediols with the proviso that the amounts with water and optionally other auxiliaries and additives add up to 100 wt .-%.

9. Composition according to at least one of claims 1 to 8, characterized in that it has a Have a pH in the range of 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) alkanediols

for the production of cleaning agents for hard surfaces.