EP1131394A1

EP1131394A1 - Gel-type cleaning agent for w.c. pans

Info

Publication number: EP1131394A1
Application number: EP99972249A
Authority: EP
Inventors: Rita Köster; Ansgar Behler; Jutta Stute; Ditmar Kischkel
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1998-11-18
Filing date: 1999-11-09
Publication date: 2001-09-12
Also published as: DE19853110A1; WO2000029532A1; US6683035B1

Abstract

The present invention relates to a gel-type cleaning agent for W.C. pans, wherein said agent contains a non-ionogenic surfactant that consists of an alkoxylated carboxylic acid ester mainly of the type of those produced by the alkoxylation of carboxylic acid esters in the presence of calcinated hydrotalcits as catalysts. This invention further relates to the use of such alkoxylated carboxylic acid esters in the production of gel-type cleaning agents for W.C. pans.

Description

"Gel-form detergent for flush toilets"

The present invention relates to gel-form detergents for flushing toilets containing carboxylate esters alkoxylated as nonionic surfactant, in particular those which have been prepared by alkoxylation of carboxylic acid esters in the presence of calcined hydrotalcites as catalysts, and to the use of such alkoxylated carboxylic acid esters for the production of gel-form detergents for flushing toilets.

Fixed toilet blocks have long been used as cleaning agents for flushing toilets, which are either hung in the cistern using 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 dyes 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 surfactant component. From EP-A 0014979 (Henkel) toilet blocks are known which contain alkylbenzenesulfonates and alkylsulfates as well as fatty alcohol or alkylphenol ethoxylates. DE-C2 4337032 (Henkel) relates to toilet blocks containing alkyl sulfates, alkyl ether sulfates and alkyl glucosides. EP-A 0268967 (Henkel) discloses toilet blocks which contain sodium lauryl sulfate and fatty acid monoethanolamide. The toilet blocks described are usually after casting, pressing, extruding or

Granulation processes are manufactured, which require a high level of technical effort and often suffer undesirable loss of perfume due to the temperature load (casting / extrusion process).

It also proves to be disadvantageous that the refill units, which are widespread for ecological reasons, can only be used after the piece-like body has been completely used up. A desirable, arbitrary refill e.g. for more active ingredient release or in particular the more intense fragrance development is not possible.

From the German patent DE-C-197 15 872 gel-shaped toilet cleaners with pseudoplastic properties are known, which significantly reduce the effort of production and are cheaper to produce 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. Amongst others, fatty acid polyglycol esters are generally listed as nonionic surfactants without further specification.

Although such gel-type toilet cleaners certainly meet the requirements placed on them with regard to viscosity behavior and storage stability, there is a need in the market for further gel-type toilet cleaners which have good cleaning performance and good ecological compatibility.

The object of the present invention was to provide further gel-type toilet cleaners for flush toilets which meet the requirements placed on them with regard to viscosity behavior, cleaning performance, storage stability and ecological compatibility. In addition, the gel-shaped toilet cleaners for flush toilets should have a very good initial foam behavior and show a clear appearance. Furthermore, a wide variety of perfume oils should be able to be incorporated without problems, in particular in amounts of at least 5% by weight. Accordingly, the present invention relates to gel-form cleaning agents for flush toilets containing thickeners and surfactants, characterized in that alkoxylated carboxylic acid esters of the formula (I)

R'CCOAlk ^ OR ² (I)

O

in which R'CO represents an aliphatic acyl radical, AlkO represents CH ₂ CH ₂ O, CHCH ₃ CH ₂ O and / or CH ₂ CHCH ₃ O, n represents numbers from 1 to 20 and R ^{2 represents} an aliphatic alkyl radical .

The surfactants according to the invention necessarily contain alkoxylated carboxylic acid esters of the formula (I). Alkoxylated carboxylic acid esters are known from the prior art. For example, such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with alcohols. For the purposes of the present invention, however, the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite in accordance with German Offenlegungsschrift DE-A-39 14 131, which provide compounds with a restricted homolog distribution. According to the present invention, preference is given to alkoxylated carboxylic acid esters of the general formula (I) in which R'CO is an aliphatic acyl radical having 6 to 22 carbon atoms, AlkO is a CH ₂ CH ₂ O-, CHCH ₃ CH ₂ O- and / or CH ₂ -CHCH ₃ O radical, n is on average from 3 to 20 and R ^{2 is} an aliphatic alkyl radical having 1 to 22 carbon atoms.

Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, in particular from straight-chain saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from animal and / or vegetable fats and oils, for example Coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rape oil, cottonseed oil, fish oil, beef tallow and lard. Examples of such carboxylic acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and / or erucic acid. In particular, R'CO stands for a straight-chain, even-numbered acyl radical having 8 to 18 carbon atoms.

Preferred alkyl radicals R ^{2 are} derived from primary, aliphatic monofunctional alcohols having 1 to 22 carbon atoms, which can be saturated and / or unsaturated. Examples of suitable monoalcohols are methanol, ethanol, propanol, butanol, pentanol and the hydrogenation products of the above-mentioned carboxylic acids with 6 to 22 carbon atoms. In particular, R ^{2 represents} a methyl radical.

AlkO is preferably a CH ₂ CH ₂ O radical.

Particularly suitable are alkoxylated carboxylic acid esters of the formula (I) in which R'CO for a straight-chain, even-numbered acyl radical having 8 to 18 carbon atoms, AlkO for a CH ₂ CH ₂ O radical, n on average for numbers from 5 to 15 and R ² represents a methyl radical. Examples of such compounds are methyl carboxylates alkoxylated with an average of 5, 7, 9 or 11 moles of ethylene oxide.

The agents according to the invention can contain the alkoxylated carboxylic acid esters as the sole surfactant, but the agents preferably contain further anionic and / or nonionic surfactants. Anionic co-surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, fatty acid polyglycol ester sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, n-alkyl ether sulfonates, n-alkyl ether sulfonates. Also usable in the context of the present invention, but not preferred are fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates. The agents according to the invention preferably contain fatty alcohol sulfates, fatty alcohol ether sulfates and / or fatty acid polyglycol ester sulfates as anionic surfactants.

Suitable fatty acid polyglycol ester sulfates preferably follow the formula (II), 0

R ³ COO (AO) _x SO ₃ X (II)

in the R ³ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x for numbers from 1 to 3 on average and AO for a CH ₂ CH ₂ O-, CH ₂ CH (CH ₃ ) O- and / or CH (CH ₃ ) CH ₂ O radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative processes in organic chemistry. For this purpose, ethylene oxide, propylene oxide or their mixture is added to the corresponding fatty acids in a random or block distribution, this reaction being acid-catalyzed, but preferably in the presence of bases, such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkyl glycol. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se using chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1.2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 ° C and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion. For example, if molar amounts of fatty acid polyglycol ester to sulfating agent of 1: 0.5 to 1: 0.95 are selected, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained. In order to avoid hydrolysis, it is very important to carry out the neutralization at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, Palmoleic 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, which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula (II) are preferably used in which R ³ CO is an acyl radical having 12 to 18 carbon atoms, x is an average of 1 or 2, AO is a CH ₂ CH ₂ O group and X is sodium or ammonium, such as lauric acid + lEO sulfate sodium salt , Lauric acid + lEO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate ammonium salt and mixtures thereof.

Suitable fatty alcohol sulfates follow the formula (III),

R ⁴ O-SO ₃ X (III)

in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 18 carbon atoms and X represents an alkali or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. They are known anionic surfactants, which are preferably obtained by sulfating native fatty alcohols ("fatty alcohol sulfates") and subsequent neutralization. Typical examples of fatty alcohol sulfates which can be considered as additional anionic surfactant components are the sodium salts of sulfation products of capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, petro alcohol alcohol, ela alcohol alcohol, ela alcohol alcohol, ela alcohol alcohol , Gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as those technical alcohol cuts which are obtained from hydrogenation of native fatty acid methyl ester fractions or from aldehydes from Roelen's oxosynthesis. Fatty alcohol sulfates having 12 to 18 and in particular 12 to 14 carbon atoms are preferably used. Typical examples of this are technical C _12/14 and C _12/8 coconut fatty alcohol sulfates in the form of their sodium salts.

Fatty alcohol ether sulfates are also known anionic surfactants, which are obtained on an industrial scale by sulfating longer-chain primary fatty alcohol ethoxylates and subsequent neutralization. They usually follow formula (IV)

R ⁵ O- (CH ₂ CH ₂ O) _m SO ₃ X (IV) in which R ^{5 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 18 carbon atoms, m represents numbers from 1 to 10 and X represents an alkali or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl ether sulfates are the sodium salts of sulfation products of the adducts of 1 to 10, preferably 2 to 5, moles of ethylene oxide with capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, petrool alcohol , Elaeo stearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, as well as those technical alcohol cuts which are obtained from hydrogenation of native fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis. Fatty alcohol ether sulfates having 12 to 18 and in particular 12 to 14 carbon atoms and a degree of ethoxylation in the range from 2 to 5 are preferably used. Typical examples of this are technical C _12/14 or C _{12/18 coco} alcohol _ether sulfates in the form of their sodium salts, which can have a conventional or narrowed homolog distribution.

For the purposes of the invention, in addition to the alkoxylated carboxylic acid esters and the anionic surfactants which may be present, the agents can additionally comprise further nonionic surfactants. Further nonionic surfactants in the context of the present invention can be alkoxylated alcohols, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and alkyl polyglycosides. Ethylene oxide-propylene oxide block polymers and fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. The agents according to the invention particularly preferably contain alkyl polyglycosides, fatty acid alkanolamides and / or alcohol ethoxylates as further nonionic surfactants.

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (N),

R ⁶ O- [G] p (V) in which R ^{6 represents} an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents a number between 1 and 10. They can be obtained according to the relevant procedures in preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (V) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization 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 in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁶ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, from hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -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 distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁶ 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 and the technical mixtures described above, which can be obtained as described above, and their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred. As a further component, the agents according to the invention can contain fatty acid alkanolamides which preferably follow the formula (VI)

R ⁹

R ⁷ CO-NR ⁸ (VI)

in which R ⁷ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{8 represents} a hydroxyalkyl radical having 2 to 4 carbon atoms and R ^{9 represents} hydrogen or R ^s . These are also known additives which are usually prepared by condensing fatty acids with alkanolamines. Typical examples are condensation products of 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, arachic acid, gadoleic acid, behenic acid and erucic acid or their technical mixtures Diethanolamine. Fatty acid alkanolamides of the formula (VI) are preferably used in which R ⁷ CO is an acyl radical having 12 to 18 carbon atoms, R ^{8 is} a hydroxyethyl radical and R ^{9 is} R ⁸ or hydrogen. Or C _12/18 or -Kokosfettsäuremono- - - diethanolamide particularly preferred to use C _{I2 / 14.}

Finally, alcohol ethoxylates, which preferably follow the formula (VII), are suitable as a further group of nonionic surfactants,

R ¹⁰ O- (CH ₂ CH ₂ O) .H (VII)

in which R ^{10 represents} a linear or branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and z represents numbers from 1 to 50, preferably 5 to 30. These substances are also well-known large-scale products, which are usually produced by base-catalyzed addition of ethylene oxide to primary alcohols. Depending on the catalysts used (eg sodium methylate or calcined hydrotalcite), the ethoxylates can have a conventional or narrow homolog distribution. The alcohol ethoxylates can be adducts of 1 to 50 moles of ethylene oxide with fatty alcohols ("Fatty alcohol ethoxylates") or oxo alcohols ("Oxo alcohol ethoxylates") act. Typical

Examples are the ethoxylates of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselolenol alcohol, ela-noleole alcohol alcohol, , Behenyl alcohol, erucyl alcohol and brassidyl alcohol as well as their technical mixtures, for example in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Adducts of 1 to 50, preferably 5 to 30 and in particular 10 to 20 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.

In a preferred embodiment of the invention, the alkoxylated carboxylic acid esters of the formula (I) are not used alone, but in a mixture with one or more of the abovementioned anionic and / or nonionic surfactants, ie in the form of detergent mixtures. The detergent mixtures preferably contain

(a) 1 to 90, preferably 5 to 80% by weight alkoxylated carboxylic acid esters,

(b) 0 to 25, preferably 1 to 15% by weight of fatty acid polyglycol ester sulfates,

(c) 0 to 50, preferably 1 to 45% by weight of alkyl sulfates and / or alkyl ether sulfates,

(d) 0 to 50, preferably 1 to 30% by weight of alkyl and / or alkenyl oligoglycosides,

(e) 0 to 15, preferably 1 to 5% by weight of fatty acid alkanolamides and

(f) 0 to 30, preferably 1 to 20% by weight alcohol ethoxylates,

with the proviso that the amounts add up to 100% by weight, based on the detergent mixture.

The agents according to the invention contain the alkoxylated carboxylic acid esters either as the sole surfactant or in a mixture with the further surfactants described, preferably in the detergent mixture described, in amounts of 1 to 65, preferably 3 to 40,% by weight. In addition to the alkoxylated carboxylic acid esters already described and optionally further anionic and / or nonionic surfactants, the gel-like agents according to the invention additionally contain thickeners.

The agents according to the invention are preferably pseudoplastic and have a yield point, i.e. Without external forces (in the idle state), the agents are practically non-flowing and behave like a solid; when the agents are pressed (external forces), the agents become fluid and can be filled into the rinsing basket without problems. The viscosity of the agents is preferably in the range from 30,000 to 150,000 mPas, measured with the Brookfield rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.

A polysaccharide or mixtures of different polysaccharides, preferably xanthan gum and / or guar gum, are preferably used as thickeners for the preferred pseudoplastic gel-form cleaning agents. Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthomonas campestris produces xanthan under aerobic conditions with a molecular weight of 2-15 x 10 ⁶ . Xanthan is produced in batch cultures and dried and ground with propanol after killing the culture and cases. Other suitable methods are also described in the literature.

The polysaccharides are preferably present in amounts of from 1.0 to 5.0% by weight, in particular from 1.5 to 4% by weight.

Instead of the preferred polysaccharides, polyacrylates or cationic polymers such as Polygel K 100® from 3V Sigma SPA can alternatively be present as a thickener. Suitable polyacrylates are those with molecular weights of 750,000 to 2,500,000, preferably 1,000,000 to 1,500,000. Preferred polyacrylates are homopolymers of acrylic acid, which can be either in acidic or neutralized form. Polyacrylates which have been polymerized in a mixture of ethyl acetate and cyclohexane are particularly preferred. If desired, the polyacrylates can be crosslinked, for example with the allyl ethers of pentaerythritol, sucrose or propylene glycol. If the polyacrylates are in their acid form, the acid number is preferably 700 to 750. These are white powders which generally have an average particle size of 2 to 6 μ. The content of acrylic acid in the crosslinked products is preferably between 65 and 68%. A particularly suitable representative of such polyacrylates is Carbopol 981 ^R from GFGoodrich, which has an average molecular weight of 1,250,000. The polyacrylates are preferably used in amounts of from 0 to 10, preferably from 1 to 5 and in particular from 2 to 4% by weight, based on the agent.

The cationic polymers, preferably Polygel K 100®, are preferably present in amounts of 1.0 to 10% by weight, in particular 1.5 to 6% by weight, based on the composition.

If normal-thickened gel-like agents are desired instead of pseudoplastic agents, or if the pseudoplastic agents are to be modified in their viscosity behavior, conventional thickeners, e.g. urea, sodium chloride, sodium sulfate, magnesium sulfate, ammonium chloride and magnesium chloride as well as the combination of these can be used instead of or in addition to the polysaccharides Thickeners can be contained in the agents according to the invention.

In addition to the alkoxylated carboxylic acid esters described above and, if appropriate, further anionic and / or nonionic surfactants and the thickeners, the gel-form cleaning agents according to the invention can contain limescale-removing agents, builders, perfumes, solvents, perfume solubilizers, pH regulators, preservatives, dyes and germ-inhibiting agents.

Descaling agents such as citric acids such as citric acid, formic acid, acetic acid, lactic acid or their water-soluble salts are preferably present, preferably in an amount of 1 to 12% by weight, particularly preferably 2 to 7% by weight, in the cleaning agents according to the invention contain.

The preferably water-soluble dyes are contained either for the coloring of the agent or for the coloring of the liquid surrounding the container. Preferably lies the content of 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 dyes can be up 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. 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 of from 0.01% by weight to 3% 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 between 0 and 5, preferably between 0.01 and 4% 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 ^R from Henkel KGaA) and / or hardened castor oil alkoxylated with 40 or 60 mol of ethylene oxide (Eumulgin HRE 40 or 60 ^R ; the Henkel KGaA) and / or 2-hydroxyfatty alcohol ethoxylates (Eumulgin L ^R ; the 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.

Other optional constituents of the cleaning agents according to the invention are builders, preferably water-soluble builders, since they generally have less tendency to form insoluble residues on hard surfaces. Customary builders which may be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and their salts, the carbonates, phosphates and silicates. Water-insoluble builders include the Zeo- lithe, which can also be used, as well as mixtures of the aforementioned builder substances. 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 optional perfumes are those that are common in the prior art. The amount of the dosage depends on the desired fragrance intensity and is preferably in the range from 0 to 15% by weight, in particular from 2 to 12% by weight. Furthermore, conventional preservatives can also be present in the usual amounts of 0 to 1% by weight.

If the agents according to the invention contain the polyacrylates as thickeners, it has proven to be advantageous to achieve an optimal thickening result if the agents according to the invention have a pH value above 6, preferably between 6 and 8 and in particular between 6, 5 and 7.5 is set. The pH value can result from the selected composition of the agents alone or is achieved by the additional addition of pH regulators. Suitable pH regulators are alkaline agents, for example water-soluble amines such as triethanolamine or water-soluble hydroxides such as sodium hydroxide, which are preferably used as aqueous solutions.

The remaining 100% by weight of the gel detergent is water.

The gel-like, preferably pseudoplastic, cleaning agents which contain polysaccharides as thickeners can be prepared according to the already mentioned German patent DE-C-197 15 872. Then water is in a commercial mixer, such as. B. submitted to a Beco mix system, and the dye stirred. The polysaccharide used, preferably xanthan gum, is slurried separately with solvent, preferably ethanol, and the desired perfume oil. The suspension is added to the initial charge and stirred at low speeds, for example 30 rpm. It was shown in the investigations that a time between a few minutes and a few hours after the addition of all components is desirable to achieve the consistency. In the present case, the alkoxylated carboxylic acid ester was slowly added after 30 minutes, optionally in a mixture with the other surfactants. The other components are then added. According to a further production variant for the agents according to the invention with polysaccharides as thickeners, the descaling agents, preferably citric acid, are introduced together with the calculated amount of water, and for this purpose polysaccharides, preferably xanthan gum, are sprinkled in with stirring. After swelling of the thickener, preferably after about 30 minutes, a second preparation of the alkoxylated carboxylic acid esters and possibly further surfactants, as well as possibly perfume oil and possibly colorants and possibly further auxiliaries, is stirred into this template. If a bubble-free gel is to be ensured, the mixture already described should, as a rule, be placed in a suitable container, depending on the viscosity, for a short time, for example 15 minutes, under reduced pressure or under a vacuum.

For the preparation of the agents according to the invention, which contain polyacrylates, preferably Carbopol 981®, as thickeners, it is advantageous if a dispersion of polyacrylates with average molecular weights in the range from 750,000 to 2,500,000, alkoxylated carboxylic acid esters of the formula (I) and, if appropriate, . produces other ingredients in water and sets a pH value above 6. The pH adjustment should advantageously only take place when all the ingredients of the agents according to the invention are present in water, since the final viscosity is reached after the pH adjustment. The agents containing polyacrylates are preferably prepared in such a way that the alkoxylated carboxylic acid esters of the formula (I) and, if appropriate, further surfactants and, if appropriate, further constituents are stirred into the water and any solubilizers present, then the polyacrylates are added and finally the pH - Setting is done.

The agents according to the invention, which contain the cationic polymers as thickeners, can be prepared in an analogous manner to the polyacrylates, but with the difference that the pH adjustment to values above 6 can be dispensed with.

If no structurally viscous gel-form cleaning agents are desired, the agents can be produced by simply mixing the constituents and then thickening them with the thickeners. The gel-type toilet cleaners according to the invention are produced, which can be filled into flushing devices such as baskets or the like. The gel-type toilet cleaners according to the invention are stable in storage, have a good cleaning performance, have excellent initial foam behavior and can be replenished as desired and required. Furthermore, the agents according to the invention have a clear appearance, ie there are no cloudiness even after prolonged storage. Finally, relatively large quantities of perfumes can also be easily incorporated into the compositions.

Another object of the present invention relates to the use of alkoxylated carboxylic acid esters of the formula (I) as a surfactant, optionally in a mixture with other anionic and / or nonionic surfactants for the production of gel-form cleaning agents for flush toilets.

B e i s p i e l e

General manufacturing instructions for agents containing xanthan gum (polysaccharides). Analogous to DE-C-197 15 872.

General manufacturing instructions for agents containing polyacrylates (Carbopol 981®):

The calculated amount of water was initially charged and all constituents of the compositions were added in the amounts of surfactant, perfume and ethanol indicated in Table 1 and stirred in. The amount of polyacrylate (Carbopol 981®) shown in Table 1 was then added and stirred in under moderate conditions. After everything was well distributed, an aqueous sodium hydroxide solution was added until a pH of 6.5 to 7.5 was reached. Optically clear, gel-like products were obtained.

General manufacturing instructions for agents containing cationic polymers (Polygel K 100®):

The calculated amount of water was initially charged and all constituents of the compositions were added in the amounts of surfactant, perfume and ethanol indicated in Table 1 and stirred in. The amount of cationic polymer shown in Table 1 was then added and stirred in under moderate conditions. After everything had been distributed well, the amount of citric acid given in Table 1 was stirred in. Gel-shaped products were obtained. The pH of the agent was 2.5.

Table 1 :

Figures in% active substance

¹ methyl ester of a C _12/18 fatty acid, ethoxylated with 10 mol ethylene oxide (EO)

² alkyl polyglucoside with 8 and 10 carbon atoms in the alkyl radical; DP - 1.6

³ sodium salt of a C _{12 /] 4} alcohol sulphate, ethoxylated with 2 moles EO

4 sodium salt of a C _12/14 alcohol sulfate

Claims

Patent claims

1. Gel-shaped detergent for flush toilets containing thickeners and surfactants, characterized in that carboxylates of the formula (I) alkoxylated as surfactant,

R ¹ C (OAlk) _n OR ² (I)

O

2. Gel-shaped cleaning agent according to claim 1, characterized in that alkoxylated carboxylic acid esters of the formula (I) are contained in which R'CO for an aliphatic acyl radical having 8 to 18 carbon atoms, AlkO for a CH ₂ CH ₂ O radical, n on average represents numbers from 5 to 15 and R ^{2 represents} a methyl radical.

3. Gel-shaped cleaning agent according to one of claims 1 or 2, characterized in that alkoxylated carboxylic acid esters of the formula (I) are contained, which have been prepared by reacting carboxylic acids with alkylene oxides in the presence of calcined hydrotalcite.

4. Gel-shaped cleaning agent according spoke 1, characterized in that the surfactants are contained in amounts of 1 to 65, preferably from 3 to 40 wt.%.

5. Gel-shaped cleaning agent according spoke 1, characterized in that mixtures of surfactants

(a) 1 to 90, preferably 5 to 80% by weight> alkoxylated carboxylic acid esters,

(c) 0 to 50, preferably 1 to 45% by weight of alkyl sulfates and / or alkyl ether sulfates, (d) 0 to 50, preferably 1 to 30% by weight of alkyl and / or alkenyl oligoglycosides,

(e) 0 to 15, preferably 1 to 5% by weight of fatty acid alkanolamides and

(f) 0 to 30, preferably 1 to 20% by weight> alcohol ethoxylates,

6. Gel-shaped cleaning agent according to one of claims 1 to 5, characterized in that it contains polysaccharides, preferably xanthan gum, as thickeners.

7. Gel-shaped cleaning agent according to one of claims 1 to 6, characterized in that the agents have a viscosity of 30,000 to 150,000 mPas.

8. Use of alkoxylated carboxylic acid esters as a surfactant for the production of gel-form cleaning agents for flush toilets.