EP1131394A1 - Gel nettoyant pour cuvettes de w-c. - Google Patents

Gel nettoyant pour cuvettes de w-c.

Info

Publication number
EP1131394A1
EP1131394A1 EP99972249A EP99972249A EP1131394A1 EP 1131394 A1 EP1131394 A1 EP 1131394A1 EP 99972249 A EP99972249 A EP 99972249A EP 99972249 A EP99972249 A EP 99972249A EP 1131394 A1 EP1131394 A1 EP 1131394A1
Authority
EP
European Patent Office
Prior art keywords
gel
alcohol
acid
weight
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99972249A
Other languages
German (de)
English (en)
Inventor
Rita Köster
Ansgar Behler
Jutta Stute
Ditmar Kischkel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1131394A1 publication Critical patent/EP1131394A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • 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.
  • 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).
  • 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.
  • fatty acid polyglycol esters are generally listed as nonionic surfactants without further specification.
  • 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.
  • the gel-shaped toilet cleaners for flush toilets should have a very good initial foam behavior and show a clear appearance.
  • perfume oils should be able to be incorporated without problems, in particular in amounts of at least 5% by weight.
  • 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'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.
  • such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with alcohols.
  • 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.
  • alkoxylated carboxylic acid esters of the general formula (I) 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.
  • carboxylic acids examples include 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.
  • 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.
  • suitable monoalcohols are methanol, ethanol, propanol, butanol, pentanol and the hydrogenation products of the above-mentioned carboxylic acids with 6 to 22 carbon atoms.
  • R 2 represents a methyl radical.
  • AlkO is preferably a CH 2 CH 2 O radical.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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
  • X is sodium or ammonium, such as lauric acid + lEO sul
  • Suitable fatty alcohol sulfates follow the formula (III),
  • 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.
  • fatty alcohol sulfates native fatty alcohols
  • 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.
  • 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.
  • 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),
  • 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.
  • 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.
  • 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.
  • the agents according to the invention can contain fatty acid alkanolamides which preferably follow the formula (VI)
  • 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
  • R 9 represents hydrogen or R s .
  • 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.
  • C 12/18 or -Kokosfett Maschinenmono- - - diethanolamide particularly preferred to use C I2 / 14.
  • alcohol ethoxylates which preferably follow the formula (VII), are suitable as a further group of nonionic surfactants,
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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 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.
  • 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.
  • the polyacrylates can be crosslinked, for example with the allyl ethers of pentaerythritol, sucrose or propylene glycol.
  • the acid number is preferably 700 to 750. These are white powders which generally have an average particle size of 2 to 6 ⁇ .
  • 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 are preferably present in amounts of 1.0 to 10% by weight, in particular 1.5 to 6% by weight, based on the composition.
  • 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.
  • 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.
  • 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.
  • alkanolamines polyols such as ethylene glycol, propylene glycol, 1,2 glycerol and other mono- and polyhydric alcohols
  • 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.
  • 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.
  • conventional preservatives can also be present in the usual amounts of 0 to 1% by weight.
  • 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.
  • 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.
  • the descaling agents preferably citric acid
  • polysaccharides preferably xanthan gum
  • the agents according to the invention which contain polyacrylates, preferably Carbopol 981®, as thickeners
  • polyacrylates preferably Carbopol 981®
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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Abstract

L'invention concerne un gel nettoyant pour cuvettes de W-C., qui contient comme tensioactif non ionogène, des esters d'acide carboxylique alcoxylés, notamment du type de ceux produits par alcoxylation d'esters d'acide carboxylique en présence d'hydrotalcites calcinés comme catalyseurs. L'invention concerne en outre l'utilisation d'esters d'acide carboxylique alcoxylés de ce type pour produire des gels nettoyants pour cuvettes de W-C.
EP99972249A 1998-11-18 1999-11-09 Gel nettoyant pour cuvettes de w-c. Withdrawn EP1131394A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19853110 1998-11-18
DE19853110A DE19853110A1 (de) 1998-11-18 1998-11-18 Gelförmiges Reinigungsmittel für Spültoiletten
PCT/EP1999/008569 WO2000029532A1 (fr) 1998-11-18 1999-11-09 Gel nettoyant gel pour cuvettes de w-c.

Publications (1)

Publication Number Publication Date
EP1131394A1 true EP1131394A1 (fr) 2001-09-12

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ID=7888164

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EP99972249A Withdrawn EP1131394A1 (fr) 1998-11-18 1999-11-09 Gel nettoyant pour cuvettes de w-c.

Country Status (4)

Country Link
US (1) US6683035B1 (fr)
EP (1) EP1131394A1 (fr)
DE (1) DE19853110A1 (fr)
WO (1) WO2000029532A1 (fr)

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EP1029911A1 (fr) * 1999-02-17 2000-08-23 Cognis Deutschland GmbH Gel pour le nettoyage des toilettes

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US7048205B2 (en) 2000-07-12 2006-05-23 S.C. Johnson & Son, Inc. Lavatory freshening and/or cleaning system and method
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US6849751B2 (en) * 2001-12-20 2005-02-01 The Procter & Gamble Company Alkyl-capped alkoxylated esters and compositions comprising same
EP1894989A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Composition pâteuse pour articles sanitaires
EP1894578A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Procédé d'application d'une composition pâteuse pour articles sanitaires
EP1894990A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Dose d'unité de la composition pâteuse pour des articles sanitaires
WO2009024743A1 (fr) * 2007-08-17 2009-02-26 Reckitt Benckiser Inc. Compositions acides de traitement des toilettes, écologiquement acceptables
PL2254980T5 (pl) * 2008-02-21 2017-10-31 Johnson & Son Inc S C Kompozycja czyszcząca o dużej przyczepności i zapewniająca dodatkowe korzyści
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
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Also Published As

Publication number Publication date
US6683035B1 (en) 2004-01-27
DE19853110A1 (de) 2000-05-25
WO2000029532A1 (fr) 2000-05-25

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