EP0725813B1 - Use of detergent mixtures for toilet freshening blocks - Google Patents

Use of detergent mixtures for toilet freshening blocks Download PDF

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Publication number
EP0725813B1
EP0725813B1 EP94930200A EP94930200A EP0725813B1 EP 0725813 B1 EP0725813 B1 EP 0725813B1 EP 94930200 A EP94930200 A EP 94930200A EP 94930200 A EP94930200 A EP 94930200A EP 0725813 B1 EP0725813 B1 EP 0725813B1
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Prior art keywords
alkyl
carbon atoms
alcohol
radical containing
formula
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German (de)
French (fr)
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EP0725813A1 (en
Inventor
Karl Schmid
Andreas Syldath
Ditmar Kischkel
Volker Bauer
Wolfgang Schmidt
Anke Becker
Edgar Jaeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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 invention relates to the use of mixtures of selected anionic and nonionic surfactants for manufacturing of toilet blocks.
  • Toilet blocks provide cleaning agents in a solid form represent, either with the help of a device hung the cistern or under the inside edge of the toilet be attached. Your job is to use the toilet to be cleaned superficially during the rinsing process and in particular unpleasant smells due to the release of fragrances to cover. Usually used to manufacture them Surfactants, builder substances, inorganic salts and of course Fragrance and colorants used.
  • EP-A 0 268 967 discloses toilet blocks which typically contain 22% sodium lauryl sulfate, 12% coconut fatty acid monoethanolamide, 2% borax, 48% sodium sulfate, 5% sodium citrate, 6% pine oil and 5% dye.
  • the object of the invention was therefore such To provide products.
  • Fatty alcohol sulfates also known as alkyl sulfates are known anionic surfactants, which are preferred by sulfation of native fatty alcohols or synthetic oxo alcohols and subsequent neutralization be preserved.
  • Typical examples of fatty alcohol sulfates which can be considered as component a) are the sodium salts of sulfation products of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, iso alcohol, isostyl alcohol, isostyl alcohol, iso alcohol Linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behen
  • Fatty alcohol ether sulfates are also known on an industrial scale Anionic surfactants by sulfating fatty alcohol ethoxylates and subsequent neutralization can be obtained.
  • Typical examples of fatty alcohol ether sulfates which make up component b) are the sodium salts of sulfation products of the adducts of 1 to 10, preferably 2 to 5, moles of ethylene oxide to capronalcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, , Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, as well as those technical alcohol cuts, which are obtained from the hydrogenation of native fatty acid methyl ester fractions or aldehydes from Roelen'-aldehydes.
  • 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 coconut fatty alcohol ether sulfates in the form of their sodium salts, which may have a conventional or narrowed homolog distribution.
  • Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP- A1-0 301 298 and WO-A-90/3977 .
  • 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 alkyl or alkenyl radical R 3 can be derived from primary alcohols having 6 to 11, preferably 8 to 10, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 3 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, and their technical mixtures, which 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.
  • the fatty acid N-alkyl polyhydroxyalkylamides are also known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • a reducing sugar with ammonia, an alkylamine or an alkanolamine
  • subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride With regard to the process for their preparation Patents US US 1,985,424, US 2,016,962 and US 2,703,798 as well as International Patent Application WO 92/06984, reference is made to the. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Det. 25, 8 (1988).
  • the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula ( V ):
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula ( V ) in which R 5 is hydrogen or an amine group and R 4 CO is the acyl radical 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 or erucic acid or their technical mixtures.
  • Fatty acid N-alkylglucamides of the formula ( V ) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • the detergent mixtures can contain, as further optional components, fatty acid alkanolamides of the formula (VI) in which R 6 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, Z 1 is a hydroxyalkyl radical having 2 to 4 carbon atoms and Z 2 is Z 1 or hydrogen.
  • R 6 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • Z 1 is a hydroxyalkyl radical having 2 to 4 carbon atoms
  • Z 2 is Z 1 or hydrogen.
  • 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 or erucic acidethanolamine or their technical mixtures .
  • Fatty acid alkanolamides of the formula ( VI ) are preferably used in which R 6 CO is an acyl radical having 12 to 18 carbon atoms, Z 1 is a hydroxyethyl radical and Z 2 is Z 1 or hydrogen.
  • the use of C 12/14 or C 12/18 coconut fatty acid mono- or diethanolamide is particularly preferred.
  • the detergent mixtures according to the invention may contain, as further optional components, fatty alcohol ethoxylates of the formula ( VII ) R 7 O- (CH 2 CH 2 O) n H in which R 7 is a linear or branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and n is a number from 20 to 50.
  • R 7 is a linear or branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and n is a number from 20 to 50.
  • 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.
  • Typical examples are addition products from 20 to 50, preferably 25 to 40 moles of technical coconut fatty alcohols with 12 to 18, preferably 12 to 14 carbon atoms.
  • the surfactant mixtures to be used according to the invention can have the following advantageous composition: 50 to 98% by weight of fatty alcohol sulfates, 1 to 15% by weight of fatty alcohol ether sulfates, 1 to 15% by weight of alkyl and / or alkenyl oligoglycosides and / or 1 to 15% by weight of fatty acid N-alkyl polyhydroxyalkylamides.
  • the proportion of optional components according to formulas ( VI ) and ( VII ) can be 1 to 15, preferably 3 to 10% by weight. As a rule, all percentages add up to 100% by weight.
  • Auxiliaries and additives include non-surfactants Components of the recipes for commercially available toilet blocks to understand that mixed with the detergent mixtures and then be brought into the desired shape.
  • the detergent mixtures are usually used anhydrous. For easier plasticization, however, they can be used as Auxiliary water in an amount of 1 to 10, preferably 2 up to 6 wt .-% - based on the mixture - are added.
  • auxiliary substances and additives are inorganic salts, especially sodium sulfate, sodium carbonate and / or sodium chloride into consideration, their proportion in total 25 to 75, preferably 30 to 60% by weight - based on the end product - can make out.
  • Detergent mixtures in the form of SKET granules are used for example the required proportion of sodium sulfate included due to manufacturing.
  • additives are also solid or liquid builders, such as, for example, zeolite A, nitrilotriacetate, Ethylenediaminetetraacetate or sodium citrate. Your Proportions can be 5 to 15, preferably 8 to 12% by weight on the end product - make up.
  • toilet blocks usually still contain colors and fragrances, usually in amounts of 1 to 5 wt .-% - based on the End product.
  • the detergent mixtures according to the invention can be used as Use surfactant components to manufacture toilet blocks. Products on this basis are characterized by a high solubility delay, i.e. long life, one improved foam resistance and easier processing.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

PCT No. PCT/EP94/03456 Sec. 371 Date May 28, 1996 Sec. 102(e) Date May 28, 1996 PCT Filed Oct. 20, 1994 PCT Pub. No. WO95/11958 PCT Pub. Date May 4, 1995Detergent mixtures containing fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl and/or alkenyl oligoglycosides and/or fatty acid N-alkyl polyhydroxyalkyl amides are eminently suitable in solid form for the production of toilet blocks.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft die Verwendung von Gemischen ausgewählter anionischer und nichtionischer Tenside zur Herstellung von Toilettensteinen.The invention relates to the use of mixtures of selected anionic and nonionic surfactants for manufacturing of toilet blocks.

Stand der TechnikState of the art

Toilettensteine stellen Reinigungsmittel in fester Anbietungsform dar, die mit Hilfe einer Vorrichtung entweder in den Spülkasten eingehängt oder unter dem Innenrand des WC's befestigt werden. Ihre Aufgabe besteht darin, die Toilette während des Spülvorgangs oberflächlich zu reinigen und insbesondere durch Freisetzung von Duftstoffen unangenehme Gerüche zu überdecken. Üblicherweise werden zu ihrer Herstellung Tenside, Buildersubstanzen, anorganische Salze und natürlich Duft- und Farbstoffe eingesetzt.Toilet blocks provide cleaning agents in a solid form represent, either with the help of a device hung the cistern or under the inside edge of the toilet be attached. Your job is to use the toilet to be cleaned superficially during the rinsing process and in particular unpleasant smells due to the release of fragrances to cover. Usually used to manufacture them Surfactants, builder substances, inorganic salts and of course Fragrance and colorants used.

Aus dem Stand der Technik sind eine Vielzahl von Formulierungen bekannt. In der US-A-4,534,879 (Procter & Gamble) werden beispielsweise feste Reinigungsmittel beansprucht, die als Tensidkomponente Alkylsulfate mit 9 bis 15 Kohlenstoffatomen, Alkylbenzolsulfonate und wasserunlösliche anorganische Salze enthalten.A large number of formulations are known from the prior art. For example, US-A-4,534,879 (Procter & Gamble) claims solid cleaning agents which contain alkyl sulfates having 9 to 15 carbon atoms, alkylbenzenesulfonates and water-insoluble inorganic salts as the surfactant component.

Aus der EP-A 0 014 979 (Henkel) sind Toilettensteine bekannt, die als anionische Tenside Alkylbenzolsulfonate, Alkylsulfate und Olefinsulfonate sowie als nichtionische Tenside Fettalkohol- bzw. Alkylphenolethoxylate enthalten.From EP-A 0 014 979 (Henkel) toilet blocks are known which contain alkyl benzene sulfonates, alkyl sulfates and olefin sulfonates as anionic surfactants and fatty alcohol or alkyl phenol ethoxylates as nonionic surfactants.

Weitere Toilettensteine auf Basis von anionischen Tensiden mit Sulfat- und/oder Sulfonatstruktur sind beispielsweise aus den Schriften EP-A 018 679, EP-A 0 114 427, EP-A 0 114 429, EP-A 0 122 664, EP-A 0 167 210, EP-A 0 184 416 und EP-A 0 206 725 geläufig.Further toilet blocks based on anionic surfactants with a sulfate and / or sulfonate structure are known, for example, from the documents EP-A 018 679, EP-A 0 114 427, EP-A 0 114 429, EP-A 0 122 664, EP-A 0 167 210, EP-A 0 184 416 and EP-A 0 206 725 common.

In der EP-A 0 268 967 (Henkel) werden Toilettensteine offenbart, die typischerweise 22 % Natriumlaurylsulfat, 12 % Kokosfettsäuremonoethanolamid, 2 % Borax, 48 % Natriumsulfat, 5 % Natriumcitrat, 6 % Pine oil und 5 % Farbstoff enthalten. EP-A 0 268 967 (Henkel) discloses toilet blocks which typically contain 22% sodium lauryl sulfate, 12% coconut fatty acid monoethanolamide, 2% borax, 48% sodium sulfate, 5% sodium citrate, 6% pine oil and 5% dye.

Es hat sich nun erwiesen, daß die Produkte des Stands der Technik aus anwendungstechnischer Sicht nicht immer zufriedenstellend sind. Ein besonderes Interesse besteht vor allem an Produkten mit einer verzögerten Auflösegeschwindigkeit, d. h. Toilettensteine mit einer verbesserten Spülzahl. Weiterhin gilt es Formulierungen zu entwickeln, die im Hinblick auf ihre Verarbeitbarkeit (Knetbarkeit, Formstabilität, Versumpfungsneigung etc.) Vorteile bieten und einen stabileren Schaum besitzen. It has now been shown that the products of the state of the art Technology is not always satisfactory from an application perspective are. Above all, there is a particular interest on products with a delayed dissolution rate, d. H. Toilet blocks with an improved flushing number. Farther It is important to develop formulations that are relevant to their Processability (kneadability, dimensional stability, tendency to sump) etc.) offer advantages and a more stable Own foam.

Die Aufgabe der Erfindung hat somit darin bestanden, derartige Produkte zur Verfügung zu stellen.The object of the invention was therefore such To provide products.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist die Verwendung von Detergensgemischen zur Herstellung von Toilettensteinen, enthaltend

  • a) Fettalkoholsulfate der Formel (I) R1O-SO3X in der R1 für einen linearen oder verzweigten Alkyl-und/oder Alkenylrest mit 6 bis 18 Kohlenstoffatomen und X für ein Alkali- oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht,
  • b) Fettalkoholethersulfate der Formel (II), R2O-(CH2CH2O)mSO3X in der R2 für einen linearen oder verzweigten Alkyl-und/oder Alkenylrest mit 6 bis 18 Kohlenstoffatomen, m für Zahlen von 1 bis 10 und X für ein Alkali- oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht, und
  • c1) Alkyl- und/oder Alkenyloligoglykoside der Formel (III), R3-O-[G]p in der R3 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für eine Zahl zwischen 1 und 10 steht, und/oder
  • c2) Fettsäure-N-alkylpolyhydroxyalkylamide der Formel (IV),
    Figure 00040001
    in der R4CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R5 für Wasserstoff, einen Alkyl-oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.
    • Überraschenderweise wurde gefunden, daß die erfindungsgemäße Verwendung der Detergensgemische zu Toilettensteinen führt, die sich gegenüber Produkten des Marktes durch eine höhere Lebensdauer, d.h. höhere Löslichkeitsverzögerung, verbesserten Schaum und leichtere Verarbeitbarkeit auszeichnen.The invention relates to the use of detergent mixtures for the production of toilet blocks containing
  • a) fatty alcohol sulfates of the formula (I) R 1 O-SO 3 X in which R 1 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,
  • b) fatty alcohol ether sulfates of the formula (II), R 2 O- (CH 2 CH 2 O) m SO 3 X in which R 2 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, and
  • c1) alkyl and / or alkenyl oligoglycosides of the formula (III), R 3 -O- [G] p in which R 3 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, and / or
  • c2) fatty acid N-alkylpolyhydroxyalkylamides of the formula (IV),
    Figure 00040001
    in the R 4 CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 5 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
    • Surprisingly, it was found that the use of the detergent mixtures according to the invention leads to toilet blocks which are distinguished from products on the market by a longer service life, ie a higher solubility delay, improved foam and easier processing.

    FettalkoholsulfateFatty alcohol sulfates

    Fettalkoholsulfate, die auch als Alkylsulfate bezeichnet werden, stellen bekannte anionische Tenside dar, die vorzugsweise durch Sulfatierung von nativen Fettalkoholen oder synthetischen Oxoalkoholen und nachfolgende Neutralisation erhalten werden.Fatty alcohol sulfates, also known as alkyl sulfates are known anionic surfactants, which are preferred by sulfation of native fatty alcohols or synthetic oxo alcohols and subsequent neutralization be preserved.

    Typische Beispiele für Fettalkoholsulfate, die als Komponente a) in Betracht kommen, stellen die Natriumsalze von Sulfatierungsprodukten des Capronalkohols, Caprylalkohols, 2-Ethylhexylalkohols, Caprinalkohols, Laurylalkohols, Myristylalkohols, Cetylalkohols, Palmoleylalkohols, Stearylalkohols, Isostearylalkohols, Oleylalkohols, Elaidylalkohols, Petroselinylalkohols, Linolylalkohols, Linolenylalkohols, Elaeostearylalkohols, Arachylalkohols, Gadoleylalkohols, Behenylalkohols und Erucylalkohols sowie solchen technischen Alkoholschnitten dar, die durch Hydrierung nativer Fettsäuremethylesterfraktionen oder von Aldehyden aus der Roelen'schen Oxosynthese gewonnen werden. Vorzugsweise werden Fettalkoholsulfate mit 12 bis 18 und insbesondere 12 bis 14 Kohlenstoffatomen eingesetzt. Typische Beispiele hierfür sind technische C12/14- bzw. C12/18-Kokosfettalkoholsulfate in Form ihrer Natriumsalze.Typical examples of fatty alcohol sulfates which can be considered as component a) are the sodium salts of sulfation products of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, isostyl alcohol, iso alcohol, isostyl alcohol, isostyl alcohol, iso alcohol Linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as technical alcohol cuts obtained by 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 12/18 coconut fatty alcohol sulfates in the form of their sodium salts.

    FettalkoholethersulfateFatty alcohol ether sulfates

    Auch Fettalkoholethersulfate stellen bekannte großtechnische Aniontenside dar, die durch Sulfatierung von Fettalkoholethoxylaten und nachfolgende Neutralisation erhalten werden.Fatty alcohol ether sulfates are also known on an industrial scale Anionic surfactants by sulfating fatty alcohol ethoxylates and subsequent neutralization can be obtained.

    Typische Beispiele für Fettalkoholethersulfate, die die Komponente b) ausmachen, stellen die Natriumsalze von Sulfatierungsprodukten der Addukte von 1 bis 10, vorzugsweise 2 bis 5 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie solchen technischen Alkoholschnitten dar, die durch Hydrierung von nativen Fettsäuremethylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese gewonnen werden. Vorzugsweise werden Fettalkoholethersulfate mit 12 bis 18 und insbesondere 12 bis 14 Kohlenstoffatomen und einem Ethoxylierungsgrad im Bereich von 2 bis 5 eingesetzt. Typische Beispiele hierfür sind technische C12/14- bzw. C12/18-Kokosfettalkoholethersulfate in Form ihrer Natriumsalze, die eine konventionelle oder auch eingeengte Homologenverteilung aufweisen können.Typical examples of fatty alcohol ether sulfates which make up component b) are the sodium salts of sulfation products of the adducts of 1 to 10, preferably 2 to 5, moles of ethylene oxide to capronalcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, , Isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, as well as those technical alcohol cuts, which are obtained from the hydrogenation of native fatty acid methyl ester fractions or aldehydes from Roelen'-aldehydes. 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 coconut fatty alcohol ether sulfates in the form of their sodium salts, which may have a conventional or narrowed homolog distribution.

    Alkyl- und/oder AlkenyloligoglykosideAlkyl and / or alkenyl oligoglycosides

    Alkyl- und Alkenyloligoglykoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1-0 301 298 und WO-A-90/3977 verwiesen. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside.Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP- A1-0 301 298 and WO-A-90/3977 . 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.

    Die Indexzahl p in der allgemeinen Formel (III) gibt den Oligomerisierungsgrad (DP-Grad), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylund/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt.The index number p in the general formula (III) gives the Degree of oligomerization (DP degree), i.e. H. the distribution of Mono- and oligoglycosides and stands for a number between 1 and 10. While p is always an integer in a given connection must be and assume here the values p = 1 to 6 is the value p for a particular alkyl oligoglycoside an analytically calculated quantity, the mostly represents a fractional number. Preferably be Alkyl and / or alkenyl oligoglycosides with a medium degree of oligomerization p used from 1.1 to 3.0. For application technology Such are alkyl and / or alkenyl oligoglycosides preferred whose degree of oligomerization is smaller is 1.7 and is in particular between 1.2 and 1.4.

    Der Alkyl- bzw. Alkenylrest R3 kann sich von primären Alkoholen mit 6 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese anfallen. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3).The alkyl or alkenyl radical R 3 can be derived from primary alcohols having 6 to 11, preferably 8 to 10, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of 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 can be contaminated and alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3).

    Der Alkyl- bzw. Alkenylrest R3 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.The alkyl or alkenyl radical R 3 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, and their technical mixtures, which 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.

    Fettsäure-N-alkylpolyhydroxyalkylamideFatty acid N-alkyl polyhydroxyalkylamides

    Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich ebenfalls um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1 985 424, US 2 016 962 und US 2 703 798 sowie die Internationale Patentanmeldung WO 92/06984 verwiesen. Eine Übersicht zu diesem Thema von H.Kelkenberg findet sich in Tens.Surf.Det. 25, 8 (1988). The fatty acid N-alkyl polyhydroxyalkylamides are also known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the process for their preparation Patents US US 1,985,424, US 2,016,962 and US 2,703,798 as well as International Patent Application WO 92/06984, reference is made to the. An overview of this topic by H.Kelkenberg can be found in Tens.Surf.Det. 25, 8 (1988).

    Vorzugsweise leiten sich die Fettsäure-N-alkylpolyhydroxyalkylamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Die bevorzugten Fettsäure-N-alkylpolyhydroxyalkylamide stellen daher Fettsäure-N-alkylglucamide dar, wie sie durch die Formel (V) wiedergegeben werden:

    Figure 00090001
    Vorzugsweise werden als Fettsäure-N-alkylpolyhydroxyalkylamide Glucamide der Formel (V) eingesetzt, in der R5 für Wasserstoff oder eine Amingruppe steht und R4CO für den Acylrest der Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. derer technischer Mischungen steht. Besonders bevorzugt sind Fettsäure-N-alkylglucamide der Formel (V), die durch reduktive Aminierung von Glucose mit Methylamin und anschließende Acylierung mit Laurinsäure oder C12/14-Kokosfettsäure bzw. einem entsprechenden Derivat erhalten werden. Weiterhin können sich die Polyhydroxyalkylamide auch von Maltose und Palatinose ableiten.The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula ( V ):
    Figure 00090001
    The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula ( V ) in which R 5 is hydrogen or an amine group and R 4 CO is the acyl radical 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 or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula ( V ) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

    FettsäurealkanolamideFatty acid alkanolamides

    Die Detergensgemische können als weitere fakultative Bestandteile Fettsäurealkanolamide der Formel (VI) enthalten,

    Figure 00090002
    in der R6CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, Z1 für einen Hydroxyalkylrest mit 2 bis 4 Kohlenstoffatomen und Z2 für Z1 oder Wasserstoff steht. Auch hierbei handelt es sich um bekannte Zusatzstoffe, die gewöhnlich durch Kondensation von Fettsäuren mit Alkanolaminen hergestellt werden.The detergent mixtures can contain, as further optional components, fatty acid alkanolamides of the formula (VI)
    Figure 00090002
    in which R 6 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, Z 1 is a hydroxyalkyl radical having 2 to 4 carbon atoms and Z 2 is Z 1 or hydrogen. These are also known additives which are usually prepared by condensing fatty acids with alkanolamines.

    Typische Beispiele sind Kondensationsprodukte von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure bzw. deren technischen Mischungen mit Monoethanolamin, und Diethanolamin. Vorzugsweise werden Fettsäurealkanolamide der Formel (VI) eingesetzt, in der R6CO für einen Acylrest mit 12 bis 18 Kohlenstoffatomen, Z1 für einen Hydroxyethylrest und Z2 für Z1 oder Wasserstoff steht. Besonders bevorzugt ist der Einsatz von C12/14- bzw. C12/18-Kokosfettsäuremono- bzw. -diethanolamid.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 or erucic acidethanolamine or their technical mixtures . Fatty acid alkanolamides of the formula ( VI ) are preferably used in which R 6 CO is an acyl radical having 12 to 18 carbon atoms, Z 1 is a hydroxyethyl radical and Z 2 is Z 1 or hydrogen. The use of C 12/14 or C 12/18 coconut fatty acid mono- or diethanolamide is particularly preferred.

    FettalkoholethoxylateFatty alcohol ethoxylates

    Als weitere fakultative Komponenten können in den erfindungsgemäßen Detergensgemischen Fettalkoholethoyxlate der Formel (VII) enthalten sein, R7O-(CH2CH2O)nH in der R7 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 12 bis 18 Kohlenstoffatomen und n für Zahlen von 20 bis 50 steht. Auch diese Stoffe stellen bekannte großtechnische Produkte dar, die für gewöhnlich durch basenkatalysierte Anlagerung von Ethylenoxid an primäre Alkohole hergestellt werden. In Abhängigkeit der verwendeten Katalysatoren (z.B. Natriummethylat oder calcinierter Hydrotalcit) können die Ethoxylate eine konventionelle oder eingeengte Homologenverteilung aufweisen.The detergent mixtures according to the invention may contain, as further optional components, fatty alcohol ethoxylates of the formula ( VII ) R 7 O- (CH 2 CH 2 O) n H in which R 7 is a linear or branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and n is a number from 20 to 50. 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.

    Typische Beispiele stellen Anlagerungsprodukte von 20 bis 50, vorzugsweise 25 bis 40 Mol an technische Kokosfettalkohole mit 12 bis 18, vorzugsweise 12 bis 14 Kohlenstoffatomen dar.Typical examples are addition products from 20 to 50, preferably 25 to 40 moles of technical coconut fatty alcohols with 12 to 18, preferably 12 to 14 carbon atoms.

    Zusammensetzung der DetergensgemischeComposition of the detergent mixtures

    Die erfindungsgemäß zu verwendenden Tensidgemische können folgende vorteilhafte Zusammensetzung aufweisen:
    50 bis 98 Gew.-% Fettalkoholsulfate,
    1 bis 15 Gew.-% Fettalkoholethersulfate,
    1 bis 15 Gew.-% Alkyl- und/oder Alkenyloligoglykoside und/oder
    1 bis 15 Gew.-% Fettsäure-N-alkylpolyhydroxyalkylamide.    The surfactant mixtures to be used according to the invention can have the following advantageous composition:
    50 to 98% by weight of fatty alcohol sulfates,
    1 to 15% by weight of fatty alcohol ether sulfates,
    1 to 15% by weight of alkyl and / or alkenyl oligoglycosides and / or
    1 to 15% by weight of fatty acid N-alkyl polyhydroxyalkylamides.

    Der Anteil der fakultativen Komponenten gemäß der Formeln (VI) und (VII) kann 1 bis 15, vorzugsweise 3 bis 10 Gew.-% betragen. Als Maßgabe gilt dabei, daß sich alle Prozentanteile zu 100 Gew.-% ergänzen. The proportion of optional components according to formulas ( VI ) and ( VII ) can be 1 to 15, preferably 3 to 10% by weight. As a rule, all percentages add up to 100% by weight.

    Herstellung trockener AnbietungsformenManufacture of dry forms of supply

    Die erfindungsgemäßen Detergensgemische werden vorzugsweise wasserfrei, beispielsweise in Form von Pulvern, Granulaten, Extrudaten oder Nadeln eingesetzt.

  • a) Sprühneutralisation/Sprühtrocknung. Zur Herstellung der Pulver kann man sich üblicher Techniken bedienen. Es ist beispielsweise möglich, die sauren Sulfatierungsprodukte der Fettalkohole und Fettalkoholethoxylate gemeinsam oder getrennt einer Sprühneutralisation zu unterwerfen und den trockenen Pulvern wasserfreie Glykoside und/oder Polyhydroxyfettsäureamide zuzusetzen. Ferner ist es möglich, wäßrige Mischungen der Komponenten herzustellen und gemeinsam zu sprühtrocknen. Gleichfalls können bereits getrocknete Pulver der einzelnen Komponenten beispielsweise in einem Schaufelmischer der Fa.Lödige oder einem Sprühmischer der Fa.Schugi zu den Detergensgemischen verarbeitet werden. Zu Einzelheiten der Sprühtrocknung bzw. Sprühneutralisation von Tensiden sei auf ROEMPP Chemielexikon, 9. Aufl., Thieme-Verlag, Stuttgart, 1992, S.4259/4260 verwiesen.
  • b) Heißdampftrocknung. Unter dem Begriff "Heißdampftrocknung" ist eine spezielle Sprühtrocknung unter Ausschluß von Luftsauerstoff in Gegenwart von überhitztem Wasserdampf zu verstehen. Das Prinzip dieses neuartigen technischen Verfahrens ist von der Anmelderin in ihrer Deutschen Patentanmeldung DE-A1 40 30 688 offengelegt worden. Dem Verfahren liegt das Prinzip zugrunde, daß durch Kondensation des Heißdampfes auf dem kühleren Einsatzgut und Abgabe der Kondensationswärme an das zu trocknende Gut eine spontane Aufheizung des wäßrigen Tropfens auf die Siedetemperatur des Wassers unter Arbeitsbedingungen, bei Normaldruck also auf Temperaturen von etwa 100°C, stattfindet. Diese Siedetemperatur wird als Mindesttemperatur während des gesamten Trocknungszeitraums im Guttropfen beibehalten. Ein erwünschter Effekt der Heißdampftrocknung der erfindungsgemäß zu verwendenden Detergensgemische ist darin zu sehen, daß ein getrocknetes Gut mit hoher innerer Oberfläche gewonnen wird, welches sich besonders leicht in Wasser lösen bzw. dispergieren läßt.Grundsätzlich gilt, daß im geschlossenen System mit einem Wasserdampfkreislaufstrom gearbeitet wird, dem der verdampfte Wasseranteil des Einsatzgutes entzogen wird, während der insbesondere im Trocknungsschritt abgegebene Energiebetrag dem Kreislaufstrom wieder zugeführt wird. Während bei der konventionellen Sprühtrocknung ein Arbeiten bei höheren Temperaturen stets mit der Gefahr einer partiellen Verkohlung des zu trocknenden Gutes verbunden ist, macht hier die Abwesenheit von Luftsauerstoff Trocknungstemperaturen von 200 bis 250°C ohne weiteres möglich. Der abgezogene Wasserdampfteilstrom kann nach der Reinigung von mitgetragenen Gutanteilen vorteilhafterweise als Brauchdampf anderweitiger Verwendung zugeführt werden.
  • c) SKET-Granulierung. Eine weitere Möglichkeit besteht darin, die Detergensgemische einer sogenannten SKET-Granulierung zu unterwerfen. Hierunter ist eine Granulierung unter gleichzeitiger Trocknung zu verstehen, die vorzugsweise batchweise oder kontinuierlich in der Wirbelschicht erfolgt. Dabei können die Tenside vorzugsweise in Form wäßriger Pasten gleichzeitig oder nacheinander über eine oder mehrere Düsen in die Wirbelschicht eingebracht werden. Bevorzugt eingesetzte Wirbelschicht-Apparate besitzen Bodenplatten mit Abmessungen von 0,4 bis 5 m. Vorzugsweise wird die SKET-Granulierung bei Wirbelluftgeschwindigkeiten im Bereich von 1 bis 8 m/s durchgeführt. Der Austrag der Granulate aus der Wirbelschicht erfolgt vorzugsweise über eine Größenklassierung der Granulate. Die Klassierung kann beispielsweise mittels einer Siebvorrichtung oder durch einen entgegengeführten Luftstrom (Sichterluft) erfolgen, der so reguliert wird, daß erst Teilchen ab einer bestimmten Teilchengröße aus der Wirbelschicht entfernt und kleinere Teilchen in der Wirbelschicht zurückgehalten werden. Üblicherweise setzt sich die einströmende Luft aus der beheizten oder unbeheizten Sichterluft und der beheizten Bodenluft zusammen. Die Bodenlufttemperatur liegt dabei zwischen 80 und 400, vorzugsweise 90 und 350°C. Vorteilhafterweise wird zu Beginn der SKET-Granulierung eine Startmasse, beispielsweise Natriumsulfat oder ein SKET-Granulat aus einem früheren Versuchsansatz, vorgelegt. In der Wirbelschicht verdampft das Wasser aus der Tensidpaste, wobei angetrocknete bis getrocknete Keime entstehen, die mit weiteren Mengen Tensid umhüllt, granuliert und wiederum gleichzeitig getrocknet werden.
  • d) Extrusion. In einer weiteren bevorzugten Ausführungsform der Erfindung werden die Detergensgemische in einer Schneckenpresse homogenisiert und verfestigt. Die Extrusion erfolgt über eine Lochscheibe, so daß Preßstränge entstehen, die nach bekannten Verfahren zu Extrudaten oder Nadeln gewünschter Form und Abmessung mechanisch zerkleinert werden können.
  • e) Strukturbrecher. Schließlich besteht die Möglichkeit, die trockenen Detergensgemische mit hydrophoben Strukturbrechern, beispielsweise einem Anlagerungsprodukt von 3 Mol Ethylenoxid an einen C12/14-Kokosfettalkohol, zu vermischen und anschließend mechanisch zu verfestigen. Der flüssige Strukurbrecher wird vom trockenen Pulver aufgesogen und führt zu einer "Marmorierung" des Tensidkorns. Auf diese Weise werden beispielsweise nach Granulierung bzw. Extrusion Produkte mit besonders hoher innerer Oberfläche erhalten. Zur Verfestigung des Korns können ferner Polyethylenglycole mit Molekulargewichten im Bereich von 10.000 bis 100.000 zugesetzt werden.
    • The detergent mixtures according to the invention are preferably used in anhydrous form, for example in the form of powders, granules, extrudates or needles.
  • a) Spray neutralization / spray drying. Conventional techniques can be used to produce the powders. It is possible, for example, to subject the acid sulfation products of the fatty alcohols and fatty alcohol ethoxylates to a spray neutralization jointly or separately and to add anhydrous glycosides and / or polyhydroxy fatty acid amides to the dry powders. It is also possible to prepare aqueous mixtures of the components and to spray-dry them together. Likewise, already dried powders of the individual components can be processed into the detergent mixtures, for example in a blade mixer from Lödige or a spray mixer from Schugi. For details of the spray drying or spray neutralization of surfactants, reference is made to ROEMPP Chemistry Lexicon, 9th edition, Thieme-Verlag, Stuttgart, 1992, p.4259 / 4260 .
  • b) superheated steam drying. The term "superheated steam drying" is to be understood as a special spray drying in the absence of atmospheric oxygen in the presence of superheated steam. The principle of this new technical method has been disclosed by the applicant in its German patent application DE-A1 40 30 688 . The process is based on the principle that condensation of the superheated steam on the cooler feed and release of the heat of condensation to the material to be dried spontaneously heats the aqueous drop to the boiling point of the water under working conditions, i.e. at normal pressure to temperatures of about 100 ° C. takes place. This boiling temperature is maintained as a minimum temperature in the droplet during the entire drying period. A desired effect of the superheated steam drying of the detergent mixtures to be used according to the invention can be seen in the fact that a dried material with a high inner surface is obtained which is particularly easy to dissolve or disperse in water. The basic principle is that a steam system is used in a closed system , from which the evaporated water portion of the feed is withdrawn, while the amount of energy given off in particular in the drying step is fed back into the circulating stream. While conventional spray drying always involves working at higher temperatures with the risk of partial charring of the material to be dried, the absence of atmospheric oxygen makes drying temperatures of 200 to 250 ° C readily possible. The stripped water vapor partial stream can advantageously be used as service steam for other use after the cleaning of carried-along material portions.
  • c) SKET granulation. Another possibility is to subject the detergent mixtures to so-called SKET granulation. This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. The surfactants can be introduced into the fluidized bed, preferably in the form of aqueous pastes, simultaneously or successively via one or more nozzles. Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The SKET granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s. The granules are preferably discharged from the fluidized bed via a size classification of the granules. The classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. The inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. A starting mass, for example sodium sulfate or SKET granules from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation. In the fluidized bed, the water evaporates from the surfactant paste, producing dried to dried germs, which are coated with further amounts of surfactant, granulated and in turn dried at the same time.
  • d) extrusion. In a further preferred embodiment of the invention, the detergent mixtures are homogenized and solidified in a screw press. The extrusion is carried out via a perforated disc, so that press strands are formed which can be mechanically comminuted to extrudates or needles of the desired shape and dimension by known processes.
  • e) structure breaker . Finally, there is the possibility of mixing the dry detergent mixtures with hydrophobic structure breakers, for example an adduct of 3 moles of ethylene oxide with a C 12/14 coconut oil alcohol, and then mechanically solidifying them. The liquid structure breaker is absorbed by the dry powder and leads to a "marbling" of the tenside grain. In this way, products with a particularly high inner surface are obtained, for example, after granulation or extrusion. Polyethylene glycols with molecular weights in the range from 10,000 to 100,000 can also be added to solidify the grain.

    • Hilfs- und ZusatzstoffeAuxiliaries and additives

    Unter Hilfs- und Zusatzstoffen sind die nichttensidischen Bestandteile der Rezepturen handelsüblicher Toilettensteine zu verstehen, die mit den Detergensgemischen vermischt und anschließend in die gewünschte Form gebracht werden.Auxiliaries and additives include non-surfactants Components of the recipes for commercially available toilet blocks to understand that mixed with the detergent mixtures and then be brought into the desired shape.

    Die Detergensgemische werden in der Regel wasserfrei eingesetzt. Zur leichteren Plastifizierung kann ihnen jedoch als Hilfsstoff Wasser in einer Menge von 1 bis 10, vorzugsweise 2 bis 6 Gew.-% - bezogen auf die Mischung - zugesetzt werden.The detergent mixtures are usually used anhydrous. For easier plasticization, however, they can be used as Auxiliary water in an amount of 1 to 10, preferably 2 up to 6 wt .-% - based on the mixture - are added.

    Als weitere Hilfs- und Zusatzstoffe kommen aorganische Salze, insbesondere Natriumsulfat, Natriumcarbonat und/oder Natriumchlorid in Betracht, deren Anteil in Summe 25 bis 75, vorzugsweise 30 bis 60 Gew.-% - bezogen auf das Endprodukt - ausmachen kann. In einer bevorzugten Ausführungsform werden Detergensgemische in Form von SKET-Granulaten eingesetzt, die beispielsweise den erforderlichen Anteil an Natriumsulfat herstellungsbedingt enthalten.Other auxiliary substances and additives are inorganic salts, especially sodium sulfate, sodium carbonate and / or sodium chloride into consideration, their proportion in total 25 to 75, preferably 30 to 60% by weight - based on the end product - can make out. In a preferred embodiment Detergent mixtures in the form of SKET granules are used for example the required proportion of sodium sulfate included due to manufacturing.

    Von weiterer Bedeutung als Zusatzstoffe sind des ferner feste oder flüssige Builder, wie beispielsweise Zeolith A, Nitrilotriacetat, Ethylendiamintetraacetat oder Natriumcitrat. Ihre Anteile können 5 bis 15, vorzugsweise 8 bis 12 Gew.-% - bezogen auf das Endprodukt - ausmachen. Schließlich enthalten die Toilettensteine in aller Regel noch Farb- und Duftstoffe, üblicherweise in Mengen von 1 bis 5 Gew.-% - bezogen auf das Endprodukt.Of further importance as additives are also solid or liquid builders, such as, for example, zeolite A, nitrilotriacetate, Ethylenediaminetetraacetate or sodium citrate. Your Proportions can be 5 to 15, preferably 8 to 12% by weight on the end product - make up. Finally included the toilet blocks usually still contain colors and fragrances, usually in amounts of 1 to 5 wt .-% - based on the End product.

    Gewerbliche AnwendbarkeitIndustrial applicability

    Die erfindungsgemäßen Detergensgemische lassen sich als Tensidkomponenten zur Herstellung von Toilettensteinen einsetzen. Produkte auf dieser Basis zeichnen sich durch eine hohe Löslichkeitsverzögerung, d.h. lange Lebensdauer, eine verbesserte Schaumbeständigkeit und leichtere Verarbeitbarkeit aus.The detergent mixtures according to the invention can be used as Use surfactant components to manufacture toilet blocks. Products on this basis are characterized by a high solubility delay, i.e. long life, one improved foam resistance and easier processing.

    Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail, without referring thereto restrict.

    BeispieleExamples I. Rezepturen I. Recipes

    Erfindungsgemäße und Vergleichsrezepturen Prozentangaben als %-Aktivsubstanz; Parfum- und Farbstoffe ad % AktivsubstanzInvention and comparison formulations Percentages as% active substance; Perfume and colorants ad% active substance R1 % R1 % R2 % R2 % R3 % R3 % R5 % R5 % R5 % R5 % R6 % R6 % Sulfopon(R) LS 35Sulfopon (R) LS 35 2525th 2525th 2525th 2525th 2525th 2525th Texapon(R) N 70Texapon (R) N 70 66 44th 33rd 33rd 66 33rd Plantaren(R) APG 600Plantaren (R) APG 600 66 44th 33rd -- -- -- GlucamidGlucamide -- -- -- 33rd -- -- Maranil(R) A 55Maranil (R) A 55 -- -- -- -- -- 33rd Comperlan(R) 100Comperlan (R) 100 -- 1010th 99 99 99 99 Dehydol(R) TA 25Dehydol (R) TA 25 66 -- 33rd 33rd 33rd 33rd NatriumsulfatSodium sulfate 2525th 2525th 2525th 2525th 2525th 2525th NatriumchloridSodium chloride 2525th 2525th 2525th 2525th 2525th 2525th NatriumcitratSodium citrate 77 77 55 55 55 55 Legende: Sulfopon(R) LS 35 : C12/14-Kokosfettalkoholsulfat-Na-Salz; Texapon(R) N70 : C12/14-Kokosfettalkohol2EO-sulfat-Na-Salz; Plantaren(R) APG 600 : C12/14-Kokosalkyloligoglucosid (DP = 1,3); Glucamid : C12/14-Kokosfettsäure-N-methylglucamid Maranil(R) A55 : Dodecylbenzolsulfonat-Na-Salz; Comperlan(R) 100 : C12/14-Kokosfettsäureethanolamid; Dehydol(R) TA 25 : Talgalkohol25EO-Addukt; Produkte der Henkel KGaA, Düsseldorf/FRG. Legend: Sulfopon (R) LS 35 : C 12/14 coconut fatty alcohol sulfate Na salt; Texapon (R) N70 : C 12/14 coconut fatty alcohol 2EO sulfate Na salt; Plantaren (R) APG 600 : C 12/14 cocoalkyl oligoglucoside (DP = 1.3); Glucamide : C 12/14 coconut fatty acid N-methylglucamide Maranil ( R ) A55 : dodecylbenzenesulfonate Na salt; Comperlan (R) 100 : C 12/14 coconut fatty acid ethanolamide; Dehydol (R) TA 25 : tallow alcohol 25EO adduct; Products from Henkel KGaA, Düsseldorf / FRG.

    II. Anwendungstechnische Prüfung II. Application test

    Toilettensteine entsprechend der erfindungsgemäßen Rezepturen R1 bis R4 und der Vergleichsrezepturen R5 und R6 wurden nach folgenden Kriterien beurteilt:

  • a) Verarbeitbarkeit (V):
       I (weniger hart) bis VI (extrem hart)
  • b) Zusammenhalt der Masse (Z):
       I (sehr leicht formbar) bis VI (praktisch nicht formbar)
  • c) Lebensdauer (Zahl der Spülungen, L)
  • d) Basisschaum der Detergensmischung (S0) sowie Schaumhöhe nach 20 min (S20) gemäß der Schlagschaummethode (DIN 53 902-II).
    • Toilet stones according to the formulations R1 to R4 according to the invention and the comparative formulas R5 and R6 were assessed according to the following criteria:
  • a) Processability (V):
    I (less hard) to VI (extremely hard)
  • b) Cohesion of the mass (Z):
    I (very easy to form) to VI (practically not formable)
  • c) service life (number of rinses, L)
  • d) Base foam of the detergent mixture (S 0 ) and foam height after 20 min (S 20 ) according to the whipped foam method (DIN 53 902-II).

    • Die Ergebnisse sind in Tab.2 zusammengefaßt: Anwendungstechnische Prüfungenn Bsp. Rezeptur V Z L S0 ml S20 ml 1 R1 II II 530 110 90 2 R2 II I 520 110 90 3 R3 I I 550 110 90 4 R4 I II 525 110 95 V1 R5 III II 278 50 20 V2 R6 VI V 212 80 70 The results are summarized in Tab. 2: Application tests E.g. Recipe V Z. L S 0 ml S 20 ml 1 R1 II II 530 110 90 2nd R2 II I. 520 110 90 3rd R3 I. I. 550 110 90 4th R4 I. II 525 110 95 V1 R5 III II 278 50 20th V2 R6 VI V 212 80 70

    Claims (5)

    1. The use of detergent mixtures for the production of toilet blocks containing
      a) fatty alcohol sulfates corresponding to formula (I): R1O-SO3X in which R1 is a linear or branched alkyl and/or alkenyl radical containing 6 to 18 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium,
      b) fatty alcohol ether sulfates corresponding to formula (II): R2O-(CH2CH2O)mSO3X in which R2 is a linear or branched alkyl and/or alkenyl radical containing 6 to 18 carbon atoms, m is a number of 1 to 10 and X is an alkali or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium, and
      c1) alkyl and/or alkenyl oligoglycosides corresponding to formula (III): R3-O-[G]p in which R3 is an alkyl and/or alkenyl radical containing 6 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10, and/or
      C2) fatty acid N-alkyl polyhydroxyalkyl amides corresponding to formula (IV):
      Figure 00240001
      in which R4CO is an aliphatic acyl radical containing 6 to 22 carbon atoms, R5 is hydrogen, an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical containing 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
    2. The use claimed in claim 1, characterized in that the detergent mixtures contain as further constituents fatty acid alkanolamides corresponding to formula (VI):
      Figure 00240002
      in which R6CO is an aliphatic acyl radical containing 6 to 22 carbon atoms, Z1 is a hydroxyalkylene radical containing 2 to 4 carbon atoms and Z2 has the same meaning as Z1 or is hydrogen.
    3. The use claimed in claims 1 and 2, characterized in that the detergent mixtures contain as further constituents fatty alcohol ethoxylates corresponding to formula (VII): R7O-(CH2CH2O)nH in which R7 is a linear or branched alkyl and/or alkenyl radical containing 12 to 18 carbon atoms and n is a number of 20 to 50.
    4. The use claimed in claims 1 to 3, characterized in that the detergent mixtures contain
      50 to 98% by weight    of fatty alcohol sulfates,
      1 to 15% by weight    of fatty alcohol ether sulfates,
      1 to 15% by weight    of alkyl and/or alkenyl oligoglycosides and/or
      1 to 15% by weight of fatty acid N-alkyl polyhydroxyalkyl amides, with the proviso that the quantities add up to 100% by weight.
    5. The use claimed in claims 1 to 4, characterized in that the detergent mixtures are used in the form of powders, granules, extrudates or needles.
    EP94930200A 1993-10-29 1994-10-20 Use of detergent mixtures for toilet freshening blocks Expired - Lifetime EP0725813B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE4337032A DE4337032C1 (en) 1993-10-29 1993-10-29 Use of detergent mixtures for the production of toilet blocks
    DE4337032 1993-10-29
    PCT/EP1994/003456 WO1995011958A1 (en) 1993-10-29 1994-10-20 Use of detergent mixtures for toilet freshening blocks

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    EP0725813A1 EP0725813A1 (en) 1996-08-14
    EP0725813B1 true EP0725813B1 (en) 1998-05-20

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    EP (1) EP0725813B1 (en)
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    DE (2) DE4337032C1 (en)
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    DK0725813T3 (en) 1999-03-08
    ATE166384T1 (en) 1998-06-15
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    DE59406050D1 (en) 1998-06-25

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