EP0997521A1 - Detergent compositions containing alkoxylated fatty acid alkyl esters - Google Patents

Detergent compositions containing alkoxylated fatty acid alkyl esters Download PDF

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Publication number
EP0997521A1
EP0997521A1 EP99120730A EP99120730A EP0997521A1 EP 0997521 A1 EP0997521 A1 EP 0997521A1 EP 99120730 A EP99120730 A EP 99120730A EP 99120730 A EP99120730 A EP 99120730A EP 0997521 A1 EP0997521 A1 EP 0997521A1
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EP
European Patent Office
Prior art keywords
fatty acid
acid alkyl
alkyl ester
detergent
groups
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Withdrawn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
EP99120730A
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German (de)
French (fr)
Inventor
Cheryl Ann Dr. Littau
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.)
Clariant Finance BVI Ltd
Original Assignee
Clariant GmbH
Clariant Finance BVI Ltd
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Filing date
Publication date
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Publication of EP0997521A1 publication Critical patent/EP0997521A1/en
Withdrawn legal-status Critical Current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
    • 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
    • C11D1/02—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
    • C11D1/143—Sulfonic 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the invention relates to solid and liquid detergents and cleaning agents containing Fatty acid alkyl ester alkoxylates with a very narrow homolog distribution as Skin-friendly, low-foaming and environmentally compatible surfactant with one very good washing power and good solubility behavior.
  • anionic surfactants for example alkyl sulfates in high Concentrations, that is, in amounts above 8 wt .-%, especially in Combination with nonionic surfactants to form a strong gel and thus worse Can be washed in the washing machine.
  • WO 93/02176 a method for the production of solid washing and Detergent with a high bulk density proposed, in which one for Improving the dissolution behavior of structure breakers, for example Polyethylene glycol or polypropylene glycol, their sulfates and / or disulfates, Sulfosuccinate and / or sulfosuccinate or mixtures thereof is used.
  • structure breakers for example Polyethylene glycol or polypropylene glycol, their sulfates and / or disulfates, Sulfosuccinate and / or sulfosuccinate or mixtures thereof is used.
  • solubility of solid detergents and cleaning agents can also be increased the surfactant content, especially through the use of non-ionic surfactants, such as. ethoxylated fatty alcohols can be improved. Adhesion is disadvantageous the solid detergent particles, which makes them free-flowing and washable is affected.
  • Ethoxylated fatty alcohols in liquid concentrates tend to dilute to form a gel phase with water.
  • Other surfactant systems in washing and Detergents give the agent good solubility, but show one poorer washing power, so that larger amounts of detergents and cleaning agents must be used.
  • Another goal in the manufacture of detergents and cleaning agents is to use detergents with high levels of active detergent and low foaming.
  • EP-A-0 814 152 describes the production of solid detergents and cleaning agents containing, as an anionic surfactant, C 8 -C 22 alkyl sulfates in solid form and 3 to 20% by weight, based on the C 8 -C 22 alkyl sulfates , Carboxylic acid alkyl ester alkoxylates.
  • DE-A-195 09 752 claims a process for the production of compressed washing and cleaning agents with a high bulk density, anionic surfactants, builder substances and alkalizing agents being used as solid constituents and nonionic surfactants with more than 50% by weight of fatty acid alkyl ester alkoxylates as liquid constituents the non-ionic surfactant content can be used.
  • WO 96/05284 describes non-aqueous bleaching liquid washing and Cleaning agents containing 20 to 78% by weight of nonionic surfactants are preferred Fatty acid methyl ester ethoxylates.
  • Fatty acid alkyl ester alkoxylates can, according to the information given there, in accordance with Methods described by WO 91/15441 and WO 90/13533 by alkoxylation of Fatty acid esters in the presence of hydrophobicized hydrotalcites or calcined Hydrotalcites can be produced as catalysts.
  • US-A-5 220 046 and US-A-5 386 045 show that the alkoxylation of Fatty acid alkyl esters in the presence of the catalysts sodium hydroxide, Sodium methoxide or hydrotalcites to products with a high percentage of not converted fatty acid alkyl ester and a relatively wide distribution Fatty acid alkyl ester alkoxylates leads.
  • the object of the invention was to liquid and solid washing and To develop cleaning agents that have good solubility and low gel formation, low foaming and at the same time improved washing performance show the state of the art.
  • the invention relates to detergents and cleaning agents, the fatty acid alkyl ester alkoxylates of the formula 1 R 1 - COO (AO) n -R 2 contain, wherein R 1 is a straight-chain or branched alkyl or alkenyl group having 5 to 22, preferably 8 to 18 carbon atoms, R 2 C 1 -C 6 alkyl or C 2 -C 6 alkenyl, preferably methyl, AO a C.
  • n is a number from 1 to 20, preferably 3 to 12, in particular 4 to 10, and these fatty acid alkyl ester oxalkylates contain less than 14% by weight of compounds containing not more than (a - 3 ) -AO groups and less than 16 wt .-% of compounds containing not less than (a + 3) -AO groups, where a denotes the number of -AO groups with the maximum frequency.
  • the narrow homolog distribution of the alkoxylation products as defined above is essential for the present invention.
  • the amount of the alkoxylated analog compounds which contain 7 and less than 7 -AO groups (a - 3) should be less than 14% by weight.
  • the amount of alkoxylated compounds with a degree of alkoxylation of 13 or more than 13 should be less than 16% by weight.
  • the homolog distribution thus defined is significantly narrower than that of the fatty acid alkyl ester oxyalkylates, as is the case with the products obtained by the method described in WO 90/13533 and WO 91/15441 and the connections defined here with the narrower homolog distribution are characterized by a much better washing performance and a low Gel formation during the dissolving process.
  • the compounds of formula 1 thus defined are hereinafter referred to as "narrow range" fatty acid alkyl ester alkoxylates.
  • the “narrow range" fatty acid alkyl ester alkoxylates of the formula 1 used in the washing and cleaning agents according to the invention with the specified narrow homolog distribution can be prepared by two different methods: 1. By alkoxylation, especially ethoxylation of fatty acid alkyl esters in the presence of a catalyst or a catalyst mixture.
  • the following catalysts are suitable: alkaline earth metal salts from monoesters Dicarboxylic acids and oxalkylated alcohols as described in EP-A-337 239.
  • the non-esterified carboxyl group is completely in the form of the alkaline earth metal salt transferred.
  • alkoxylation catalysts are partially neutralized Alkaline earth metal salts of dicarboxylic acid half esters as described in DE 198 07 991.5.
  • “Narrow range” fatty acid alkyl ester alkoxylates of the formula 1 can also be obtained by direct esterification of "narrow range” alkoxylated alkyl alcohols or Hydroxyalkyl alcohols, for example methyl polyglycols with fatty acid in Be prepared in the presence of an acid catalyst.
  • Acidic catalysts which can be used are those customary for esterifications, such as sulfuric acid, p-toluenesulfonic acid, alkylsulfonic acids, alkylarylsulfonic acids, ZnCl 2 , phosphoric acids, etc.
  • washing and cleaning agents according to the invention can be in the form of powder, granular and tablet-shaped, i.e. as solid washing and cleaning agents are present or as liquid formulations, for example as dishwashing detergents.
  • a method for producing powders is preferred, with a first being a Premix of detergent ingredients without fatty acid alkyl ester alkoxylate is produced and then the fatty acid alkyl ester alkoxylate is sprayed on.
  • powdered detergents and cleaning agents can be used can be prepared by heating the alkoxylate, if necessary by heating low viscosity, sprayed in the spray tower and solid at the same time
  • Detergent ingredients for example zeolites, diatomaceous earth, magnesium aluminum, Sodium or calcium aluminum silicates, activated silica or aluminum oxide added.
  • both methods can be combined, so that one after the first Powder coated with fatty acid alkyl ester alkoxylate in one process second step, a fatty acid alkyl ester alkoxylate sprayed in the spray tower becomes.
  • a mixing unit e.g. Ploughshare mixer
  • the mixture of fatty acid alkyl ester alkoxylates and powdery mixtures of solid and liquid washing and Detergent ingredients mixed intimately In a second step this will be The mixture is compressed into larger particles. Suitable for this include Roller compactors. The compacts are then crushed Subjected (grinding) and crushed to the desired grain size. To this Toothed pulley rollers and / or strainers are suitable for this purpose.
  • Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-shredded, the fine fraction is added to the compacting stage.
  • the grain size of the product is generally in the range from 100 to 2000 ⁇ m, preferably 300 to 1800 ⁇ m.
  • the bulk density of the granules according to the invention is above 500 kg / m 3 , preferably above 600 kg / m 3 .
  • a method for the production of molded granules, a method is preferred in which Fatty acid alkyl ester alkoxylates together with other liquid and solid Detergent ingredients homogeneously mixed and with the addition of a plasticizer and / or Sliding center over hole shapes with opening widths of the predetermined Pellet size at high pressures between 25 and 200 bar in string form pressed.
  • the strand is cut directly after leaving the hole shape by means of a Cutting device cut to the predetermined granule dimension.
  • Plasticizers and / or lubricants become aqueous solutions of polymers Polycarboxylates as well as highly concentrated anionic surfactant pastes and non-ionic Preferred surfactants.
  • the granules obtained in this way can be used directly in washing and Suitable detergents. You can also add a coating sleeve become.
  • the granulate according to the invention is treated in an additional step with a film-forming substance envelops, making the product properties significant can be influenced.
  • All film-forming substances, nonionic are suitable as coating agents
  • Surfactants for example fatty acid alkyl ester oxyalkylates, anionic surfactants and cationic surfactants, as well as anionic and cationic polymers, e.g. E.g. Polyacrylic acid, waxes, silicones, fatty acids and soaps.
  • anionic and cationic polymers e.g. E.g. Polyacrylic acid, waxes, silicones, fatty acids and soaps.
  • Coating substances with a melting point of 30 - 100 ° C are used.
  • the use of these coating materials can include Dissolution behavior influenced the dust content is reduced, the abrasion resistance is increased and the Storage stability can be improved. Should the granules in dishwasher detergents Waxes with melting points of are particularly suitable for this purpose 40 to 50 ° C.
  • the coating materials are usually applied by Spray on the melted or dissolved in a solvent Coating materials.
  • the coating material can be used in amounts of 0-20, preferably 1 - 10 wt .-%, based on the total weight, applied to the granulate core become.
  • Tablets can be prepared, for example, in such a way that Builder substances, for example zeolites, diatomaceous earth, magnesium aluminum, Sodium or calcium aluminum silicates, activated silica or aluminum oxide metered in, as well as all other components such as surfactants, enzymes, bleach activators, Brightener etc. homogeneously mixed together and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic Presses or rotary presses with pressures in the range of 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 50 bar pressed.
  • the Compression provided premixes, however, by mixing the individual Ingredients that are at least partially in pre-assembled form as granular Compound present, are produced. These include, for example roller-compacted crystalline layered or amorphous sodium disilicates, the optionally with liquid to waxy components, for example have been impregnated with nonionic surfactants.
  • the "narrow range" fatty acid alkyl ester alkoxylates can be used alone or in a mixture with other nonionic surfactants are used, for example with alkyl and / or Alkenyl oligoglycosides, fatty alcohol polyglycol ethers, Alkylphenol polyglycol ethers, fatty acid polyglycol esters, Fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, fatty acid glucamides, poly oil fatty acid esters, sugar esters, Sorbitan esters and polysorbates and / or alkoxylated fatty alcohols.
  • nonionic surfactants also include the usual ones Fatty acid alkyl ester oxyalkylates with a broad homolog distribution.
  • the share of the "narrow range" Fatty acid alkyl ester alkoxylates in the total amount of nonionic surfactants can 10 to 100, preferably 35 to 95, in particular 45 to 90% by weight.
  • Structural breakers in particular ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol can be used as further components or polypropylene glycol or mixtures of these can be used.
  • Other suitable disintegrants are physically modified disintegrants such as sorbitols, dextrins, in particular maltodextrins.
  • the nonionic surfactants and the structure breakers can be used in a weight ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.
  • anionic surfactants can be included.
  • anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, alkyl polyglycol ether sulfonates, glycerin ether sulfonates, alpha methyl ester sulfonates, sulfo fatty acids, alkyl sulfate sulfate, sulfate ether sulfates, hydroxymethane sulfates, hydroxymate sulfates , C 6 -C 18 fatty acid amide ether sulfates, fatty acid soaps, alkyl carboxylates, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates, acyl lact
  • secondary C 8 -C 12 - in addition to the "narrow-range fatty acid alkyl ester alkoxylates and also other nonionic surfactants, secondary C 8 -C 12 -, in particular C 12 -C 18 alkanesulfonate, for example that available under the trade name Hostapur SAS (Clariant GmbH), optionally in a mixture with C 8 -C 18 , in particular C 12 -C 16 ether sulfate, but also alkylbenzenesulfonates, primary and secondary alkyl sulfates and fatty acid ester sulfonates are used as anionic surfactants.
  • the content of anionic surfactants is 2 to 50% by weight, preferably 5 to 40 wt .-%, in particular 8 to 30 wt .-%, based on the total amount of Surfactants.
  • amphoteric or zwitterionic surfactants such as alkyl betaines, alkyl amido betaines, Aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
  • the solid washing and cleaning agents according to the invention can be conventional builders in amounts of 2 to 80% by weight, preferably in an amount of 15 to 65 wt .-%, based on the agent included.
  • Suitable builders are zeolites, amorphous alkali silicates, carbonate-silicate compounds, crystalline silicates, preferably layered silicates, for example d-disilicate (Clariant GmbH) available under the trade name SKS-6, Diatomaceous earth, magnesium aluminum, sodium or calcium aluminum silicates, activated silica, aluminum oxide or mixtures of the above Substances.
  • Polymeric carboxylates or polymeric substances can also be used as additional structural substances Carboxylic acids in the amounts 2 to 15 wt .-%, based on the total proportion, be included.
  • Carboxylic acids in the amounts 2 to 15 wt .-%, based on the total proportion, be included.
  • Polymeric carboxylates or polymeric carboxylic acids come along a relative molar mass of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, into consideration, such as Polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular Copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 up to 120,000, based on the free acid.
  • Copolymers of are also suitable Acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, Ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight is.
  • terpolymers can also be used become.
  • These organic builders can be used in an amount of 2 to 20% by weight, preferably 5 to 15 wt .-%, based on the agent.
  • organic framework substances are, for example, those in the preferred form their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, Nitriloacetic acid and mixtures thereof.
  • polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, Nitriloacetic acid and mixtures thereof.
  • the detergents according to the invention preferably contain peroxy bleaches and in particular bleaches in combination with bleach activators.
  • bleach activators are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular N, N, N ', N''- tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglucoluril (TAGU), N-acylated hydantoins, Triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodiumisononanoyloxybenzenesulfonate and acylated sugar derivatives, especially pentaacetylglycose, glucose pentaacetate (GPA), sodium benzoxetoyl (TAA), xoxybenzoyl oxybenzoyl oxybenzoyl (benzo) oxybenzoyl (benzo)
  • dirt-removing polymers in particular Polymers containing ethylene terephthalate, polyoxyethylene terephthalate, propylene glycol, Polypropylene glycol, alkylene or alkylene dicarboxylic acids, isophthalic acid, carboxy or sulfo-substituted phthalic acid isomers as monomer units and also End-capped derivatives included.
  • salts or adjusting agents are alkali sulfates, alkali carbonates, Alkali bicarbonates, amorphous silicates or mixtures thereof.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, optionally silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanized silica, as well as mixtures of silicone oil, paraffin oil or waxes.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases, peroxidases or oxidases or their mixtures in question.
  • the amount the enzyme can be 0.2 to 8% by weight, preferably 0.1 to 3% by weight.
  • composition SKS-6 20% Zeolite 23% Hostapur SAS (powder) 10% Sodium soap 2% C 12 -C 14 + 7.5 EO NRFAAEE 15% Perborate 15% TAED 5% PEG 600 3% citric acid 3.5% Sodium bicarbonate 2.0% Strength 1.0% Defoamer 0.5%
  • composition SKS-6 20% Zeolite 23% C 10 -C 14 LAS 10% Sodium soap 1 % C 12 -C 14 + 7.5 EO NRFAAEE 12% C 12 -C 14 + 4 EO NRFAAEE 5% Perborate 15% TAED 5% citric acid 3.5% Sodium bicarbonate 4% Strength 1.0% Defoamer 0.5%
  • composition C 10 -C 14 LAS 9.0% C 8 -C 18 + 8 EO NRMEE 10% Soap 15% Genapol LA 050 3.0% Citric acid, sodium salt 3.0% borax 1.0% Enzymes Sodium sulfate 1.0% optical brightener Perfume, dye water 58%
  • Liquid detergent concentrate non-aqueous
  • composition C 10 -C 14 LAS 5.0% C 8 -C 18 + 7.5 EO NRMEE 30% C 8 -C 18 + 5 EO NRMEE 10% Soap 0.5% Genapol LA 050 7.0% Citric acid, sodium salt 12.0% SKS-6 6.0% Enzymes Perborate (monohydrate) 20% TAED 6% SRC-1 2% Enzymes 1 % optical brighteners 0.5%

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Abstract

Dishwasher and laundry detergent compositions contain narrow-range fatty acid alkyl ester alkoxylates. Detergent compositions contain fatty acid alkyl ester alkoxylates of formula (I): R<1>-COO(AO)m-R<2> (I) R<1> = 5-22C (preferably 7-17C) alkyl or alkenyl; R<2> = 1-6C alkyl, preferably Me or Et; AO = a 2-4C alkylene oxide unit; m = 1-20, preferably 5-12); provided that the alkoxylates include less than 14 wt.% of compounds containing (a-3) or fewer AO groups and less than 16 wt.% of compounds containing (a+3) or more AO groups, where a is the median number of AO groups.

Description

Die Erfindung betrifft feste und flüssige Wasch- und Reinigungsmittel, enthaltend Fettsäurealkylesteralkoxylate mit sehr enger Homologenverteilung als hautfreundliches, wenig schäumendes und umweltverträgliches Tensid mit einem sehr guten Waschvermögen und gutem Löslichkeitsverhalten.The invention relates to solid and liquid detergents and cleaning agents containing Fatty acid alkyl ester alkoxylates with a very narrow homolog distribution as Skin-friendly, low-foaming and environmentally compatible surfactant with one very good washing power and good solubility behavior.

Moderne Wasch- und Reinigungsmittel, sowohl in fester als auch in flüssiger Form, kommen als Formulierungen mit hohen Konzentrationen an Waschaktivsubstanzen in den Handel. Vorteilhaft ist hierbei die Minimierung von Transport-, Lager- und Verpackungskosten, sowie eine verbesserte Handhabung für den Verbraucher. Problematisch für den Hersteller von Flüssigkonzentraten und festen, insbesondere verpreßten Produkten mit hohen Tensidgehalten ist jedoch ein ungünstiges Löseverhalten in wäßriger Flotte.Modern washing and cleaning agents, both in solid and in liquid form, come as formulations with high concentrations of detergent substances in the trade. The minimization of transport, storage and Packaging costs, as well as improved handling for the consumer. Problematic for the manufacturer of liquid concentrates and solid, in particular pressed products with high surfactant contents is an unfavorable one Dissolving behavior in an aqueous liquor.

Es ist bekannt, daß Aniontenside, beispielsweise Alkylsulfate in hohen Konzentrationen, das heißt, in Mengen oberhalb 8 Gew.-%, insbesondere in Kombination mit Niotensiden zu einer starken Gelbildung und damit schlechter Einspülbarkeit in der Waschmaschine führen.It is known that anionic surfactants, for example alkyl sulfates in high Concentrations, that is, in amounts above 8 wt .-%, especially in Combination with nonionic surfactants to form a strong gel and thus worse Can be washed in the washing machine.

Um Gelbildung bei der Herstellung oder Lagerung von Flüssigwaschmittel zu vermeiden und geeignete Viskositäten der Formulierungen zu erreichen, werden häufig nichtoberflächenaktive organische Lösungsmittel zugesetzt. So werden in den Schriften WO 98/00510 und WO 98/00511 nichtwäßrige Flüssigwaschmittel beschrieben, die als Löslichkeitsvermittler annähernd 20 Gew.-% Polyethylenglykole oder Glykolether enthalten. Wünschenswert ist, auf Verbindungen verzichten zu können, die kein oder wenig Waschaktivvermögen zeigen. To prevent gel formation in the manufacture or storage of liquid detergents avoid and achieve suitable viscosities of the formulations often non-surfactant organic solvents added. So be in the documents WO 98/00510 and WO 98/00511 non-aqueous liquid detergents described that as a solubilizer, approximately 20 wt .-% polyethylene glycols or contain glycol ether. It is desirable to avoid connections who show little or no detergent power.

In WO 93/02176 wird ein Verfahren zur Herstellung von festen Wasch- und Reinigungsmitteln mit hohem Schüttgewicht vorgeschlagen, worin man zur Verbesserung des Auflöseverhaltens Strukturbrecher, beispielsweise Polyethylenglykol oder Polypropylenglykol, deren Sulfate und/oder Disulfate, Sulfosuccinate und/oder Sulfosuccinate oder Mischungen aus diesen einsetzt.In WO 93/02176 a method for the production of solid washing and Detergent with a high bulk density proposed, in which one for Improving the dissolution behavior of structure breakers, for example Polyethylene glycol or polypropylene glycol, their sulfates and / or disulfates, Sulfosuccinate and / or sulfosuccinate or mixtures thereof is used.

Die Löslichkeit der festen Wasch- und Reinigungsmittel kann auch durch Erhöhung des Tensidgehaltes, insbesondere durch den Einsatz von nichtionischen Tensiden, wie z.B. ethoxilierten Fettalkoholen verbessert werden. Nachteilig ist ein Verkleben der festen Waschmittelteilchen, wodurch die Rieselfähigkeit und die Einspülbarkeit beeinträchtigt wird.The solubility of solid detergents and cleaning agents can also be increased the surfactant content, especially through the use of non-ionic surfactants, such as. ethoxylated fatty alcohols can be improved. Adhesion is disadvantageous the solid detergent particles, which makes them free-flowing and washable is affected.

Ethoxylierte Fettalkohole in Flüssigkonzentraten tendieren dazu, beim Verdünnen mit Wasser eine Gelphase zu bilden. Andere Tensidsysteme in Wasch- und Reinigungsmittel verleihen dem Mittel zwar eine gute Löslichkeit, zeigen aber eine schlechtere Waschkraft, so daß größere Mengen an Wasch- und Reinigungsmittel eingesetzt werden müssen.Ethoxylated fatty alcohols in liquid concentrates tend to dilute to form a gel phase with water. Other surfactant systems in washing and Detergents give the agent good solubility, but show one poorer washing power, so that larger amounts of detergents and cleaning agents must be used.

Ein weiteres Ziel bei der Herstellung von Wasch- und Reinigungsmitteln ist es, Mittel mit hohen Waschaktivsubstanzgehalten und geringe Schaumbildung zu liefern.Another goal in the manufacture of detergents and cleaning agents is to use detergents with high levels of active detergent and low foaming.

In der japanischen Patentanmeldung Heisei 6-116 599 werden granulatförmige Waschmittel beschrieben, die zur Verbesserung der Löslichkeit als nichtionische Tenside Fettsäurealkylesteralkoxylate enthalten.
EP-A-0 814 152 beschreibt die Herstellung von festen Wasch- und Reinigungsmitteln, enthaltend als anionisches Tensid C8-C22-Alkylsulfate in fester Form und 3 bis 20 Gew.-%, bezogen auf die C8-C22-Alkylsulfate, Carbonsäurealkylesteralkoxylate.
In DE-A-195 09 752 wird ein Verfahren zur Herstellung von verpreßten Wasch- und Reinigungsmittel mit hohem Schüttgewicht beansprucht, wobei als feste Bestandteile Aniontenside, Buildersubstanzen und Alkalisierungsmittel und als flüssige Bestandteile Niotenside mit mehr als 50 Gew.-% Fettsäurealkylesteralkoxylaten, bezogen auf den Niotensidanteil eingesetzt werden.The Japanese patent application Heisei 6-116 599 describes granular detergents which contain fatty acid alkyl ester alkoxylates to improve solubility as nonionic surfactants.
EP-A-0 814 152 describes the production of solid detergents and cleaning agents containing, as an anionic surfactant, C 8 -C 22 alkyl sulfates in solid form and 3 to 20% by weight, based on the C 8 -C 22 alkyl sulfates , Carboxylic acid alkyl ester alkoxylates.
DE-A-195 09 752 claims a process for the production of compressed washing and cleaning agents with a high bulk density, anionic surfactants, builder substances and alkalizing agents being used as solid constituents and nonionic surfactants with more than 50% by weight of fatty acid alkyl ester alkoxylates as liquid constituents the non-ionic surfactant content can be used.

WO 96/05284 beschreibt nicht-wäßrige bleichmittelhaltige flüssige Wasch- und Reinigungsmittel, enthaltend 20 bis 78 Gew.-% nichtionische Tenside, bevorzugt Fettsäuremethylesterethoxylate.WO 96/05284 describes non-aqueous bleaching liquid washing and Cleaning agents containing 20 to 78% by weight of nonionic surfactants are preferred Fatty acid methyl ester ethoxylates.

Die in DE-A-195 09 752 und in WO 96/05284 genannten Fettsäurealkylesteralkoxylate können gemäß den dortigen Angaben nach dem in WO 91/15441 und WO 90/13533 beschriebenen Verfahren durch Alkoxylierung von Fettsäureestern in Gegenwart von hydrophobierten Hydrotalciten oder calcinierten Hydrotalcite als Katalysatoren hergestellt werden.Those mentioned in DE-A-195 09 752 and in WO 96/05284 Fatty acid alkyl ester alkoxylates can, according to the information given there, in accordance with Methods described by WO 91/15441 and WO 90/13533 by alkoxylation of Fatty acid esters in the presence of hydrophobicized hydrotalcites or calcined Hydrotalcites can be produced as catalysts.

In US-A-5 220 046 und US-A-5 386 045 wird gezeigt, daß die Alkoxylierung von Fettsäurealkylestern in Gegenwart der Katalysatoren Natriumhydroxid, Natriummethoxid oder Hydrotalciten zu Produkten mit einem hohen Anteil an nicht umgesetztem Fettsäurealkylester und einer relativ breiten Verteilung an Fettsäurealkylesteralkoxylaten führt.US-A-5 220 046 and US-A-5 386 045 show that the alkoxylation of Fatty acid alkyl esters in the presence of the catalysts sodium hydroxide, Sodium methoxide or hydrotalcites to products with a high percentage of not converted fatty acid alkyl ester and a relatively wide distribution Fatty acid alkyl ester alkoxylates leads.

Die Aufgabe der Erfindung lag darin, flüssige und feste Wasch- und Reinigungsmittel zu entwickeln, die eine gute Löslichkeit und geringe Gelbildung, geringe Schaumbildung und gleichzeitig eine verbesserte Waschleistung gegenüber dem Stand der Technik zeigen.The object of the invention was to liquid and solid washing and To develop cleaning agents that have good solubility and low gel formation, low foaming and at the same time improved washing performance show the state of the art.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß man wäßrige oder nicht-wäßrige Wasch- und Reinigungsmittel herstellt, die solche Fettsäurealkylesteralkoxylate enthalten, die im Vergleich zum Stand der Technik eine wesentlich engere Homologenverteilung haben.The object is achieved in that aqueous or non-aqueous Detergents and cleaning agents manufactures such Fatty acid alkyl ester alkoxylates contain compared to the prior art have a much narrower homolog distribution.

Gegenstand der Erfindung sind Wasch- und Reinigungsmittel, die Fettsäurealkylesteralkoxylate der Formel 1 R1- COO(AO)n -R2 enthalten, wobei R1 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 5 bis 22, vorzugsweise 8 bis 18 C-Atomen, R2 C1-C6-Alkyl oder C2-C6-Alkenyl, vorzugsweise Methyl, AO eine C2-C4-Alkylenoxid-Einheit und n eine Zahl von 1 bis 20, vorzugsweise 3 bis 12, insbesondere 4 bis 10 bedeuten und diese Fettsäurealkylesteroxalkylate weniger als 14 Gew.-% an Verbindungen mit einem Gehalt von nicht mehr als (a - 3) -AO-Gruppen und weniger als 16 Gew.-% an Verbindungen mit einem Gehalt von nicht unter (a + 3) -AO-Gruppen, wobei a die Anzahl der -AO-Gruppen mit der maximalen Häufigkeit bezeichnet, enthalten.The invention relates to detergents and cleaning agents, the fatty acid alkyl ester alkoxylates of the formula 1 R 1 - COO (AO) n -R 2 contain, wherein R 1 is a straight-chain or branched alkyl or alkenyl group having 5 to 22, preferably 8 to 18 carbon atoms, R 2 C 1 -C 6 alkyl or C 2 -C 6 alkenyl, preferably methyl, AO a C. 2 -C 4 alkylene oxide unit and n is a number from 1 to 20, preferably 3 to 12, in particular 4 to 10, and these fatty acid alkyl ester oxalkylates contain less than 14% by weight of compounds containing not more than (a - 3 ) -AO groups and less than 16 wt .-% of compounds containing not less than (a + 3) -AO groups, where a denotes the number of -AO groups with the maximum frequency.

Wesentlich für die vorliegende Erfindung ist die enge Homologenverteilung der Alkoxylierungsprodukte wie zuvor definiert. Diese Definition soll im folgenden für eine Verbindung der Formel 1 mit der maximalen Häufigkeit der -AO-Gruppen von 10
(a = 10) näher erläutert werden. Für diesen Fall soll die Menge der alkoxylierten analogen Verbindungen, die 7 und weniger als 7 -AO-Gruppen enthalten (a - 3), weniger als 14 Gew.-% betragen. Umgekehrt soll die Menge der alkoxylierten Verbindungen mit einem Alkoxylierungsgrad von 13 oder mehr als 13 weniger als 16 Gew.-% betragen.The narrow homolog distribution of the alkoxylation products as defined above is essential for the present invention. This definition is intended in the following for a compound of formula 1 with the maximum frequency of the -AO groups of 10
(a = 10) are explained in more detail. In this case, the amount of the alkoxylated analog compounds which contain 7 and less than 7 -AO groups (a - 3) should be less than 14% by weight. Conversely, the amount of alkoxylated compounds with a degree of alkoxylation of 13 or more than 13 should be less than 16% by weight.

Entsprechendes gilt für die Fettsäurealkytesteralkoxylate mit anderen Zahlen für die maximale Häufigkeit der -AO-Gruppen. Die so definierte Homologenverteilung ist deutlich enger als bei den Fettsäurealkylesteroxalkylaten, wie sie bei den Produkten nach dem in WO 90/13533 und WO 91/15441 beschriebenen Verfahren erhalten werden und die hier definierten Verbindungen mit der engeren Homologenverteilung zeichnen sich aus durch eine wesentlich bessere Waschleistung sowie eine geringe Gelbildung beim Lösevorgang. Die so definierten Verbindungen der Formel 1 sind im folgenden als "narrow range" Fettsäurealkylesteralkoxylate bezeichnet.The same applies to the fatty acid alkoxylates with different numbers for the maximum frequency of the -AO groups. The homolog distribution thus defined is significantly narrower than that of the fatty acid alkyl ester oxyalkylates, as is the case with the products obtained by the method described in WO 90/13533 and WO 91/15441 and the connections defined here with the narrower homolog distribution are characterized by a much better washing performance and a low Gel formation during the dissolving process. The compounds of formula 1 thus defined are hereinafter referred to as "narrow range" fatty acid alkyl ester alkoxylates.

Die in den erfindungsgemäßen Wasch- und Reinigungsmittel eingesetzten "narrow range" Fettsäurealkylesteralkoxylate der Formel 1 mit der angegebenen engen Homologenverteilung können nach zwei unterschiedlichen Methoden hergestellt werden:
1. Durch Alkoxylierung, insbesondere Ethoxylierung von Fettsäurealkylestern in Gegenwart eines Katalysators oder einer Katalysator-Mischung.The "narrow range" fatty acid alkyl ester alkoxylates of the formula 1 used in the washing and cleaning agents according to the invention with the specified narrow homolog distribution can be prepared by two different methods:
1. By alkoxylation, especially ethoxylation of fatty acid alkyl esters in the presence of a catalyst or a catalyst mixture.

Zur Synthese der erfindungsgemäßen "narrow range" Fettsäurealkylesteralkoxylate sind folgende Katalysatoren geeignet: Erdalkalisalze von Monoestern aus Dicarbonsäuren und oxalkylierten Alkoholen wie in EP-A-337 239 beschrieben. Die nicht veresterte Carboxylgruppe ist dabei vollständig in die Form des Erdalkalisalzes überführt.For the synthesis of the "narrow range" fatty acid alkyl ester alkoxylates according to the invention the following catalysts are suitable: alkaline earth metal salts from monoesters Dicarboxylic acids and oxalkylated alcohols as described in EP-A-337 239. The The non-esterified carboxyl group is completely in the form of the alkaline earth metal salt transferred.

Teilneutralisierte Ca-Salze von mit C8-C30-Alkylresten substituierten Bernsteinsäurehalbestern (EP-A-657 410);
Alkali- und Erdalkalimetallverbindungen aus der Gruppe der Hydroxide, Oxide und Alkoholate (EP-A-0 335 295);
Ca/Al-haltige bzw. Ca/Ti-haltige Katalysatorsysteme (US-A-5 220 046).Partially neutralized Ca salts of succinic acid half-esters substituted with C 8 -C 30 -alkyl radicals (EP-A-657 410);
Alkali and alkaline earth metal compounds from the group of hydroxides, oxides and alcoholates (EP-A-0 335 295);
Ca / Al-containing or Ca / Ti-containing catalyst systems (US-A-5 220 046).

Besonders geeignete Alkoxylierungskatalysatoren sind teilneutralisierte Erdalkalisalze von Dicarbonsäurehalbestern wie in DE 198 07 991.5 beschrieben.Particularly suitable alkoxylation catalysts are partially neutralized Alkaline earth metal salts of dicarboxylic acid half esters as described in DE 198 07 991.5.

"narrow range" Fettsäurealkylesteralkoxylate der Formel 1 können auch durch direkte Veresterung von "narrow range" alkoxylierten Alkylalkoholen oder Hydroxyalkylalkoholen, beispielsweise Methylpolyglykolen mit Fettsäure in Gegenwart eines sauren Katalysators hergestellt werden."Narrow range" fatty acid alkyl ester alkoxylates of the formula 1 can also be obtained by direct esterification of "narrow range" alkoxylated alkyl alcohols or Hydroxyalkyl alcohols, for example methyl polyglycols with fatty acid in Be prepared in the presence of an acid catalyst.

Als saure Katalysatoren können die für Veresterungen üblichen Katalysatoren wie Schwefelsäure, p-Toluolsulfonsäure, Alkylsulfonsäuren, Alkylarylsulfonsäuren, ZnCl2, Phosphorsäuren usw. eingesetzt werden.Acidic catalysts which can be used are those customary for esterifications, such as sulfuric acid, p-toluenesulfonic acid, alkylsulfonic acids, alkylarylsulfonic acids, ZnCl 2 , phosphoric acids, etc.

Die erfindungsgemäßen Wasch- und Reinigungsmittel können als pulverförmige, granulatförmige und tablettenförmige, d.h. als feste Wasch- und Reinigungsmittel vorliegen oder als flüssige Formulierungen beispielsweise als Geschirrspülmittel.The washing and cleaning agents according to the invention can be in the form of powder, granular and tablet-shaped, i.e. as solid washing and cleaning agents are present or as liquid formulations, for example as dishwashing detergents.

Zur Herstellung von Pulvern ist ein Verfahren bevorzugt, wobei zuerst ein Vorgemisch aus Waschmittelbestandteilen ohne Fettsäurealkylesteralkoxylat hergestellt wird und anschließend das Fettsäurealkylesteralkoxylat aufgesprüht wird. In einem weiteren Verfahren können pulverförmige Wasch- und Reinigungsmittel hergestellt werden, indem man beim Alkoxylat gegebenenfalls durch Aufheizen eine niedrige Viskosität erzeugt, im Sprühturm versprüht und gleichzeitig feste Waschmittelbestandteile, beispielsweise Zeolithe, Kieselgur, Magnesium-Aluminium, Natrium- oder Calciumaluminiumsilikate, aktivierte Kieselsäure oder Aluminiumoxid zudosiert.A method for producing powders is preferred, with a first being a Premix of detergent ingredients without fatty acid alkyl ester alkoxylate is produced and then the fatty acid alkyl ester alkoxylate is sprayed on. In a further process, powdered detergents and cleaning agents can be used can be prepared by heating the alkoxylate, if necessary by heating low viscosity, sprayed in the spray tower and solid at the same time Detergent ingredients, for example zeolites, diatomaceous earth, magnesium aluminum, Sodium or calcium aluminum silicates, activated silica or aluminum oxide added.

Auch können beide Verfahren kombiniert werden, so daß einem nach dem ersten Verfahren hergestellten mit Fettsäurealkylesteralkoxylat gecoateten Pulver in einem zweiten Schritt ein im Sprühturm versprühtes Fettsäurealkylesteralkoxylat zudosiert wird.Also both methods can be combined, so that one after the first Powder coated with fatty acid alkyl ester alkoxylate in one process second step, a fatty acid alkyl ester alkoxylate sprayed in the spray tower becomes.

Zur Herstellung von Aufbauagglomeraten, enthaltend Fettsäurealkylesteralkoxylate, werden Pulvermischungen aus festen und flüssigen Waschmittelbestandteilen hergestellt und das flüssige, eventuell erwärmte oder in einem Lösungsmittel gelöste Fettsäuremethylesteralkoxylat aufgesprüht und vermischt.For the production of structural agglomerates containing fatty acid alkyl ester alkoxylates, become powder mixtures of solid and liquid detergent components prepared and the liquid, possibly heated or dissolved in a solvent Fatty acid methyl ester alkoxylate sprayed on and mixed.

Zur Herstellung von Granulaten wird zunächst in einem Mischaggregat (z.B. Pflugscharmischer) die Mischung aus Fettsäurealkylesteralkoxylaten und pulverförmigen Mischungen aus festen und flüssigen Wasch- und Reinigungsmittelbestandteilen innig vermischt. In einem zweiten Schritt wird das Gemisch zu größeren Partikeln verpreßt. Geeignet hierfür sind u.a. Walzenkompaktoren. Die Preßlinge werden anschließend der Zerkleinerung (Mahlung) unterworfen und auf die gewünschte Korngröße zerkleinert. Zu diesem Zweck eignen sich Zahnscheibenwalzen und/oder Passiersiebe. To produce granules, a mixing unit (e.g. Ploughshare mixer) the mixture of fatty acid alkyl ester alkoxylates and powdery mixtures of solid and liquid washing and Detergent ingredients mixed intimately. In a second step this will be The mixture is compressed into larger particles. Suitable for this include Roller compactors. The compacts are then crushed Subjected (grinding) and crushed to the desired grain size. To this Toothed pulley rollers and / or strainers are suitable for this purpose.

Feinanteil und Grobgut werden abgesiebt und in den Prozeß zurückgeführt. Während der Grobanteil direkt einer erneuten Zerkleinerung zugeführt wird, wird der Feinanteil der Kompaktierstufe zugesetzt. Die Korngröße des Produktes liegt im allgemeinen im Bereich von 100 - 2000 µm, vorzugsweise 300 - 1800 µm. Das Schüttgewicht der erfindungsgemäßen Granulate liegt oberhalb 500 kg/m3, vorzugsweise oberhalb 600 kg/m3.Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-shredded, the fine fraction is added to the compacting stage. The grain size of the product is generally in the range from 100 to 2000 μm, preferably 300 to 1800 μm. The bulk density of the granules according to the invention is above 500 kg / m 3 , preferably above 600 kg / m 3 .

Zur Herstellung von Formgranulaten ist ein Verfahren bevorzugt, bei dem man Fettsäurealkylesteralkoxylate zusammen mit anderen flüssigen und festen Waschmittelbestandteilen homogen vermischt und unter Zusatz eines Plastifizier- und/oder Gleitmitteis über Lochformen mit Öffnungsweiten der vorbestimmten Granulatdimension bei hohen Drucken zwischen 25 und 200 bar strangförmig verpreßt. Der Strang wird direkt nach dem Austritt aus der Lochform mittels einer Schneidevorrichtung auf die vorbestimmte Granulatdimension zugeschnitten. Als Plastifizier- und/oder Gleitmittel werden wäßrige Lösungen von polymeren Polycarboxylaten sowie hochkonzentrierten Aniontensidpasten und nichtionische Tenside bevorzugt.For the production of molded granules, a method is preferred in which Fatty acid alkyl ester alkoxylates together with other liquid and solid Detergent ingredients homogeneously mixed and with the addition of a plasticizer and / or Sliding center over hole shapes with opening widths of the predetermined Pellet size at high pressures between 25 and 200 bar in string form pressed. The strand is cut directly after leaving the hole shape by means of a Cutting device cut to the predetermined granule dimension. As Plasticizers and / or lubricants become aqueous solutions of polymers Polycarboxylates as well as highly concentrated anionic surfactant pastes and non-ionic Preferred surfactants.

Die auf diese Weise erhaltenen Granulate sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. Sie können zusätzlich mit einer Coatinghülle versehen werden.The granules obtained in this way can be used directly in washing and Suitable detergents. You can also add a coating sleeve become.

Hierzu wird das erfindungsgemäße Granulat in einem zusätzlichen Schritt mit einer filmbildenden Substanz umhüllt, wodurch die Produkteigenschaften erheblich beeinflußt werden können.For this purpose, the granulate according to the invention is treated in an additional step with a film-forming substance envelops, making the product properties significant can be influenced.

Als Coatingmittel geeignet sind alle filmbildenden Substanzen, nichtionische Tenside, beispielsweise Fettsäurealkylesteroxalkylate, anionische Tenside und kationische Tenside, sowie anionische und kationische Polymere, z. Bsp. Polyacrylsäure, Wachse, Silikone, Fettsäuren und Seifen. Bevorzugt werden Coatingsubstanzen mit einem Schmelzpunkt von 30 - 100°C verwendet. Durch Verwendung dieser Coatingmaterialien kann u.a. Auflöseverhalten beeinflußt werden, der Staubgehalt reduziert, die Abriebfestigkeit erhöht sowie die Lagerstabilität verbessert werden. Soll das Granulat in Maschinengeschirrspülmitteln Verwendung finden, eignen sich hierzu vor allem Wachse mit Schmelzpunkten von 40 bis 50°C. Das Aufbringen der Coatingmaterialien erfolgt in der Regel durch Aufsprühen der geschmolzenen oder in einem Lösemittel gelösten Coatingmaterialien. Das Coatingmaterial kann in Mengen von 0 - 20, vorzugsweise 1 - 10 Gew.-%, bezogen auf das Gesamtgewicht, auf den Granulatkern aufgebracht werden.All film-forming substances, nonionic, are suitable as coating agents Surfactants, for example fatty acid alkyl ester oxyalkylates, anionic surfactants and cationic surfactants, as well as anionic and cationic polymers, e.g. E.g. Polyacrylic acid, waxes, silicones, fatty acids and soaps. To be favoured Coating substances with a melting point of 30 - 100 ° C are used. By The use of these coating materials can include Dissolution behavior influenced the dust content is reduced, the abrasion resistance is increased and the Storage stability can be improved. Should the granules in dishwasher detergents Waxes with melting points of are particularly suitable for this purpose 40 to 50 ° C. The coating materials are usually applied by Spray on the melted or dissolved in a solvent Coating materials. The coating material can be used in amounts of 0-20, preferably 1 - 10 wt .-%, based on the total weight, applied to the granulate core become.

Tabletten können beispielsweise derart hergestellt werden, daß man Buildersubstanzen, beispielsweise Zeolithe, Kieselgur, Magnesium-Aluminium, Natrium- oder Calciumaluminiumsilikate, aktivierte Kieselsäure oder Aluminiumoxid zudosiert, sowie alle anderen Bestandteile, wie Tenside, Enzyme, Bleichaktivatoren, Aufheller etc. homogen miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen, hydraulischen Pressen oder Rundläuferpressen mit Preßdrucken im Bereich von 300 bar, vorteilhafterweise im Bereich von etwa 5 bis 200 bar und insbesondere zwischen 10 und 50 bar verpreßt. In einer bevorzugten Ausführungsform können die zur Verpressung vorgesehenen Vorgemische jedoch durch Vermischen der einzelnen Inhaltsstoffe, die wenigstens anteilsweise in vorkonfektionierter Form als granulares Compound vorliegen, hergestellt werden. Hierzu zählen beispielsweise walzenkompaktierte kristalline schichtförmige oder amorphe Natriumdisilikate, die gegebenenfalls mit flüssigen bis wachsartigen Komponenten, beispielsweise nichtionischen Tensiden imprägniert wurden.Tablets can be prepared, for example, in such a way that Builder substances, for example zeolites, diatomaceous earth, magnesium aluminum, Sodium or calcium aluminum silicates, activated silica or aluminum oxide metered in, as well as all other components such as surfactants, enzymes, bleach activators, Brightener etc. homogeneously mixed together and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic Presses or rotary presses with pressures in the range of 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 50 bar pressed. In a preferred embodiment, the Compression provided premixes, however, by mixing the individual Ingredients that are at least partially in pre-assembled form as granular Compound present, are produced. These include, for example roller-compacted crystalline layered or amorphous sodium disilicates, the optionally with liquid to waxy components, for example have been impregnated with nonionic surfactants.

Die "narrow range" Fettsäurealkylesteralkoxylate können allein oder im Gemisch mit anderen nichtionischen Tensiden eingesetzt werden, beispielsweise mit Alkyl- und/oder Alkenyloligoglykosiden, Fettalkoholpolyglycolethern, Alkylphenolpolyglykolethern, Fettsäurepolyglykolestern, Fettsäureamidpolyglykolethern, Fettaminpolyglykolethern, alkoxylierten Triglyceriden, Fettsäureglucamiden, Polyölfettsäureestern, Zuckerestern, Sorbitanestern und Polysorbaten und/oder alkoxylierten Fettalkoholen. Zu diesen anderen nichtionischen Tensiden zählen außerdem die üblichen Fettsäurealkylesteroxalkylate mit breiter Homologenverteilung. Im fertigen Mittel können die nichtionischen Tenside insgesamt in einer Menge von 1 bis 25 Gew.-%, bevorzugt 2 bis 20 Gew.-%, besonders bevorzugt 10 bis 15 Gew.-% bezogen auf den Gesamtanteil enthalten sein. Der Anteil der "narrow range" Fettsäurealkylesteralkoxylate in der Gesamtmenge der nichtionischen Tenside kann 10 bis 100, bevorzugt 35 bis 95, insbesondere 45 bis 90 Gew.-% betragen.The "narrow range" fatty acid alkyl ester alkoxylates can be used alone or in a mixture with other nonionic surfactants are used, for example with alkyl and / or Alkenyl oligoglycosides, fatty alcohol polyglycol ethers, Alkylphenol polyglycol ethers, fatty acid polyglycol esters, Fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, fatty acid glucamides, poly oil fatty acid esters, sugar esters, Sorbitan esters and polysorbates and / or alkoxylated fatty alcohols. To this other nonionic surfactants also include the usual ones Fatty acid alkyl ester oxyalkylates with a broad homolog distribution. In the finished mean the nonionic surfactants in total in an amount of 1 to 25 wt .-%, preferably 2 to 20% by weight, particularly preferably 10 to 15% by weight, based on the total share should be included. The share of the "narrow range" Fatty acid alkyl ester alkoxylates in the total amount of nonionic surfactants can 10 to 100, preferably 35 to 95, in particular 45 to 90% by weight.

Als weitere Komponenten können Strukturbrecher, insbesondere ethoxylierte C8-C18-Fettalkohole mit 20 bis 45 EO, vorzugsweise Talgfettalkohole mit 30 und 40 EO, Polyethylenglykol oder Polypropylenglykol, Sulfate und/oder Disulfate von Polyethylenglykol oder Polypropylenglykol, Sulfosuccinate und/oder Disulfosuccinate von Polyethylenglykol oder Polypropylenglykol oder Mischungen aus diesen eingesetzt werden. Weitere geeignete Sprengmittel sind physikalisch modifizierte Sprengmittel wie Sorbitole, Dextrine, insbesondere Maltodextrine. Die nichtionischen Tenside und die Strukturbrecher können in einem Gewichtsverhältnis von nichtionischem Tensid zu Strukturbrecher von 1:1 bis 15:1 eingesetzt werden.Structural breakers, in particular ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol can be used as further components or polypropylene glycol or mixtures of these can be used. Other suitable disintegrants are physically modified disintegrants such as sorbitols, dextrins, in particular maltodextrins. The nonionic surfactants and the structure breakers can be used in a weight ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.

Neben den voranstehend beschriebenen Tensiden können anionische Tenside enthalten sein. Typische Beispiele für anionische Tenside sind Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Alkylpolyglykolethersulfonate, GlycerinethersuIfonate, alpha-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid-(ether)sulfate, Fettsäureamid(ether)sulfate, Sulfosccinate, Sulfosuccinamate, Sulfotriglyceride, C6-C18-Fettsäureamid-ethersulfate, Fettsäureseifen, Alkylcarboxylate, Ethercarbonsäuren, Isethionate, Sarcosinate, Tauride, Alkyloligoglucosidesulfate, Acyllactylate und Alkyl(ether)phosphate. Die anionischen Tenside können in Form ihrer Natrium-, Kalium- und Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin vorliegen.In addition to the surfactants described above, anionic surfactants can be included. Typical examples of anionic surfactants are alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, alkyl polyglycol ether sulfonates, glycerin ether sulfonates, alpha methyl ester sulfonates, sulfo fatty acids, alkyl sulfate sulfate, sulfate ether sulfates, hydroxymethane sulfates, hydroxymate sulfates , C 6 -C 18 fatty acid amide ether sulfates, fatty acid soaps, alkyl carboxylates, ether carboxylic acids, isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates, acyl lactylates and alkyl (ether) phosphates. The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.

In einer bevorzugten Ausführungsform wird neben den "narrow rangen Fettsäurealkylesteralkoxylaten und auch weiteren nichtionischen Tensiden, sekundäres C8-C12-, insbesondere C12-C18-Alkansulfonat, beispielsweise das unter dem Handelsnamen Hostapur SAS (Clariant GmbH) erhältliche, gegebenenfalls im Gemisch mit C8-C18, insbesondere C12-C16-Ethersulfat, aber auch Alkylbenzolsulfonate, primäre und sekundäre Alkylsulfate und Fettsäureestersulfonate als anionische Tenside eingesetzt.In a preferred embodiment, in addition to the "narrow-range fatty acid alkyl ester alkoxylates and also other nonionic surfactants, secondary C 8 -C 12 -, in particular C 12 -C 18 alkanesulfonate, for example that available under the trade name Hostapur SAS (Clariant GmbH), optionally in a mixture with C 8 -C 18 , in particular C 12 -C 16 ether sulfate, but also alkylbenzenesulfonates, primary and secondary alkyl sulfates and fatty acid ester sulfonates are used as anionic surfactants.

Der Gehalt an anionischen Tensiden beträgt 2 bis 50 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, insbesondere 8 bis 30 Gew.-%, bezogen auf die Gesamtmenge der Tenside.The content of anionic surfactants is 2 to 50% by weight, preferably 5 to 40 wt .-%, in particular 8 to 30 wt .-%, based on the total amount of Surfactants.

Weitere mögliche waschaktive Bestandteile der erfindungsgemäßen Mittel sind amphotere bzw. zwitterionische Tenside wie Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine.Other possible wash-active components of the agents according to the invention are amphoteric or zwitterionic surfactants such as alkyl betaines, alkyl amido betaines, Aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

Die erfindungsgemäßen festen Wasch- und Reinigungsmittel können übliche Builder in den Mengen von 2 bis 80 Gew.-%, vorzugsweise in einer Menge von 15 bis 65 Gew.-%, bezogen auf das Mittel enthalten.The solid washing and cleaning agents according to the invention can be conventional builders in amounts of 2 to 80% by weight, preferably in an amount of 15 to 65 wt .-%, based on the agent included.

Als Buildersubstanzen geeignet sind Zeolithe, amorphe Alkalisilikate, Carbonat-Silikat-Compounds, kristalline Silikate, vorzugsweise Schichtsilikate, beispielsweise das unter dem Handelsnamen SKS-6 erhältliche d-Disilikat (Clariant GmbH), Kieselgur, Magnesium-Aluminium, Natrium- oder Calciumaluminiumsilikate, aktivierte Kieselsäure, Aluminiumoxid oder Mischungen aus den genannten Substanzen.Suitable builders are zeolites, amorphous alkali silicates, carbonate-silicate compounds, crystalline silicates, preferably layered silicates, for example d-disilicate (Clariant GmbH) available under the trade name SKS-6, Diatomaceous earth, magnesium aluminum, sodium or calcium aluminum silicates, activated silica, aluminum oxide or mixtures of the above Substances.

Als weitere Gerüstsubstanzen können auch polymere Carboxylate bzw. polymere Carbonsäuren in den Mengen 2 bis 15 Gew.-%, bezogen auf den Gesamtanteil, enthalten sein. Es kommen polymere Carboxylate bzw. polymere Carbonsäuren mit einer relativen Molmasse von mindestens 350 in Form ihrer wasserlöslichen Salze, insbesondere in Form der Natrium- und/oder Kaliumsalze, in Betracht, wie Polyacrytate, Polyhydroxyacrylate, Polymethacrylate, Polymaleate und insbesondere Copolymere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhydrid, vorzugsweise solche aus 50 bis 70% Acrylsäure und 50 bis 10 % Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100 000, die der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf die freie Säure. Geeignet sind auch Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylether, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Anstelle der genannten Copolymere können auch Terpolymere eingesetzt werden. Diese organischen Builder können in einer Menge von 2 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-%, bezogen auf das Mittel, enthalten sein.Polymeric carboxylates or polymeric substances can also be used as additional structural substances Carboxylic acids in the amounts 2 to 15 wt .-%, based on the total proportion, be included. Polymeric carboxylates or polymeric carboxylic acids come along a relative molar mass of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, into consideration, such as Polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular Copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 up to 120,000, based on the free acid. Copolymers of are also suitable Acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, Ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight is. Instead of the copolymers mentioned, terpolymers can also be used become. These organic builders can be used in an amount of 2 to 20% by weight, preferably 5 to 15 wt .-%, based on the agent.

Weitere organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäure, Aminocarbonsäure, Nitriloessigsäure und Mischungen aus diesen.Other organic framework substances are, for example, those in the preferred form their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, Nitriloacetic acid and mixtures thereof.

Die erfindungsgemäßen Waschmittel enthalten vorzugsweise Peroxybleichmittel und insbesondere Bleichmittel in Kombination mit Bleichaktivatoren. Als Bleichmittel dienen Natriumperborattetrahydrat, Natriumperboratmonohydrat, Natriumpercarbonat, Peroxypyrophosphat, Citratperhydrat sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperoxyazelainsäure oder Diperoxydodecandisäure.
Repräsentative Beispiele für Bleichaktivatoren sind N- oder O-Acyl-Verbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere N,N,N',N''-Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglucoluril (TAGU), N-acylierte Hydantoine, Triazole, Triazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natriumisononanoyloxybenzolsulfonat und acylierte Zuckerderivate, insbesondere Pentaacetylglycose, Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG) und 1-Phenyl-3-acetylhydantoin (PAH), Amidoesterverbindungen sowie kationische Bleichaktivatoren, beispielsweise Ammoniumnitrile.
Bleichmittel werden in den Gewichtsmengen 5 bis 30 Gew.-%, bevorzugt 8 bis 25 Gew.-% Bleichaktivatoren in den Mengen 1 bis 15 Gew.-%, bevorzugt 2 bis 10 Gew.-%, eingesetzt.The detergents according to the invention preferably contain peroxy bleaches and in particular bleaches in combination with bleach activators. Sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphate, citrate perhydrate and peracid salts or peracids providing H 2 O 2 , such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid, are used as bleaching agents.
Representative examples of bleach activators are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular N, N, N ', N''- tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglucoluril (TAGU), N-acylated hydantoins, Triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodiumisononanoyloxybenzenesulfonate and acylated sugar derivatives, especially pentaacetylglycose, glucose pentaacetate (GPA), sodium benzoxetoyl (TAA), xoxybenzoyl oxybenzoyl oxybenzoyl (benzo) oxybenzoyl (benzo) oxybenzoyl (benzo) oxybenzoyl oxybenzoyl (benzo) oxybenzolate (GPA), xoxybenzolate (GPA), xoxybenzoyl oxybenzoyl (benzo) oxybenzolate (GPA), xylosulfonate STHOBS), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH), amido ester compounds and cationic bleach activators, for example ammonium nitriles.
Bleaching agents are used in the amounts by weight of 5 to 30% by weight, preferably 8 to 25% by weight, of bleach activators in the amounts of 1 to 15% by weight, preferably 2 to 10% by weight.

Weitere geeignete Inhaltsstoffe sind schmutzablösende Polymere, insbesondere Polymere, die Ethylenterephthalat-, Polyoxyethylenterephthalat, Propylenglykol, Polypropylenglykol, Alkylen- oder Alkylendicarbonsäuren, Isophthalsäure, carboxy- oder sulfosubstituierte Phthalsäureisomere als Monomereinheiten und auch endgruppenverschlossene Derivate enthalten.Other suitable ingredients are dirt-removing polymers, in particular Polymers containing ethylene terephthalate, polyoxyethylene terephthalate, propylene glycol, Polypropylene glycol, alkylene or alkylene dicarboxylic acids, isophthalic acid, carboxy or sulfo-substituted phthalic acid isomers as monomer units and also End-capped derivatives included.

Als Salze bzw. Stellmittel kommen beispielsweise Alkalisulfate, Alkalicarbonate, Alkalibicarbonate, amorphe Silikate oder Mischungen daraus in Betracht.Examples of salts or adjusting agents are alkali sulfates, alkali carbonates, Alkali bicarbonates, amorphous silicates or mixtures thereof.

Zu den sonstigen Waschmittelbestandteilen, deren Anteil im allgemeinen 0,1 bis 5 Gew.-% beträgt, zählen Schauminhibitoren, optische Aufheller, Enzyme, weichmachende Stoffe, Farb- und Duftstoffe. Es können auch Neutralsalze in einer Menge bis zu 20 Gew.-%, bevorzugt bis zu 10 Gew.-% enthalten sein sowie Vergrauungsinhibitoren in den Mengen, vorzugsweise von 0,1 bis 5 Gew.-%, beispielsweise wasserlösliche, meist organische Kolloide wie lösliche Stärkepräparate, Aldehydstärken usw. Carboxymethylcellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Gemische sowie Polyvinylpyrrolidon werden bevorzugt eingesetzt.The other detergent components, the proportion of which is generally 0.1 to Is 5% by weight, include foam inhibitors, optical brighteners, enzymes, softening substances, colors and fragrances. Neutral salts can also be used in one Amount up to 20 wt .-%, preferably up to 10 wt .-% may be included as well Graying inhibitors in amounts, preferably from 0.1 to 5% by weight, for example water-soluble, mostly organic colloids such as soluble Starch preparations, aldehyde starches etc. carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and Polyvinyl pyrrolidone are preferably used.

Geeignete Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure, sowie Gemische aus Silikonöl, Paraffinöl oder Wachsen.Suitable foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, optionally silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanized silica, as well as mixtures of silicone oil, paraffin oil or waxes.

Die erfindungsgemäßen Mittel können als optische Aufheller, Diaminostilbendisulfonsäure bzw. deren Alkalimetalle enthalten. Der maximale Gehalt an Aufhellern beträgt 0,5 Gew.-%. Vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.The agents according to the invention can be used as optical brighteners, Contain diaminostilbenedisulfonic acid or its alkali metals. The maximum Brightener content is 0.5% by weight. Amounts of 0.02 are preferred up to 0.25% by weight.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen, Peroxydasen oder Oxydasen bzw. deren Gemische in Frage. Der Anteil der Enzyme kann 0,2 bis 8 Gew.-%, bevorzugt 0,1 bis 3 Gew.-% betragen.Enzymes come from the class of proteases, lipases, amylases, Cellulases, peroxidases or oxidases or their mixtures in question. The amount the enzyme can be 0.2 to 8% by weight, preferably 0.1 to 3% by weight.

Wenn die erfindungsgemäßen Wasch- und Reinigungsmittel in flüssiger Form vorliegen, handelt es sich vorzugsweise um wäßrige Formulierungen die ungefähr 30 bis 70 Gew.-% Wasser enthalten.If the washing and cleaning agents according to the invention are in liquid form are present, it is preferably about aqueous formulations Contain 30 to 70 wt .-% water.

Die erfindungsgemäßen Produkte zeichnen sich durch eine sehr gute Lagerstabilität in flüssigen, pulverförmigen oder verpreßten Wasch-, Reinigungs- und Desinfektionsmittelformulierungen bei gleichzeitig hohem Aktivgehalt aus.The products according to the invention are characterized by very good storage stability in liquid, powdered or compressed washing, cleaning and Disinfectant formulations with a high active content.

Sie sind ideal zum Einsatz in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln und Allzweckreinigern.They are ideal for use in heavy-duty detergents, stain salts, Dishwashing detergents and all-purpose cleaners.

Nachfolgende Beispiele sollen die Erfindung näher erläutern ohne sie darauf einzuschränken.The following examples are intended to explain the invention in more detail without referring to it restrict.

BeispieleExamples

Alle Prozentangaben sind Gewichtsprozente. All percentages are percentages by weight.

Beispiel 1example 1 VollwaschmittelHeavy duty detergent

Zusammensetzung:Composition: SKS-6SKS-6 20 %20% ZeolitZeolite 23 %23% Hostapur SAS (Pulver)Hostapur SAS (powder) 10 %10% NatriumseifeSodium soap 2 %2% C12-C14 + 7.5 EO NRFAAEEC 12 -C 14 + 7.5 EO NRFAAEE 15 %15% PerboratPerborate 15 %15% TAEDTAED 5 %5% PEG 600PEG 600 3 %3% Zitronensäurecitric acid 3,5 %3.5% NatriumbicarbonatSodium bicarbonate 2,0 %2.0% StärkeStrength 1,0 %1.0% EntschäumerDefoamer 0,5 %0.5%

Beispiel 2Example 2 VollwaschmittelHeavy duty detergent

Zusammensetzung:Composition: SKS-6SKS-6 20 %20% ZeolitZeolite 23 %23% C10-C14-LASC 10 -C 14 LAS 10 %10% NatriumseifeSodium soap 1 %1 % C12-C14 + 7.5 EO NRFAAEEC 12 -C 14 + 7.5 EO NRFAAEE 12 %12% C12-C14 + 4 EO NRFAAEEC 12 -C 14 + 4 EO NRFAAEE 5 %5% PerboratPerborate 15 %15% TAEDTAED 5 %5% Zitronensäurecitric acid 3,5 %3.5% NatriumbicarbonatSodium bicarbonate 4 %4% StärkeStrength 1,0 %1.0% EntschäumerDefoamer 0,5 %0.5%

Beispiel 3Example 3 VollwaschmittelHeavy duty detergent

Zusammensetzung:Composition: SKS-6SKS-6 20 %20% ZeolitZeolite 15 %15% Hostapur SAS (Pulver)Hostapur SAS (powder) 10 %10% NatriumseifeSodium soap 2 %2% C12-C14 + 7.5 EO NRFAAEEC 12 -C 14 + 7.5 EO NRFAAEE 10 %10% Genapol = A 3070Genapol = A 3070 6 %6% PerboratPerborate 15 %15% TAEDTAED 5 %5% PEG 600PEG 600 3 %3% Zitronensäurecitric acid 3,5 %3.5% NatriumbicarbonatSodium bicarbonate 1,5 %1.5% StärkeStrength 1,0 %1.0% EntschäumerDefoamer 0,5 %0.5%

Beispiel 4Example 4 Flüssigwaschmittel, wäßrigLiquid detergent, aqueous

Zusammensetzung:Composition: C10-C14-LASC 10 -C 14 LAS 5 %5% C8-C18 + 8 EO NRMEEC 8 -C 18 + 8 EO NRMEE 53 %53% SeifeSoap 10 %10% SRC 1SRC 1 2 %2% NatriumsulfatSodium sulfate 1 %1 % Zitronensäure, NatriumsalzCitric acid, sodium salt 1 %1 % Parfüm, FarbstoffPerfume, dye Wasserwater 28 %28%

Beispiel 5Example 5 Flüssigwaschmittel, wäßrigLiquid detergent, aqueous

Zusammensetzung:Composition: C10-C14-LASC 10 -C 14 LAS 9,0 %9.0% C8-C18 + 8 EO NRMEEC 8 -C 18 + 8 EO NRMEE 10 % 10% SeifeSoap 15 %15% Genapol LA 050Genapol LA 050 3,0 %3.0% Zitronensäure, NatriumsalzCitric acid, sodium salt 3,0 %3.0% Boraxborax 1,0 %1.0% EnzymeEnzymes NatriumsulfatSodium sulfate 1,0 %1.0% optischer Aufhelleroptical brightener Parfüm, FarbstoffPerfume, dye Wasserwater 58 %58%

Beispiel 6Example 6 Flüssigwaschmittelkonzentrat, nicht-wäßrigLiquid detergent concentrate, non-aqueous

Zusammensetzung:Composition: C10-C14 LASC 10 -C 14 LAS 5,0 %5.0% C8-C18 + 7,5 EO NRMEEC 8 -C 18 + 7.5 EO NRMEE 30 %30% C8-C18 + 5 EO NRMEEC 8 -C 18 + 5 EO NRMEE 10 %10% SeifeSoap 0,5 %0.5% Genapol LA 050Genapol LA 050 7,0 %7.0% Zitronensäure, NatriumsalzCitric acid, sodium salt 12,0 %12.0% SKS-6SKS-6 6,0 %6.0% EnzymeEnzymes Perborat (monohydrat)Perborate (monohydrate) 20 %20% TAEDTAED 6 %6% SRC-1SRC-1 2 %2% EnzymeEnzymes 1 %1 % optische Aufhelleroptical brighteners 0,5 %0.5%

Verzeichnis der eingesetzten Handelsprodukte: Hostapur® SAS, Pulver sekundäres Alkansulfonat-Natriumsalz (ca. 93 % WAS) (Clariant GmbH) SKS-6 kristallines Schichtsilikat (Clariant GmbH) Zeolith 4A Wessalith P (Degussa) C12-C14 +7,5 EO NRFAAEE (a = 7,5) "narrow range"-C12-C14-Fettsäurealkylester-ethoxylat (7,5 EO) C12-C14 + 4 EO NRFAAEE (a = 4) "narrow range"-C12-C14-Fettsäurealkylester-ethoxylat (4 EO) C8-C18 + 8 EO NRMEE (a = 8) "narrow range"-C8-C18-Methylestermethoxylat (8 EO) C8-C18 + 7,5 EO NRMEE (a = 7,5) "narrow range"-C8-C18-Methylestermethoxylat (7,5 EO) C8-C18 + 5 EO NRMEE (a = 5) "narrow range"-C8-C18-Methylestermethoxylat (5 EO) TAED N,N,N',N''-Tetraacetylethylendiamin Enzyme Protease, Amylase, Lipase PEG 600 Polyethylenglykol (Molmasse 600) Genapol® OA 3070 C14-C15-Oxoalkoholpolyglykolether mit 3 EO und 7 EO (Clariant GmbH) Natriumseife C8-C18 Fettsäurecarboxylat, Natrium C10-C14-LAS lineares C10-C14-Alkylbenzolsulfonat, Na-Salz Genapol C12-C14 Fettsäurealkoholethoxylat mit 5 EO SRC1 Soil Release Polymer (Clariant GmbH) List of commercial products used: Hostapur® SAS, powder secondary alkanesulfonate sodium salt (approx. 93% WAS) (Clariant GmbH) SKS-6 crystalline layered silicate (Clariant GmbH) Zeolite 4A Wessalith P (Degussa) C 12 -C 14 +7.5 EO NRFAAEE (a = 7.5) "narrow range" -C 12 -C 14 fatty acid alkyl ester ethoxylate (7.5 EO) C 12 -C 14 + 4 EO NRFAAEE (a = 4) "narrow range" -C 12 -C 14 fatty acid alkyl ester ethoxylate (4 EO) C 8 -C 18 + 8 EO NRMEE (a = 8) "narrow range" -C 8 -C 18 methyl ester methoxylate (8 EO) C 8 -C 18 + 7.5 EO NRMEE (a = 7.5) "narrow range" -C 8 -C 18 methyl ester methoxylate (7.5 EO) C 8 -C 18 + 5 EO NRMEE (a = 5) "narrow range" -C 8 -C 18 methyl ester methoxylate (5 EO) TAED N, N, N ', N''- tetraacetylethylene diamine Enzymes Protease, amylase, lipase PEG 600 Polyethylene glycol (molar mass 600) Genapol® OA 3070 C 14 -C 15 oxo alcohol polyglycol ether with 3 EO and 7 EO (Clariant GmbH) Sodium soap C 8 -C 18 fatty acid carboxylate, sodium C 10 -C 14 LAS linear C 10 -C 14 alkylbenzenesulfonate, Na salt Genapol C 12 -C 14 fatty acid alcohol ethoxylate with 5 EO SRC1 Soil Release Polymer (Clariant GmbH)

Die als "narrow range" bezeichneten Verbindungen entsprechen der Definition in Anspruch 1.

  • Waschleistung:
    Zur Bestimmung des Waschvermögens von "narrow range" Fettsäurealkylesteralkoxylaten und vergleichend dazu von Fettsäurealkylesteralkoxylaten mit breiter Homologenverteilung wurden Linitestversuche mit "narrow range" C12-C14 Fettsäuremethylesterethoxylat C12-C14-NRMEE + 7,6 EO, "narrow range" C8-C18-Fettsäuremethylesterethoxylaten C8-C18 NRMEE + 7 EG, "narrow range" C8-C18 Fettsäuremethylesterethoxylat + 10,4 EO und den "broad range" Fettsäuremethylesterethoxylat C12-C14 BRFSME + 6,7 EO und C12-C14 BRFSME + 10,9 EO durchgeführt.
  • Linitestbedingungen: 40°C, 30 Minuten Waschzeit, Tensidkonz.: 2 g/l Wasserhärte 10°dH oder 18°dH, Testgewebe: 65:35 Polyester/Baumwolle Verschmutzung mit Hautfett (WGK 20 D) oder Mineralöl (WGK 20 M), bezogen von der Wäschereiforschung Krefeld.
    • Produkt Delta Remisson WFK 20 D Delta Remisson WFK 20 M 18°dH 10°dH 18°dH 10°dH NRFAAEE C12-C14 + 7,6 EO 24,4 28,93 13,72 14,13 NRFAAEE C8-C18 + 7 EO 26,33 27,48 13,71 14,17 BRFSME + 6,7 EO 10,01 8,25 8,27 11,71 NRFAAEE C8-C18 + 10,4 EO 11,58 11,73 9,02 10,92 BRFAAWE C12-C14+ 10,9 EO 6,25 6,5 8,82 8,15 The "narrow range" connections correspond to the definition in claim 1.
  • Washing performance:
    To determine the washability of "narrow range" fatty acid alkyl ester alkoxylates and, in comparison, of fatty acid alkyl ester alkoxylates with a broad homolog distribution, line test tests were carried out using "narrow range" C 12 -C 14 fatty acid methyl ester ethoxylate C 12 -C 14 -NRMEE + 7.6 EO, "narrow range" C 8 -C 18 fatty acid methyl ester ethoxylates C 8 -C 18 NRMEE + 7 EG, "narrow range" C 8 -C 18 fatty acid methyl ester ethoxylate + 10.4 EO and the "broad range" fatty acid methyl ester ethoxylate C 12 -C 14 BRFSME + 6.7 EO and C 12 -C 14 BRFSME + 10.9 EO.
  • Linitest conditions: 40 ° C, 30 minutes washing time, tenside concentration: 2 g / l water hardness 10 ° dH or 18 ° dH, test fabric: 65:35 polyester / cotton soiled with skin fat (WGK 20 D) or mineral oil (WGK 20 M), sourced from the Krefeld laundry research.
    • product Delta Remisson WFK 20 D Delta Remisson WFK 20 M 18 ° dH 10 ° dH 18 ° dH 10 ° dH NRFAAEE C 12 -C 14 + 7.6 EO 24.4 28.93 13.72 14.13 NRFAAEE C 8 -C 18 + 7 EO 26.33 27.48 13.71 14.17 BRFSME + 6.7 EO 10.01 8.25 8.27 11.71 NRFAAEE C 8 -C 18 + 10.4 EO 11.58 11.73 9.02 10.92 BRFAAWE C 12 -C 14 + 10.9 EO 6.25 6.5 8.82 8.15

    Claims (5)

    Wasch- und Reinigungsmittel, die Fettsäurealkylesteralkoxylate der Formel R1- COO(AO)n - R2 enthalten, wobei R1 eine geradkettige oder verzweigte Alkyl- oder Alkenylgruppe mit 5 bis 22, vorzugsweise 8 bis 18 C-Atomen, R2 C1-C6-Alkyl oder C2-C6-Alkenyl, vorzugsweise Methyl, AO eine C2-C4-Alkylenoxid-Einheit und n eine Zahl von 1 bis 20, vorzugsweise 3 bis 12, insbesondere 4 bis 10 bedeuten und diese Fettsäurealkylesteroxalkylate weniger als 14 Gew.-% an Verbindungen mit einem Gehalt von nicht mehr als (a - 3) -AO-Gruppen und weniger als 16 Gew.-% an Verbindungen mit einem Gehalt von nicht unter (a + 3) -AO-Gruppen, wobei a die Anzahl der -AO-Gruppen mit der maximalen Häufigkeit bezeichnet, enthalten.Detergents and cleaning agents, the fatty acid alkyl ester alkoxylates of the formula R 1 - COO (AO) n - R 2 contain, wherein R 1 is a straight-chain or branched alkyl or alkenyl group having 5 to 22, preferably 8 to 18 carbon atoms, R 2 C 1 -C 6 alkyl or C 2 -C 6 alkenyl, preferably methyl, AO a C. 2 -C 4 alkylene oxide unit and n is a number from 1 to 20, preferably 3 to 12, in particular 4 to 10, and these fatty acid alkyl ester oxalkylates contain less than 14% by weight of compounds containing not more than (a - 3 ) -AO groups and less than 16 wt .-% of compounds containing not less than (a + 3) -AO groups, where a denotes the number of -AO groups with the maximum frequency. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie neben den Fettsäurealkylesteroxalkylaten der Formel 1 weitere anionische Tenside anderer Strukturen enthalten.Detergent and cleaning agent according to claim 1, characterized in that in addition to the fatty acid alkyl esteroxyalkylates of the formula 1, they are further anionic Contain surfactants of other structures. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie neben den Feltsäurealkylesteroxalkylaten der Formel 1 Fettsäurealkylesteroxalkylate mit breiter Homologenverteilung enthalten.Detergent and cleaning agent according to claim 1, characterized in that in addition to the Feltsäurealkylesteroxalkylaten of formula 1 Contain fatty acid alkyl esteroxyalkylates with a broad homolog distribution. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß die Gesamtmenge an nichtionischen Tensiden 1 bis 25 Gew.-% beträgt.Detergent and cleaning agent according to claim 1, characterized in that the total amount of nonionic surfactants is 1 to 25 wt .-%. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß sie Fettsäurealkylesteroxalkylate der Formel 1 in einer Menge von 10 bis 100 Gew.-%, bezogen auf die Gesamtmenge an nichtionischen Tensiden, enthalten.Detergent and cleaning agent according to claim 1, characterized in that they are fatty acid alkyl ester oxyalkylates of the formula 1 in an amount of 10 to 100 wt .-%, based on the total amount of nonionic surfactants.
    EP99120730A 1998-10-31 1999-10-20 Detergent compositions containing alkoxylated fatty acid alkyl esters Withdrawn EP0997521A1 (en)

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    DE19850223A DE19850223A1 (en) 1998-10-31 1998-10-31 Detergents and cleaning agents containing alkoxylated fatty acid alkyl esters
    DE19850223 1998-10-31

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