EP1445301A1 - Aqueous liquid detergent dispersions - Google Patents

Aqueous liquid detergent dispersions Download PDF

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Publication number
EP1445301A1
EP1445301A1 EP04001425A EP04001425A EP1445301A1 EP 1445301 A1 EP1445301 A1 EP 1445301A1 EP 04001425 A EP04001425 A EP 04001425A EP 04001425 A EP04001425 A EP 04001425A EP 1445301 A1 EP1445301 A1 EP 1445301A1
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EP
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Prior art keywords
liquid detergent
aqueous liquid
alkyl
dispersions according
detergent dispersions
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EP04001425A
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German (de)
French (fr)
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EP1445301B1 (en
Inventor
Johannes Dr. Himmrich
Ulrike Reploeg
Werner Dr. Skrypzak
Dennis Dr. Miller
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • Aqueous-based liquid detergent dispersions containing surfactants, quaternary alkyldimethylhydroxyethylammonium salt and / or alkylmethylbishydroxyethylammonium salt, one or more electrolytes and one or more builders By adding hydroxyethyl quats to an aqueous solution of surfactants, electrolytes and builders, a very stable dispersion with good detergency and favorable viscosity behavior is obtained.
  • Liquid detergents have some performance advantages over solid, powdered or particulate products. They are easy to measure, dissolve quickly in the wash water and can be applied in concentrated solutions or dispersions on soiled areas of the textiles to be washed. In addition, it is possible to incorporate into liquid detergent formulations substances which would decompose during drying processes and are unsuitable for solid detergents. In clear liquid detergent formulations only limited amounts of soluble ingredients such as builders and surfactants can be incorporated due to limited solubility and accordingly must be higher doses in the wash to ensure a good wash performance even at high water hardness and corresponding partial inactivation of anionic surfactants. In liquid detergent dispersions much larger amounts of ingredients can be used and thus a reduction in the dosage per wash can be achieved.
  • liquid detergent dispersions allow the use of only poorly water-soluble ingredients. Furthermore, liquid detergent dispersions generally have significantly higher viscosities than clear liquid detergent formulations. Liquid detergent dispersions, on the other hand, tend to phase separate for longer storage times and greater temperature fluctuations.
  • the object was to prepare liquid-disperse detergent formulations, which in addition to a good cleaning power over long periods and also at large temperature fluctuations show no phase separation, a favorable one have rheological behavior and can be produced inexpensively.
  • EP 170 091 claims waterborne disperse liquid detergents containing linear alkylbenzenesulfonate, potassium or sodium tripolyphosphate and a solid builder.
  • the formulations are characterized in that in the presence of the electrolyte, the solubility of the surfactant is reduced in water and this is dispersed due to the salting-out effect in the aqueous phase.
  • Our own investigations show that surfactants with better water solubility compared to alkylbenzenesulfonate, for example sec. Alkanesulfonates, in the presence of electrolytes show a low salting-out effect and consequently can not be formulated in the same way as dispersions.
  • the agents according to the invention preferably contain quaternary alkylhydroxyethylammonium salt according to the formula 1 wherein R 1 is a linear or branched, saturated or unsaturated alkyl group having 5 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, R 2 is a methyl group, R 3 is a methyl group or a group of the formula -A - (OA) n -OH, where A is a -C 2 H 4 and / or C 3 H 6 group and n is a number from 0 to 20, R 4 is a group of the formula -A- ( OA) n is -OH and X is an anion, X is, for example, chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, bicarbonate, acetate, citrate, phosphate, mono- and dihydrogen phosphate, pyrophosphate,
  • the compound of the formula (1) is C 12 -C 14 quaternary alkyldimethylhydroxyethylammonium chloride or methosulfate.
  • Suitable anionic surfactants are especially sec. Alkanesulfonates, but also alkyl ester sulfonates, alkyl sulfates, carboxylates, phosphates, sulfonates, Arylalkylsulfonate, alkyl ether sulfates and mixtures of the above Links. The following are some of the candidate types of anionic surfactants are described in more detail.
  • Secondary alkanesulfonates are surfactants of the formula R-SO 3 M, whose alkyl group R is saturated or unsaturated, linear or branched and which can also carry hydroxyl groups, wherein the terminal carbon atoms of the alkyl chain have no sulfonate group.
  • Counterion M may be sodium, potassium, ammonium, mono-, di- or tri-alkanol ammonium, calcium, magnesium ion or mixtures thereof.
  • Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by SO 3 .
  • Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.
  • Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably has a C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 -alkyl or Represents hydroxyalkyl.
  • M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, eg a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below about 50 ° C) and alkyl chains with C 16 -C 18 preferably for higher washing temperatures (eg above about 50 ° C).
  • the alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C 12 -C 20 -alkyl radical. or hydroxyalkyl radical, particularly preferably a C 12 -C 18 -alkyl or hydroxyalkyl radical.
  • A is an ethoxy or propoxy moiety
  • m is a number greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3
  • M is a hydrogen atom or a cation such as for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium, or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
  • C 12 -C 18 -alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 -alkyl polyethoxylate (2,25) sulfate, C 12 -C 18 -alkyl polyethoxylate (3.0 ) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, wherein the cation is sodium or potassium.
  • anionic surfactants useful in laundry detergents and cleaners are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrrole products of alkaline earth metal citrates such as described in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, Alkylphenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (
  • the disperse liquid detergents according to the invention contain one or more builders as further component.
  • Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which precipitate or complex calcium ions.
  • Builders such as orthophosphates and condensed phosphates, eg pyrophosphates, triphosphates, tetraphosphates, polyphosphates and metaphosphates, as well as fine crystalline, synthetic hydrous zeolites are preferred.
  • Particularly suitable are alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts.
  • phosphates and zeolites it is also preferred to use sheet silicates and amorphous silicates, as well as carbonates and bicarbonates.
  • Useful organic builders include citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, preferably in the form of their salts are used, and phosphonic and polyphosphonic. Analogous to this also polymeric carboxylates and their salts are used. These include for example, the salts of homopolymeric or copolymeric polyacrylates, Polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid, and polyaspartic acid and also polyvinylpyrrolidone and urethanes.
  • the molecular weight of the Homopolymers is generally between 1000 and 100 000, which is the Copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular are water-soluble polyacrylates suitable, for example, with about 1% of a polyallyl ether of sucrose are cross-linked and have a molecular weight above one million have.
  • examples include the carbopol 940 and 941 available polymers.
  • phosphonates for example Acetodiphosphonates, aminotrismethylene phosphonates and Ethylene tetramethylene phosphonates in question.
  • Electrodes are non-boundary surface active, water soluble, ionic Compounds understood to be the solubility or micelle concentration of Degrade surfactants in the aqueous formulation and have a "salting-out effect" cause. Suitable are alkali or ammonium chlorides, nitrates, phosphates, - carbonates, sulphates, silicates, acetates, citrates or polyphosphates. Prefers potassium chloride, potassium sulfate, potassium carbonate, Pentasodium triphosphate and pentapotassium triphosphate.
  • the disperse liquid detergents according to the invention can be used in addition to the anionic surfactants still nonionic, amphoteric, but also cationic Containing surfactants.
  • Preferred nonionic surfactants are fatty alcohol ethoxylates containing from about 1 to about 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl chain of 10 to 20 carbons with 2 to 18 moles of ethylene oxide per mole of alcohol.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates may have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol TM brands from Clariant GmbH.
  • nonionic surfactants such as polyethylene, polypropylene and Polybutylene oxide adducts of fatty alcohols containing 8 to 22 C atoms in the alkyl chain and of alkylphenols having 6 to 12 C atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base formed from the condensation of Propylene oxide with propylene glycol or addition products of ethylene oxide with a Reaction product of propylene oxide and ethylenediamine, but also Fatty acid polyhydroxyamides and fatty acid amido alkoxylates.
  • nonionic surfactants such as polyethylene, polypropylene and Polybutylene oxide adducts of fatty alcohols containing 8 to 22 C atoms in the alkyl chain and of alkylphenols having 6 to 12 C atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base formed from the condensation of Propylene oxide with propylene glycol or addition products of ethylene oxide with a Reaction product of
  • semipolar nonionic surfactants for example amine oxides of the formula where R 8 is an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof having a chain length of 8 to 22 carbon atoms; R 9 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; R 10 is an alkyl or hydroxyalkyl group with. 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units.
  • the R 10 / R 9 groups may be linked together via an oxygen or nitrogen atom and thus form a ring.
  • These amine oxides particularly include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides.
  • amphoteric surfactants which can be used in the formulations of the present invention are, above all, those which are described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic substituents contains between 8 to 18 carbon atoms and contains an anionic, water-soluble group, such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
  • Amphoteric surfactants in this context include amphoteric imidazolinium surfactants as represented by the following formula: wherein R 11 is C 8 -C 22 alkyl or alkenyl, preferably C 12 -C 16 , R 12 is hydrogen or a group of the formula CH 2 CO 2 M, R 13 is a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 14 is hydrogen or a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonia or alkanolammonium.
  • Preferred amphoteric surfactants of the above formula are monocarboxylates and Dicarboxylates. Close examples of these connections Cocoamphocarboxypropionate, cocoamidocaboxypropionic acid, Cocoamphocarboxyglycinate (or also called cocoamphodiacetate) and Cocoamphoacetate.
  • alkyl dimethyl betaines alkylamido betaines and alkyl dipolyethoxybetaines having an alkyl group which may be linear or branched can, with 8 to 22 carbon atoms, preferably with 8 to 18 carbon atoms and particularly preferably having 12 to 18 carbon atoms.
  • These connections will be e.g. marketed by Clariant GmbH under the trade name Genagen®.
  • cationic surfactants are quaternary ammonium compounds and esterquats, in particular quaternized fatty acid alkanolamine ester salts and Dialkylaminopropylaminester salts.
  • the liquid detergents according to the invention may be those customary for these products Auxiliaries and additives, for example bleach activators, bleach catalysts, optical brighteners, grayness inhibitors, color transfer inhibitors, Solubilizers, hydrotropes, enzymes, enzyme stabilizers, thickeners, Preservatives, fragrances and dyes, pearlescers, foam inhibitors, Contain sequestering agents, corrosion inhibitors and antioxidants.
  • bleach activators for example bleach activators, bleach catalysts, optical brighteners, grayness inhibitors, color transfer inhibitors, Solubilizers, hydrotropes, enzymes, enzyme stabilizers, thickeners, Preservatives, fragrances and dyes, pearlescers, foam inhibitors, Contain sequestering agents, corrosion inhibitors and antioxidants.
  • bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoyl-caprolactam phenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonates (eg nonanoyloxybenzenesulfonate (NOBS), sodium 4-benzoyloxybenzenesulfonate ( SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS)), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH)
  • Examples include perborate monohydrate, perborate tetrahydrate, percarbonates, alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal, as well as hydrogen peroxide adducts of urea or amine oxides.
  • peroxycarboxylic acids for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, may be present.
  • bleach stabilizers such as phosphonates, borates, or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be advantageous.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare and their alkali metal salts. Suitable examples are salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar construction, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-Methoxyethylamino distr carry.
  • substituted diphenylstyryls for example alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • the maximum content of brighteners in the compositions according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.
  • Graying inhibitors have the task of keeping the loosened soil suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch and cellulose and their derivatives, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, in amounts of from 0.3% by weight to 5% by weight, based on the finished composition.
  • Suitable color transfer inhibitors are polyvinylpyrrolidones, Polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • color protective additives such as e.g. quaternary Polyamine derivatives, cationic methylolamides or formaldehyde condensation products, can be used.
  • the agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
  • foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
  • foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
  • foam inhibitors e.g. those made of silicone oil, paraffin oil or waxes.
  • the desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
  • organic solvents all mono- or polyhydric alcohols are suitable as organic solvents.
  • Alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. More preferred alcohols are polyethylene glycols having a molecular weight less than 2,000.
  • polyethylene glycol having a molecular weight of between 200 and 600 and up to 45% by weight and polyethylene glycol having a molecular weight of between 400 and 600 in amounts of 5 to 25 wt .-% preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, wherein the liquid detergent according to the invention may contain 8 to 12 wt .-% of such a mixture.
  • suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • a thickener are preferably hydrogenated castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2 wt .-%, for example sodium.
  • Potassium-, Aluminum, magnesium and titanium stearates or the sodium and / or potassium salts behenic acid, as well as polysaccharides, especially xanthan gum, guar guar, Agar-agar, alginates and tyloses, carboxymethylcellulose and Hydroxyethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone used.
  • copolymers based on acryloyldimethyltaurine as in EP 10 60142, EP 10 28129, EP 11 16 733 and Hostacerin® AMPS.
  • Suitable hydrotropes are, for example, sodium toluene sulphonate, Sodium cumulosulphonate, sodium xylene sulphonate, alkanephosphonic acids and Alkenyldicarboxylic acids and their anhydrides.
  • Suitable enzymes are those from the class of proteases, lipases, amylases and Cellulases or mixtures thereof in question. Their proportion can be 0.2 to 3 wt .-% be.
  • the enzymes can be adsorbed to carrier substances and / or in Be embedded nesting substances.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP Ethylenediaminetetramethylenephosphonic acid
  • DTPMP Diethylentriaminpentamethylenphosphonklare
  • Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, isothiazolinones, pentanediol or sorbic acid.
  • glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters.
  • liquid detergents according to the invention can be achieved by simple Mix the ingredients in bulk or as a solution in an automatic Mixer can be given done.
  • the clear mixture 2 is then added to the mixture 1 with a glass rod stirred until no more particles of the surfactant phase on the wall of the Beaker are located.

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Abstract

Aqueous liquid detergent dispersion comprises 5-35 wt.% anionic surfactant, 10-50 wt.% builder, 0-10 wt.% electrolytes and 0.1-10 wt.% quaternary alkyl hydroxyethyl ammonium salt (I). The weight ratio of anionic surfactant to (I) is 2-50:1.

Description

Flüssigwaschmittel in disperser Form auf wässriger Basis, enthaltend Tenside, quaternäres Alkyldimethylhydroxyethyl-ammoniumsalz und/oder Alkylmethylbishydroxyethylammoniumsalz, einen oder mehrere Elektrolyte und einen oder mehrere Builder.
Durch Zusatz von Hydroxyethyl-Quats zu einer wässrigen Lösung aus Tensiden, Elektrolyten und Builder wird eine sehr stabile Dispersion mit gutem Waschvermögen und günstigem Viskositätsverhalten erhalten.Aqueous-based liquid detergent dispersions containing surfactants, quaternary alkyldimethylhydroxyethylammonium salt and / or alkylmethylbishydroxyethylammonium salt, one or more electrolytes and one or more builders.
By adding hydroxyethyl quats to an aqueous solution of surfactants, electrolytes and builders, a very stable dispersion with good detergency and favorable viscosity behavior is obtained.

Flüssige Waschmittel haben gegenüber festen, pulverförmigen oder teilchenförmigen Produkten einige anwendungstechnische Vorteile. Sie lassen sich leicht abmessen, lösen sich schnell im Waschwasser und können in konzentrierten Lösungen oder Dispersionen auf verschmutzte Stellen der zu waschenden Textilien aufgebracht werden. Darüber hinaus kann man in flüssige Waschmittelformulierungen Substanzen einbauen, die sich bei Trocknungsvorgängen zersetzen würden und für feste Mittel nicht geeignet sind.
In klaren Flüssigwaschmittel-Formulierungen können infolge begrenzter Löslichkeit nur begrenzte Mengen löslicher Inhaltsstoffe, z.B. Builder und Tenside, eingearbeitet werden und dementsprechend muss im Waschgang höher dosiert werden, um auch bei hohen Wasserhärten und entsprechender partieller Inaktivierung der anionischen Tenside eine gute Waschleistung sicherzustellen.
In Flüssigwaschmittel-Dispersionen können sehr viel größere Mengen an Inhaltsstoffen eingesetzt werden und damit kann eine Verminderung der Dosierung pro Waschgang erzielt werden. Zudem erlauben Flüssigwaschmittel-Dispersionen die Verwendung von nur schlecht wasserlöslichen Inhaltsstoffen. Des weiteren haben Flüssigwaschmittel-Dispersionen in der Regel deutlich höhere Viskositäten als klare Flüssigwaschmittel-Formulierungen.
Flüssigwaschmittel-Dispersionen tendieren auf der anderen Seite zur Phasentrennung bei längeren Lagerzeiten und größeren Temperaturschwankungen. Liquid detergents have some performance advantages over solid, powdered or particulate products. They are easy to measure, dissolve quickly in the wash water and can be applied in concentrated solutions or dispersions on soiled areas of the textiles to be washed. In addition, it is possible to incorporate into liquid detergent formulations substances which would decompose during drying processes and are unsuitable for solid detergents.
In clear liquid detergent formulations only limited amounts of soluble ingredients such as builders and surfactants can be incorporated due to limited solubility and accordingly must be higher doses in the wash to ensure a good wash performance even at high water hardness and corresponding partial inactivation of anionic surfactants.
In liquid detergent dispersions much larger amounts of ingredients can be used and thus a reduction in the dosage per wash can be achieved. In addition, liquid detergent dispersions allow the use of only poorly water-soluble ingredients. Furthermore, liquid detergent dispersions generally have significantly higher viscosities than clear liquid detergent formulations.
Liquid detergent dispersions, on the other hand, tend to phase separate for longer storage times and greater temperature fluctuations.

So erfahren manche Produkte eine Trennung beim Lagern, andere beim Kühlen und lassen sich nicht leicht wieder dispergieren. In manchen Fällen ändert sich die Viskosität des Produktes, das entweder zu dick und nicht mehr fließfähig wird oder zu wässrig dünn erscheint.So some products experience a separation during storage, others during cooling and can not be redispersed easily. In some cases, that changes Viscosity of the product that either becomes too thick and no longer flowable or appears too watery thin.

Es stellte sich die Aufgabe, flüssig-disperse Waschmittelformulierungen zu bereiten, die neben einem guten Reinigungsvermögen über lange Zeiträume und auch bei großen Temperaturschwankungen keine Phasentrennung zeigen, ein günstiges rheologisches Verhalten aufweisen und kostengünstig hergestellt werden können.The object was to prepare liquid-disperse detergent formulations, which in addition to a good cleaning power over long periods and also at large temperature fluctuations show no phase separation, a favorable one have rheological behavior and can be produced inexpensively.

In EP 170 091 werden disperse Flüssigwaschmittel auf wässriger Basis beansprucht, enthaltend lineares Alkylbenzolsulfonat, Kalium- oder Natriumtripolyphosphat und einen festen Builder. Die Formulierungen zeichnen sich dadurch aus, dass in Gegenwart des Elektrolyten die Löslichkeit des Tensides in Wasser reduziert wird und dieses infolge des Aussalzeffektes dispergiert in der wässrigen Phase vorliegt.
Eigene Untersuchungen zeigen, dass Tenside mit besserer Wasserlöslichkeit im Vergleich zu Alkylbenzolsulfonat, beispielsweise sek. Alkansulfonate, in Gegenwart von Elektrolyten einen geringen Aussalzeffekt zeigen und sich folglich nicht in gleicher Weise als Dispersionen formulieren lassen.EP 170 091 claims waterborne disperse liquid detergents containing linear alkylbenzenesulfonate, potassium or sodium tripolyphosphate and a solid builder. The formulations are characterized in that in the presence of the electrolyte, the solubility of the surfactant is reduced in water and this is dispersed due to the salting-out effect in the aqueous phase.
Our own investigations show that surfactants with better water solubility compared to alkylbenzenesulfonate, for example sec. Alkanesulfonates, in the presence of electrolytes show a low salting-out effect and consequently can not be formulated in the same way as dispersions.

Überraschenderweise wurde gefunden, dass durch Zusatz geringer Mengen einer quaternären Alkylhydroxyethylammoniumverbindung zu einer wässrigen Mischung, enthaltend anionische Tenside, Builder und gegebenenfalls Elektrolyte, die Phasenstabilität und Löslichkeit von Flüssigwaschmittel-Dispersionen verbessert werden kann.
Neben der verbesserten Lagerstabilität wurde für spezielle Anschmutzungen, insbesondere gegenüber öl- oder fetthaltigen Flecken, eine bessere Waschleistung der erfindungsgemäßen Flüssigwaschmittel-Dispersionen gefunden.Surprisingly, it has been found that by adding small amounts of a quaternary Alkylhydroxyethylammoniumverbindung to an aqueous mixture containing anionic surfactants, builders and optionally electrolytes, the phase stability and solubility of liquid detergent dispersions can be improved.
In addition to the improved storage stability, a better washing performance of the liquid detergent dispersions according to the invention was found for special stains, in particular against oily or greasy stains.

Gegenstand der Erfindung sind wässrige Flüssigwaschmittel-Dispersionen, die im wesentlichen

  • 5 bis 35, vorzugsweise 5 bis 25, insbesondere 5 bis 20 Gew.-% anionisches Tensid
  • 10 bis 50, vorzugsweise 10 bis 40, insbesondere 10 bis 30 Gew.-% Builder,
  • 0 bis 10, vorzugsweise 0 bis 7, insbesondere 0 bis 4 Gew.-% Elektrolyten und
  • 0,1 bis 10 Gew.-% quaternäres Alkylhydroxyethylammoniumsalz
    • enthalten, wobei das Gew.-%-Verhältnis anionisches Tensid zu quaternärem Alkylhydroxyethylammoniumsalz 50:1 bis 2:1, vorzugsweise 30:1 bis 2:1, insbesondere 15:1 bis 2:1 beträgt.The invention relates to aqueous liquid detergent dispersions which are substantially
  • 5 to 35, preferably 5 to 25, in particular 5 to 20 wt .-% anionic surfactant
  • 10 to 50, preferably 10 to 40, in particular 10 to 30 wt .-% builder,
  • 0 to 10, preferably 0 to 7, in particular 0 to 4 wt .-% of electrolytes and
  • 0.1 to 10% by weight of quaternary alkylhydroxyethylammonium salt
    • wherein the weight .-% ratio of anionic surfactant to quaternary alkylhydroxyethylammonium 50: 1 to 2: 1, preferably 30: 1 to 2: 1, in particular 15: 1 to 2: 1.

    Die erfindungsgemäßen Mittel enthalten bevorzugt quaternäres Alkylhydroxyethylammoniumsalz gemäß der Formel 1

    Figure 00030001
    wobei R1 für eine lineare oder verzweigte, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 22 Kohlenstoffatomen, bevorzugt 8 bis 18 Kohlenstoffatomen, besonders bevorzugt 12 bis 14 Kohlenstoffatomen, R2 für eine Methylgruppe, R3 für eine Methylgruppe oder eine Gruppe der Formel -A-(OA)n-OH steht, wobei A eine -C2H4 - und/oder -C3H6-Gruppe und n eine Zahl von 0 bis 20 sein kann, R4 für eine Gruppe der Formel -A-(OA)n-OH steht und X ein Anion bedeutet, X ist beispielsweise Chlorid, Bromid, Iodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Acetat, Citrat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Polyphosphat, Metaphosphat, Nitrat, Methylsulfat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat oder ein Anion der Formeln R6SO3, R7SO4 oder R6COO, worin R6 und R7 C2-C20-, vorzugsweise C10-C18-Alkyl, und R7 zusätzlich auch C1-C18-Alkylphenyl bedeuten.The agents according to the invention preferably contain quaternary alkylhydroxyethylammonium salt according to the formula 1
    Figure 00030001
    wherein R 1 is a linear or branched, saturated or unsaturated alkyl group having 5 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, R 2 is a methyl group, R 3 is a methyl group or a group of the formula -A - (OA) n -OH, where A is a -C 2 H 4 and / or C 3 H 6 group and n is a number from 0 to 20, R 4 is a group of the formula -A- ( OA) n is -OH and X is an anion, X is, for example, chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, bicarbonate, acetate, citrate, phosphate, mono- and dihydrogen phosphate, pyrophosphate, polyphosphate, metaphosphate, Nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonate or an anion of the formulas R 6 SO 3 , R 7 SO 4 or R 6 COO, wherein R 6 and R 7 are C 2 -C 20 -, preferably C 10 -C 18 alkyl, and R 7 additionally also C 1 -C 18 alkylphenyl mean.

    Besonders bevorzugt als Verbindung der Formel (1) ist quaternäres C12-C14-Alkyldimethylhydroxyethylammoniumchlorid oder -methosulfat.Particularly preferred as the compound of the formula (1) is C 12 -C 14 quaternary alkyldimethylhydroxyethylammonium chloride or methosulfate.

    Als anionische Tenside kommen in Betracht vor allem sek. Alkansulfonate, aber auch Alkylestersulfonate, Alkylsulfate, -carboxylate, -phosphate, -sulfonate, Arylalkylsulfonate, Alkylethersulfate und Mischungen aus den genannten Verbindungen. Im folgenden sollen einige der in Frage kommenden Typen von anionischen Tensiden näher beschrieben werden.Suitable anionic surfactants are especially sec. Alkanesulfonates, but also alkyl ester sulfonates, alkyl sulfates, carboxylates, phosphates, sulfonates, Arylalkylsulfonate, alkyl ether sulfates and mixtures of the above Links. The following are some of the candidate types of anionic surfactants are described in more detail.

    Sekundäre AlkansulfonateSecondary alkanesulfonates

    Sekundäre Alkansulfonate sind Tenside der Formel R-SO3M, deren Alkylgruppe R gesättigt oder ungesättigt, linear oder verzweigt ist und die auch Hydroxylgruppen tragen können, wobei die endständigen Kohlenstoffatome der Alkylkette keine Sulfonatgruppe aufweisen.
    Bevorzugt sind sekundäre Alkansulfonate mit linearen Alkylgruppen mit 9 bis 25 Kohlenstoffatomen, bevorzugt mit 10 bis 20 Kohlenstoffatomen, besonders bevorzugt mit 13 bis 17 Kohlenstoffatomen. Gegenion M kann Natrium-, Kalium-, Ammonium-, Mono-, Di- oder Tri-Alkanol-Ammonium, Calcium-, Magnesiumion oder Mischungen daraus sein. Bevorzugt sind Natriumsalze der sekundären Alkansulfonate.    Secondary alkanesulfonates are surfactants of the formula R-SO 3 M, whose alkyl group R is saturated or unsaturated, linear or branched and which can also carry hydroxyl groups, wherein the terminal carbon atoms of the alkyl chain have no sulfonate group.
    Preference is given to secondary alkanesulfonates having linear alkyl groups having 9 to 25 carbon atoms, preferably having 10 to 20 carbon atoms, particularly preferably having 13 to 17 carbon atoms. Counterion M may be sodium, potassium, ammonium, mono-, di- or tri-alkanol ammonium, calcium, magnesium ion or mixtures thereof. Preference is given to sodium salts of the secondary alkanesulfonates.

    AlkylestersulfonateAlkyl

    Alkylestersulfonate stellen lineare Ester von C8-C20-Carboxylsäuren (d.h. Fettsäuren) dar, die durch SO3 sulfoniert werden. Geeignete Ausgangsmaterialien sind natürliche Fettderivate, wie z.B. Talg- oder Palmölfettsäure.Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by SO 3 . Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.

    Alkylsulfatealkyl sulfates

    Alkylsulfate sind wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R bevorzugt einen C10-C24-Kohlenwasserstoffrest, bevorzugt einen Alkyl- oder Hydroxyalkylrest mit 10 bis 20 C-Atomen, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. M ist Wasserstoff oder ein Kation, z.B. ein Alkalimetallkation (z.B. Natrium, Kalium, Lithium) oder Ammonium oder substituiertes Ammonium, z.B. ein Methyl-, Dimethyl- und Trimethylammoniumkation oder ein quaternäres Ammoniumkation, wie Tetramethylammonium- und Dimethylpiperidiniumkation und quatäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylamin, Diethylamin, Triethylamin und deren Mischungen. Alkylketten mit C12-C16 sind dabei bevorzugt für niedrige Waschtemperaturen (z.B. unter ca. 50°C) und Alkylketten mit C16-C18 bevorzugt für höhere Waschtemperaturen (z.B. oberhalb ca. 50°C). Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably has a C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 -alkyl or Represents hydroxyalkyl. M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, eg a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below about 50 ° C) and alkyl chains with C 16 -C 18 preferably for higher washing temperatures (eg above about 50 ° C).

    Alkylethersulfatealkyl ether

    Die Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A)mSO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder Hydroxyalkylrest mit 10 bis 24 C-Atomen, bevorzugt einen C12-C20-Alkyl- oder Hydroxyalkylrest, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl von größer als 0, typischerweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. ein Metallkation (z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, etc.), Ammonium oder ein substituiertes Ammoniumkation. Beispiele für substituierte Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quaternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen, sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin, Mischungen davon und ähnliche, abgeleitet sind. Als Beispiele seien genannt C12-C18-Alkyl-polyethoxylat(1,0)-sulfat, C12-C18-Alkyl-polyethoxylat (2,25)sulfat, C12-C18-Alkyl-polyethoxylat (3,0)sulfat, C12-C18-Alkyl-polyethoxylat (4,0)sulfat, wobei das Kation Natrium oder Kalium ist.The alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C 12 -C 20 -alkyl radical. or hydroxyalkyl radical, particularly preferably a C 12 -C 18 -alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy moiety, m is a number greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is a hydrogen atom or a cation such as for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium, or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples which may be mentioned are C 12 -C 18 -alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 -alkyl polyethoxylate (2,25) sulfate, C 12 -C 18 -alkyl polyethoxylate (3.0 ) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, wherein the cation is sodium or potassium.

    Andere anionische Tenside die nützlich für den Einsatz in Wasch- und Reinigungsmitteln sind, sind C8-C24-Olefinsulfonate, sulfonierte Polycarboxylsäuren, hergestellt durch Sulfonierung der Pyrrolyseprodukte von Erdalkalimetallcitraten, wie z.B. beschrieben im britischen Patent GB 1,082,179, Alkylglycerinsulfate, Fettacylglycerinsulfate, Oleylglycerinsulfate, Alkylphenolethersulfate, primäre Paraffinsulfonate, Alkylphosphate, Alkyletherphosphate, Isethionate, wie Acylisethionate, N-Acyltauride, Alkylsuccinamate, Sulfosuccinate, Monoester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Monoester) und Diester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Diester), Acylsarcosinate, Sulfate von Alkylpolysacchariden wie Sulfate von Alkylglycosiden, verzweigte primäre Alkylsulfate und Alkylpolyethoxycarboxylate wie die der Formel RO(CH2CH2)kCH2COO-M+ worin R ein C8-C22Alkyl, k eine Zahl von 0 bis 10 und M ein lösliches Salz bildendes Kation ist. Harzsäuren oder hydrierte Harzsäuren, wie Rosin oder hydriertes Rosin oder Tallölharze und Tallölharzsäuren sind ebenfalls einsetzbar. Other anionic surfactants useful in laundry detergents and cleaners are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrrole products of alkaline earth metal citrates such as described in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, Alkylphenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 - C 18 diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl glycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH 2 CH 2 ) k CH 2 COO - M + wherein R is C 8 -C 22 alkyl, k a number from 0 to 10 and M a soluble S alz is forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil rosin acids are also useful.

    Die erfindungsgemäßen dispersen Flüssigwaschmittel enthalten als weitere Komponente einen oder mehrere Builder.
    Als organische und anorganische Builder eignen sich neutral oder insbesondere alkalisch reagierende Salze, die Calciumionen auszufällen oder komplex zu binden vermögen. Builder wie Orthophosphate und kondensierte Phosphate, z.B. Pyrophosphate, Triphosphate, Tetraphosphate, Polyphosphate und Metaphosphate, sowie feinkristalline, synthetische wasserhaltige Zeolithe sind bevorzugt. Besonders geeignet sind Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogenphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie Gemische aus Natrium- und Kaliumsalzen. Neben Phosphaten und Zeolithen werden auch bevorzugt Schichtsilikate und amorphe Silikate sowie Carbonate und Hydrogencarbonate eingesetzt.    The disperse liquid detergents according to the invention contain one or more builders as further component.
    Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which precipitate or complex calcium ions. Builders such as orthophosphates and condensed phosphates, eg pyrophosphates, triphosphates, tetraphosphates, polyphosphates and metaphosphates, as well as fine crystalline, synthetic hydrous zeolites are preferred. Particularly suitable are alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts. In addition to phosphates and zeolites, it is also preferred to use sheet silicates and amorphous silicates, as well as carbonates and bicarbonates.

    Brauchbare organische Builder sind beispielsweise Citronensäure, Nitriloacetat (NTA) sowie Ethylendiamintetraessigsäure die bevorzugt in Form ihrer Salze eingesetzt werden, und Phosphon- und Polyphosphonsäuren . Analog hierzu können auch polymere Carboxylate und deren Salze eingesetzt werden. Hierzu gehören beispielsweise die Salze homopolymerer oder copolymerer Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure, sowie Polyasparaginsäure und auch Polyvinylpyrrolidon und Urethane. 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, insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol 940 und 941 erhältlichen Polymere. Als Phosphonate kommen beispielsweise Acetodiphosphonate, Aminotrismethylenphosphonate und Ethylentetramethylenphosphonate in Frage. Useful organic builders include citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, preferably in the form of their salts are used, and phosphonic and polyphosphonic. Analogous to this also polymeric carboxylates and their salts are used. These include for example, the salts of homopolymeric or copolymeric polyacrylates, Polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid, and polyaspartic acid and also polyvinylpyrrolidone and urethanes. The molecular weight of the Homopolymers is generally between 1000 and 100 000, which is the Copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular are water-soluble polyacrylates suitable, for example, with about 1% of a polyallyl ether of sucrose are cross-linked and have a molecular weight above one million have. Examples include the carbopol 940 and 941 available polymers. As phosphonates, for example Acetodiphosphonates, aminotrismethylene phosphonates and Ethylene tetramethylene phosphonates in question.

    Unter "Elektrolyte" werden nicht-grenzenflächenaktive, wasserlösliche, ionische Verbindungen verstanden, die die Löslichkeit oder die Micellkonzentration von Tensiden in der wässrigen Formulierung herabsetzen und einen "Aussalz-Effekt" bewirken. Geeignet sind Alkali- oder Ammoniumchloride, -nitrate, -phosphate, - carbonate, -sulfate, -silikate, -acetate, -citrate oder -polyphosphate. Bevorzugt eingesetzt werden Kaliumchlorid, Kaliumsulfat, Kaliumcarbonat, Pentanatriumtriphosphat und Pentakaliumtriphosphat."Electrolytes" are non-boundary surface active, water soluble, ionic Compounds understood to be the solubility or micelle concentration of Degrade surfactants in the aqueous formulation and have a "salting-out effect" cause. Suitable are alkali or ammonium chlorides, nitrates, phosphates, - carbonates, sulphates, silicates, acetates, citrates or polyphosphates. Prefers potassium chloride, potassium sulfate, potassium carbonate, Pentasodium triphosphate and pentapotassium triphosphate.

    Die erfindungsgemäßen dispersen Flüssigwaschmittel können zusätzlich zu den anionischen Tensiden noch nichtionische, amphotäre, aber auch kationische Tenside enthalten.The disperse liquid detergents according to the invention can be used in addition to the anionic surfactants still nonionic, amphoteric, but also cationic Containing surfactants.

    Bevorzugte nichtionische Tenside sind Fettalkoholoxethylate mit ca. 1 bis ca. 25 mol Ethylenoxid. Die Alkylkette der aliphatischen Alkohole kann linear oder verzweigt, primär oder sekundär sein, und enthält im allgemeinen von 8 bis 22 Kohlenstoffatome. Besonders bevorzugt sind die Kondensationsprodukte von Alkoholen, die eine Alkylkette von 10 bis 20 Kohlenstoffen enthalten, mit 2 bis 18 mol Ethylenoxid pro mol Alkohol. Die Alkylkette kann gesättigt oder auch ungesättigt sein. Ebenso können die Alkoholethoxylate eine enge Homologenverteilung des Ethylenoxides ("Narrow Range Ethoxylates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Beispiele von kommerziell erhältlichen nichtionischen Tensiden dieses Types sind Tergitol™ 15-S-9 (Kondensationsprodukt eines C11-C15 linearen sekundären Alkohols mit 9 mol Ethylenoxid), Tergitol™ 24-L-NMW (Kondensationsprodukt eines C12-C14-linearen primären Alkohols mit 6 mol Ethylenoxid mit enger Molgewichtsverteilung). Ebenfalls unter diese Produktklasse fallen die Genapol™-Marken der Clariant GmbH.Preferred nonionic surfactants are fatty alcohol ethoxylates containing from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl chain of 10 to 20 carbons with 2 to 18 moles of ethylene oxide per mole of alcohol. The alkyl chain can be saturated or unsaturated. Likewise, the alcohol ethoxylates may have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol ™ 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol ™ 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol ™ brands from Clariant GmbH.

    Darüber hinaus kommen erfindungsgemäß auch andere bekannte Typen von nichtionischen Tensiden in Frage, wie Polyethylen-, Polypropylen- und Polybutylenoxidaddukte von Fettalkoholen mit 8 bis 22 C-Atomen in der Alkylkette sowie von Alkylphenolen mit 6 bis 12 C-Atomen in der Alkylkette, Additionsprodukte von Ethylenoxid mit einer hydrophoben Base, gebildet aus der Kondensation von Propylenoxid mit Propylenglykol oder Additionsprodukte von Ethylenoxid mit einem Reaktionsprodukt von Propylenoxid und Ethylendiamin, aber auch Fettsäurepolyhydroxyamide und Fettsäureamidoalkoxylate.In addition, according to the invention, other known types of nonionic surfactants such as polyethylene, polypropylene and Polybutylene oxide adducts of fatty alcohols containing 8 to 22 C atoms in the alkyl chain and of alkylphenols having 6 to 12 C atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base formed from the condensation of Propylene oxide with propylene glycol or addition products of ethylene oxide with a Reaction product of propylene oxide and ethylenediamine, but also Fatty acid polyhydroxyamides and fatty acid amido alkoxylates.

    Des weiteren können semipolare nichtionische Tenside, beispielsweise Aminoxide der Formel

    Figure 00080001
    eingesetzt werden, worin R8 eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe oder Mischungen hiervon darstellt mit einer Kettenlänge von 8 bis 22 Kohlenstoffatome; R9 ist eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon; R10 ist eine Alkyl- oder Hydroxyalkylgruppe mit. 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten. Die R10/R9-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden.
    Diese Aminoxide umfassen besonders C10-C18-Alkyldimethylaminoxide und C8-C12-Alkoxyethyl-Dihydroxyethylaminoxide.Furthermore, semipolar nonionic surfactants, for example amine oxides of the formula
    Figure 00080001
    where R 8 is an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof having a chain length of 8 to 22 carbon atoms; R 9 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; R 10 is an alkyl or hydroxyalkyl group with. 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units. The R 10 / R 9 groups may be linked together via an oxygen or nitrogen atom and thus form a ring.
    These amine oxides particularly include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxyethyl dihydroxyethyl amine oxides.

    Beispiele für amphotäre Tenside, die in den Formulierungen der vorliegenden Erfindung Einsatz finden können, sind vor allem solche, die als Derivate von aliphatischen sekundären und tertiären Aminen beschrieben werden, in denen der aliphatische Rest linear oder verzweigt sein kann und in denen einer der aliphatischen Substituenten zwischen 8 bis 18 Kohlenstoffatome enthält und eine anionische, wasserlösliche Gruppe, wie z.B. Carboxy, Sulfonat, Sulfat, Phosphat oder Phosphonat enthält. Amphotäre Tenside in diesem Zusammenhang schließen amphotäre Imidazolinium-Tenside ein, wie sie in der nachfolgenden Formel dargestellt sind:

    Figure 00090001
    worin R11 C8-C22-Alkyl oder Alkenyl, bevorzugt C12-C16, R12 Wasserstoff oder eine Gruppe der Formel CH2CO2M, R13 eine Gruppe der Formeln CH2CH2OH oder CH2CH2OCH2CHCOOM, R14 Wasserstoff oder eine Gruppe der Formeln CH2CH2OH oder CH2CH2OCH2CHCOOM, Z CO2M oder CH2CO2M bedeutet,
    n ist 2 oder 3, bevorzugt 2, M ist Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, Ammoniak oder Alkanolammonium.Examples of amphoteric surfactants which can be used in the formulations of the present invention are, above all, those which are described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic substituents contains between 8 to 18 carbon atoms and contains an anionic, water-soluble group, such as carboxy, sulfonate, sulfate, phosphate or phosphonate. Amphoteric surfactants in this context include amphoteric imidazolinium surfactants as represented by the following formula:
    Figure 00090001
    wherein R 11 is C 8 -C 22 alkyl or alkenyl, preferably C 12 -C 16 , R 12 is hydrogen or a group of the formula CH 2 CO 2 M, R 13 is a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 14 is hydrogen or a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M,
    n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonia or alkanolammonium.

    Bevorzugte amphotäre Tenside der obigen Formel sind Monocarboxylate und Dicarboxylate. Bespiele dieser Verbindungen schließen Cocoamphocarboxypropionat, Cocoamidocaboxypropionsäure, Cocoamphocarboxyglycinat (oder auch als Cocoamphodiacetat bezeichnet) und Cocoamphoacetat ein.Preferred amphoteric surfactants of the above formula are monocarboxylates and Dicarboxylates. Close examples of these connections Cocoamphocarboxypropionate, cocoamidocaboxypropionic acid, Cocoamphocarboxyglycinate (or also called cocoamphodiacetate) and Cocoamphoacetate.

    Weitere bevorzugte amphotäre Tensid sind Alkyldimethylbetaine, Alkylamidobetaine und Alkyldipolyethoxybetaine mit einem Alkylrest, der linear oder verzweigt sein kann, mit 8 bis 22 Kohlenstoffatomen, bevorzugt mit 8 bis 18 Kohlenstoffatomen und besonders bevorzugt mit 12 bis 18 Kohlenstoffatomen. Diese Verbindungen werden z.B. von der Clariant GmbH unter dem Handelnamen Genagen® vermarktet.Other preferred amphoteric surfactants are alkyl dimethyl betaines, alkylamido betaines and alkyl dipolyethoxybetaines having an alkyl group which may be linear or branched can, with 8 to 22 carbon atoms, preferably with 8 to 18 carbon atoms and particularly preferably having 12 to 18 carbon atoms. These connections will be e.g. marketed by Clariant GmbH under the trade name Genagen®.

    Typische Beispiele für kationische Tenside sind quartäre Ammoniumverbindungen und Esterquats, insbesondere quaternierte Fettsäurealkanolaminester-Salze und Dialkylaminopropylaminester-Salze.Typical examples of cationic surfactants are quaternary ammonium compounds and esterquats, in particular quaternized fatty acid alkanolamine ester salts and Dialkylaminopropylaminester salts.

    Hilfs- und ZusatzstoffeAuxiliaries and additives

    Die erfindungsgemäßen Flüssigwaschmittel können die für diese Produkte üblichen Hilfs- und Zusatzstoffe, beispielsweise Bleichaktivatoren, Bleichkatalysatoren, optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Lösungsvermittler, Hydrotrope, Enzyme, Enzymstabilisatoren, Verdickungsmittel , Konservierungsmittel, Duft- und Farbstoffe, Perlglanzmittel, Schauminhibitoren, Sequestriermittel, Korrosionsinhibitoren und Antioxidantien enthalten.The liquid detergents according to the invention may be those customary for these products Auxiliaries and additives, for example bleach activators, bleach catalysts, optical brighteners, grayness inhibitors, color transfer inhibitors, Solubilizers, hydrotropes, enzymes, enzyme stabilizers, thickeners, Preservatives, fragrances and dyes, pearlescers, foam inhibitors, Contain sequestering agents, corrosion inhibitors and antioxidants.

    Repräsentative Beispiele für Bleichaktivatoren sind etwa N,N,N',N'-Tetraacetylethylendiamin (TAED), Nonanoylcaprolactamphenylsulfonatester (APES), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Acyloxybenzolsulfonate (z.B. Nonanoyloxybenzolsulfonat (NOBS), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS)), Diacetyldioxohexahydrotriazin (DADHT), Tetraacetylglucoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG) und 1-Phenyl-3-acetylhydantoin (PAH) und Nitrilotriacetat (NTA), sowie Ammoniumnitrile ("Nitrilquats"), die in Kombination mit einer Wasserstoffperoxidquelle eingesetzt werden. Beispiele hierfür sind Perborat-Monohydrat, Perborat-Tetrahydrat, Percarbonate, Alkalipersulfate, -persilikate und -percitrate, wobei Natrium das bevorzugte Alkalimetall ist, sowie Wasserstoffperoxid-Addukte an Harnstoff oder Aminoxiden. Zusätzlich oder alternativ können Peroxycarbonsäuren, zum Beispiel Dodecandipersäure oder Phthalimidopercarbonsäuren, die gegebenenfalls am Aromaten substituiert sein können, enthalten sein. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten, beziehungsweise Metaboraten und Metasilikaten, sowie Magnesiumsalzen wie Magnesiumsulfat kann vorteilhaft sein.
    Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure und deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Ebenso eignen sich substituierte Diphenylstyryle, z.B. Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls.
    Der maximale Gehalt an Aufhellern in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.     Representative examples of bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoyl-caprolactam phenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonates (eg nonanoyloxybenzenesulfonate (NOBS), sodium 4-benzoyloxybenzenesulfonate ( SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS)), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH) and nitrilotriacetate (NTA), as well Ammonium nitriles ("nitrile quats"), which are used in combination with a hydrogen peroxide source. Examples include perborate monohydrate, perborate tetrahydrate, percarbonates, alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal, as well as hydrogen peroxide adducts of urea or amine oxides. Additionally or alternatively, peroxycarboxylic acids, for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, may be present. The addition of small amounts of known bleach stabilizers such as phosphonates, borates, or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be advantageous.
    The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure and their alkali metal salts. Suitable examples are salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar construction, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Likewise suitable are substituted diphenylstyryls, for example alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl).
    The maximum content of brighteners in the compositions according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.

    Vergrauungsinhibitoren haben die Aufgabe, den abgelösten Schmutz in der Flotte suspendiert zu halten. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Stärke und Cellulose sowie deren Derivate, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkederivate verwenden, z.B. Aldehydstärken.
    Bevorzugt werden Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose in Mengen von 0,3 Gew.-% bis 5 Gew.-% bezogen auf das fertige Mittel eingesetzt.    Graying inhibitors have the task of keeping the loosened soil suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch and cellulose and their derivatives, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches.
    Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, in amounts of from 0.3% by weight to 5% by weight, based on the finished composition.

    Als Farbübertragungsinhibitoren eignen sich Polyvinylpyrrolidone, Polyvinylimidazole, polymere N-Oxide wie Poly-(vinylpyridin-N-oxid) und Copolymere von Vinylpyrrolidon mit Vinylimidazol. Auch Farbschutzadditive wie z.B. quaternäre Polyaminderivate, kationische Methylolamide oder Formaldehydkondensationsprodukte, können eingesetzt werden.Suitable color transfer inhibitors are polyvinylpyrrolidones, Polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole. Also color protective additives such as e.g. quaternary Polyamine derivatives, cationic methylolamides or formaldehyde condensation products, can be used.

    Die erfindungsgemäßen Mittel können als Schauminhibitoren Fettsäurealkylesteralkoxylate, Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure, enthalten. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen.The agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica. With Advantage may also be used mixtures of different foam inhibitors, e.g. those made of silicone oil, paraffin oil or waxes.

    Die gewünschte Viskosität der Mittel kann durch Zugabe von Wasser und/oder organischen Lösungsmitteln oder durch Zugabe einer Kombination aus organischen Lösungsmitteln und Verdickungsmitteln eingestellt werden.
    Prinzipiell kommen als organische Lösungsmittel alle ein- oder mehrwertigen Alkohole in Betracht. Bevorzugt werden Alkohole mit 1 bis 4 Kohlenstoffatomen wie Methanol, Ethanol, Propanol, Isopropanol, geradkettige und verzweigtes Butanol, Glycerin und Mischungen aus den genannten Alkoholen eingesetzt. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 in Mengen von 5 bis 25 Gew.-% bevorzugt. Eine vorteilhafte Mischung aus Lösungsmitteln besteht aus monomerem Alkohol, beispielsweise Ethanol und Polyethylenglykol im Verhältnis 0.5 : 1 bis 1.2 : 1, wobei die erfindungsgemäßen Flüssigwaschmittel 8 bis 12 Gew.-% einer solchen Mischung enthalten können. Weitere geeignete Lösungsmittel sind beispielsweise Triacetin (Glycerintriacetat) und 1-Methoxy-2-propanol.    The desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
    In principle, all mono- or polyhydric alcohols are suitable as organic solvents. Alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. More preferred alcohols are polyethylene glycols having a molecular weight less than 2,000. In particular, use of polyethylene glycol having a molecular weight of between 200 and 600 and up to 45% by weight and polyethylene glycol having a molecular weight of between 400 and 600 in amounts of 5 to 25 wt .-% preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, wherein the liquid detergent according to the invention may contain 8 to 12 wt .-% of such a mixture. Other suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

    Als Verdickungsmittel werden bevorzugt gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-. Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder KaliumSalze der Behensäure, sowie Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon eingesetzt. Ebenso geeignet sind Copolymere auf Basis von Acryloyldimethyltaurinsäure, wie in EP 10 60142, EP 10 28129, EP 11 16 733 und Hostacerin® AMPS beschrieben.As a thickener are preferably hydrogenated castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2 wt .-%, for example sodium. Potassium-, Aluminum, magnesium and titanium stearates or the sodium and / or potassium salts behenic acid, as well as polysaccharides, especially xanthan gum, guar guar, Agar-agar, alginates and tyloses, carboxymethylcellulose and Hydroxyethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone used. Also suitable are copolymers based on acryloyldimethyltaurine, as in EP 10 60142, EP 10 28129, EP 11 16 733 and Hostacerin® AMPS.

    Als Hydrotrope eignen sich beispielsweise Natriumtoluolsulphonat, Natriumcumolsulphonat, Natriumxylolsulphonat, Alkanphosphonsäuren und Alkenyldicarbonsäuren sowie deren Anhydride.Suitable hydrotropes are, for example, sodium toluene sulphonate, Sodium cumulosulphonate, sodium xylene sulphonate, alkanephosphonic acids and Alkenyldicarboxylic acids and their anhydrides.

    Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen und Cellulasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 bis 3 Gew.-% betragen. Die Enzyme können an Trägersubstanzen adsorbiert werden und/oder in Hüllsubstanzen eingebettet sein.Suitable enzymes are those from the class of proteases, lipases, amylases and Cellulases or mixtures thereof in question. Their proportion can be 0.2 to 3 wt .-% be. The enzymes can be adsorbed to carrier substances and / or in Be embedded nesting substances.

    Um Spuren von Schwermetallen zu binden, können die Salze von Polyphosphorsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), Ethylendiamintetramethylenphosphonsäure (EDTMP) und Diethylentriaminpentamethylenphosphonsäure (DTPMP) eingesetzt werden.To bind traces of heavy metals, the salts of Polyphosphoric acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Ethylenediaminetetramethylenephosphonic acid (EDTMP) and Diethylentriaminpentamethylenphosphonsäure (DTPMP) can be used.

    Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Isothiazolinone, Pentandiol oder Sorbinsäure.Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, isothiazolinones, pentanediol or sorbic acid.

    Als Perlglanzmittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremonoglycolester in Betracht.As pearlescing agents, for example, glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters.

    Die Herstellung der erfindungsgemäßen Flüssigwaschmittel kann durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, erfolgen.The preparation of liquid detergents according to the invention can be achieved by simple Mix the ingredients in bulk or as a solution in an automatic Mixer can be given done.

    Nachfolgende Beispiele sollen die Erfindung näher erläutern, ohne sie darauf einzuschränken. Alle Prozentangaben verstehen sich als Gewichtsprozent.The following examples are intended to explain the invention in more detail, without it limit. All percentages are by weight.

    Beispiele:Examples: 1. Formulierungen I (* Vergleichsbeispiele)1. Formulations I (* Comparative Examples)

    Inhaltsstoffeingredients Gehalt [%]Salary [%] 1*1* 2*2 * 33 44 55 66 LASREAD 99 -- -- -- -- -- Alkylsulfatalkyl sulfate 11 11 11 11 -- -- TEATEA 0,50.5 0,50.5 0,50.5 0,50.5 -- -- Hostapur SASHostapur SAS -- 99 99 99 99 99 Genapol DU 030Genapol DU 030 22 22 22 22 22 22 STPPSTPP 1414 1414 1414 -- 1414 1414 PTPPPTPP -- -- -- 1414 -- -- Natriumdisilikatsodium disilicate 0,50.5 0,50.5 0,50.5 0,50.5 0,50.5 0,50.5 Praepagen HYPraepagen HY -- -- 2,02.0 1,01.0 0,80.8 1,41.4 KCIKCI -- -- -- -- 2,32.3 - - K2SO4 K 2 SO 4 -- -- -- -- -- 2,02.0 Opt. AufhellerOpt. Brightener 0,10.1 0,10.1 0,10.1 0,10.1 0,10.1 0,10.1 Enzym (Cellulase)Enzyme (cellulase) 0,250.25 0,250.25 0,250.25 0,250.25 0,250.25 0,250.25 Viskosität [mPa·s]Viscosity [mPa · s] 27502750 -- 22002200 950950 16501650 16501650 (Brookfield RVT, 20 rpm, 22°C)(Brookfield RVT, 20 rpm, 22 ° C) (Spdl 3)(Spdl 3) -- (Spdl 3)(Spdl 3) (Spdl 3)(Spdl 3) (Spdl 3)(Spdl 3) (Spdl 3)(Spdl 3)

    2. Lagertest mit Formulierungen I2. Storage test with formulations I

    Bedingungenconditions 1*1* 2*2 * 33 44 55 66 RT, 28 TageRT, 28 days okOK zwei Phasentwo phases okOK okOK okOK okOK 40°C, 28 Tage40 ° C, 28 days zwei Phasentwo phases zwei Phasentwo phases okOK okOK okOK okOK 5°C, 28 Tage5 ° C, 28 days okOK zwei Phasentwo phases okOK okOK okOK okOK ok = homogene Dispersion, keine Phasentrennung beobachtbarok = homogeneous dispersion, no phase separation observable

    3. Waschversuche mit Formulierungen I3. Washing Tests with Formulations I

    Bedingungen:Conditions:
    LINITEST
    Temperatur: 40°C Waschzeit: 30 min Wasserhärte: 12 °d
    Dosierung: 10 g/l    LINITEST
    Temperature: 40 ° C Washing time: 30 min Water hardness: 12 ° d
    Dosage: 10 g / l
    Testgewebetest fabric Remission (457 nm, UV-Filter) [%]Remission (457 nm, UV filter) [%] 1*1* 33 44 55 66 Rotweinred wine 5151 5151 5050 5151 5151 Kaffeecoffee 5757 5858 5858 5959 5959 Teetea 4343 4343 4343 -- -- Chlorphyll/PflanzenölChlorophyll / vegetable oil 4343 4242 4242 4141 41 41 Pigment/ÖlPigment / oil 4848 4949 4848 n.d.n.d. n.d.n.d. Hautfettsebum 5757 5858 5858 5858 6060 Blut/Milch/TuscheBlood / milk / ink 3434 3434 3333 3131 3232 Kakaococoa 3838 3939 3939 -- -- 4. Formulierungen II (* Vergleichsbeispiele)4. Formulations II (* Comparative Examples)

    Inhaltsstoffeingredients Gehalt [%]Salary [%] 1*1* 7*7 * 88th 99 LASREAD 99 -- -- -- Alkylsulfatalkyl sulfate 11 -- -- -- TEATEA 0,50.5 -- -- -- Hostapur SASHostapur SAS -- 99 99 99 Genapol UD 030Genapol UD 030 22 11 11 11 STPPSTPP 1414 1212 1212 1212 PTPPPTPP -- -- -- -- Natriumdisilikatsodium disilicate 0,50.5 0,50.5 0,50.5 0,50.5 Praepagen HYPraepagen HY -- -- 2,12.1 1,51.5 KCIKCI -- -- -- 2,02.0 K2SO4 K 2 SO 4 -- -- -- -- Opt. AufhellerOpt. Brightener 0,10.1 0,050.05 0,050.05 0,050.05 Enzym (Cellulase)Enzyme (cellulase) 0,250.25 0,250.25 0,250.25 0,250.25 Viskosität [mPa·s]Viscosity [mPa · s] 27502750 -- 680680 740740 (Brookfield RVT, 20 rpm, 22°C)(Brookfield RVT, 20 rpm, 22 ° C) (Spdl 3)(Spdl 3) -- (Spdl 2)(Spdl 2) (Spdl 2)(Spdl 2)

    5. Lagertest mit Formulierungen II5. Storage test with formulations II

    Bedingungenconditions 1*1* 7*7 * 88th 99 RT, 28 TageRT, 28 days okOK zwei Phasentwo phases okOK okOK 40°C, 28 Tage40 ° C, 28 days zwei Phasentwo phases zwei Phasentwo phases okOK okOK 5°C, 28 Tage5 ° C, 28 days okOK zwei Phasentwo phases okOK ok OK ok = homogene Dispersion, keine Phasentrennung beobachtbarok = homogeneous dispersion, no phase separation observable

    6. Waschversuche mit Formulierungen II6. Washing Tests with Formulations II

    Bedingungen:Conditions:
    LINITEST
    Temperatur: 40°C Waschzeit: 30 min Wasserhärte: 12 °d
    Dosierung: 10 g/l    LINITEST
    Temperature: 40 ° C Washing time: 30 min Water hardness: 12 ° d
    Dosage: 10 g / l
    Testgewebetest fabric Remissionsdifferenz (457 nm, UV-Filter) [%]Remission difference (457 nm, UV filter) [%] 1*1* 7*7 * 88th 99 Lippenstiftlipstick 1414 1212 2020 2020

    Dieses Beispiel zeigt, dass die erfindungsgemäßen Formulierungen mit sek. Alkansulfonat und quaternärem Alkylhydroxyethylammoniumsalz deutliche Vorteile in der Waschleistung an bestimmten Anschmutzungen gegenüber den Vergleichsbeispielen haben.This example shows that the formulations of the invention with sec. Alkanesulfonate and quaternary Alkylhydroxyethylammoniumsalz significant advantages in the washing performance of certain stains against the Comparative examples have.

    7. Herstellung der Formulierungen im Labor7. Preparation of the formulations in the laboratory

    In einem Becherglas wird zunächst der optische Aufheller mit dem nichtionischen Tensid Genapol UD 030 mit einem Glasstab angeteigt, dann falls erforderlich Alkylsulfat und TEA zugemischt und anschließend das Hostapur SAS 60 ebenfalls mit einem Glasstab eingerührt (Mischung 1).In a beaker is first the optical brightener with the nonionic Surfactant Genapol UD 030 pasted with a glass rod, then if necessary Alkyl sulfate and TEA mixed and then the Hostapur SAS 60 also stirred with a glass rod (mixture 1).

    In einem zweiten Becherglas wird die benötigte Menge VE-Wasser vorgelegt und unter Rühren mit einem Magnetrührer zunächst 9 % STPP bzw. PTPP gelöst (Mischung 2).In a second beaker, the required amount of deionized water is submitted and with stirring with a magnetic stirrer initially solved 9% STPP or PTPP (Mix 2).

    Die klare Mischung 2 wird anschließend mit einem Glasstab in die Mischung 1 eingerührt, bis sich keine Teilchen der Tensidphase mehr an der Wandung des Becherglases befinden.The clear mixture 2 is then added to the mixture 1 with a glass rod stirred until no more particles of the surfactant phase on the wall of the Beaker are located.

    Danach wird die resultierende Mischung so lange mit einem Magnetrührer weitergerührt, bis sich eine homogene Dispersion bildet. Dabei wird die restliche Menge STPP bzw. PTPP (3 % bzw. 5 %) und anschließend das Natriumdisilikat zugegeben.Thereafter, the resulting mixture is so long with a magnetic stirrer further stirred until forms a homogeneous dispersion. It will be the rest Amount of STPP or PTPP (3% and 5% respectively) and then the sodium disilicate added.

    Nach Korrektur des pH-Wertes auf einen Wert von pH 8.3 wird die erforderliche Menge Praepagen HY und Kaliumsalz eingerührt. Zum Schluss wird die Cellulase untergemischt und eventuell verdampftes VE-Wasser ersetzt.After correcting the pH to a value of pH 8.3, the required Amount of Praepagen HY and potassium salt stirred. Finally, the cellulase mixed and possibly replaced deionized water replaced.

    Chemische Bezeichnung der eingesetzten HandelsprodukteChemical name of the commercial products used

    LASREAD
    lineares C12/14-Alkylbenzolsulfonatlinear C 12/14 alkyl benzene sulfonate
    Alkylsulfatalkyl sulfate
    C12/14-AlkylsulfatC 12/14 alkyl sulfate
    TEATEA
    Triethanolamintriethanolamine
    Hostapur SASHostapur SAS
    sek. C13-17-Alkansulfonatsec. C 13-17 alkane sulfonate
    Genapol DU 030Genapol DU 030
    C11-Oxalkoholpolyglykolether, 3EOC 11 oxalcohol polyglycol ether, 3EO
    STPPSTPP
    Natriumtripolyphosphatsodium tripolyphosphate
    PTPPPTPP
    Kaliumtripolyphosphatpotassium
    Praepagen HYPraepagen HY
    C12/14-AlkyldimethylhydroxyethylammoniumchloridC 12/14 -Alkyldimethylhydroxyethylammoniumchlorid

    Claims (13)

    Wässrige Flüssigwaschmittel-Dispersionen, die im wesentlichen 5 Gew.-% bis 35 Gew.-% anionisches Tensid 10 Gew.-% bis 50 Gew.-% Builder, 0 Gew.-% bis 10 Gew.-% Elektrolyten und 0,1 Gew.-% bis 10 Gew.-% quaternäres Alkylhydroxyethylammoniumsalz enthalten, wobei das Gew.-%-Verhältnis anionisches Tensid zu quaternärem Alkylhydroxyethylammoniumsalz 50:1 bis 2:1 beträgt.Aqueous liquid detergent dispersions which are substantially 5 wt .-% to 35 wt .-% anionic surfactant From 10% to 50% by weight of builder, 0 wt .-% to 10 wt .-% of electrolytes and 0.1 wt .-% to 10 wt .-% quaternary alkylhydroxyethylammonium salt wherein the weight% ratio of anionic surfactant to quaternary alkylhydroxyethylammonium salt is 50: 1 to 2: 1. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, enthaltend sek. Alkansulfonat als anionisches Tensid.Aqueous liquid detergent dispersions according to claim 1, containing sec. Alkanesulfonate as anionic surfactant. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, enthaltend C13-C17-sek. Alkansulfonat-Na-Salz als anionisches Tensid.Aqueous liquid detergent dispersions according to claim 1, containing C 13 -C 17 sec. Alkanesulfonate Na salt as anionic surfactant. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, enthaltend C12-C14-Alkyldimethyl-hydroxyethyl-ammonium-chlorid oder -methosulfat als quaternäres Alkylhydroxyethyl-ammonium-salz.Aqueous liquid detergent dispersions according to claim 1, containing C 12 -C 14 -alkyldimethyl-hydroxyethyl-ammonium chloride or methosulfate as quaternary alkylhydroxyethyl-ammonium salt. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 5 bis 25 Gew.-% anionisches Tensid enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 5 to 25 wt .-% of anionic surfactant. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 5 bis 20 Gew.-% anionisches Tensid enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 5 to 20 wt .-% of anionic surfactant. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 10 bis 40 Gew.-% Builder enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 10 to 40 wt .-% builder. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 10 bis 30 Gew.-% Builder enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 10 to 30 wt .-% builder. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 0 bis 7 Gew.-% Elektrolyt enthalten. Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 0 to 7 wt .-% electrolyte. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie 0 bis 4 Gew.-% Elektrolyt enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain 0 to 4 wt .-% electrolyte. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass das Gewichtsverhältnis anionisches Tensid zu quaternärem Alkylhydroxyethylammonium-Salz 30:1 bis 2:1 beträgt.Aqueous liquid detergent dispersions according to claim 1, characterized in that the weight ratio of anionic surfactant to quaternary alkylhydroxyethylammonium salt is 30: 1 to 2: 1. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass das Gewichtsverhältnis anionisches Tensid zu quaternärem Alkylhydroxyethylammonium-Salz 15:1 bis 2:1 beträgt.Aqueous liquid detergent dispersions according to Claim 1, characterized in that the weight ratio of anionic surfactant to quaternary alkylhydroxyethylammonium salt is 15: 1 to 2: 1. Wässrige Flüssigwaschmittel-Dispersionen nach Anspruch 1, dadurch gekennzeichnet, dass sie übliche Hilfs- und Zusatzstoffe enthalten.Aqueous liquid detergent dispersions according to claim 1, characterized in that they contain customary auxiliaries and additives.
    EP04001425.0A 2003-01-28 2004-01-23 Aqueous liquid detergent dispersions Expired - Lifetime EP1445301B1 (en)

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    DE10303130A DE10303130A1 (en) 2003-01-28 2003-01-28 Aqueous liquid detergent dispersion useful as a laundry detergent comprises anionic surfactant, builder and quaternary alkyl hydroxyethyl ammonium salt
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