EP2711413B2 - Waschmittel und Verfahren zur Dosierung eines Waschmittels - Google Patents

Waschmittel und Verfahren zur Dosierung eines Waschmittels Download PDF

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Publication number
EP2711413B2
EP2711413B2 EP13401032.1A EP13401032A EP2711413B2 EP 2711413 B2 EP2711413 B2 EP 2711413B2 EP 13401032 A EP13401032 A EP 13401032A EP 2711413 B2 EP2711413 B2 EP 2711413B2
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Prior art keywords
component
detergent
weight
booster
acid
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German (de)
English (en)
French (fr)
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EP2711413A1 (de
EP2711413B1 (de
Inventor
Werner Strothoff
Bernd Wolff-Schladitz
Jürgen Souren
Jessica Dichter
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Dalli Werke GmbH and Co KG
Miele und Cie KG
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Dalli Werke GmbH and Co KG
Miele und Cie KG
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the invention relates to a detergent for washing laundry (textiles) with two separate phases (components) and a method for dosing a detergent using an automatic dosing device for separately dosing different components of a detergent.
  • liquid detergents do not achieve the cleaning performance of powder detergents. This is essentially due to the lack of bleaching power and a poorer builder system. If effective builders were integrated into liquid detergents, the formulation would become unstable. If liquid bleach were integrated into liquid detergents, enzymes would be damaged and the cleaning performance would decrease.
  • the DE 25 54 592 A1 refers to a process for washing textiles in which surfactants are added to the wash liquor first and builders at a somewhat later point in time.
  • component 2 of the detergent system also contains surfactants WO2011/060109 describes a washing process with at least two washing processes, with bleach and optical brightener being added one after the other.
  • the invention was therefore based on the object of proposing a detergent with as few separate components as possible, on the one hand to obtain an effective, stably storable liquid detergent for washing laundry and on the other hand to keep the structural complexity required for dosing in a washing machine as low as possible.
  • the detergent according to claim 1 contains only two components, the design and structural complexity (for example in washing machines) for dosing these components is kept within limits. On the other hand, a significantly better cleaning performance can be achieved even when using only two components compared to using a liquid detergent that contains the ingredients in only one component.
  • component is used in connection with the present invention in such a way that it describes the different, separate phases of the detergent, each “component” containing at least one, preferably several ingredients that serve the cleaning performance of the detergent.
  • the “components” of the detergent together make up the efficiently working composition of the detergent.
  • the term “booster” describes the second component of the detergent that is added to the washing process to enhance or improve the cleaning performance of the detergent.
  • the “booster” preferably contains ingredients that would either have a negative impact on storage with ingredients of the first component of the detergent or would be experienced by them, or ingredients that would suitably get into the wash liquor at a later point in time during the washing process are delivered as the ingredients of the first component.
  • liquid detergents Due to the separate storage and combination only in the washing machine, a combination of active substances that previously could not be combined with one another can now also take place in the case of liquid detergents.
  • components that are not compatible with one another such as bleaches and enzymes, can now interact with one another during washing without having to be mixed with one another beforehand during storage and transport.
  • liquid detergent as the first component and the booster as the second component
  • two highly effective components are combined with one another directly in the washing process.
  • a cleaning performance comparable to that of powder detergents can also be achieved with liquid detergents.
  • a detergent according to the invention can contain all ingredients customary in such agents, such as, for example Surfactants, builders, co-builders, bleaches, bleach activators and/or bleach catalysts, soil repellents, alkaline salts and foam inhibitors, complexing agents, sequestering agents, enzyme stabilizers, color transfer inhibitors, graying inhibitors, optical brighteners and UV absorbers, thickeners, dyes and fragrances or the like without that it is limited to this.
  • Surfactants such as, for example Surfactants, builders, co-builders, bleaches, bleach activators and/or bleach catalysts, soil repellents, alkaline salts and foam inhibitors, complexing agents, sequestering agents, enzyme stabilizers, color transfer inhibitors, graying inhibitors, optical brighteners and UV absorbers, thickeners, dyes and fragrances or the like without that it is limited to this.
  • component 1 contains at least (one) anionic surfactant(s), preferably at least (one) nonionic surfactant(s), preferably at least one organic solvent and less than 5% by weight builders.
  • component 1 can contain at least one of the following ingredients: bleach activators and/or bleach catalysts, enzymes, dye transfer inhibitors and fat and oil solvents.
  • the booster contains a water softener and a bleaching agent, but the booster does not have to contain all of the other ingredients mentioned, rather further ingredients of the booster can be selected from those mentioned. It is particularly preferable to separate the following ingredients from one another: enzymes should be separated from bleaches, so the enzymes are preferably used in component 1, bleaches in component 2.
  • Optical brighteners should be separated from color transfer inhibitors, so the color transfer inhibitors are preferably used in component 1, the optical brighteners preferably in component 2.
  • At least component 1 of the detergent is in the form of a liquid.
  • This component contains surfactants selected from anionic, nonionic, cationic and amphoteric surfactants, with component 1 containing at least (one) anionic surfactant(s) and the presence of anionic and nonionic surfactants being preferred.
  • Surfactants of the sulfonate type alk(en)yl sulfates, alkoxylated alk(en)yl sulfates, ester sulfonates and/or soaps are preferably used as anionic surfactants.
  • Surfactants of the sulfonate type are preferably C 9 -C 13 -alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous Receives sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • Alk(en)yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid monoesters of the C 10 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred for washing reasons.
  • 2,3-Alkyl sulfates which can be obtained, for example, as commercial products from the Shell Oil Company under the name DAN® , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -C 18 -Fatty alcohols with 1 to 4 EO are suitable. Owing to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.
  • esters of ⁇ -sulfofatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Soaps come into consideration as further anionic surfactants.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular those made from natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants are preferably in an amount of 10% by weight to 60% by weight, preferably from 12.5% by weight to 50% by weight and particularly preferably from 15 to 50% by weight, in particular from 15 to 30% by weight in the first component.
  • nonionic surfactants are preferably alkoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and/or 1 to 10 moles of propylene oxide (PO) per mole of alcohol.
  • Particular preference is given to C 8 -C 16 alcohol alkoxylates, advantageously ethoxylated and/or propoxylated C 10 -C 15 alcohol alkoxylates, in particular C 12 -C 14 alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and/or or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
  • the degrees of ethoxylation and propoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product.
  • Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates/propoxylates, NRE/NRP).
  • fatty alcohols with more than 12 EO can also be used. Examples are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO(G) x e.g. B. as compounds, especially with anionic surfactants, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.1 to 1.4.
  • An example of a suitable alkyl polyglucoside is Lutensol GD 70 from BASF.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Cationic surfactants contain the high-molecular hydrophobic residue that causes the surface activity when dissociated in aqueous solution in the cation.
  • the most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R 1 R 2 R 3 R 4 N + )X - .
  • R 1 is C 1 -C 8 -alk(en)yl
  • R 2 to R 4 are each independently C n H 2n+1-px- (Y 1 CO)R 5 ) p -(Y 2 H) x , where n is an integer other than 0 and p and x are integers or 0.
  • Y 1 and Y 2 are independently O, N or NH.
  • R 5 denotes a C 3 -C 23 alk(en)yl chain.
  • X is a counterion which is preferably selected from the group consisting of alkyl sulfates and alkyl carbonates. Cationic surfactants in which the nitrogen group is substituted with two long acyl and two short alk(en)yl radicals are particularly preferred.
  • Amphoteric or ampholytic surfactants have several functional groups that can ionize in aqueous solution and, depending on the conditions of the medium, give the compounds anionic or cationic character. Near the isoelectric point, the amphoteric surfactants form internal salts, which can make them sparingly or insoluble in water. Amphoteric surfactants are divided into ampholytes and betaines, the latter existing in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie compounds that have both acidic and basic hydrophilic groups and are therefore acidic or basic depending on the conditions. Betaines are compounds with the atom group R 3 N + -CH 2 -COO - which show typical properties of zwitterions.
  • gemini surfactants are so-called gemini surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups are spaced enough for them to act independently. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris-sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, gemini polyhydroxy fatty acid amides or polypolyhydroxy fatty acid amides can also be used.
  • the total amount of surfactants contained in component 1 according to the invention is preferably 1% by weight to 75% by weight, preferably 10% by weight to 60% by weight, and particularly preferably 20% by weight. up to 55% by weight.
  • Mixtures of anionic and nonionic surfactants are preferably used. It is preferred that the anionic surfactants are present in an amount of from 10% to 60% by weight, preferably from 15% to 55% by weight and particularly preferably from 20 to 50% by weight, in particular from 25 to 40% by weight or the nonionic surfactants in an amount of from 1 to 25% by weight, preferably from 2.5% by weight to 20% by weight, particularly preferably from 5% by weight up to 15% by weight.
  • Surfactants are also preferably used in component 2.
  • a selection can be made from anionic, nonionic or amphoteric surfactants, preference being given to using (at least) nonionic surfactants and optionally anionic and/or amphoteric surfactants in the booster component.
  • the amount of surfactants used in component 2 is 0.2 to 15% by weight, preferably 0.5 to 10% by weight and more preferably 1 to 5% by weight.
  • Suitable enzymes are in particular those from the class of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the wash. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help retain the color and increase the softness of the textile. Oxidoreductases can also be used to bleach or to inhibit color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the wash. By removing pilling and microfibril
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease- and/or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and beta-glucosidases, which are also called cellobiases, or mixtures of these are preferably used as cellulases. Since the various cellulase types differ in their CMCase and Avicelase activities, the desired activities can be set by mixing the cellulases in a targeted manner.
  • the proportion of the enzymes or enzyme mixtures in the overall detergent composition can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight, with the enzymes preferably being present only in the first component used in these amounts.
  • Substances are referred to as builders which are able to bind or complex certain substances, in particular ions present in the washing liquor.
  • ions in particular ions present in the washing liquor.
  • Ca 2+ ions and Mg 2+ ions present in the water are bound, so that the builders also serve as water softeners.
  • Finely crystalline, synthetic zeolite containing bound water can be used as builder, for example, preferably zeolite A and/or P.
  • Zeolite P for example, is particularly preferably zeolite MAP (R) (commercial product from Crosfield).
  • zeolite X and mixtures of A, X and/or P are also suitable.
  • a cocrystallized sodium/potassium aluminum silicate of zeolite A and zeolite X which is available as VEGOBOND AX (R) (commercial product from Condea) in is commercially available.
  • the zeolite can preferably be used as a spray-dried powder.
  • the zeolite is used as a suspension, this can contain small amounts of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on the zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates can also be used as builder substances.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x+1 y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the given formula are those in which M is sodium and x is 2 or 3.
  • beta and d sodium disilicates Na 2 Si 2 O 5 y H 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed in dissolution and have secondary washing properties.
  • the delay in dissolving compared to conventional amorphous sodium silicates can be attributed to different factors Way, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” also means "X-ray amorphous”.
  • the silicates do not produce sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation, which have a width of several degree units of the diffraction angle.
  • the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments.
  • the products have microcrystalline areas with a size of 10 to a few hundred nm, with values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred.
  • Particularly preferred are densified/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • water-soluble polymers for example polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mol.
  • the molar masses given for polymeric polycarboxylates are weight-average molar masses M w of the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC) using a UV detector.
  • the measurement was carried out against an external polyacrylic acid standard which, due to its structural relationship with the polymers examined, provides realistic molecular weight values. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as the standard.
  • the molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses given in this document.
  • Polymers suitable as builders are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20 000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of 2000 to 10 000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may in turn be preferred from this group.
  • suitable polyacrylates are those from the Sokalan® series from BASF; for example, but not limited to, Sokalan CP10 and Sokalan PA25 Cl.
  • Suitable polymers can also include substances that consist partially or completely of units from vinyl alcohol or its derivatives.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular mass, based on the free acids, is generally from 2000 to 70,000 g/mol, preferably from 20,000 to 50,000 g/mol and in particular from 30,000 to 40,000 g/mol.
  • the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as a monomer.
  • allyl sulfonic acids such as allyloxybenzene sulfonic acid and methallyl sulfonic acid
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers or salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.
  • copolymers suitable as builders are those which contain, for example, acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
  • the polymers mentioned here so far are used in the detergents according to the invention as preferred builder components (water softeners).
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid- or enzyme-catalyzed processes. These are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g/mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. These are products oxidized at C 6 and/or with ring opening at C 2 / C 3 of the saccharide ring. A product oxidized at C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are further suitable cobuilders.
  • ethylenediamine-N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and/or containing silicate are from 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.
  • the builders are used in small amounts in the first component, preferably in amounts of less than 10% by weight, more preferably less than 5% by weight, even more preferably less than 2.5% by weight. in particular less than 1% by weight.
  • component 1 contains no builders.
  • builders are preferably used in the booster component (component 2), in amounts of 1 to 40% by weight, preferably in amounts of 2.5 to 35% by weight, particularly preferably in amounts of 5 to 25% wt%. If a bleaching agent is present in the booster component, the proportion of builder can be further reduced, so that if a bleaching agent is present, the preferred amount of builder in component 2 is 5 to 20% by weight.
  • Particularly preferred builders in the booster component are the water-soluble polymers mentioned above.
  • Sequestering agents keep mineral salts in solution and thereby prevent their precipitation from solutions containing mineral salts.
  • the abovementioned builders, in particular the polymeric builders, are therefore also suitable as sequestering agents, as are the complexing agents described below.
  • Phosphonates are also used as suitable sequestering agents, for example 1-hydroxyethane-1,1-diphosphonic acid (HEDP), amino-tris(methylenephosphonic acid) (ATMP), ethylenediamine-tetra(methylenephosphonic acid) (EDTMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP ), hexamethylenediamine-tetra(methylenephosphonic acid) (HDTMP), hydroxyethylaminodi(methylenephosphonic acid) (HEMPA), bis(hexamethylene)triaminepenta(methylenephosphonic acid) or their respective salts, 2-phosphonobutane-1,2, 4-tricarboxylic acid (PBTC), 2-phosphonobutane
  • Suitable complexing agents are all agents known as such; in particular, amino carboxylates, (poly)phosphates, dicarboxylic acids or hydroxy acids can be used.
  • amino carboxylates methylglycine diacetic acid (MGDA, available e.g. as Trilon ® M from BASF), IDA (iminodiacetic acid), NTA (nitrilotriacetic acid), EDTA (ethylenediaminetetraacetic acid), EGTA (ethylene glycol tetraacetic acid) and iminodisuccinate tetrasodium salt are preferred, as well as triethanolamine, without these to be limited.
  • MGDA methylglycine diacetic acid
  • IDA iminodiacetic acid
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • EGTA ethylene glycol tetraacetic acid
  • iminodisuccinate tetrasodium salt are
  • Organic substances which can be used as complexing agents are, for example, the polycarboxylic acids or hydroxy acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are the salts of citric acid, lactic acid, adipic acid, succinic acid, oxalic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives (derivatives) and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH value in detergents or cleaning agents.
  • Other acidifying agents that can be used are known pH regulators such as sodium hydrogen carbonate and sodium hydrogen sulfate.
  • Complexing agents from the BayPure® series from Bayer Ag, Germany can also be suitable complexing agents.
  • the complexing agents are also used in small amounts in the first component, preferably in amounts of less than 5% by weight, more preferably less than 2.5% by weight, even more preferably less than 1% by weight. .
  • component 1 contains no complexing agents.
  • complexing agents are preferably used in the booster component (component 2), specifically in amounts of 1 to 40% by weight, preferably in amounts of 2.5 to 35% by weight, particularly preferably in amounts of 5 to 25% wt%. Due to the presence of a bleaching agent in the booster component, the proportion of complexing agent can still be somewhat reduced, so that if a bleaching agent is present, the preferred amount of complexing agent in component 2 is 5 to 20% by weight.
  • Particularly preferred complexing agents are the amino carboxylates mentioned above.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and yield H 2 O 2 in water.
  • bleaches which can be used are peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • peroxyacids examples being the alkylperoxyacids and the arylperoxyacids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-alpha-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, epsilon-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • Particularly preferred bleaches according to the present invention are those that generate H 2 O 2 or the H 2 O 2 itself.
  • preferred bleaches are phthalimido-peroxo-caproic acid (PAP), sodium nonanonyloxybenzene sulfonate (NOBS) and sodium 4- (2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS) and decanoyloxybenzoic acid (DOBA) or dioxyranes.
  • Substances which release chlorine or bromine can also be used as bleaching agents, but are not preferred.
  • suitable chlorine or bromine releasing materials are heterocyclic N-bromo- and N-chloroamides, e.g. trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium.
  • trichloroisocyanuric acid e.g. trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also useful.
  • the bleaching agent content in the bleaching agent-containing component is preferably 1 to 40% by weight, preferably 2 to 20% by weight and in particular 3 to 15% by weight, with perborate monohydrate and/or percarbonate or directly H 2 O 2 being particularly preferred is used. If H 2 O 2 is to be used directly, it is preferable to use 5 to 10% by weight, particularly preferably 6 to 8% by weight.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid.
  • Polyacylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA , Acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI).
  • TAED tetraacetylethylenediamine
  • TAMD t
  • Phenolsulfonates in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium -Acetonitrile methyl sulfate (MMA), and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetyl
  • bleach activators are TAED, acetylcaprolactam (available as Peractive LAC), or photocatalysts that use atmospheric oxygen.
  • bleach catalysts can also be used.
  • These substances are bleach-boosting transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo shell complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can also be used as bleach catalysts.
  • manganese III catalysts particularly manganese salts, manganese triazacyclononane complexes, manganese Schiff base complexes, manganese cross-bridged macrocyclic complexes, manganese complexes with 2,2':6,2"-terpyrides and manganese complexes with polypyridinamine Ligands;iron catalysts, in particular Fe complexes with pentadentate nitrogen donor ligands and those with macrocyclic tetraamidate ligands;cobalt-based catalysts for H 2 O 2 activation, in particular cobalt-pentaamine complexes and cobalt complexes with polypyridinamine ligands prefers.
  • the bleach catalysts are usually used in amounts of up to 5% by weight, in particular from 0.0025% % by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, based in each case on the composition as a whole.
  • the bleach activator can be used as required, preferably in amounts of from 0.05 to 15% by weight.
  • the first component contains, in particular, 1 to 10% by weight of bleach activator or 0.01 to 2% by weight of a bleach catalyst.
  • a bleach activator or bleach catalysts in the first component can significantly increase the cleaning performance.
  • any substance known for this purpose can be used as the color transfer inhibitor.
  • these are, for example, polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride and mixtures thereof.
  • a particularly preferred color transfer inhibitor is a vinylpyrrolidone-vinylimidazole copolymer, for example Sokalan® HP 56 from BASF.
  • the fatty alkyl dialkyl hydroxyethyl ammonium salt is a fatty alkyl dimethyl hydroxyethyl ammonium salt, preferably a C 12 -C 18 fatty alkyl dimethyl hydroxyethyl ammonium salt. It is particularly preferred that the fatty alkyl dimethyl hydroxyethyl ammonium salt is C 12 -C 14 fatty alkyl dimethyl hydroxyethyl ammonium chloride.
  • the salts can contain halide, methosulfate, methophosphate or phosphate ions and mixtures of these as counterions. Preferably the counterion is chloride.
  • fatty alkyl dimethyl hydroxyethyl ammonium salt is Praepagen® HY (from Clariant), a C 12 /C 14 fatty alkyl dimethyl hydroxyethyl ammonium chloride.
  • fatty alkyl dialkyl hydroxyethyl ammonium salts are particularly effective dye transfer inhibitors.
  • the fatty alkyldialkylhydroxyethylammonium salts mentioned can also be used in combination with at least one second color transfer inhibitor.
  • the fatty alkyldialkylhydroxyethylammonium salts are preferably mixed with at least one of the abovementioned polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride and mixtures thereof combined.
  • color transfer inhibitors are known and commercially available (co)polymers which can be easily and stably incorporated into detergents or cleaning agents.
  • the amount of dye transfer inhibitor in the washing or cleaning agent can be between 0.001 and 10% by weight, based on the agent as a whole, but is preferably used in component 1.
  • the amount of dye transfer inhibitor in component 1 is preferably between 0.01 and 5% by weight and particularly preferably between 0.1 and 2% by weight (active ingredient).
  • the task of graying inhibitors is to keep the dirt that has been detached from the fibers suspended in the liquor and thus prevent the dirt from being reattached.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co)polymeric carboxylic acids, 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 also suitable for this purpose.
  • soluble starch preparations and starch products other than those mentioned above can be used, e.g. B. degraded starch, aldehyde starches, etc.
  • polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone are preferably used.
  • the graying inhibitors are used, for example, in amounts of from 0.1 to 5% by weight, based on the total amount of the detergent.
  • the used as a booster component 2 of the detergent according to the invention can optical brighteners such.
  • Suitable stilbene derivatives include derivatives of bis(triazinyl)aminostilbene, bisacylamino derivatives of stilbene, triazole derivatives of stilbene, oxadiazole derivatives of stilbene, oxazole derivatives of stilbene, and styryl derivatives of stilbene.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the 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)diphenyls.
  • a particularly preferred optical brightener is disodium 2,2'-((1,1'-biphenyl)-4,4'-diyldivinylene)bis(benzenesulfonate) sold as Tinopal CBS- X® by BASF.
  • the optical brighteners Tinopal CBS-CL, Tinopal 5 BM-GX and Tinopal AMS-GX are also suitable derivatives of diphenylstyryles. Mixtures of the aforementioned brighteners can also be used.
  • the amount of optical brightener can be 0 to 3% by weight in component 2, preferably 0 to 2 wt%. If optical brightener is used, a proportion of 0.05 to 1.0% by weight, preferably 0.1 to 0.5% by weight, in particular 0.2 to 0.4% by weight (active ingredient) is preferred.
  • component 1 contains a vinylpyrrolidone-vinylimidazole copolymer as a color transfer inhibitor and component 2 contains disodium 2,2'-((1,1'-biphenyl)-4,4'-diyldivinylene)bis as an optical brightener (benzenesulfonate), particularly preferably when H 2 O 2 or an H 2 O 2 -generating agent is additionally used as a bleaching agent.
  • component 1 contains a vinylpyrrolidone-vinylimidazole copolymer as a color transfer inhibitor and component 2 contains disodium 2,2'-((1,1'-biphenyl)-4,4'-diyldivinylene)bis as an optical brightener (benzenesulfonate), particularly preferably when H 2 O 2 or an H 2 O 2 -generating agent is additionally used as a bleaching agent.
  • UV absorbers can also be used. These are compounds with a pronounced ability to absorb ultraviolet radiation, which, as light stabilizers (UV stabilizers), contribute both to improving the light resistance of dyes and pigments and textile fibers and also protecting the skin of the wearer of textile products from UV radiation penetrating the textile.
  • UV stabilizers light stabilizers
  • the compounds effective through radiationless deactivation are derivatives of benzophenone, the substituents of which, such as hydroxyl and/or alkoxy groups, are usually in the 2- and/or 4-position.
  • substituted benzotriazoles are also suitable, as well as acrylates phenyl-substituted in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural substances such as umbelliferone and endogenous urocanic acid.
  • the UV absorbers absorb UV-A and UV-B radiation and, if appropriate, UV-C radiation and reflect light with wavelengths of blue, so that they also have the effect of an optical brightener.
  • Preferred UV absorbers are also triazine derivatives, e.g. B.
  • UV absorbers Hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and derivatives thereof.
  • Pigments which absorb ultraviolet radiation, such as titanium dioxide, can also be used as UV absorbers.
  • the detergents can also contain components that have a positive effect on the ability to wash oil and grease out of textiles, so-called soil repellents. This effect becomes particularly clear when a textile is soiled which has already been washed several times with a detergent according to the invention which contains this oil- and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, each based on the nonionic cellulose ether, and polymers of phthalic acid and/or terephthalic acid or derivatives thereof known from the prior art, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • foam inhibitors When used in machine washing processes, it can be advantageous to add customary foam inhibitors to the agents.
  • suitable foam inhibitors are soaps of natural or synthetic origin which have a high proportion of C 18 -C 24 fatty acids.
  • suitable non-surfactant foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantage, for example those made from silicones, paraffins or waxes.
  • the foam inhibitors are preferably used in the second component.
  • liquid detergents according to the invention can contain customary thickeners and anti-settling agents and viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and derivatives thereof, polyurethanes, polyvinylpyrrolidone, castor oil derivatives, polyamine derivatives such as quaternized and/or ethoxylated hexamethylenediamines and any mixtures thereof in at least one phase.
  • customary thickeners and anti-settling agents and viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and derivatives thereof, polyurethanes, polyvinylpyrrolidone, castor oil derivatives, polyamine derivatives such as quaternized and/or ethoxylated hexamethylenediamines and any mixtures thereof in at least one phase.
  • the detergents can contain other typical detergent ingredients such as perfumes and/or dyes, preference being given to dyes which have no or negligible coloring effect on the textiles to be washed. Preferred amounts of all the dyes used are less than 1% by weight, preferably less than 0.1% by weight, based on the agent.
  • the funds can optionally also white pigments such. B. TiO 2 included.
  • component 1 is liquid.
  • Component 2 is also a liquid, both liquids being solutions or else dispersions or emulsions. Both components are preferably solutions of the ingredients mentioned.
  • the viscosity of the two component liquids can be the same or different, depending on the desired application behavior.
  • the liquid agents are preferably hydrous. In addition, they can also contain organic solvents, preferably those that are miscible with water.
  • Organic solvents which can be used in the liquid agents according to the invention are preferably polydiols, ethers, alcohols, ketones, amides and/or esters in amounts of up to 80% by weight, preferably 0.1 to 70% by weight, in particular 0.1 up to 60% by weight.
  • Low molecular weight polar substances are preferred, such as methanol, ethanol, propanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, Glycerin, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.
  • At least component 1 preferably contains a proportion of 1 to 20% by weight of at least one alcohol, preferably 2.5% by weight to 15% by weight, particularly preferably 5 to 15% by weight, the alcohol being selected can be selected from propylene glycol, methanol, ethanol and propanol, with propylene glycol or ethanol being preferred.
  • the pH of component 1 of the liquid detergent according to the invention is preferably between 5 and 10, in particular between 6 and 9 and particularly preferably in the range from 7 to 8.5. If desired, such agents according to the invention can contain water in amounts of up to 90% by weight, in particular 20% by weight to 75% by weight; if necessary, however, these ranges can also be exceeded or fallen below.
  • the pH of component 2 is preferably in the range from pH 3 to pH 6, particularly preferably between pH 4.5 and 5.5.
  • Liquid agents can have densities of 0.5 to 2.0 g/cm 3 , in particular 0.7 to 1.5 g/cm 3 . Should the liquid agent or one of the components of the liquid agent be provided as a dispersion, it is preferred that the density difference between the solid particles used in the components and the liquid phase of the agent is preferably no more than 10% of the density of one of the two, and in particular is so low that the solid particles float in the liquid phase.
  • the liquid component 1 of the detergent contains at least 25 to 40% by weight anionic surfactants and 5 to 15% by weight nonionic surfactants and less than 5% by weight builders and 5 to 15% by weight alcohols.
  • the booster contains at least one ingredient from the group of water softeners, preferably complexing agents, sequestering agents and builders, water-soluble polymers being particularly preferred when builders are used.
  • the booster is based on builders and bleaches. This allows the cleaning performance to be further improved.
  • the booster contains an optical brightener.
  • the light/white areas appear particularly radiant as a result.
  • the integration of an optical brightener in the form of low-foam, nonionic surfactants in the booster is particularly advantageous. These surfactants also enable foam control in the washing process.
  • the choice of an optical brightener that is largely stable to oxidizing agents is advantageous.
  • Optical brighteners to be used with preference are mentioned above, with Tinopal CBS-X being a particularly preferred brightener.
  • the booster contains a bleaching agent, particularly preferably hydrogen peroxide (H 2 O 2 ) or an H 2 O 2 generating agent as bleaching agent.
  • a bleaching agent particularly preferably hydrogen peroxide (H 2 O 2 ) or an H 2 O 2 generating agent as bleaching agent.
  • the booster preferably has a pH of 3-6, preferably in the range from 4.5 to 5.5.
  • the acidic formulation stabilizes the bleaching agent, especially if it is hydrogen peroxide or an agent that generates H 2 O 2 .
  • both the advantage of a color detergent and that of a heavy-duty detergent can be used and the washing result can be controlled as desired by using different amounts of the components.
  • component 1 corresponds to a color detergent which can be combined with component 2 to form a heavy-duty detergent, particularly if component 2 contains a bleach and/or an optical brightener.
  • the desired cleaning performance is set.
  • K1:K2 a mixing ratio of component 1 to component 2 (K1:K2) of 2:1 to 10:1
  • the overall detergent is more like a color detergent
  • K1:K2 a mixing ratio of (K1:K2) below 2:1 to 1:10 the detergent is more like corresponds to a heavy-duty detergent.
  • the automatic washing machine has a dosing device, with which the individual components that are present separately from one another can be dosed separately into the washing process at a time interval from one another.
  • the first component is preferably metered in at the start of a wash cycle.
  • the second component is then metered in preferably within 45 minutes, particularly advantageously within 20 to 40 minutes and even more advantageously approximately 30 minutes after metering in the first component.
  • This time interval is particularly advantageous if the first component was added at the start of a wash cycle and a booster containing bleach and a water softener, preferably at least one complexing or sequestering agent, is used with an acidic to neutral setting (pH 3 to 7).
  • Example formulation for component 1 corresponds to an anhydrous formulation in the form of a super concentrate with bleach activator
  • component 1 with bleach activator or bleach catalyst contains 28 percent by weight of an anionic surfactant (e.g. Marlon AMI 80) and 17 percent by weight of another anionic surfactant (e.g. Texapon N 70 (Na lauryl ether sulfate with 2 EO units)) and 21 percent by weight of one nonionic surfactant (for example Lutensol M 7) and 6 percent by weight of an alcohol (for example propylene glycol) and 4.5 percent by weight of another nonionic surfactant (for example Lutensol GD 70) and 4.5 percent by weight of the solubilizer sodium cumene sulfonate (40%) and 4, 5% by weight of an amphoteric surfactant (e.g.
  • an anionic surfactant e.g. Marlon AMI 80
  • another anionic surfactant e.g. Texapon N 70 (Na lauryl ether sulfate with 2 EO units)
  • one nonionic surfactant for example Luten
  • Rewoteric AMV N-2-hydroxyethyl-N-carboxymethyl-fatty acid amido-ethylamine-Na salt
  • dye transfer inhibitor 1.5% by weight oil release polymers
  • enzymes 3.5% by weight enzymes and 8% by weight bleach activator (e.g. Peractive LAC).
  • bleach activator e.g. Peractive LAC
  • such a booster contains 5 to 25 percent by weight of water-soluble polymers as water softeners (e.g. polyacrylates, maleic acid-acrylic acid copolymers, such as Sokalan CP10 (45%), Sokalan PA25CL (49%)), and 5 to 25 percent by weight Amino carboxylates as complexing agents (e.g. Trilon M (40%)), and 0 to 2 percent by weight optical brighteners (e.g. Tinopal CBS CL or Tinopal CBS X), and 1 to 5 percent by weight nonionic, anionic or amphoteric surfactants (e.g. Rewoteric AMV, Lutensol GD70 ), and the rest water.
  • water softeners e.g. polyacrylates, maleic acid-acrylic acid copolymers, such as Sokalan CP10 (45%), Sokalan PA25CL (49%)
  • Amino carboxylates as complexing agents
  • optical brighteners e.g. Tinopal CBS CL or Tinopal CBS
  • such a booster contains 5 to 20 percent by weight of water-soluble polymers as a water softener (e.g. Sokalan PA25CL (49%)), and 5 to 20 percent by weight of amino carboxylates as complexing agents (e.g. Trilon M (40%)) and 0 to 1 percent by weight optical brighteners (e.g. Tinopal CBS CL or Tinopal CBS X), and 1 to 5% by weight surfactants (e.g. Lutensol GD70), and 3 to 15% by weight hydrogen peroxide or an H 2 O 2 generating bleach and the balance water.
  • water softener e.g. Sokalan PA25CL (49%)
  • amino carboxylates as complexing agents
  • optical brighteners e.g. Tinopal CBS CL or Tinopal CBS X
  • surfactants e.g. Lutensol GD70
  • the washing tests were carried out as follows: colored test textiles with 17 different stains were washed with the following batches: in a first batch, 50 g of a liquid detergent available on the market (Miele UltraColor) without a booster were used, in a second batch 75 g of Miele UltraColor liquid detergent was used without a booster; in a third batch, 50 g Miele UltraColor liquid detergent and 25 g booster were used.
  • a liquid detergent available on the market Miele UltraColor
  • a bleach-free alkaline booster (pH 11) according to Example 2 was combined with the base detergent (Miele UltraColor).
  • figure 1 shows a representation of the cleaning performance with a first booster in an alkaline environment.
  • the Y-axis shows the cleaning performance as the sum of the measured remission units.
  • Three columns are shown. Each column shows the cleaning performance of a test wash on 17 different soilings with the detergent quantities and/or detergent compositions mentioned above.
  • the cleaning performance with 50 grams of Miele UltraColor liquid detergent without a booster is shown on the left.
  • the cleaning performance with 75 grams of Miele UltraColor liquid detergent without a booster is shown in the middle.
  • a bleach-containing booster according to Example 3 was combined with the base detergent (Miele UltraColor) once without and once with bleach activator (Peractive LAC).
  • figure 2 shows a representation of the cleaning performance with the second booster in an acidic environment.
  • the Y-axis shows the cleaning performance as the sum of the reflectance measurements for 17 stains/soilings. Four columns are shown. Each column reflects the cleaning performance of a test wash with different detergent amounts and/or detergent compositions.
  • the cleaning performance with 50 grams of liquid detergent without a booster (e.g. Miele UltraColor or Ariel) is shown on the left.
  • the cleaning performance with 75 grams of Miele UltraColor liquid detergent without a booster is shown in the second column.
  • the second bar from the right shows the cleaning performance with 50 grams of liquid detergent (first component), for example Miele UltraColor (without bleach activator) or Ariel, and 50 grams of booster (second component) according to the invention.
  • first component for example Miele UltraColor (without bleach activator) or Ariel
  • booster second component
  • the booster described in example 3 was used at pH 5.
  • figure 3 shows a graphic representation of the cleaning performance in relation to the time interval between dosing the first and the second component.
  • the Y-axis shows the average cleaning performance in reflectance units of 20 spots of Miele UltraColor liquid detergent with the above-described booster with hydrogen peroxide (second component according to example 3) for a cotton program at 60° C. in a Miele washing machine W1935.
  • the x-axis indicates the time difference between dosing Miele UltraColor liquid detergent and the booster in minutes.
  • the bleach booster should preferably be added between 20 and 40 minutes after the start of the washing process, particularly preferably not more than 30 minutes later. With later dosing, the advantage of dosing is reduced. The booster also develops its best effect when added 30 minutes after adding the Miele UltraColor liquid detergent (component 1).
  • the best time to add the entire second component is around 30 minutes after adding the Miele UltraColor liquid detergent at the beginning of the wash cycle.
  • a color transfer inhibitor was used in component 1 of the detergent and an optical brightener in component 2.
  • Sokalan HP 56 a vinylpyrrolidone-vinylimidazole copolymer from BASF
  • Three different brighteners were tested as optical brighteners: in a first batch FB-71 (from Aako), in a second batch Leukophor BSB (from Clariant) and in a third batch Tinopal CBS-X (from BASF).
  • the dye transfer inhibitor does not recognize the optical brightener as a "dye" and prevents it from being absorbed onto the fabric.
  • FIG 4 it can be seen that the separate use of color transfer inhibitor in component 1 of the detergent and optical brightener in component 2 of the detergent can achieve a significant lightening of the laundry in each case. Especially when using Tinopal CBS-X, the color transfer inhibitor does not seem to bind this brightener and the degree of whiteness is not affected after 15 washes.
  • component 1 was used as described in Example 1, and a composition according to Example 3 was used as a booster, to which Tinopal CBS-X optical brightener was also added in an amount such that the final concentration in the total detergent was 0.15% or 0.073% became.
  • a commercially available heavy-duty detergent was used as a comparison. It was found that the component detergent did not adversely affect the colors of the laundry, there was no further color damage or color shift in the colored laundry, while the use of heavy-duty detergent resulted in a clear fading of the colors after 15 washes.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP13401032.1A 2012-09-25 2013-04-08 Waschmittel und Verfahren zur Dosierung eines Waschmittels Active EP2711413B2 (de)

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AU2020227836B2 (en) 2019-02-28 2022-09-22 Ecolab Usa Inc. Hardness additives and block detergents containing hardness additives to improve edge hardening
EP3892707A1 (en) * 2020-04-06 2021-10-13 Dalli-Werke GmbH & Co. KG Liquid detergent composition, kit and dosing system
DE102021114772A1 (de) 2021-06-09 2022-12-15 Miele & Cie. Kg Waschmittel, Verfahren zur Dosierung des Waschmittels und Verwendung des Waschmittels
DE102021114786A1 (de) 2021-06-09 2022-12-15 Miele & Cie. Kg Waschmittel, Verfahren zur Dosierung des Waschmittels und Verwendung des Waschmittels
DE102022204754A1 (de) 2022-05-16 2023-11-16 Henkel Ag & Co. Kgaa Textilwaschverfahren
EP4335914A1 (de) 2022-09-07 2024-03-13 Henkel AG & Co. KGaA Textilwaschverfahren

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4000882A1 (de) † 1990-01-13 1991-07-18 Licentia Gmbh Programmgesteuerte waschmaschine
EP0601967A1 (de) † 1992-11-17 1994-06-15 Ciba-Geigy Ag Flüssigwaschmittel
EP1394065A1 (en) † 2002-06-17 2004-03-03 Unilever N.V. Detergent sachets
DE102010027992A1 (de) † 2010-04-20 2011-10-20 Henkel Ag & Co. Kgaa Dosiersystem zur Freisetzung von wenigstens drei unterschiedlichen Zubereitungen während eines Waschprogramms einer Waschmaschine

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DE2101340A1 (en) * 1971-01-13 1972-07-27 Henkel & Cie. GmbH, 4000 Düsseldorf Cold-washing and bleaching of textiles - in two liquids contg per cpds and activators respectively
DE2554592C3 (de) * 1975-12-04 1981-11-26 Bosch-Siemens Hausgeräte GmbH, 7000 Stuttgart In einer automatischen Waschmaschine durchzuführendes Waschverfahren für Textilien sowie Vorrichtung zu dessen Durchführung
GB2189520A (en) * 1986-03-21 1987-10-28 Unilever Plc Washing and bleaching process
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
PL1917343T3 (pl) * 2005-09-02 2011-12-30 Henkel Ag & Co Kgaa Środek do czyszczenia
ES2395044T3 (es) * 2005-09-02 2013-02-07 Henkel Ag & Co. Kgaa Detergentes
US8449626B2 (en) * 2009-11-11 2013-05-28 The Procter & Gamble Company Cleaning method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4000882A1 (de) † 1990-01-13 1991-07-18 Licentia Gmbh Programmgesteuerte waschmaschine
EP0601967A1 (de) † 1992-11-17 1994-06-15 Ciba-Geigy Ag Flüssigwaschmittel
EP1394065A1 (en) † 2002-06-17 2004-03-03 Unilever N.V. Detergent sachets
DE102010027992A1 (de) † 2010-04-20 2011-10-20 Henkel Ag & Co. Kgaa Dosiersystem zur Freisetzung von wenigstens drei unterschiedlichen Zubereitungen während eines Waschprogramms einer Waschmaschine

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EP2711413A1 (de) 2014-03-26
ES2704102T3 (es) 2019-03-14
EP2711413B1 (de) 2018-11-28
TR201818916T4 (tr) 2019-01-21
ES2704102T5 (es) 2022-06-20
PL2711413T3 (pl) 2019-04-30
PL2711413T5 (pl) 2022-08-29

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