EP1440141B1 - Detergent ou nettoyant dispersible sensiblement exempt de sediments - Google Patents

Detergent ou nettoyant dispersible sensiblement exempt de sediments Download PDF

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Publication number
EP1440141B1
EP1440141B1 EP02785254A EP02785254A EP1440141B1 EP 1440141 B1 EP1440141 B1 EP 1440141B1 EP 02785254 A EP02785254 A EP 02785254A EP 02785254 A EP02785254 A EP 02785254A EP 1440141 B1 EP1440141 B1 EP 1440141B1
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European Patent Office
Prior art keywords
washing
acid
weight
cleaning composition
composition according
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EP02785254A
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German (de)
English (en)
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EP1440141B2 (fr
EP1440141A2 (fr
Inventor
Birgit GLÜSEN
Maria Liphard
Ingrid Kraus
Ulrich Pegelow
René-Andres ARTIGA GONZALEZ
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to a particulate, aluminosilicate-, silicate- and phosphate-free washing or cleaning agent whose aqueous dispersion has a mild pH and which can be dispersed substantially sediment-free in tap water.
  • the invention also deals with the use of this detergent for washing textiles, especially delicate textiles.
  • Builders or builder systems perform a variety of tasks in detergents or cleaners that have changed significantly in recent years and decades with the constant changes in composition, formulation, and detergent manufacture. Modern detergents today contain about 30 to 60 wt .-% builders. These are among the most important substance classes for the construction of detergents and cleaners.
  • aluminosilicates such as zeolite NaA
  • zeolite NaA aluminosilicates
  • amorphous sodium silicate compounds are described as builder substances which are prepared by spray-drying aqueous waterglass solutions, then grinding and subsequent compacting and rounding with additional removal of water from the mahogany.
  • EP-A-0 444 415 are detergents with 5 to 50 wt .-% of at least one surfactant, 0.5 to 60 wt .-% of a Builder and conventional auxiliary detergents proposed, the mark being that an amorphous low-sodium disilicate with a water content of 0.3 to 6 wt .-% is used as builder.
  • German Offenlegungsschrift DE-A-22 40 309 (Unilever ) describes a zeolite-free composition which comprises 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali carbonate, 1 to 30% by weight of complexing agents, preferably citrate, and 0.05 to 15% by weight of a deposit prevention agent for calcium carbonate.
  • This anti-deposition agent is either a phosphate, a phosphonic acid or a polymeric carboxylate.
  • a phosphate- and aluminosilicate-free agent which, in addition to surfactants and polyethylene glycol, contains a builder system based on carbonate, sulfate, silicate and polycarboxylate. Advantages of this agent are the price and the environmental behavior of the builder system. Preferred embodiments have a ratio of sodium carbonate to sodium sulfate of 1: 1 to 1: 3.
  • zeolite-free builder system which consists of alkali silicate, alkali carbonate, polymeric polycarboxylate having a molecular weight less than 10,000 g / mol, phosphonate and an acidic component consists.
  • This soluble builder system is dosed low, ie less than 40% by weight of the detergent is claimed by this builder system and the alkali product of this agent is in the range of 7.0 to 11.4.
  • this soluble builder system has advantages, especially in the residue behavior.
  • amorphous alkali silicate is limited.
  • a phosphate-free detergent or cleaning agent is described which has improved solubility and improved washing performance.
  • the agent contains a special builder system and a special surfactant system.
  • the builder system consists of at least two builders, one of which is partially or wholly water-soluble and constitutes 60 to 100% by weight of the builder system, preferably crystalline layer-structured alkali silicate. Another builder is water-insoluble and constitutes from 0 to 40% by weight of the builder system.
  • the surfactant system comprises one or more surfactants, preferably an anionic alkyl sulphate and an anionic sulphonate or mixtures thereof, wherein one of the surfactants is intimately mixed with one of the partially or wholly water-soluble builders as a particulate component.
  • the detergents or cleaning agents disclosed in this application in the examples also contain large amounts of silicates, namely of crystalline layer silicates and / or builder amounts of more than 35% by weight and / or amounts of surfactant of more than 25% by weight and / or none
  • Surfactant system comprising at least one anionic surfactant and at least one nonionic surfactant.
  • foam pad an air cushion
  • the foam should also be easy to rinse, with low foam scents when rinsing, otherwise the user finds foam residues on the laundry after finishing the rinse, when he opens his washing machine to hang the laundry to dry or to give in a machine dryer.
  • the foam is often not only visually perceived, but also tactile, as the laundry feels sticky and greasy.
  • the object of the present invention was to provide a washing or cleaning agent which has an improved foaming behavior.
  • the agent should develop a sufficient, advantageous foam height during the washing process, but the foam should be well rinsable in the course of the rinsing process.
  • the agent of the invention dissolves sediment-free or at least almost sediment-free, has an advantageous foaming during the wash cycle and a good leachable foam during the dilution and rinses, and also has a good deposition behavior.
  • Another advantage of Washing or cleaning agent according to the invention consists in the significantly improved flushability of the agent during machine washing or cleaning.
  • An additional advantage of the composition according to the invention is the relatively low pH of the compositions of the invention, which is in the range of 7 to 9, and which is particularly advantageous for washing or cleaning delicate textiles. The details of these advantageous properties of the agent according to the invention and the description of the abovementioned tests are explained below (in the example part).
  • compositions according to the invention can be used both mechanically and manually.
  • the agents are used in a machine wash, wherein the application is particularly preferred, especially with regard to the preferred textiles in fine washing programs or Vollwaschprogrammen.
  • the application takes place at temperatures of about 20 ° C to about 60 ° C and especially at temperatures of about 30 ° C to about 40 ° C instead.
  • the agents are used in manual washing, especially in hand basins, and at temperatures of about 15 ° C to about 40 ° C, preferably from 20 to 35 ° C.
  • Deposits are understood in the context of the present inventions, all substances that remain after washing on the dry laundry, the whereabouts of which is undesirable on the laundry and contributes to a deterioration of the quality of the laundry. These include so-called “residues”. These are remnants of undissolved detergent or cleaning agent that can be found after washing on the dry laundry in the form of white spots or stains. The cause of residues is a poor, in the sense of too slow, solution kinetics of the washing or cleaning agent used. The problem of the residues is v. A. In the case of machine washing, the current trend is leading to ever smaller quantities of water and to ever-increasing washing loads per wash.
  • substantially sediment-free dispersible is hereinafter understood that 8 g of the agent when dissolved or dispersed in tap water (1 l, 20 ° C, 16 ° d, stirring for 20 min, sedimentation time 24 h) a sedimentation volume per liter of at most 2 ml / l.
  • the method for determining the sedimentation volume is described in more detail in the example on page 32.
  • a preferred embodiment of the invention results in the dissolution or dispersion of 8 g of the detergent or cleaning agent according to the invention in tap water (1 1, 20 ° C, 16 ° d, stirring for 20 min, sedimentation time 24 h) a sedimentation volume per liter of at most 0.5 ml / l, in particular of at most 0.2 ml / l and most preferably of 0 ml / l.
  • the pH control agents fulfill an important task as organic builders and for adjusting a pH value suitable for the invention.
  • Suitable pH control agents are, in particular, monomeric organic polycarboxylic acids, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are preferred in this context.
  • citric acid particularly preferred is citric acid.
  • the stated polycarboxylic acids can also be used in the form of their sodium salts.
  • Preferred salts are the salts of the polycarboxylic acids citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the agents according to the invention advantageously contain these pH control agents in amounts of about 0.5 to about 25% by weight, preferably in amounts of about 5 to about 20% by weight, more preferably in amounts of about 7.5 to about 15 Wt .-% based on the total agent.
  • the pH control agents make up about 25% to about 65% by weight, preferably 35% to 45% by weight of the preferred builder system.
  • Suitable builders are polymeric polycarboxylic acids and / or their partially or fully neutralized metal and / or ammonium salts, for example the alkali metal salts of (homopolymeric) polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,200 to 8,000 g / mol, for example 4,500 or 8,000, may again be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid-containing copolymers will be described in detail below.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C 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.
  • it is Hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • 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.
  • co-builders which may be present together with phosphonates, but also as partial to complete replacement of phosphonates in liquid or particulate agents or moldings, include iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS).
  • IDS iminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • IDS- or HIDS-containing agents can positively contribute to the color retention of textiles.
  • IDS- or HIDS-containing agents can positively contribute to the color retention of textiles.
  • WO 01/94514 WO 01/92449 .
  • WO 01/88077 WO 01/46371 and WO 01/44423 directed.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • all compounds capable of forming complexes with alkaline earth ions may be included as co-builders in the particulate agents.
  • the co-builders are preferably present in the composition according to the invention in amounts such that they contain up to 5% by weight, preferably 1 to 2% by weight of the total composition or 0.5 to 12% by weight, preferably 3 to 7.5% by weight. - Make up% of the builder system.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the phosphonates are in the inventive compositions - if at all - but only in small amounts, between about 0.1 to 2 wt .-%, drawn on the total mean or in amounts of 0 to about 3 wt .-%, preferably from 0 to about 2% by weight, based on the builder system.
  • the surfactant system contains one or more anionic surfactants and one or more nonionic surfactants.
  • the surfactant system preferably constitutes from 5 to 25% by weight, in particular from 10 to 20% by weight, of the total composition.
  • Suitable anionic surfactants are, for example, sulfonate-type surfactants. Cumene sulfonate, C 10-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, are preferred, as can be obtained, for example, from C 2-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of 2-sulfo fatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of C 12-18 fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10-20 oxo alcohols and those Half-ester secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12-15 alkyl sulfates and C 14-15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 getting produced and can be obtained under the name DAN ® as commercial products from Shell Oil Company, are suitable anionic surfactants.
  • the Schwefelklasted Acidmonoester with 1 to 6 moles of ethylene ethoxylated straight-chain or branched C 7-21 alcohols such as C 2-methyl-branched 9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO, are suitable.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • surfactants are used in the form of their magnesium salts.
  • linear alkylbenzenesulfonates such as, for example, the linear C 10-13 -alkylbenzenesulfonates.
  • the content of anionic surfactants according to the invention is advantageously from 5 to 20% by weight, preferably from 7.5 to 20% by weight, particularly preferably from 10 to 20% by weight, based on the total agent.
  • the surfactant system preferably consists of 60 to 95 wt .-%, particularly preferably 70 to 90 wt .-%, of anionic surfactant.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 80, preferably 3 to 12, moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferred may be methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • the fatty alcohols are lauryl alcohol (C 12 ), myristyl alcohol (C 14 ), cetyl alcohol (C 16 ) etc., from the point of view of the availability of the compounds.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for Example of coconut, palm, tallow or Oleyfalkohol, and on average 1 to 80, preferably 2 to 8 EO per mole of alcohol is preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO, C 18-18 alcohols with 5 EO and mixtures of these, and mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alkoxyethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, 40 EO or up to 80 EO.
  • C 12-18 alcohols with 7 EO and C 16-18 alcohols with 5 EO, as well as mixtures of these have proven particularly suitable for the present invention as nonionic surfactants.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 8 carbon atoms in the alkyl chain and from 3 to 80 to 20 alkoxy groups, preferably ethoxy groups in the molecule, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferred according to the in the international patent application WO 90/13533 disclosed methods are produced.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Preference is given to using linear alkyl polyglucosides that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • 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 alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • the nonionic surfactants are used in the present invention, alone or in admixture, and advantageously so that the total niotenside content of the detergents or cleaners according to the invention is advantageously from 1 to 10% by weight, preferably from 2 to 5% by weight, or the surfactant system 5 to 25 wt .-%, preferably 10 to 20 wt .-%, of at least one nonionic surfactant.
  • anionic and nonionic surfactants it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably as a washing power booster, with only small amounts of cationic surfactants are required.
  • the washing or cleaning agents according to the invention preferably contain at least one foam regulator. These are preferably fatty acids or fatty acid soaps.
  • the foam regulators are contained in amounts of 0.5 to 8 wt .-%, preferably 1 to 5 wt .-%, based on the total agent.
  • Essential to the present invention is a specific foaming behavior of the washing or cleaning agents according to the invention. It has proven to be advantageous, for example, if the agent has a foam grade of at least 5 in the wash cycle, then, after a single dilution and three further rinse cycles, a foam grade of at most 1.
  • the washing or cleaning agent according to the invention is particulate, in particular in the form of powders, extrudates, granules and / or mixtures thereof.
  • the detergents or cleaners according to the invention may contain, in addition to the above-mentioned ingredients, all known ingredients customary in detergents and cleaners such as, for example, enzymes, dyes, optical brighteners, UV protectants, fragrances and perfumes, perfume carriers, anti-redeposition agents, grayness inhibitors, dye transfer inhibitors, Corrosion inhibitors, bleaches, bleach activators, softeners and fabric softeners.
  • the agents do not contain bleaching agents and bleach activators for the protection of delicate textiles.
  • the remaining ingredients are preferably in amounts of from 2 to 40% by weight, in particular in amounts of from 10 to 30% by weight, based on the total weight of the composition according to the invention.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • chlorine or bromine releasing substances can be used as a bleaching agent. However, these are of little importance for use in detergents.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides such as 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 suitable.
  • bleach activators may be incorporated in the compositions of the invention.
  • compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C-atoms, and / or optionally substituted perbenzoic acid, can be used.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2 , 5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the high soda-containing particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes, for example Mn, Fe, Co, Ru or Mo saline 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 ammine complexes can also be used as bleach catalysts.
  • compositions do not contain any of the abovementioned bleaches and none of the abovementioned bleach activators.
  • Agents according to the invention may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight, based on active protein.
  • the Protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gomall AG, CS Bardawill and MM David, J. Biol. Chem. 177 (1948), pp. 751-766 ).
  • subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • the subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 ) derive from the name under the name BLAP ® variants, which in particular in WO 92/21760 . WO 95/23221 and in the applications DE 10121463 and DE 10153792 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications DE 10162727 . DE 10163883 . DE 10163884 and DE 10162728 out.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
  • the enzyme from B. licheniformis is obtainable from Novozymes under the name Termamyl ® and available from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application PCT / EP01 / 13278 highlighted cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); further, those belonging to the sequence space of ⁇ -amylases described in the application DE 10131441 is defined.
  • fusion products of said molecules can be used, for example those from the application DE 10138753 ,
  • compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens .
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used whose Ranzyme originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Detergents according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
  • EG endoglucanase
  • Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ®.
  • those in the application WO 97/14804 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®.
  • compositions of the invention may contain other enzymes, which are summarized under the term hemicellulases.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • a suitable ⁇ -glucanase from a B. alcalophilus for example, from the application WO 99/06573 out.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • detergents and cleaners according to the invention may contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously concentrated as possible, low in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of caplets, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • peptide aldehydes that is, oligopeptides with reduced C-terminus are disclosed.
  • peptidic protease inhibitors include ovomucoid ( WO 93/00418 ) and leupeptin; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as from the applications EP 378261 and WO 97/05227 is known, such as succinic acid, other dicarboxylic acids or salts of said acids.
  • succinic acid other dicarboxylic acids or salts of said acids.
  • end-capped fatty acid amide alkoxylates are disclosed.
  • Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.
  • Polyamide oligomers ( WO 99/43780 ) or polymeric compounds such as lignin ( WO 97/00932 ), water-soluble vinyl copolymers (EP 828762 ) or, as in EP 702712 Cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-Oxide-Containing Polymers ( EP 587550 and EP 581751 ) act simultaneously as enzyme stabilizers and as color transfer inhibitors.
  • Other polymeric stabilizers are those in WO 97/05227 among other ingredients disclosed linear C 8 -C 18 polyoxyalkylenes.
  • Alkylpolyglycosides can according to the applications WO 97/43377 and WO 98/45396 stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • networked N-containing compounds, as in WO 98/17764 disclosed perform a dual function as soil release agents and as enzyme stabilizers.
  • Reducing reducing agents and antioxidants such as in EP 780466 discloses the stability of the enzymes to oxidative degradation.
  • Sulfur-containing reducing agents are known for example from the patents EP 080748 and EP 080223 known.
  • Other examples are sodium sulfite ( EP 533239 ) and reducing sugars ( EP 656058 ).
  • combinatons of stabilizers are used, for example polyols, boric acid and / or borax according to the application WO 96/31589 , the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids after the application EP 126505 or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts as in the application EP 080223 disclosed.
  • the effect of peptide-aldehyde stabilizers is determined according to WO 98/13462 increased by the combination with boric acid and / or boric acid derivatives and polyols and according to WO 98/13459 further enhanced by the additional use of divalent cations, such as calcium ions.
  • foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane
  • foam inhibitors as stated above not being absolutely necessary, but if desired being able to take place.
  • mixtures of these agents is possible.
  • additives which are solid at room temperature paraffin waxes, silicic acids, which may also be hydrophobized in a known manner, and in particular bismuth derivatives which are derived from C 2-7 -diamines and C 12-22 -carboxylic acids are suitable.
  • Foaming-inhibiting paraffin oils suitable for use in the detergents according to the invention which may be present in admixture with paraffin waxes, generally represent complex mixtures without a sharp melting point.
  • the melting range is usually determined by characterization Differential thermal analysis (DTA) as in “ The Analyst “87 (1962), 420 , described, and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • Paraffins with less than 17 carbon atoms are not useful in the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography.
  • paraffins are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin oils. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible, without already being 100% at this temperature.
  • Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to.
  • paraffins are flowable and pumpable at temperatures down to at least 70 ° C, preferably down to at least 60 ° C. It should also be ensured that the paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Fuller and Deawax® from DEA Mineralöl AG.
  • the paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • suitable diamines are ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoylethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • dyes in particular water-soluble or water-dispersible dyes may be incorporated.
  • dyes are usually used to improve the appearance of the optical product in detergents and cleaners.
  • the choice of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent compositions and to light and no pronounced substantivity to textile fibers in order not to stain them.
  • optical brighteners are derivatives of diaminostilbene disulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which instead of the morpholino group a Diethanoiamino Group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present in the washing or cleaning compositions according to the invention, e.g.
  • UV protective substances are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb Ciba Specialty Chemicals.
  • polymers Another class of common detergent or cleaning ingredients that can be added according to the invention are polymers.
  • these polymers are on the one hand polymers in question, which show co-washing properties during washing or cleaning or rinsing. These have already been described in detail above.
  • Another group of polymers are graying inhibitors. These have the task of keeping suspended from the hard surface and in particular of the textile fiber suspended dirt in the fleet and so to support the co-builder.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the total agent.
  • the detergents or cleaning agents may also contain antiredeposition agents, so-called soil repellents. These are polymers that are absorbed by fibers or hard surfaces and counteract re-soiling. This effect is particularly evident when a textile is dirty, which has been previously 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 methoxy groups of 15 to 30 wt .-% and to hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • color transfer inhibitors include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • detergents or cleaners according to the invention may also contain fragrances and perfume preparations (perfumes).
  • perfume oils or fragrances individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • Fragrance type compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyctohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • Ethers include, for example, benzyl ethyl ether.
  • the aldehydes include e.g. linear alkanals of 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lileal and bourgeonal.
  • the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different fragrances which are adapted to one another in such a way that together they produce an attractive fragrance note.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • fragrances may be advantageous to apply to carriers which enhance the adhesion of the perfume to the laundry and provide a lingering fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven.
  • the cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.
  • the detergents or cleaners according to the invention may contain corrosion inhibitors for the protection of the laundry or ware or the machine, with silver protectants in the area of automatic dishwashing being a special one Have meaning.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • organic redox-active compounds such as di- and trihydric phenols, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • X - may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these.
  • Examples of compounds of formula (11) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) methosulfate.
  • Commercial examples are sold by Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco.
  • Further preferred compounds are the diester quats of the formula (III) which are obtainable under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also provide stability and color protection.
  • R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • quaternary imidazolinium compounds of the formula (IV) where R 9 is H or a saturated alkyl radical having 1 to 4 carbon atoms, R 10 and R 11 are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R 10 may alternatively be O (CO) R 20 wherein R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X - is an anion.
  • q can take integer values between 1 and 4.
  • R 12 , R 13 and R 14 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, each of R 15 and R 16 independently represents a C 8-28 alkyl group and r is a number between 0 and 5 is.
  • short-chain, water-soluble, quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammoniumchforid.
  • quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl
  • cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
  • Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats. 10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium-4 copolymers, such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar hydroxypropyltriammonium chloride, and similar quaternized guar gum.
  • cationic quaternary sugar derivatives for example the commercial product Glucquat ® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, Copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymer e.
  • Polyquaternized polymers for example Luviquat Care from BASF
  • cationic biopolymers based on chitin and derivatives thereof for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ® quat 3270 and 3272 (Manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone Quat Rewoquat ® SQ 1 (Tegopren ® 6922, manufacturer: Goldschmidt-Rewo).
  • Q2-7224 manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone
  • Dow Corning 929 emulsion containing a hydroxylamino-modified silicone, also referred to as amodimethico
  • the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
  • R 17 may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5.
  • R 18 and R 19 are each independently H, C 1-4 alkyl or hydroxyalkyl.
  • Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ® X 9124, which in addition to a good conditioning effect also by their color transfer inhibiting effect and especially by their good biodegradability.
  • Tego Amid ® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ® X 9124, which in addition to a good conditioning effect also by their color transfer inhibiting effect and especially by their good biodegradability.
  • Stepantex ® X 9124 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ® X 9124.
  • the non-quaternized alkylamidoamines are preferred.
  • these include, for example, fatty acid amido
  • the agent E according to the invention gave a sediment volume per liter of 0.15 ml, that of the comparison agent V a sediment volume per liter of 2.50 ml.
  • the filter residues were left on the fabric, dried and visually examined by 3 different people according to Table 2 and graded accordingly. Criterion of grading was the degree of coverage of the filter surface with filter residue. The grades of the 3 different persons were added and divided by 3. ⁇ b> Table 2: ⁇ / b> Rating of the filter residue by visual inspection. optical impression grade No residue 0 Little residue 1 good visible residue 2 highly visible residue that covers more than half of the filter surface 3 Almost complete covering with residue 4 Complete, closed cover with residue 5 Very strong covering with residue 6
  • the filter residue of the agent E according to the invention was assessed on average with the grade 1, that of the comparison agent V with the grade 6.
  • the foaming behavior was determined using a Miele washing machine (type W 918, without fuzzy logic). For this purpose, 100 g of the means E or V were metered and 22 water hardness 16 ° dH used. The washing machine was operated with 2.0 kg of clean, standardized filling wash in the easy-care / fine program. The foam was scored according to the following chart. ⁇ b> Table 3: ⁇ / b> Grading of the foam after optical inspection. grade 0 No foam 1 Foam stand under the edge of the porthole 2 Foam level: half of the porthole 3 Foam level 2/3 of the porthole 4 Porthole full of foam 5 Washing machine full of foam, but still below Ein Hughesschitzsch 6 Foam in the dispenser
  • the agent E according to the invention had a high degree of foam during washing, whereby the laundry was spared, and a low level of foam after the last rinsing, which is equal to a good rinsability.
  • the comparison agent V on the other hand, likewise had a comparatively high degree of foam during washing, this was still unacceptably high after the last rinse, which equates to poor rinsability.
  • the agent according to the invention had a lower sediment volume than the comparison agent, ie it contained less sparingly soluble constituents. Both the deposition behavior and the foaming behavior, especially during rinsing, were better graded in the composition according to the invention than in the comparison agent. So while the actual washing process there is sufficient foam to ensure a gentle cleaning even of delicate textiles, the foam after the rinses is very low, so the foam can be rinsed well; At the same time, unwanted deposits on the laundry are formed only to a much lesser extent than in the comparison agent. Consequently, the use of the builder system according to the invention positively influences both the foam behavior and the deposition behavior.

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Claims (20)

  1. Agent de lavage ou de nettoyage en forme de particules contenant un système tensioactif et un builder mais exempt de silicate d'aluminium, de silicates et de phosphates, dont la dispersion aqueuse présente un pH compris entre 7,0 et 9,0 dans les conditions qui comprennent 8 g/l, 20°C, 16°d, l'agent comprenant
    (a) jusqu'à 35% en poids d'un système de builder, et
    (b) jusqu'à 25% en poids d'un système tensioactif qui contient au moins un tensioactif anionique et au moins un tensioactif non ionique,
    caractérisé en ce qu'il présente, après dispersion dans de l'eau du robinet, dans les conditions qui comprennent 8 g/l, 20°C, 16°d, 20 minutes d'agitation, après 24 heures de sédimentation, un volume de sédiments de maximum 0,5 ml.
  2. Agent de lavage ou de nettoyage selon la revendication 1, caractérisé en ce qu'il présente après dispersion dans de l'eau du robinet (8 g/l, 20°C, 16°d, 20 minutes d'agitation, 24 heures de sédimentation) un volume de sédiments de maximum 0,2 ml et de préférence, de 0 ml.
  3. Agent de lavage ou de nettoyage selon la revendication 1 ou 2, caractérisé en ce que sa dispersion aqueuse (8 g/l, 20°C, 16°d) présente un pH compris entre 7,5 et 8,5.
  4. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient
    (a) au moins 15 % en poids, de préférence 20 à 30 % en poids, d'un système builder et
    (b) au moins 5 % en poids, de préférence 10 à 15 % en poids, d'un système tensioactif.
  5. Agent de lavage ou de nettoyage selon la revendication 4, caractérisé en ce que le système builder contient
    (a) 35 à 75 % en poids, de préférence 50 à 60 % en poids, d'au moins une source d'alcalinité,
    (b) 25 à 65 % en poids, de préférence 35 à 45 % en poids, d'au moins un régulateur de pH,
    (c) 0,5 à 12 % en poids, de préférence 3 à 7,5 % en poids, d'au moins un co-builder organique,
    (d) 0 à 3 % en poids, de préférence 0 à 2 % en poids, d'au moins un agent complexant, toujours par rapport au système builder entier.
  6. Agent de lavage ou de nettoyage selon la revendication 5, caractérisé en ce que la source d'alcalinité est constituée par du carbonate de métal alcalin, de l'hydrogénocarbonate de métal alcalin et/ou du sesquicarbonate de métal alcalin, de préférence de l'hydrogénocarbonate de sodium et/ou du carbonate de sodium et/ou du sesquicarbonate de sodium, de manière particulièrement préférée du carbonate de sodium et le cas échéant de l'hydrogénocarbonate.
  7. Agent de lavage ou de nettoyage selon la revendication 5 ou 6, caractérisé en ce qui concerne le régulateur de pH il s'agit d'au moins un acide polycarboxylique organique monomère.
  8. Agent de lavage ou de nettoyage selon la revendication 7, caractérisé en ce que l'acide polycarboxylique organique monomère est choisi dans le groupe comprenant l'acide citrique, l'acide adipique, l'acide succinique, l'acide glutarique, l'acide malique, l'acide tartrique, l'acide maléique, l'acide fumarique, les acides sacchariques, des acides aminocarboxyliques et/ou l'acide nitrilotriacétique et/ou leurs sels, de préférence dans le groupe comprenant l'acide citrique, l'acide succinique, l'acide glutarique, l'acide adipique et/ou l'acide gluconique et/ou leurs sels, l'acide citrique et/ou ses sels étant particulièrement préférés.
  9. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 8, caractérisé en ce qui concerne le co-builder organique il s'agit d'au moins un acide polycarboxylique polymère et/ou de son/ses sel(s) métallique(s) et/ou d'ammonium partiellement ou complètement neutralisé(s), de préférence de son/ses sel(s) de métal alcalin, de manière particulièrement préférée son/ses sel(s) de sodium et/ou des mélanges de ceux-ci.
  10. Agent de lavage ou de nettoyage selon la revendication 9, caractérisé en ce qui concerne l'acide polycarboxylique polymère et/ou son/ses sel(s) métallique(s) et/ou d'ammonium partiellement ou complètement neutralisé(s) il s'agit de polyacrylate(s) ayant une masse molaire de 1000 à 20 000 g/mole, de préférence de 1000 à 10 000 g/mole et de préférence en particulier de 1200 à 8 000 g/mole et/ou d'acides polycarboxyliques copolymères ayant des masses molaires de 20 000 à 90 000 g/mole, en particulier de 30 000 à 80 000 g/mole.
  11. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'en tant qu'agent complexant, il contient au moins un phosphonate.
  12. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le système tensioactif contient
    (a) 60 à 95 % en poids, de préférence 70 à 90 % en poids, d'au moins un tensioactif anionique,
    (b) 5 à 25 % en poids, de préférence 10 à 20 % en poids, d'au moins un tensioactif non ionique, toujours par rapport au système tensioactif complet.
  13. Agent de lavage ou de nettoyage selon la revendication 12, caractérisé en ce que les tensioactifs anioniques sont sélectionnés dans le groupe comprenant les sulfonates d'alkylbenzènes en C10 à C13, les disulfonates en C12 à C18, les sulfonates d'alcanes en C12 à C18, les esters d'acides gras sulfonés en C8 à C20, les esters glycéryliques d'acide gras en C6 à C22 sulfonés, les sulfates d'alkyle ou d'alcényle en C12 à C18, les sulfates d'oxoalkyle ou d'oxoalcényle en C10 à C20, les 2,3-alkylsulfates, les sulfates de (glycoléther)3,5 d'alcool gras en C7 à C21, les esters d'acide alkylsulfosuccinique en C8 à C18, les sarcosides, les sarcosinates, les savons d'acides gras en C12 à C22, de préférence dans le groupe comprenant les sulfonates linéaires d'alkylbenzène en C10 à C13, les savons d'acides gras en C12 à C22.
  14. Agent de lavage ou de nettoyage selon la revendication 12 ou 13, caractérisé en ce que les tensioactifs non ioniques sont choisis dans le groupe comprenant des alcools gras en C8 à C18 qui contiennent 1 à 12 EO, des alkylglycosides de formule RO(G)1-10, des esters d'acides gras en C12 à C18 -(alkyle en C1 à C4)(glycoléthers)5-12, des aminoxydes, des amides d'acide gras polyhydroxylés, les tensioactifs non ioniques préférés étant cependant des alcools gras en C8 à C18 comprenant 1 à 12 EO.
  15. Agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'il se présente sous forme de particules, de préférence sous forme de poudre, d'extrudat, de granules et/ou de mélanges de ceux-ci, de manière particulièrement préférée sous forme de poudres.
  16. Utilisation de l'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 15 pour laver ou nettoyer des matières textiles, de préférence des matières textiles délicates.
  17. Utilisation selon la revendication 16, caractérisée en ce qui concerne les matières textiles délicates il s'agit de matières textiles en laine, en coton, en soie, en lin, en viscose et/ou mélanges de ceux-ci, de préférence de laine.
  18. Utilisation selon la revendication 16 ou 17 pour réduire les dépôts lors du lavage ou du nettoyage de matières textiles, notamment lors du lavage ou du nettoyage de matières textiles délicates.
  19. Utilisation selon l'une quelconque des revendications 16 à 18 dans un bain de lavage en machine, à une température comprise entre 20 et 60°C, de préférence entre 30 et 40°C, ou dans un bain de lavage à la main, à une température comprise entre 15 et 40°C, de préférence entre 20 et 35°C.
  20. Procédé de lavage ou de nettoyage de matières textiles, notamment de matières textiles délicates, caractérisé en ce que
    (a) un agent de lavage ou de nettoyage selon l'une des revendications 1 à 16 est dissous dans de l'eau,
    (b) la ou les matières textiles sont mises en contact avec la solution aqueuse de l'agent,
    (c) la solution aqueuse de l'agent de lavage ou de nettoyage est passée sur la ou les matière(s) textile(s) ou inversement,
    (d) la solution aqueuse de l'agent de lavage ou de nettoyage est éliminée de la ou des matière(s) textile(s), en rinçant plusieurs fois avec de l'eau du robinet fraiche, c'est-à-dire jusqu'à rinçage complet,
    (e) la ou les matière(s) textile(s) sont séchée(s).
EP02785254.0A 2001-10-30 2002-10-19 Detergent ou nettoyant dispersible sensiblement exempt de sediments Expired - Lifetime EP1440141B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10153551A DE10153551A1 (de) 2001-10-30 2001-10-30 Im wesentlichen sedimentfrei dispergierbares Wasch- oder Reinigungsmittel
DE10153551 2001-10-30
PCT/EP2002/011726 WO2003038028A2 (fr) 2001-10-30 2002-10-19 Detergent ou nettoyant dispersible sensiblement exempt de sediments

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EP1440141A2 EP1440141A2 (fr) 2004-07-28
EP1440141B1 true EP1440141B1 (fr) 2007-08-01
EP1440141B2 EP1440141B2 (fr) 2014-05-14

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EP (1) EP1440141B2 (fr)
AT (1) ATE368726T1 (fr)
DE (2) DE10153551A1 (fr)
ES (1) ES2289163T5 (fr)
WO (1) WO2003038028A2 (fr)

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WO2003038028A3 (fr) 2003-10-23
DE50210602D1 (de) 2007-09-13
WO2003038028A2 (fr) 2003-05-08
ATE368726T1 (de) 2007-08-15
EP1440141B2 (fr) 2014-05-14
EP1440141A2 (fr) 2004-07-28
ES2289163T5 (es) 2014-09-12
DE10153551A1 (de) 2003-05-22
ES2289163T3 (es) 2008-02-01

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