EP1084224B1 - Aqueous bleaching agent with viscose structure - Google Patents

Aqueous bleaching agent with viscose structure Download PDF

Info

Publication number
EP1084224B1
EP1084224B1 EP99926391A EP99926391A EP1084224B1 EP 1084224 B1 EP1084224 B1 EP 1084224B1 EP 99926391 A EP99926391 A EP 99926391A EP 99926391 A EP99926391 A EP 99926391A EP 1084224 B1 EP1084224 B1 EP 1084224B1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
viscosity
water
textile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP99926391A
Other languages
German (de)
French (fr)
Other versions
EP1084224A1 (en
Inventor
Hans-Jürgen Riebe
Theodor Völkel
Florence Lambert
Josef Penninger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7869720&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1084224(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1084224A1 publication Critical patent/EP1084224A1/en
Application granted granted Critical
Publication of EP1084224B1 publication Critical patent/EP1084224B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0084Antioxidants; Free-radical scavengers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/722Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to an aqueous bleaching agent based on hydrogen peroxide, especially for use as laundry pretreatment agents, but also as Additive in conventional washing processes is suitable for its use as Laundry pretreatment agent and a washing method using such Agent.
  • Common liquid peroxide-containing pretreatment agents are relatively low-viscosity means that they generally have viscosities not exceeding 200 mPa.s. They contain alongside the peroxide is usually water and surfactants, which improve wettability the stains should apply when applying the agent. Due to the high network effect and the low viscosity of the agent causes the product to run badly on the treated textile, so that even with careful application of the agent in all Usually a much larger area than the actual stain is wetted. this leads to that part of the peroxide applied to the textile does not bleach the Soiling is available, but is wasted, so to speak, because it is not in appropriate direct contact with the stain.
  • Structural viscosity is understood here to mean the effect that the liquid agent has a higher viscosity when exposed to low shear forces than when applied higher shear forces.
  • the change in viscosity is usually not directly proportional the change in acting shear forces, but the viscosity increases with decreases in shear force in the low shear range more than in the high Shear area. This property can be checked experimentally by: measures viscosity under various shear conditions. One way to do this offers a common rotary viscometer at different speeds the spindle.
  • the invention relates to a liquid water-based bleaching or Laundry pretreatment agent containing 0.2% by weight to 25% by weight of hydrogen peroxide, Complexing agent for heavy metals in an amount up to 5 wt .-%, surfactant in one Amount up to 15% by weight, radical scavengers in an amount up to 0.1% by weight and water in amounts of 55% by weight to 90% by weight and as much polysaccharide thickening agent, that it was at 20 ° C at 20 revolutions per minute (Brookfield Rotational viscometer) a viscosity in the range of 200 mPa.s to 5000 mPa.s, in particular 300 mPa.s to 3000 mPa.s and at 5 revolutions per minute (Brookfield Rotational viscometer) at least by a factor of 1.5, in particular 2 to 50 and particularly preferably 2.5 to 30 higher viscosity than at 50 revolutions per Minute.
  • Brookfield Rotational viscometer a viscosity in the range of
  • the agents according to the invention contain hydrogen peroxide as an essential constituent, which is responsible for the bleaching performance, in amounts of preferably 0.5% by weight up to 20% by weight, in particular 2% by weight to 10% by weight. For the production of such agents can also be assumed from more concentrated hydrogen peroxide.
  • a polysaccharide thickening agent is an optionally modified one Polymer from saccharides such as glucose, galactose, mannose, gulose, old rose, allose etc. into consideration.
  • a water-soluble xanthan is preferred, as described, for example, under the product names Kelzan®, Rhodopol®, Ketrol® or Rheozan® are commercially available is used.
  • Xanthan is a polysaccharide that corresponds to that of the bacterial strain Xanthomas campestris from aqueous solutions is produced by glucose or starch (J. Biochem. Micobiol. Technol. Engineer. Vol. III (1961), pp. 51 to 63).
  • the polysaccharide thickening agent is preferably in amounts of Contain 0.05 wt .-% to 2.5 wt .-%, in particular 0.1 wt .-% to 2 wt .-%. He wears crucial not only to the viscosity, but also to the intrinsic viscosity of the invention Means at. It is particularly advantageous that when using such Thickening agents, especially of xanthan, have a wide viscosity Temperature range from about -5 ° C to 40 ° C changes only slightly and also when leaving of this temperature range there are reversible values in the viscosity range mentioned above adjust when the medium is brought back to room temperature.
  • Agents according to the invention contain one or more surfactants in amounts of preferably 0.1% by weight to 9% by weight, anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable.
  • Suitable anionic surfactants are, in particular, those which contain sulfate or sulfonate groups.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • MES methyl esters of ⁇ -sulfofatty acids
  • their saponified disalts can also be used.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -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, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • the sarcosides or sarcosinates and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 3 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 4 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 5 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 6 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as 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 international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • 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, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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 them.
  • So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic 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 have a sufficient distance so that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • the term gemini surfactants is understood not only to mean “dimeric” but also "trimeric” surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized 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.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.
  • an agent according to the invention contains a surfactant system composed of alkyl ether sulfate of the general formula R 1 O- (CH 2 CH 2 O) n -SO 3 X, in which R 1 is a linear or branched-chain alkyl or alkenyl radical with 6 to 22 C - Atoms, n is a number from 1 to 10 and X is an alkali metal or ammonium ion, and alkyl polyglycol ethers of the general formula R 2 O- (C 3 H 6 O) 1 - (CH 2 CH 2 O) m - (C 3 H 6 O) n -OH, in which R 2 is a linear or branched-chain alkyl or alkenyl radical having 6 to 22 carbon atoms and m is a number from 1 to 10 and 1 and n is a number from 0 to 10, in a weight ratio of 1: 10 to 10: 1, in particular from 2: 1 to 5: 1.
  • R 1 is a linear or branched-
  • Suitable complexing agents contained in agents according to the invention for Heavy metals include aminocarboxylic acids and optionally functionally modified Phosphonic acids, for example hydroxy or aminoalkanephosphonic acids.
  • aminocarboxylic acids include, for example, nitrilotriacetic acid, methylglycinediacetic acid and diethylenethamine pentaacetic acid.
  • phosphonic acids come for example 1-hydroxyethane-1,1-diphosphonic acid (HEDP) respectively the disodium salt or the tetrasodium salt of this acid, ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP) as well as their higher homologues in question.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP ethylenediamine-tetramethylenephosphonic acid
  • DTPMP diethylenetriamine-pentamethylenephosphonic acid
  • Complexing agents also include ethylenediamine-N, N'-disuccinic acid (EDDS).
  • EDDS ethylenediamine-N, N'-disuccinic acid
  • the one in her Complexing agents called acid form can be used as such or in the form of the sodium salts be used.
  • Mixtures of aminocarboxylic acids are preferred with phosphonic acids.
  • Complexing agents for heavy metals are in agents according to the invention preferably contained in amounts of 0.05% by weight to 1% by weight.
  • Agents are preferably contained in amounts of 0.01% by weight to 0.1% by weight, include phenols such as 1,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT), Hydroquinones such as di-tert-butyl hydroquinone, catechols such as allyl catechol, alkylated Diphenylamine or N-phenyl- ⁇ -naphthylamine and dihydroquinolines. As a preferred Radical scavenger is used BHT.
  • Agents according to the invention are preferably acidic and in particular have a pH in the range of 2 to 4.
  • acids which are compatible with the system, in particular those mentioned above Aminocarboxylic or phosphonic acids, citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also Mineral acids such as sulfuric acid, phosphoric acid or alkali hydrogen sulfates, or Contain bases, especially ammonium or alkali hydroxides.
  • all agents according to the invention can be used in Liquid detergents contain the usual ingredients with the essential Constituents, especially the hydrogen peroxide and the thickening system, are tolerated. These include, for example, foam regulator active ingredients, color and Fragrances and, if desired, optical brighteners.
  • Agents according to the invention can be done in a simple manner by simple means Mixing their ingredients can be made. They are homogeneous systems with one high storage stability and good stain removal performance with low textile damage potential. They are preferably contaminated for pretreatment Textiles used before washing. In addition or instead, you can also put them in Form of an additive to a detergent, especially for machine washing of textiles.
  • a washing process using the inventive Agents are preferably carried out in such a way that a liquid agent according to the invention undiluted on the soiled textile or a part of the soiled textile, the embraces the stain to be removed, applies it, preferably there only so long lets it not dry out, and the textile using water or optionally an aqueous wash liquor which contains a conventional detergent, washes especially using a machine.
  • a simple blending of the ingredients in the proportions indicated in the table below produced a liquid bleach-containing laundry pretreatment agent B1 , which was adjusted to a pH of 3 by adding small amounts of phosphoric acid and the viscosity (in mPa. s at 20 ° C).
  • Composition (% by weight) medium B1 hydrogen peroxide 5 ether sulfate 2 nonionic surfactant 0.5 Keltrol® T 0.45 complexing 0.2 BHT 0.03 ethanol 0.2 water to 100 viscosity 910

Abstract

The invention aims at solving the problem of hydrogen peroxide wastage when the agent is poured on dirty textiles and the increased oxidative load on the textile when pretreatment agents containing peroxide are used in an aqueous bleaching agent serving as laundry pretreatment agent. This is substantially achieved by an agent containing 0.2 to 25 % by weight of hydrogen peroxide, complexing agents for heavy metals in a quantity of up to 5 % by weight, surfactants in a quantity of up to 15 % by weight, free-radical scavengers in a quantity of up to 0.1 % by weight and water in quantities ranging from 55 to 90 % by weight and a polysaccharide thickening active substance in quantities such that the substance has a viscosity in the range of from 200 mPa.s to 5,000 mPa.s at 20 DEG C and at rpm 20 (Brookfield rotational viscometer) and a viscosity at rpm 5 (Brookfield rotational viscometer) that is at least 1.5 higher than at rpm 50.

Description

Die vorliegende Erfindung betrifft ein wäßriges Bleichmittel auf WasserstoffperoxidBasis, das insbesondere zur Anwendung als Wäschevorbehandlungsmittel, aber auch als Additiv in üblichen Waschverfahren geeignet ist, seine Verwendung als Wäschevorbehandlungsmittel sowie ein Waschverfahren unter Einsatz eines derartigen Mittels.The present invention relates to an aqueous bleaching agent based on hydrogen peroxide, especially for use as laundry pretreatment agents, but also as Additive in conventional washing processes is suitable for its use as Laundry pretreatment agent and a washing method using such Agent.

Um hartnäckige Anschmutzungen, sogenannte Flecken, von Textilien zu entfernen, werden diese häufig vor dem eigentlichen Waschprozeß mit speziellen Vorbehandlungsmitteln behandelt. Soweit es sich dabei um das Problem des Entfernens von bleichbaren Anschmutzungen handelt, kommen in der Regel peroxidhaltige Vorbehandlungsmittel zum Einsatz. Wegen der dann erleichterten Anwendungsbedingungen sind derartige Vorbehandlungsmittel normalerweise flüssig und werden direkt oder gegebenenfalls nach Verdünnen mit Wasser auf den Fleck gegossen. Dabei wird durch intensive und längere Einwirkzeit des peroxidhaltigen Mittels eine verbesserte Entfernung der bleichbaren Flecken aus dem Textil erreicht, wenn man das Textil anschließend einem haushaltsüblichen Waschprozeß unterwirft, wobei neben maschinellen Waschverfahren auch die sogenannte Handwäsche zum Einsatz kommen kann.To remove stubborn stains from textiles these are often with special before the actual washing process Pretreatment agents treated. So far this is the problem of removal bleachable stains are usually peroxide-containing Pretreatment agent for use. Because of the then relieved Such pretreatment agents are normally liquid and use conditions are poured onto the stain directly or, if necessary, after dilution with water. Due to the intensive and longer exposure time of the peroxide-containing agent, a improved removal of the bleachable stains from the textile when this is achieved Textile then subjected to a household washing process, in addition to machine washing processes, so-called hand washing can also be used can.

Übliche flüssige peroxidhaltige Vorbehandlungsmittel sind relativ niedrigviskos, das heißt sie weisen in der Regel Viskositäten nicht über 200 mPa.s auf. Sie enthalten neben dem Peroxid üblicherweise Wasser und Tenside, die eine Verbesserung der Benetzbarkeit der Flecken beim Auftrag des Mittels bewirken sollen. Durch die hohe Netzwirkung und die niedrige Viskosität des Mittels kommt es zu einem starken Verlaufen des Produktes auf dem behandelten Textil, so daß auch bei sorgfältigem Auftrag des Mittels in aller Regel eine wesentlich größere Fläche als der eigentliche Fleck benetzt wird. Dies führt dazu, daß ein Teil des auf das Textil aufgebrachten Peroxids nicht zur Bleiche der Anschmutzung zur Verfügung steht, sondern sozusagen vergeudet wird, weil er sich nicht in entsprechendem direkten Kontakt zum Fleck befindet. Ein weiteres Problem ergibt sich beim Eintrocknen des wäßrigen Vorbehandlungsmittels auf dem Textil dadurch, daß das Verdunsten des Wassers verstärkt an den Rändern der Flüssigkeit stattfindet, wodurch es im Sinne eines Chromatographieeffektes zu Konzentrationsgradienten der Flüssigkeitsinhaltsstoffe kommt. Hierdurch findet in der Randzone der Flüssigkeit eine Aufkonzentrierung von Flüssigkeitsinhaltsstoffen statt. Auch aus der Textiloberfläche stammende Substanzen, wie zum Beispiel Schwermetallionen, wandern verstärkt an den Rand der benetzten Fläche und treten dort in relativ hoher Konzentration auf. Dies führt zu verstärkter schwermetallkatalysierter Wasserstoffperoxid-Zersetzung im Randbereich der benetzten Fläche und damit zu einer erhöhten oxidativen Belastung der Textilfasern in diesem Bereich, was sich in bleibenden Veränderungen des Farbeindrucks bis hin zu Schädigungen des Textils äußern kann.Common liquid peroxide-containing pretreatment agents are relatively low-viscosity means that they generally have viscosities not exceeding 200 mPa.s. They contain alongside the peroxide is usually water and surfactants, which improve wettability the stains should apply when applying the agent. Due to the high network effect and the low viscosity of the agent causes the product to run badly on the treated textile, so that even with careful application of the agent in all Usually a much larger area than the actual stain is wetted. this leads to that part of the peroxide applied to the textile does not bleach the Soiling is available, but is wasted, so to speak, because it is not in appropriate direct contact with the stain. Another problem arises when drying the aqueous pretreatment agent on the textile in that the Evaporation of the water intensifies at the edges of the liquid, causing it to in the sense of a chromatography effect on concentration gradients Liquid ingredients come. As a result, one finds in the edge zone of the liquid Concentration of liquid ingredients instead. Even from the textile surface Originating substances, such as heavy metal ions, migrate to the Edge of the wetted surface and occur there in a relatively high concentration. this leads to increased heavy metal-catalyzed hydrogen peroxide decomposition in the edge area the wetted surface and thus to an increased oxidative load on the textile fibers in this area, which results in permanent changes in color perception Can express damage to the textile.

In der internationalen Patentanmeldung WO 96/26999 wird vorgeschlagen, diesem Problem durch den Einsatz von Chelatisierungsmitteln für Eisen, Kupfer oder Mangan zu begegnen, wohingegen in der europäischen Patentanmeldung EP 0 751 214 der Einsatz bestimmter Polyamine zur Vermeidung von Farb- und/oder Faserschädigungen empfohlen wird. Beides führt nicht in allen Fällen zu einer völlig zufriedenstellenden Lösung.In international patent application WO 96/26999 it is proposed to counter this problem by using chelating agents for iron, copper or manganese, whereas in European patent application EP 0 751 214 the use of certain polyamines is recommended to avoid damage to color and / or fibers becomes. Both do not lead to a completely satisfactory solution in all cases.

Überraschenderweise wurde nun gefunden, daß sowohl das Problem der Vergeudung von Wasserstoffperoxid wie auch das der erhöhten oxidativen Belastung des Textils durch den Einsatz von peroxidhaltigen Vorbehandlungsmittlen gelöst werden kann, die mit Hilfe eines speziellen Verdickungswirkstoffs auf eine erhöhte Viskosität eingestellt worden sind und eine bestimmte Strukturviskosität aufweisen, das heißt ein nicht-newton sches Fließverhalten besitzen.Surprisingly, it has now been found that both the problem of wasting Hydrogen peroxide as well as the increased oxidative stress on the textile due to the Use of peroxide-containing pretreatment agents can be solved with the help a special thickening agent has been adjusted to an increased viscosity and have a certain structural viscosity, i.e. a non-Newtonian Have flow behavior.

Unter Strukturviskosität soll hier der Effekt verstanden werden, daß das flüssige Mittel bei Einwirken geringer Scherkräfte eine höhere Viskosität aufweist als bei Einwirken höherer Scherkräfte. Üblicherweise ist die Viskositätsänderung nicht direkt proportional der Änderung der einwirkenden Scherkräfte, sondern die Viskosität steigt bei Scherkraftabnahmen im niedrigen Scherkraftbereich stärker an als bei solchen im hohen Scherkraftbereich. Diese Eigenschaft läßt sich experimentell dadurch überprüfen, daß man die Viskosität unter verschiedenen Scherbedingungen mißt. Eine Möglichkeit hierzu bietet ein übliches Rotationsviskosimeter bei verschiedenen Umdrehungsgeschwindigkeiten der Spindel.Structural viscosity is understood here to mean the effect that the liquid agent has a higher viscosity when exposed to low shear forces than when applied higher shear forces. The change in viscosity is usually not directly proportional the change in acting shear forces, but the viscosity increases with decreases in shear force in the low shear range more than in the high Shear area. This property can be checked experimentally by: measures viscosity under various shear conditions. One way to do this offers a common rotary viscometer at different speeds the spindle.

Gegenstand der Erfindung ist ein flüssiges wasserhaltiges Bleich- beziehungsweise Wäschevorbehandlungsmittel, enthaltend 0,2 Gew.-% bis 25 Gew.-% Wasserstoffperoxid, Komplexbildner für Schwermetalle in einer Menge bis zu 5 Gew.-%, Tensid in einer Menge bis zu 15 Gew.-%, Radikalfänger in einer Menge bis zu 0,1 Gew.-% sowie Wasser in Mengen von 55 Gew.-% bis 90 Gew.-% und so viel an polysaccharidischem Verdickungswirkstoff, daß es bei 20°C bei 20 Umdrehungen pro Minute (Brookfield Rotationsviskosimeter) eine Viskosität im Bereich von 200 mPa.s bis 5000 mPa.s, insbesondere 300 mPa.s bis 3000 mPa.s und bei 5 Umdrehungen pro Minute (Brookfield Rotationsviskosimeter) eine mindestens um den Faktor 1,5, insbesondere 2 bis 50 und besonders bevorzugt 2,5 bis 30 höhere Viskosität aufweist als bei 50 Umdrehungen pro Minute.The invention relates to a liquid water-based bleaching or Laundry pretreatment agent containing 0.2% by weight to 25% by weight of hydrogen peroxide, Complexing agent for heavy metals in an amount up to 5 wt .-%, surfactant in one Amount up to 15% by weight, radical scavengers in an amount up to 0.1% by weight and water in amounts of 55% by weight to 90% by weight and as much polysaccharide thickening agent, that it was at 20 ° C at 20 revolutions per minute (Brookfield Rotational viscometer) a viscosity in the range of 200 mPa.s to 5000 mPa.s, in particular 300 mPa.s to 3000 mPa.s and at 5 revolutions per minute (Brookfield Rotational viscometer) at least by a factor of 1.5, in particular 2 to 50 and particularly preferably 2.5 to 30 higher viscosity than at 50 revolutions per Minute.

Zur Bestimmung der Strukturviskosität sind mehrere Messungen notwendig, wobei man bei Verwendung von üblichen Brookfield-Rotationsviskosimetern in der Regel nicht den gesamten Viskositätsbereich mit Hilfe der gleichen Spindel messen kann, sondern die für den jeweiligen Meßbereich vorgeschriebene Spindel einsetzt.Several measurements are necessary to determine the intrinsic viscosity, whereby one when using conventional Brookfield rotary viscometers, usually not the can measure the entire viscosity range with the help of the same spindle, but the one for uses the spindle specified in the respective measuring range.

Als wesentlichen Bestandteil enthalten die erfindungsgemäßen Mittel Wasserstoffperoxid, das für die Bleichleistung verantwortlich ist, in Mengen von vorzugsweise 0,5 Gew.-% bis 20 Gew.-%, insbesondere 2 Gew.-% bis 10 Gew.-%. Zur Herstellung derartiger Mittel kann auch von höher konzentriertem Wasserstoffperoxid ausgegangen werden.The agents according to the invention contain hydrogen peroxide as an essential constituent, which is responsible for the bleaching performance, in amounts of preferably 0.5% by weight up to 20% by weight, in particular 2% by weight to 10% by weight. For the production of such agents can also be assumed from more concentrated hydrogen peroxide.

Als polysaccharidischer Verdickungswirkstoff kommt ein gegebenenfalls modifiziertes Polymer aus Sacchariden wie Glukose, Galactose, Mannose, Gulose, Altrose, Allose etc. in Betracht. Vorzugsweise wird ein wasserlösliches Xanthan, wie es beispielsweise unter den Produktbezeichnungen Kelzan®, Rhodopol®, Ketrol® oder Rheozan® handelsüblich ist, eingesetzt. Unter Xanthan versteht man ein Polysaccharid, welches demjenigen entspricht, das von dem Bakterienstamm Xanthomas campestris aus wäßrigen Lösungen von Glukose oder Stärke erzeugt wird (J. Biochem. Micobiol. Technol. Engineer. Vol. III (1961), S. 51 bis 63). Es besteht im wesentlichen aus Glukose, Mannose, Glucuronsäure und deren Acetylierungsprodukten und enthält ferner untergeordnete Mengen chemisch gebundener Brenztraubensäure. Auch der Einsatz wasserlöslicher Polysaccharidderivate, wie sie zum Beispiel durch Oxalkylierung mit beispielsweise Ethylenoxid, Propylenoxid und/oder Butylenoxid, durch Alkylierung mit beispielsweise Methylhalogeniden und/oder Dimethylsulfat, durch Acylierung mit Carbonsäurehalogeniden oder durch verseifende Desacetylierung erhalten werden können, ist möglich. Der polysaccharidische Verdickungswirkstoff ist in erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,05 Gew.-% bis 2,5 Gew.-%, insbesondere 0,1 Gew.-% bis 2 Gew.-% enthalten. Er trägt ganz entscheidend nicht nur zur Viskosität, sondern auch zur Strukturviskosität der erfindungsgemäßen Mittel bei. Von besonderem Vorteil ist, daß bei Einsatz derartiger Verdickungswirkstoffe, insbesondere von Xanthan, sich die Viskosität über einen breiten Temperaturbereich von etwa -5 °C bis 40 °C nur unwesentlich ändert und auch bei Verlassen dieses Temperaturbereiches sich reversibel wieder Werte im obengenannten Viskositätsbereich einstellen, wenn man das Mittel wieder auf Raumtemperatur bringt.A polysaccharide thickening agent is an optionally modified one Polymer from saccharides such as glucose, galactose, mannose, gulose, old rose, allose etc. into consideration. A water-soluble xanthan is preferred, as described, for example, under the product names Kelzan®, Rhodopol®, Ketrol® or Rheozan® are commercially available is used. Xanthan is a polysaccharide that corresponds to that of the bacterial strain Xanthomas campestris from aqueous solutions is produced by glucose or starch (J. Biochem. Micobiol. Technol. Engineer. Vol. III (1961), pp. 51 to 63). It consists essentially of glucose, mannose, glucuronic acid and their acetylation products and also contains minor amounts chemically bound pyruvic acid. The use of water-soluble polysaccharide derivatives, such as, for example, by oxyalkylation with, for example, ethylene oxide or propylene oxide and / or butylene oxide, by alkylation with, for example, methyl halides and / or Dimethyl sulfate, by acylation with carboxylic acid halides or by saponification Deacetylation can be obtained is possible. The polysaccharide thickening agent is preferably in amounts of Contain 0.05 wt .-% to 2.5 wt .-%, in particular 0.1 wt .-% to 2 wt .-%. He wears crucial not only to the viscosity, but also to the intrinsic viscosity of the invention Means at. It is particularly advantageous that when using such Thickening agents, especially of xanthan, have a wide viscosity Temperature range from about -5 ° C to 40 ° C changes only slightly and also when leaving of this temperature range there are reversible values in the viscosity range mentioned above adjust when the medium is brought back to room temperature.

Erfindungsgemäße Mittel enthalten ein Tensid oder mehrere Tenside in Mengen von vorzugsweise 0,1 Gew.-% bis 9 Gew.-%, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete anionische Tenside sind insbesondere solche, die Sulfat- oder Sulfonat-Gruppen enthalten. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse beziehungsweise Neutralisation gewonnen werden. Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren, die durch α-Sulfonierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen hergestellt werden, in Betracht. Vorzugsweise handelt es sich hierbei um die α-sulfonierten Ester der hydrierten Kokos-, Palm-, Palmkern- oder Talgfettsäuren, wobei auch Sulfonierungsprodukte von ungesättigten Fettsäuren, beispielsweise Ölsäure, in geringen Mengen, vorzugsweise in Mengen nicht oberhalb etwa 2 bis 3 Gew.-%, vorhanden sein können. Insbesondere sind α-Sulfofettsäurealkylester bevorzugt, die eine Alkylkette mit nicht mehr als 4 C-Atomen in der Estergruppe aufweisen, beispielsweise Methylester, Ethylester, Propylester und Butylester. Neben den Methylestern der α-Sulfofettsäuren (MES) können auch deren verseifte Disalze eingesetzt werden. Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate insbesondere bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-amerikanischen Patentschriften US 3 234 258 oder US 5 075 041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Anitontenside. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C21-Alkohole, wie 2-Methylverzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.Agents according to the invention contain one or more surfactants in amounts of preferably 0.1% by weight to 9% by weight, anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable. Suitable anionic surfactants are, in particular, those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. In addition to the methyl esters of α-sulfofatty acids (MES), their saponified disalts can also be used. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved. The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -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, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. The anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen. z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohole mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl - die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann- zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Ebenfalls geeignet sind Polyhydroxyfettsäureamide der Formel (I), in der R3CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R4 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht:

Figure 00070001
The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms. eg from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). The nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R 3 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 4 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
Figure 00070001

Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II),

Figure 00070002
in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R5 für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R6 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-C4-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig "dimere", sondern auch entsprechend "trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether gemäß der deutschen Patentanmeldung DE 43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der deutschen Patentanmeldung DE 195 03 061. Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE 195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so daß sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den internationalen Patentanmeldungen WO 95/19953, WO 95/19954 und WO 95/19955 beschrieben werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
Figure 00070002
in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 5 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 6 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as 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 international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used 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, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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 them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic 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 have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean "dimeric" but also "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized 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. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.

In einer bevorzugten Ausgestaltung enthält ein erfindungsgemäß Mittel ein Tensidsystem aus Alkylethersulfat der allgemeinen Formel R1O-(CH2CH2O)n-SO3X, in der R1 ein linearer oder verzweigtkettiger Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, n eine Zahl von 1 bis 10 und X ein Alkali- oder Ammoniumion ist, und Alkylpolyglykolether der allgemeinen Formel R2O-(C3H6O)1-(CH2CH2O)m-(C3H6O)n-OH, in der R2 ein linearer oder verzweigtkettiger Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen und m eine Zahl von 1 bis 10 und 1 sowie n eine Zahl von 0 bis 10 ist, im Gewichtsverhältnis von 1:10 bis 10:1, insbesondere von 2:1 bis 5:1.In a preferred embodiment, an agent according to the invention contains a surfactant system composed of alkyl ether sulfate of the general formula R 1 O- (CH 2 CH 2 O) n -SO 3 X, in which R 1 is a linear or branched-chain alkyl or alkenyl radical with 6 to 22 C - Atoms, n is a number from 1 to 10 and X is an alkali metal or ammonium ion, and alkyl polyglycol ethers of the general formula R 2 O- (C 3 H 6 O) 1 - (CH 2 CH 2 O) m - (C 3 H 6 O) n -OH, in which R 2 is a linear or branched-chain alkyl or alkenyl radical having 6 to 22 carbon atoms and m is a number from 1 to 10 and 1 and n is a number from 0 to 10, in a weight ratio of 1: 10 to 10: 1, in particular from 2: 1 to 5: 1.

Zu den in erfindungsgemäßen Mitteln enthaltenen geeigneten Komplexbildnern für Schwermetalle gehören Aminocarbonsäuren und gegebenenfalls funktionell modifizierte Phosphonsäuren, beispielsweise Hydroxy- oder Aminoalkanphosphonsäuren. Zu den brauchbaren Aminocarbonsäuren gehören beispielsweise Nitrilotriessigsäure, Methylglycindiessigsäure und Diethylenthaminpentaessigsäure. Unter den Phosphonsäuren kommen beispielsweise 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) beziehungsweise das Dinatriumsalz oder das Tetranatriumsalz dieser Säure, Ethylendiamin-tetramethylenphosphonsäure (EDTMP), Diethylentriamin-pentamethylenphosphonsäure (DTPMP) sowie deren höhere Homologe in Frage. Auch die den genannten stickstoffhaltigen Verbindungen entsprechenden N-Oxide können eingesetzt werden. Zu den brauchbaren Komplexbildnern gehört auch Ethylendiamin-N,N'-dibernsteinsäure (EDDS). Die in ihrer Säureform genannten Komplexbildner können als solche oder in Form der Natriumsalze eingesetzt werden. Bevorzugt ist der Einsatz von Mischungen aus Aminocarbonsäuren mit Phosphonsäuren. Komplexbildner für Schwermetalle sind in erfindungsgemäß Mitteln vorzugsweise in Mengen von 0,05 Gew.-% bis 1 Gew.-% enthalten.Suitable complexing agents contained in agents according to the invention for Heavy metals include aminocarboxylic acids and optionally functionally modified Phosphonic acids, for example hydroxy or aminoalkanephosphonic acids. To the usable aminocarboxylic acids include, for example, nitrilotriacetic acid, methylglycinediacetic acid and diethylenethamine pentaacetic acid. Among the phosphonic acids come for example 1-hydroxyethane-1,1-diphosphonic acid (HEDP) respectively the disodium salt or the tetrasodium salt of this acid, ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP) as well as their higher homologues in question. Also the nitrogenous ones mentioned Compounds corresponding to N-oxides can be used. Among the usable ones Complexing agents also include ethylenediamine-N, N'-disuccinic acid (EDDS). The one in her Complexing agents called acid form can be used as such or in the form of the sodium salts be used. Mixtures of aminocarboxylic acids are preferred with phosphonic acids. Complexing agents for heavy metals are in agents according to the invention preferably contained in amounts of 0.05% by weight to 1% by weight.

Zu den bekannten als Radikalfänger wirksamen Inhaltsstoffe, die in erfindungsgemäßen Mitteln vorzugsweise in Mengen von 0,01 Gew.-% bis 0,1 Gew.-% enthalten sind, gehören Phenole wie 1,6-Di-tert.-butyl-4-methylphenol (Butylhydroxytoluol, BHT), Hydrochinone wie Di-tert.-butyl-hydrochinon, Catechole wie Allylcatechol, alkylierte Diphenylamine oder N-Phenyl-α-Naphthylamine und Dihydrochinoline. Als bevorzugter Radikalfδnger wird BHT eingesetzt. Um derartige normalerweise schlecht wasserlösliche Substanzen rasch in erfindungsgemäße Mittel einarbeiten zu können, hat es sich bewährt, sie in Form einer Lösung in einem wassermischbaren Lösungsmittel, zum Beispiel einem niederen Alkohol wie Ethanol oder Isopropanol, einzuarbeiten. Dabei ist es bevorzugt, sie so konzentriert einzusetzen, daß nur geringe Mengen derartiger Lösungsmittel, insbesondere höchstens 0,5 Gew.-%, in das erfindungsgemäße Mittel eingebracht werden.Among the known ingredients effective as radical scavengers, which are in the invention Agents are preferably contained in amounts of 0.01% by weight to 0.1% by weight, include phenols such as 1,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT), Hydroquinones such as di-tert-butyl hydroquinone, catechols such as allyl catechol, alkylated Diphenylamine or N-phenyl-α-naphthylamine and dihydroquinolines. As a preferred Radical scavenger is used BHT. These are usually poorly water-soluble To be able to incorporate substances rapidly into agents according to the invention, it has proven useful it in the form of a solution in a water-miscible solvent, for example one lower alcohol such as ethanol or isopropanol. It is preferable to them so concentrated that only small amounts of such solvents, in particular at most 0.5% by weight, can be introduced into the agent according to the invention.

Erfindungsgemäße Mittel sind vorzugsweise sauer und weisen insbesondere einen pH-Wert im Bereich von 2 bis 4 auf. Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel systemverträgliche Säuren, insbesondere oben genannte Aminocarbon- oder Phosphonsäuren, Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren wie Schwefelsäure, Phosphorsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten.Agents according to the invention are preferably acidic and in particular have a pH in the range of 2 to 4. To set a desired one, through the The mixture of the other components of non-self-determined pH can Agents according to the invention acids which are compatible with the system, in particular those mentioned above Aminocarboxylic or phosphonic acids, citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also Mineral acids such as sulfuric acid, phosphoric acid or alkali hydrogen sulfates, or Contain bases, especially ammonium or alkali hydroxides.

Neben den genannten Inhaltsstoffen können erfindungsgemäße Mittel alle weiteren in Flüssigwaschmitteln üblichen Inhaltsstoffe enthalten, die mit den wesentlichen Bestandteilen, insbesondere dem Wasserstoffperoxid und dem Verdickungssystem, verträglich sind. Zu diesen gehören beispielsweise Schaumregulatorwirkstoffe, Farb- und Duftstoffe sowie gewünschtenfalls optische Aufheller.In addition to the ingredients mentioned, all agents according to the invention can be used in Liquid detergents contain the usual ingredients with the essential Constituents, especially the hydrogen peroxide and the thickening system, are tolerated. These include, for example, foam regulator active ingredients, color and Fragrances and, if desired, optical brighteners.

Erfindungsgemäße Mittel können in wenig aufwendiger Weise durch einfaches Vermischen ihrer Inhaltsstoffe hergestellt werden. Sie sind homogene Systeme mit einer hohen Lagerstabilität und guter Fleckentfernungsleistung bei geringem Textilschädigungspotential. Vorzugsweise werden sie zur Vorbehandlung verschmutzter Textilien vor deren Wäsche verwendet. Zusätzlich oder stattdessen kann man sie auch in Form eines Additivs zu einem Waschmittel bei der insbesondere maschinellen Wäsche von Textilien einsetzen. Bei einem Waschverfahren unter Einsatz erfindungsgemäßer Mittel geht man vorzugsweise so vor, daß man ein flüssiges erfindungsgemäßes Mittel unverdünnt auf das verschmutzte Textil oder einen Teil des verschmutzten Textils, der den zu entfernenden Fleck umfaßt, aufbringt, es vorzugsweise dort nur so lange einwirken läßt, daß es nicht eintrocknet, und das Textil unter Verwendung von Wasser oder gegebenenfalls einer wäßrigen Waschlauge, die ein übliches Waschmittel enthält, insbesondere unter Einsatz einer maschinellen Vorrichtung wäscht. Dabei kann man eine weitere Menge des erfindungsgemäßen Mittels dem üblichen Waschmittel und/oder der wäßrigen Waschlauge zusetzen. Agents according to the invention can be done in a simple manner by simple means Mixing their ingredients can be made. They are homogeneous systems with one high storage stability and good stain removal performance with low textile damage potential. They are preferably contaminated for pretreatment Textiles used before washing. In addition or instead, you can also put them in Form of an additive to a detergent, especially for machine washing of textiles. In a washing process using the inventive Agents are preferably carried out in such a way that a liquid agent according to the invention undiluted on the soiled textile or a part of the soiled textile, the embraces the stain to be removed, applies it, preferably there only so long lets it not dry out, and the textile using water or optionally an aqueous wash liquor which contains a conventional detergent, washes especially using a machine. You can do one further amount of the agent according to the invention the usual detergent and / or add aqueous wash liquor.

BeispieleExamples

Durch einfaches Vermischen der in der nachfolgenden Tabelle angegebenen Inhaltsstoffe in den angegebenen Mengenanteilen wurde ein flüssiges bleichmittelhaltiges Wäschevorbehandlungsmittel B1 hergestellt, das durch Zusatz geringer Mengen an Phosphorsäure auf einen pH-Wert von 3 eingestellt wurde und die ebenfalls in der Tabelle angebenen Viskosität (in mPa.s bei 20 °C) aufwies. Zusammensetzung (Gew.-%) Mittel B1 Wasserstoffperoxid 5 Ethersulfat 2 Niotensid 0,5 Keltrol® T 0,45 Komplexbildner 0,2 BHT 0,03 Ethanol 0,2 Wasser auf 100 Viskosität 910 A simple blending of the ingredients in the proportions indicated in the table below produced a liquid bleach-containing laundry pretreatment agent B1 , which was adjusted to a pH of 3 by adding small amounts of phosphoric acid and the viscosity (in mPa. s at 20 ° C). Composition (% by weight) medium B1 hydrogen peroxide 5 ether sulfate 2 nonionic surfactant 0.5 Keltrol® T 0.45 complexing 0.2 BHT 0.03 ethanol 0.2 water to 100 viscosity 910

1 ml oder 2 ml des Mittels B1, je nach Größe der Flecken, wurde auf künstlich hergestellte, standardisierte Anschmutzungen auf Baumwollgewebe aufgetragen, mit einem Gummiwischer verteilt und man läßt 10 Minuten einwirken. Anschließend wurde die so behandelte Textilprobe zusammen mit 2 kg sauberer Füllwäsche unter Verwendung eines handelsüblichen bleichmittelfreien Feinwaschmittelpulvers V1 (Dosierung 68 g) gewaschen (Miele Novotronic® 918, 1-Gangverfahren, 40°C Kurzprogramm, Wasserhärte 16°dH). Die Remission der Gewebeproben wurde nach dem Trocknen gemessen; in der nachfolgenden Tabelle ist der Farbabstandswert (ΔΔE) zum angeschmutzten Gewebe angegeben. Zum Vergleich sind die Werte, die man ohne Verwendung des erfindungsgemäßen Mittels erhält, mit angegeben. Farbabstandswerte Anschmutzung V1 V1+B1 Rotwein 3,0 7,4 Tee 1,0 8,1 Makeup 17,7 30,6 1 ml or 2 ml of agent B1, depending on the size of the stains, was applied to artificially produced, standardized soiling on cotton fabric, spread with a rubber wiper and allowed to act for 10 minutes. The textile sample treated in this way was then washed together with 2 kg of clean laundry using a commercially available bleach-free mild detergent powder V1 (dosage 68 g) (Miele Novotronic® 918, 1-step process, 40 ° C short program, water hardness 16 ° dH). The reflectance of the tissue samples was measured after drying; The following table shows the color distance value (ΔΔE) from the soiled fabric. For comparison, the values which are obtained without using the agent according to the invention are also given. Color difference values soiling V1 V1 + B1 red wine 3.0 7.4 tea 1.0 8.1 Make up 17.7 30.6

Man erkennt, daß bei Einsatz des erfindungsgemäßen Mittels deutlich mehr an Anschmutzung abgelöst wird als mit dem herkömmlichen Waschmittel ohne vorherige Anwendung des erfindungsgemäßen Mittels.It can be seen that when using the agent according to the invention, significantly more soiling is replaced as with the conventional detergent without previous Use of the agent according to the invention.

Claims (14)

  1. A liquid water-containing bleaching or laundry pretreatment composition containing 0.2% by weight to 25% by weight of hydrogen peroxide, heavy metal complexing agents in a quantity of up to 5% by weight, surfactant in a quantity of up to 15% by weight, radical trappers in a quantity of up to 0.1% by weight and water in quantities of 55% by weight to 90% by weight and a polysaccharide thickener in such a quantity that the composition has a viscosity at 20°C/20 r.p.m. (Brookfield rotational viscosimeter) in the range from 200 mPa.s to 5,000 mPa.s and, at 5 r.p.m. (Brookfield rotational viscosimeter), a viscosity higher by a factor of at least 1.5 than at 50 r.p.m.
  2. A composition as claimed in claim 1, characterized in that it contains the polysaccharide thickener in a quantity of 0.05% by weight to 2.5% by weight and more particularly in a quantity of 0.1% by weight to 2% by weight.
  3. A composition as claimed in claim 1 or 2, characterized in that it contains 1.5% by weight to 20% by weight and more particularly 2% by weight to 10% by weight of hydrogen peroxide.
  4. A composition as claimed in any of claims 1 to 3, characterized in that it has a viscosity at 5 r.p.m. higher by a factor of 2 to 50 and more particularly 2.5 to 30 than at 50 r.p.m.
  5. A composition as claimed in any of claims 1 to 4, characterized in that the polysaccharide thickener is a xanthan.
  6. A composition as claimed in any of claims 1 to 5, characterized in that it contains 0.1% by weight to 9% by weight of surfactant.
  7. A composition as claimed in any of claims 1 to 6, characterized in that it contains a surfactant system of alkyl ether sulfate corresponding to the general formula R1O-(CH2CH2O)n-SO3X, in which R1 is a linear or branched alkyl or alkenyl group containing 6 to 22 carbon atoms, n is a number of 1 to 10 and X is an alkali metal or ammonium ion, and alkyl polyglycol ethers corresponding to the general formula R2O-(C3H6O)1-(CH2CH2O)m-(C3H6O)n-OH, in which R2 is a linear or branched alkyl or alkenyl group containing 6 to 22 carbon atoms and m is a number of 1 to 10 and I and n are numbers of 0 to 10, in a ratio by weight of 1:10 to 10:1 and more particularly in a ratio by weight of 2:1 to 5:1.
  8. A composition as claimed in any of claims 1 to 7, characterized in that it contains 0.05% by weight to 1% by weight of heavy metal complexing agents.
  9. A composition as claimed in any of claims 1 to 8, characterized in that it contains 0.01% by weight to 0.1% by weight of radical trappers.
  10. A composition as claimed in any of claims 1 to 9, characterized in that it is acidic and, in particular, has a pH value of 2 to 4.
  11. The use of the composition claimed in any of claims 1 to 10 for pretreating soiled textiles before washing.
  12. The use of the composition claimed in any of claims 1 to 10 as a detergent additive in the washing, particularly machine washing, of textiles.
  13. A process for washing textiles, characterized in that the liquid composition claimed in any of claims 1 to 10 is applied without dilution to the soiled textile or to part of the soiled textile and the textile is washed using water or a water-containing wash liquor containing a standard detergent, more particularly in a washing machine.
  14. A process as claimed in claim 13, characterized in that the composition claimed in any of claims 1 to 10 is added to the standard detergent and/or to the water-containing wash liquor in addition to the quantity introduced via the textile.
EP99926391A 1998-06-03 1999-05-25 Aqueous bleaching agent with viscose structure Revoked EP1084224B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19824708A DE19824708A1 (en) 1998-06-03 1998-06-03 Structurally viscous aqueous bleach
DE19824708 1998-06-03
PCT/EP1999/003573 WO1999063042A1 (en) 1998-06-03 1999-05-25 Aqueous bleaching agent with viscose structure

Publications (2)

Publication Number Publication Date
EP1084224A1 EP1084224A1 (en) 2001-03-21
EP1084224B1 true EP1084224B1 (en) 2003-01-22

Family

ID=7869720

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99926391A Revoked EP1084224B1 (en) 1998-06-03 1999-05-25 Aqueous bleaching agent with viscose structure

Country Status (5)

Country Link
EP (1) EP1084224B1 (en)
AT (1) ATE231543T1 (en)
DE (2) DE19824708A1 (en)
ES (1) ES2191434T3 (en)
WO (1) WO1999063042A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19961659A1 (en) * 1999-12-21 2001-07-12 Henkel Kgaa Agents for the treatment of substrates
DE102007028509A1 (en) * 2007-06-18 2008-12-24 Henkel Ag & Co. Kgaa Liquid, highly foaming washing or cleaning agent with stable viscosity
US7879744B2 (en) * 2007-08-30 2011-02-01 Kimberly-Clark Worldwide, Inc. Stabilized decolorizing composition
US8569221B2 (en) * 2007-08-30 2013-10-29 Kimberly-Clark Worldwide, Inc. Stain-discharging and removing system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3709348A1 (en) * 1987-03-21 1988-10-06 Degussa PEROXYCARBONIC ACID CONTAINING AQUEOUS FLEMING SOLUTIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE
CA2126382C (en) * 1993-06-30 1998-12-15 Josephine L. Kong-Chan Stable pourable aqueous liquid laundry detergent compositions with peroxyacid bleach
CA2125719C (en) * 1993-06-30 1998-12-15 Josephine L. Kong-Chan Stable pourable aqueous liquid laundry detergent compositions with peroxyacid bleach and high nonionic surfactant
EP0843001B1 (en) * 1996-11-13 2003-04-23 The Procter & Gamble Company Aqueous alkaline peroxygen bleach-containing compositions

Also Published As

Publication number Publication date
ES2191434T3 (en) 2003-09-01
WO1999063042A1 (en) 1999-12-09
EP1084224A1 (en) 2001-03-21
DE59904101D1 (en) 2003-02-27
DE19824708A1 (en) 1999-12-09
ATE231543T1 (en) 2003-02-15

Similar Documents

Publication Publication Date Title
DE69918849T2 (en) PROCEDURE FOR PRE-TREATMENT OR PRE-DEFINITION OF WASH
EP0876460B1 (en) Cleaning agent for hard surfaces
DE69835769T2 (en) HIGH ALKALINE COMPOSITIONS CONTAINING HEXYL GLYCOSIDE AS HYDROTROP
EP0712436B1 (en) Low-foaming washing or cleaning agents
EP0355551B1 (en) Pasty washing and cleaning agent, and method for its preparation
WO2011117079A1 (en) Washing, cleaning or pretreatment composition with increased fat dissolving power
EP0633927A1 (en) Detergents for hard surfaces.
DE10032589A1 (en) Thickened aqueous liquid bleach, washing or prewash composition based on hydrogen peroxide has a defined pH to improve its viscosity stability and reduce oxidative decolorization of dyed textiles
DE19854267A1 (en) Encapsulated detergent
DE69928808T2 (en) CLEANSING AGENT AND ITS USE IN REMOVING PATCHES AND TEXTILES
EP1084224B1 (en) Aqueous bleaching agent with viscose structure
EP1059350A1 (en) Encapsulated detergent composition
DE19853720A1 (en) Aqueous cleaners for hard surfaces, e.g. floors in public areas, contain surfactant, including anionic surfactant, and diquaternary polysiloxane to reduce drying time
DE19853845A1 (en) Viscous liquid aqueous bleach or laundry detergent concentrate containing hydrogen peroxide and surfactant is thickened with magnesium salt of mineral acid
EP1080175A1 (en) Aqueous bleaching agent
EP2267216A1 (en) Use of aqueous wax dispersions for improving mechanical characteristics of textile fibres
DE10032588A1 (en) Increasing viscosity stability of thickened aqueous liquid bleach or prewash compositions based on hydrogen peroxide comprises increasing the pH
EP3250668B1 (en) Acid liquid compact washing agent containing hydroxycarboxylic acid, non-ionic surfactant and -amylase
EP0642572B1 (en) Floor cleaning process
EP0715647B1 (en) Liquid washing product
DE4210364A1 (en) Detergent for hard surfaces, especially glass
WO2008012141A2 (en) Detergent having improved dispersing power
DE10046251A1 (en) Detergents and cleaning agents based on alkyl and / or alkenyl oligoglycosides and fatty alcohols
DE10253109A1 (en) Improving the storage-stability of aqueous bleaching or washing pre-treatment agents containing hydrogen peroxide by combining with a UV absorber and storing in a UV-absorbing container
EP0729502B1 (en) Liquid detergent and cleaner containing combinations of enzymes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20001124

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20020214

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59904101

Country of ref document: DE

Date of ref document: 20030227

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20030520

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2191434

Country of ref document: ES

Kind code of ref document: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20031020

NLR1 Nl: opposition has been filed with the epo

Opponent name: THE PROCTER & GAMBLE COMPANY

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060503

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20060511

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060515

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060518

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060524

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060531

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060621

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20060712

Year of fee payment: 8

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

APBW Interlocutory revision of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNIRAPO

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20070124

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20070124

NLR2 Nl: decision of opposition

Effective date: 20070124

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO