EP0874890A1 - Washing agents with specific oxidized oligosaccharides - Google Patents

Washing agents with specific oxidized oligosaccharides

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Publication number
EP0874890A1
EP0874890A1 EP96944014A EP96944014A EP0874890A1 EP 0874890 A1 EP0874890 A1 EP 0874890A1 EP 96944014 A EP96944014 A EP 96944014A EP 96944014 A EP96944014 A EP 96944014A EP 0874890 A1 EP0874890 A1 EP 0874890A1
Authority
EP
European Patent Office
Prior art keywords
weight
group
washing
acid
reducing end
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.)
Granted
Application number
EP96944014A
Other languages
German (de)
French (fr)
Other versions
EP0874890B1 (en
Inventor
Beatrix Kottwitz
Jörg Poethkow
Horst Upadek
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
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0874890A1 publication Critical patent/EP0874890A1/en
Application granted granted Critical
Publication of EP0874890B1 publication Critical patent/EP0874890B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised

Definitions

  • the present invention relates to detergents and cleaning agents which contain, as a builder or co-builder component, an oligosaccharide which has been modified at the reducing end in such a way that a carboxy unit is present instead of a hydroxymethylene aldehyde unit
  • detergents and cleaning agents In addition to the surfactants that are indispensable for the washing or cleaning performance, detergents and cleaning agents normally also contain so-called builder substances, which have the task of supporting the performance of the surfactants by hardening agents, that is to say essentially calcium and magnesium ions should eliminate from the wash liquor that they do not interact in a negative way with the surfactants
  • builder substances which have the task of supporting the performance of the surfactants by hardening agents, that is to say essentially calcium and magnesium ions should eliminate from the wash liquor that they do not interact in a negative way with the surfactants
  • a well-known example of such builders that improve the washing power is zeolite Na-A, which is known to be able to form complexes with calcium ions in particular that their complexes Reaction with water hardness-forming anions, in particular carbonate, to insoluble compounds is suppressed.
  • the builders in particular in textile detergents, are supposed to redistribute the dirt detached from the fiber or generally from the surface to be cleaned, and also through the reaction of water-hardness-forming substances Prevent cations with water-hardness-forming anions from forming insoluble compounds on the cleaned textile or the surface.
  • so-called co-builders usually polymeric polycarboxylates, are usually used, which, in addition to their contribution to the secondary washing ability, advantageously also have a complexing action against the water-hardness-forming cations
  • biodegradable builder substances which are understood to mean substances which occur in nature or derivatives of such natural substances which are modified as little as possible, and which are believed to have better degradability than synthetic polymers of unsaturated mono - and dicarboxylic acids
  • the invention relates to a washing or cleaning agent containing surfactant, inorganic builder, oxygen-based bleach, bleach activator and / or Enzyme, which is characterized in that it contains, as a builder or cobuilder component, an oligosaccharide which has a -COOH group instead of the -CH (OH) -CHO group at its originally reducing end.
  • oligosaccharides which contain a group -COOH instead of the group -CH (OH) -CHO at their originally reducing end as graying inhibitors in detergents and aqueous washing liquors for textile washing .
  • a further subject of the invention is a washing process for textiles in aqueous, in particular surfactant-containing liquor using the modified oligosaccharides mentioned as graying inhibitors.
  • the preferred monomer in the builder or cobuilder to be used according to the invention after oxidative modification is glucose.
  • the average degree of oligomerization n which can also assume fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10.
  • the oligosaccharide used according to the invention as a builder or cobuilder has been oxidatively modified at its originally reducing end with the loss of a carbon atom. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification:
  • This oxidative modification can be carried out, for example, with the aid of Fe, Cu, Ag, Co or Ni catalysts, as described in international patent application WO 92/18542, with the aid of Pd, Pt, Rh or Os catalysts , as described in European patent EP 0 232 202, or by means of a quinone / hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment. with hydrogen peroxide.
  • the oligosaccharide starting material which can be modified by means of such oxidation processes is preferably an oligosaccharide with a dextrose equivalent (DE) in the range from 20 to 50, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100.
  • DE dextrose equivalent
  • So-called glucose syrups (DE 20-37) and dextrins are particularly useful, both of which are accessible by partial hydrolysis of starch, which can be carried out by customary, for example acid- or enzyme-catalyzed, processes and which are as such or in higher polymer form, for example as starch can be used in the above-mentioned oxidation processes if the polymer chain structure of the starch also degrades accordingly under the conditions of the oxidation.
  • Washing and cleaning agents according to the invention preferably contain 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight, of the oxidatively modified oligosaccharide, which is normally used in the form of its alkali metal salt.
  • concentrations of oxidatively modified oligosaccharide in the wash liquor of from 0.001% by weight to 0.05% by weight are preferred.
  • the detergents and cleaning agents according to the invention which can be present in particular as particulate solids, pastes, homogeneous solutions or suspensions, can in principle contain all the ingredients known and customary in such agents, in addition to the active ingredient used according to the invention.
  • the washing and cleaning agents according to the invention can in particular include surface-active surfactants, bleaching agents, bleach activators, water-miscible organic solvents, enzymes, additional builder substances, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, color transfer inhibitors, foam regulators, abrasives and dye - and fragrances.
  • an agent according to the invention preferably contains a water-soluble and / or water-insoluble, organic and / or inorganic (main) builder.
  • Builder substances are total in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, zeolite P and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12837, is generally in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 y H 2 O
  • ⁇ -sodium di silicate can be obtained, for example, by the method described in the international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260610.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of agents according to the invention.
  • alkali alumino-silicate in particular zeolite
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the water-soluble organic builder substances include aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and polycarboxylic acids, in particular citric acids, in particular citric acids , as well as polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 which are accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
  • aminopolycarboxylic acids in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid
  • polyphosphonic acids in particular aminotris (m
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer.
  • the first acidic monomer or its salt is derived from a monoethylene-unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, preferably a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or an esterified vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
  • the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical , or an aromatic radical, which is preferably derived from benzene or benzene derivatives.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight .-%, preferably 15 wt .-% to 25 wt .-% methallyl sulfonic acid or methallylsulfonate and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of one Carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, where mono-, di- or oligosaccharides are preferred. Among these, sucrose is particularly preferred.
  • the third monomer predetermined breaking points are presumably built into the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be prepared in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular mass between 1,000 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000.
  • copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.
  • the conventional organic builder substances mentioned can be present in amounts of up to 5% by weight, in particular from 1% by weight to 4% by weight. Amounts close to the above upper limit are preferably used in paste-like or liquid agents according to the invention.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type which can be used include linear alkylbenzenesulfonates with 9 to 14 C atoms in the alkyl part, alkanesulfonates with 12 to 18 C atoms, and olefin sulfonates with 12 to 18 C atoms, which are used in the reaction of corresponding monoolefins arise with sulfur trioxide, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the cleaning or washing agents according to the invention in amounts of preferably 5% by weight to 50% by weight, in particular 8% to 30% by weight. In agents according to the invention for cleaning dishes, however, the lower limits mentioned may be undershot; the surfactant content in such compositions is preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight.
  • Suitable peroxygen-based bleaching agents which may be present in agents according to the invention are, in particular, organic peracids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. If a washing or cleaning agent according to the invention contains peroxygen compounds, they are present in amounts of preferably 10% by weight to 30% by weight, in particular 15% by weight to 25% by weight, sodium percarbonate being particularly preferred .
  • WO 94/24044 WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 or WO 95/15292 are known.
  • An alkali percarbonate stabilized with special borates as known from European patent applications EP 459 625, EP 487 256 or EP 567 140, or an alkali percarbonate coated with a combination of alkali salts, such as from European patent applications EP 623 553 or EP 592 969, is preferably used known a.
  • the bleach activators optionally contained in the agents according to the invention include, in particular, compounds which, under perhydrolysis conditions, give substituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms.
  • Particularly suitable are substances which have O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated glycolurils, in particular tetraacetyiglycolouril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyI-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are preferred.
  • TAED tetraacetylethylene diamine
  • TAGU tetraacetyiglycolouril
  • DADHT 1,5-diacetyI-2,4-dioxohexahydro-1,3,5-triazine
  • acylated phenol sulfonates especially nonanoyl or isononanoyloxybenzenesulfonate
  • acylated polyhydric alcohols especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetyiated sorbitol and mannitol
  • acylated sugar derivatives in particular pentaacetylfacylacetylglucose (p and octaacetyl lactose and acetylene, optionally N-alkyated, glucamine and gluconolactone.
  • the bleach activator combinations known from German patent application DE 4443 177 can also be used.
  • salts or complexes of transition metals such as Mn, Co or Fe can be used as so-called bleach catalysts.
  • Enzymes which can be used in the agents are those from the class of the proteases, ⁇ lipase, cutinases, amylases, pullutanases, hemicellulases, xylanases, cellulases, oxidases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
  • the enzymes which may be used can, as for example in the international patent applications be described in WO 92/11347 or WO 94/23005, adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing and cleaning agents according to the invention in amounts of preferably not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.
  • the organic solvents which can be used in the agents according to the invention include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
  • Such water-miscible solvents are preferably present in the washing, cleaning and disinfecting agents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, enzyme stabilizers, additional graying inhibitors such as carboxymethyl cellulose, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyrdine-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.
  • the preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, with enzymes, bleaching agents and any other thermally sensitive ingredients if necessary, be added separately later.
  • agents according to the invention with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method known from European patent EP 486 592 and having an extrusion step is preferred.
  • Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally prepared by simply mixing the ingredients, which can be added in substance or as a solution to an automatic mixer.
  • Foam inhibitor granules, water and salts, based on the basic detergent were 5.5% by weight at the reducing end of oxidatively modified oligosaccharide co-builder B1 with an average degree of oligomerization of approximately 2.5 (M1), 5.5% by weight on reducing end of oxidatively modified oligosaccharide co-builder B2 with an average degree of oligomerization of approximately 15 (M2) or, for comparison, 5.5% by weight of maleic acid / acrylic acid copolymer (V1).
  • Fabric A WFK test fabric B: bleaching nettle C: terry cloth
  • tissue samples were weighed out as described above and then boiled out in a 5% EDTA solution with a liquor ratio of 1:20 (textile weight to EDTA solution) and then rinsed thoroughly several times with distilled water. The tissues were dried and weighed again. The difference in weight of the samples before and after treatment, expressed as a percentage of the weight, gives the soluble incrustation.
  • Tissue A WFK test fabric B: stinging nettle
  • the reflectance of the test fabric washed 25 times with the respective agent was determined in order to determine the graying of the fabric caused by the washing processes.
  • Table 4 below shows the measured reflectance values (low values mean high graying) as mean values of duplicate determinations.
  • Fabric A WFK test fabric B: bleaching nettle C: terry cloth

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

A detergent composition containing surfactant, builder component, oxygen-based bleaching agent, bleach activator, and enzyme, wherein the builder component is an oxidatively modified oligosaccharide which contains a -COOH group instead of a -CH(OH)-CHO group at its originally reducing end group and which has an average degree of oligomerization of from 2 to 20.

Description

Waschmittel mit bestimmten oxidierten Oligosacchaπden Detergent with certain oxidized oligosacchaπden
Die vorliegende Erfindung betrifft Wasch- und Reinigungsmittel, die als Builder- oder Co¬ builderkomponente ein Oligosaccharid enthalten, welches am reduzierenden Ende der¬ art modifiziert worden ist, daß dort an Stelle einer Hydroxymethylenaldehyd-Einheit eine Carboxyleinheit vorliegtThe present invention relates to detergents and cleaning agents which contain, as a builder or co-builder component, an oligosaccharide which has been modified at the reducing end in such a way that a carboxy unit is present instead of a hydroxymethylene aldehyde unit
Wasch- und Reinigungsmittel enthalten normalerweise neben den für die Wasch- be¬ ziehungsweise Reinigungsleistung unverzichtbaren Tensiden auch sogenannte Builder¬ substanzen, welche die Aufgabe haben, die Leistung der Tenside zu unterstutzen, indem sie Härtebildner, das heißt im wesentlichen Calcium- und Magnesiumionen, so aus der Waschlauge eliminieren sollen, daß sie nicht in negativer Weise mit den Tensiden wechselwirken Ein bekanntes Beispiel für solche, die Pπmarwaschkraft verbessernden Buildersubstanzen ist Zeolith Na-A, welcher bekanntermaßen in der Lage ist, mit insbesondere Calciumionen so stabile Komplexe zu bilden, daß deren Reaktion mit wasserhartebildenden Anionen, insbesondere Carbonat, zu unlöslichen Verbindungen unterdrückt wird Zusätzlich sollen die Builder, insbesondere in Textiiwaschmitteln, die Wiederablagerung des von der Faser oder allgemein von der zu reinigenden Oberfläche abgelösten Schmutzes wie auch durch die Reaktion von wasserhartebildenden Kationen mit wasserhärtebildenden Anionen sich bildenden unlöslichen Verbindungen auf das gereinigte Textil beziehungsweise die Oberflache verhindern. Zu diesem Zweck setzt man üblicherweise sogenannte Co-Builder, in der Regel polymere Polycarboxylate, ein, die neben ihrem Beitrag zum Sekundarwaschvermogen vorteilhafterweise auch eine Komplexierwirkung gegen die wasserhartebildenden Kationen aufweisenIn addition to the surfactants that are indispensable for the washing or cleaning performance, detergents and cleaning agents normally also contain so-called builder substances, which have the task of supporting the performance of the surfactants by hardening agents, that is to say essentially calcium and magnesium ions should eliminate from the wash liquor that they do not interact in a negative way with the surfactants A well-known example of such builders that improve the washing power is zeolite Na-A, which is known to be able to form complexes with calcium ions in particular that their complexes Reaction with water hardness-forming anions, in particular carbonate, to insoluble compounds is suppressed. In addition, the builders, in particular in textile detergents, are supposed to redistribute the dirt detached from the fiber or generally from the surface to be cleaned, and also through the reaction of water-hardness-forming substances Prevent cations with water-hardness-forming anions from forming insoluble compounds on the cleaned textile or the surface. For this purpose, so-called co-builders, usually polymeric polycarboxylates, are usually used, which, in addition to their contribution to the secondary washing ability, advantageously also have a complexing action against the water-hardness-forming cations
Die vorliegende Erfindung will einen Beitrag zum Einsatz sogenannter biologisch abbau¬ barer Buildersubstanzen leisten worunter in der Natur vorkommende Stoffe oder mög¬ lichst gering abgewandelte Derivate von derartigen Naturstoffen verstanden werden, von denen man annimmt, daß sie eine bessere Abbaubarkeit aufweisen als synthetische Polymere ungesättigter Mono- und DicarbonsäurenThe present invention intends to make a contribution to the use of so-called biodegradable builder substances, which are understood to mean substances which occur in nature or derivatives of such natural substances which are modified as little as possible, and which are believed to have better degradability than synthetic polymers of unsaturated mono - and dicarboxylic acids
Gegenstand der Erfindung ist ein Wasch- oder Reinigungsmittel, enthaltend Tensid anorganischen Builder Bleichmittel auf Sauerstoffbasis, Bleichaktivator und/oder Enzym, welches dadurch gekennzeichnet ist, daß es als Builder- beziehungsweise Cobuilderkomponente ein Oligosaccharid enthält, welches an seinem ursprünglich reduzierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH aufweist.The invention relates to a washing or cleaning agent containing surfactant, inorganic builder, oxygen-based bleach, bleach activator and / or Enzyme, which is characterized in that it contains, as a builder or cobuilder component, an oligosaccharide which has a -COOH group instead of the -CH (OH) -CHO group at its originally reducing end.
Besonders überraschend ist, daß ein solches oxidativ modifiziertes Oligosaccharid unter Textilwaschbedingungen bei mindestens ebenso guten Aschewerten und mindestens ebenso guter Inkrustationsinhibierung eine deutlich bessere Vergrauungsinhibierung auf¬ weist als übliche Acrylsäure-Maleinsäure-Copolymere. Ein weiterer Gegenstand der Er¬ findung ist daher die Verwendung von Oligosacchariden, die an ihrem ursprünglich redu¬ zierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH enthalten, als Ver- grauungsinhibitoren in Waschmitteln und wäßrigen Waschflotten für die Textilwäsche. Ein Waschverfahren für Textilien in wäßriger, insbesondere tensidhaltiger Flotte unter Einsatz der genannten modifizierten Oligosaccharide als Vergrauungsinhibitoren ist ein weiterer Gegenstand der Erfindung.It is particularly surprising that such an oxidatively modified oligosaccharide has a significantly better graying inhibition than conventional acrylic acid-maleic acid copolymers under textile washing conditions with at least as good ash values and at least as good incrustation inhibition. Another object of the invention is therefore the use of oligosaccharides which contain a group -COOH instead of the group -CH (OH) -CHO at their originally reducing end as graying inhibitors in detergents and aqueous washing liquors for textile washing . A further subject of the invention is a washing process for textiles in aqueous, in particular surfactant-containing liquor using the modified oligosaccharides mentioned as graying inhibitors.
Bevorzugtes Monomer im nach oxidativer Modifikation erfindungsgemäß einzusetzenden Builder beziehungsweise Cobuilder ist Glukose. Der mittlere Oligomerisierungsgrad n, der als analytisch zu ermittelnde Größe auch gebrochene Zahlenwerte annehmen kann, liegt vorzugsweise im Bereich von 2 bis 20, insbesondere 2 bis 10.The preferred monomer in the builder or cobuilder to be used according to the invention after oxidative modification is glucose. The average degree of oligomerization n, which can also assume fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10.
Das erfindungsgemäß als Builder beziehungsweise Cobuilder eingesetzte Oligosaccharid ist an seinem ursprünglich reduzierenden Ende oxidativ unter Verlust eines C-Atoms modifiziert worden. Falls das ursprünglich reduzierende Ende des Oligosaccharids eine Anhydroglukose-Einheit gewesen ist, liegt nach Modifikation eine Arabinonsäure-Einheit vor:The oligosaccharide used according to the invention as a builder or cobuilder has been oxidatively modified at its originally reducing end with the loss of a carbon atom. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification:
(Glukose)n → (Glukose)n.1-Arabinonsäure.(Glucose) n → (Glucose) n . 1- arabinonic acid.
Diese oxidative Modifikation kann beispielsweise mit Hilfe von Fe-, Cu-, Ag-, Co- oder Ni-Katalysatoren, wie in der internationalen Patentanmeldung WO 92/18542 beschrieben, mit Hilfe von Pd-, Pt-, Rh- oder Os-Katalysatoren, wie in der europäischen Patentschrift EP 0 232 202 beschrieben, oder mittels eines Chinon/Hydrochinon- Systems im Alkalischen unter Zusatz von Sauerstoff und gegebenenfalls Nachbehand- lung mit Wasserstoffperoxid erfolgen.This oxidative modification can be carried out, for example, with the aid of Fe, Cu, Ag, Co or Ni catalysts, as described in international patent application WO 92/18542, with the aid of Pd, Pt, Rh or Os catalysts , as described in European patent EP 0 232 202, or by means of a quinone / hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment. with hydrogen peroxide.
Bei dem mittels derartiger Oxidationsverfahren modifizierbaren Oligosaccharid-Aus- gangsstoff handelt es sich vorzugsweise um ein Oligosaccharid mit einem Dextrose- Equivalent (DE) im Bereich von 20 bis 50, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind insbesondere sogenannte Glukosesirupe (DE 20 - 37) und Dextrine, die beide durch partielle Hydrolyse von Stärke, die nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden kann, zugänglich sind und die als solche oder in höherpolymerer Form, beispielsweise als Stärke in obengenannten Oxidationsverfahren eingesetzt werden können, wenn unter den Bedingungen der Oxidation auch ein entsprechender Abbau der Polymerketten¬ struktur der Stärke stattfindet.The oligosaccharide starting material which can be modified by means of such oxidation processes is preferably an oligosaccharide with a dextrose equivalent (DE) in the range from 20 to 50, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100. So-called glucose syrups (DE 20-37) and dextrins are particularly useful, both of which are accessible by partial hydrolysis of starch, which can be carried out by customary, for example acid- or enzyme-catalyzed, processes and which are as such or in higher polymer form, for example as starch can be used in the above-mentioned oxidation processes if the polymer chain structure of the starch also degrades accordingly under the conditions of the oxidation.
In erfindungsgemäßen Wasch- und Reinigungsmitteln ist vorzugsweise 0,5 Gew -% bis 10 Gew -%, insbesondere 2 Gew.-% bis 7 Gew.-% des oxidativ modifizierten Oligo- saccharids, das normalerweise in Form seines Alkalisalzes eingesetzt wird, enthalten. Im Rahmen der erfindungsgemäßen Verwendung und des erfindungsgemäßen Waschverfahrens sind Konzentrationen an oxidativ modifiziertem Oligosaccharid in der Waschflotte von 0,001 Gew.-% bis 0,05 Gew.-% bevorzugt.Washing and cleaning agents according to the invention preferably contain 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight, of the oxidatively modified oligosaccharide, which is normally used in the form of its alkali metal salt. In the context of the use according to the invention and the washing process according to the invention, concentrations of oxidatively modified oligosaccharide in the wash liquor of from 0.001% by weight to 0.05% by weight are preferred.
Die erfindungsgemäßen Wasch- und Reinigungsmittel, die als insbesondere teilchenför- mige Feststoffe, Pasten, homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfindungsgemäß eingesetzten Wirkstoff im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Wasch- und Reinigungsmittel können insbesondere oberflächenaktive Tenside, Bleich¬ mittel, Bleichaktivatoren, wassermischbare organische Lösungsmittel, Enzyme, zusätzliche Buildersubstanzen, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Farbübertragungsinhibitoren, Schaumregula¬ toren, Abrasivmittel sowie Färb- und Duftstoffe, enthalten.The detergents and cleaning agents according to the invention, which can be present in particular as particulate solids, pastes, homogeneous solutions or suspensions, can in principle contain all the ingredients known and customary in such agents, in addition to the active ingredient used according to the invention. The washing and cleaning agents according to the invention can in particular include surface-active surfactants, bleaching agents, bleach activators, water-miscible organic solvents, enzymes, additional builder substances, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, color transfer inhibitors, foam regulators, abrasives and dye - and fragrances.
Vorzugsweise enthält ein erfindungsgemäßes Mittel zusätzlich zum oxidativ modifizierten Oligosaccharid einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen (Haupt-)Builder. Buildersubstanzen sind insgesamt in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vorzugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten.In addition to the oxidatively modified oligosaccharide, an agent according to the invention preferably contains a water-soluble and / or water-insoluble, organic and / or inorganic (main) builder. Builder substances are total in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphos- phate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche, wasser- dispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Wasch¬ mittelqualität, insbesondere Zeolith A, Zeolith P und gegebenenfalls Zeolith X, bevor¬ zugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teil- chenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew -% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. %, used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12837, is generally in the range from 100 to 200 mg CaO per gram.
Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisi¬ likate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu Si02 unter 0,95, ins¬ besondere von 1:1 ,1 bis 1:12 auf und können amorph oder kristallin vorliegen. Be¬ vorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsili¬ kate, mit einem molaren Verhältnis Na2O:SiO2 von 1:2 bis 1:2,8. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1:1,9 bis 1:2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0425427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugs¬ weise kristalline Schichtsilikate der allgemeinen Formel Na2Six02x+1 y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt, wobei ß-Natriumdi- silikat beispielsweise nach dem Verfahren erhalten werden kann, das in der interna¬ tionalen Patentanmeldung WO 91/08171 beschrieben ist. δ-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260610 hergestellt werden. Auch aus amorphen Alkalisili¬ katen hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0548599, EP 0502325 und EP 0452428 beschrieben, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natrium¬ schichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0436835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 293 753 erhältlich sind, werden in einer weiteren Ausführungsform erfin¬ dungsgemäßer Mittel eingesetzt. Falls als zusätzliche Buiidersubstanz auch Alkalialu- mosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumo- silikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 4:1 bis 10:1. in Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amorphem Alkalisilikat zu kristallinem Alkalisilikat vorzugs¬ weise 1:2 bis 2:1 und insbesondere 1:1 bis 2:1.Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8. Those with a molar Na 2 O: SiO 2 ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0425427. As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, preference is given to using crystalline sheet silicates of the general formula Na 2 Si x 0 2x + 1 y H2O, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred, with β-sodium di silicate can be obtained, for example, by the method described in the international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as described in European patent applications EP 0548599, EP 0502325 and EP 0452428 agents according to the invention are used. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 293 753, are used in a further embodiment of agents according to the invention. If alkali alumino-silicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 4: 1 to 10: 1. in compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
Zu den wasserlöslichen organischen Buildersubstanzen gehören Aminopolycarbon- säuren, insbesondere Nitrilotriessigsäure und Ethylendiamintetraessigsäure, Poly¬ phosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamin- tetrakis(methylenphosphonsäure) und 1-Hydroxyethan-1,1-diphosphonsäure, Polycar¬ bonsäuren, insbesondere Citronensäure und Zuckersäuren, sowie polymere (Poly-)car- bonsäuren, insbesondere die durch Oxidation von Polysacchariden zugänglichen Polycarboxylate der internationalen Patentanmeldung WO 93/16110, polymere Acryl- säuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch ge¬ ringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 5000 und 200000, die der Copolymeren zwischen 2 000 und 200000, vorzugsweise 50000 bis 120000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethy lethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/ oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethy¬ lenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4- Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure, vorzugs¬ weise einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, in denen kurz- kettige Carbonsäuren, beispielsweise von mit Vinylalkohol ver- estert sind. Bevorzugte Terpolymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbe¬ sondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders be¬ vorzugt Acrylsäure bzw. Acrylat, und Maieinsäure bzw. Maleat sowie 5 Gew -% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Bevorzugt sind dabei Terpolymere, in denen das Gewichtsverhältnis von (Meth)acryl- säure beziehungsweise (Meth)acrylat zu Maleinsäure beziehungsweise Maleat zwischen 1 :1 und 4:1 , vorzugsweise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezo¬ gen. Das zweite saure Monomer beziehungsweise dessen Salz kann auch ein Derivat einer Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem C1-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure be¬ ziehungsweise (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallyl- sulfonsäure bzw. Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew -%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind. Unter diesen besonders bevorzugt ist Saccharose. Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in das Po¬ lymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000, vorzugsweise zwischen 200 und 50 000 und insbesondere zwischen 3 000 und 10 000 auf. Weitere Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acryisäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren gelangen in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkali¬ salze, zum Einsatz.The water-soluble organic builder substances include aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, and polycarboxylic acids, in particular citric acids, in particular citric acids , as well as polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 which are accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer. The first acidic monomer or its salt is derived from a monoethylene-unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, preferably a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or an esterified vinyl alcohol. Vinyl alcohol derivatives in which short-chain carboxylic acids, for example of are esterified with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate. Terpolymers are preferred in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical , or an aromatic radical, which is preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight .-%, preferably 15 wt .-% to 25 wt .-% methallyl sulfonic acid or methallylsulfonate and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of one Carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, where mono-, di- or oligosaccharides are preferred. Among these, sucrose is particularly preferred. By using the third monomer, predetermined breaking points are presumably built into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular mass between 1,000 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000. Further copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.
Durch den Einsatz von wie oben beschrieben oxidativ modifizierten Oligosacchariden ist es möglich, auf derartige konventionelle organische Co-Builder vollständig zu verzichten, ohne daß man Einbußen der Leistung des Wasch- oder Reinigungsmittels erleidet. Ge¬ wünschtenfalls können die genannten konventionellen organischen Buildersubstanzen in Mengen bis zu 5 Gew.-%, insbesondere von 1 Gew.-% bis 4 Gew -% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen erfindungsgemäßen Mittein eingesetzt.By using oxidatively modified oligosaccharides as described above, it is possible to completely dispense with such conventional organic co-builders without suffering a loss in the performance of the washing or cleaning agent. If desired, the conventional organic builder substances mentioned can be present in amounts of up to 5% by weight, in particular from 1% by weight to 4% by weight. Amounts close to the above upper limit are preferably used in paste-like or liquid agents according to the invention.
Die erfindungsgemäßen Mittel können ein oder mehrere Tenside enthalten, wobei insbe¬ sondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kom¬ men. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxy- lierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder ver¬ zweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten lang¬ kettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomem im Alkylrest brauchbar. Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfa- tierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxy- lierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkyl- benzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C- Atomen, sowie Olefinsulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entspre¬ chender Monoolefine mit Schwefeltrioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen.The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used. Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type which can be used include linear alkylbenzenesulfonates with 9 to 14 C atoms in the alkyl part, alkanesulfonates with 12 to 18 C atoms, and olefin sulfonates with 12 to 18 C atoms, which are used in the reaction of corresponding monoolefins arise with sulfur trioxide, as well as alpha-sulfofatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.
Derartige Tenside sind in den erfindungsgemäßen Reinigungs- oder Waschmitteln in Mengeπanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew - % bis 30 Gew.-%, enthalten. In erfindungsgemäßen Mitteln für die Reinigung von Geschirr können die genannten Untergrenzen jedoch unterschritten werden; der Tensidgehalt in derartigen Mitteln liegt vorzugsweise bei 0,1 Gew -% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 5 Gew.-%.Such surfactants are present in the cleaning or washing agents according to the invention in amounts of preferably 5% by weight to 50% by weight, in particular 8% to 30% by weight. In agents according to the invention for cleaning dishes, however, the lower limits mentioned may be undershot; the surfactant content in such compositions is preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight.
Als Bleichmittel auf Persauerstoffbasis, die in erfindungsgemäßen Mitteln enthalten sein können, kommen insbesondere organische Persäuren, Wasserstoffperoxid und unter den Wasch- beziehungsweise Reinigungsbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Falls ein erfindungsgemäßes Wasch- oder Reinigungsmittel Persauerstoffverbindungen enthält, sind sie in Mengen von vorzugsweise 10 Gew.-% bis 30 Gew.-%, insbesondere von 15 Gew.-% bis 25 Gew.-% enthalten, wobei Na¬ triumpercarbonat besonders bevorzugt ist. Es kann nach bekannten Verfahren herge¬ stellt und gewünschtenfalls in granulärer Form konfektioniert beziehungsweise stabilisiert werden, wie es zum Beispiel aus den internationalen Patentanmeldungen WO 91/15423, WO 92/17400, WO 92/17404, WO 93/04159, WO 93/04982, WO 93/20007, WO 94/03553, WO 94/05594, WO 94/14701, WO 94/14702, O 97/25399 PCI7EP96/05713Suitable peroxygen-based bleaching agents which may be present in agents according to the invention are, in particular, organic peracids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. If a washing or cleaning agent according to the invention contains peroxygen compounds, they are present in amounts of preferably 10% by weight to 30% by weight, in particular 15% by weight to 25% by weight, sodium percarbonate being particularly preferred . It can be prepared by known processes and, if desired, can be packaged or stabilized in granular form, as described, for example, in international patent applications WO 91/15423, WO 92/17400, WO 92/17404, WO 93/04159, WO 93/04982 , WO 93/20007, WO 94/03553, WO 94/05594, WO 94/14701, WO 94/14702, O 97/25399 PCI7EP96 / 05713
WO 94/24044, WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 oder WO 95/15292 bekannt ist. Bevorzugt setzt man ein mit speziellen Boraten stabilisiertes Alkalipercarbonat, wie aus den europäischen Patentanmeldungen EP 459 625, EP 487 256 oder EP 567 140 bekannt, oder ein mit einer Kombination von Alkalisalzen umhülltes Alkalipercarbonat, wie aus den europäischen Patentanmeldungen EP 623 553 oder EP 592 969 bekannt, ein.WO 94/24044, WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 or WO 95/15292 are known. An alkali percarbonate stabilized with special borates, as known from European patent applications EP 459 625, EP 487 256 or EP 567 140, or an alkali percarbonate coated with a combination of alkali salts, such as from European patent applications EP 623 553 or EP 592 969, is preferably used known a.
Zu den gegebenenfalls in den erfindungsgemäßen Mitteln enthaltenen Bleichaktivatoren gehören insbesondere Verbindungen, die unter Perhydrolysebedingungen gegebenen¬ falls substituierte Perbenzoesäure und/oder Peroxocarbonsäuren mit 1 bis 10 C- Atomen, insbesondere 2 bis 4 C-Atomen ergeben. Geeignet sind insbesondere Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen aufweisen. Bevorzugt sind mehrfach acylierte Alkyiendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetyiglykoluril (TAGU), acylierte Triazinderivate, insbe¬ sondere 1 ,5-DiacetyI-2,4-dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Phenolsulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy- 2,5-dihydrofuran sowie acetyiiertes Sorbit und Mannit, und acylierte Zuckerderivate, ins¬ besondere Pentaacetylglukose (PAG), Pentaacetyrfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyiiertes, gegebenenfalls N-alkyiiertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 4443 177 bekannten Bleichaktivatorkombinationen können eingesetzt werden. Zusätzlich oder anstatt derartiger Bleichaktivatoren können als sogenannte Bleichkatalysatoren Salze beziehungsweise Komplexe von Übergangsmetallen, wie Mn, Co, oder Fe eingesetzt werden.The bleach activators optionally contained in the agents according to the invention include, in particular, compounds which, under perhydrolysis conditions, give substituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms. Particularly suitable are substances which have O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated glycolurils, in particular tetraacetyiglycolouril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyI-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are preferred. acylated phenol sulfonates, especially nonanoyl or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetyiated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylfacylacetylglucose (p and octaacetyl lactose and acetylene, optionally N-alkyated, glucamine and gluconolactone. The bleach activator combinations known from German patent application DE 4443 177 can also be used. In addition or instead of such bleach activators, salts or complexes of transition metals such as Mn, Co or Fe can be used as so-called bleach catalysts.
Als in den Mitteln verwendbare Enzyme kommen solche aus der Klasse der Proteasen, Lipase π, Cutinasen, Amylasen, Pullutanasen, Hemicellulasen, Xylanasen, Cellulasen, Oxidasen und Peroxidasen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes oder Pseudomonas cepacia gewonnene enzymatische Wirkstoffe. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmel- dungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln in Mengen von vorzugsweise nicht über 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 2 Gew.-%, enthalten.Enzymes which can be used in the agents are those from the class of the proteases, π lipase, cutinases, amylases, pullutanases, hemicellulases, xylanases, cellulases, oxidases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable. The enzymes which may be used can, as for example in the international patent applications be described in WO 92/11347 or WO 94/23005, adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing and cleaning agents according to the invention in amounts of preferably not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Wasch-, Reinigungs¬ und Desinfektionsmitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.The organic solvents which can be used in the agents according to the invention, especially if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned. Such water-miscible solvents are preferably present in the washing, cleaning and disinfecting agents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Apfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den er¬ findungsgemäßen Mitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew.-% bis 17 Gew -%, enthalten.To set a desired pH value which does not result from the mixture of the other components, the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.
Zusätzlich können die Mittel weitere in Wasch- und Reinigungsmitteln übliche Bestandteile enthalten. Zu diesen fakultativen Bestandteilen gehören insbesondere Enzymstabilisatoren, zusätzliche Vergrauungsinhibitoren wie Carboxymethylcellulose, Farbübertragungsinhibitoren, beispielsweise Polyvinylpyrrolidon oder Polyvinylpyrdin-N- oxid, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, und optische Aufheller, beispielsweise Stilbendisulfonsäurederivate.In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzyme stabilizers, additional graying inhibitors such as carboxymethyl cellulose, color transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyrdine-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene disulfonic acid derivatives.
Die Herstellung erfindungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Enzyme, Bleichmittel und eventuelle weitere thermisch empfindliche Inhaltsstoffe gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein aus der europäischen Patentschrift EP 486 592 bekanntes, einen Extrusionschritt aufweisendes Verfahren bevorzugt. Flüssige beziehungsweise pastöse erfindungsge¬ mäße Wasch- oder Reinigungsmittel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Sub¬ stanz oder als Lösung in einen automatischen Mischer gegeben werden können, her¬ gestellt. The preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, with enzymes, bleaching agents and any other thermally sensitive ingredients if necessary, be added separately later. For the production of agents according to the invention with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method known from European patent EP 486 592 and having an extrusion step is preferred. Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally prepared by simply mixing the ingredients, which can be added in substance or as a solution to an automatic mixer.
BeispieleExamples
Beispiel 1 : PrimärwaschkraftExample 1: Primary washing power
Zu einem Basiswaschmittel BW, enthaltend 15 Gew.-% einer 2:1 -Mischung aus Na- triumalkylbenzolsulfonat und Natriumfettalkylsulfat, 1 Gew.-% Seife, 4 Gew.-% 5-fach ethoxylierten Ci2/ι8-Alkohol, 25 Gew.-% Zeolith Na-A, 16 Gew.-% Natriumperborat- Monohydrat, 6 Gew.-% TAED und auf 100 Gew. -% Enzymgranulate,To a base detergent BW containing 15 wt .-% of a 2: 1 mixture of Na and triumalkylbenzolsulfonat Natriumfettalkylsulfat, 1 wt .-% soap, 4 wt .-% of 5-tuply ethoxylated Ci2 / ι 8 alcohol, 25 wt. -% zeolite Na-A, 16% by weight sodium perborate monohydrate, 6% by weight TAED and to 100% by weight enzyme granules,
Schauminhibitorgranulat, Wasser und Salze wurden, bezogen auf das Basiswaschmittel, 5,5 Gew.-% am reduzierenden Ende oxidativ modifizierter Oligosaccharid-Co-Builder B1 mit mittlerem Oligomerisierungsgrad ca. 2,5 (M1), 5,5 Gew.-% am reduzierenden Ende oxidativ modifizierter Oligosaccharid-Co-Builder B2 mit mittlerem Oligomerisierungsgrad ca. 15 (M2) beziehungsweise zum Vergleich 5,5 Gew.-% Maleinsäure-Acrylsäure- Copolymer (V1) gegeben.Foam inhibitor granules, water and salts, based on the basic detergent, were 5.5% by weight at the reducing end of oxidatively modified oligosaccharide co-builder B1 with an average degree of oligomerization of approximately 2.5 (M1), 5.5% by weight on reducing end of oxidatively modified oligosaccharide co-builder B2 with an average degree of oligomerization of approximately 15 (M2) or, for comparison, 5.5% by weight of maleic acid / acrylic acid copolymer (V1).
Zur Bestimmung des Primärwaschvermögens wurde mit Staub/Hautfett (standardisierte Testanschmutzung) verunreinigtes Baumwollgewebe bei 90°C (Waschmitteldosierung 105 g; Wasserhärte 23 °d) in einer Haushaltswaschmaschine (Miele® W914 Novotronic) gewaschen. In der nachfolgenden Tabelle 1 sind die Remissionswerte in % (bestimmt unter Verwendung von Ba2SO4 als Weiß-Standard) als Ergebnis von Doppel¬ bestimmungen angegeben. Es zeigte sich, daß ein erfindungsgemäßes Mittel M1 oder M2 ein geringfügig besseres Primärwaschvermögen aufweist als ein Mittel V1, welches lediglich konventionellen organischen Co-Builder enthält.To determine the primary washability, cotton fabric contaminated with dust / skin fat (standardized test soiling) was washed at 90 ° C (detergent dosage 105 g; water hardness 23 ° d) in a household washing machine (Miele® W914 Novotronic). Table 1 below shows the reflectance values in% (determined using Ba 2 SO 4 as the white standard) as the result of double determinations. It was found that an agent M1 or M2 according to the invention has a slightly better primary washing power than an agent V1 which only contains conventional organic co-builders.
Tabelle 1 ; PrimärwaschkraftTable 1 ; Primary washing power
Beispiel 2: Bestimmung des Sekundärwaschvermögens Example 2: Determination of the secondary washing power
Saubere Gewebeproben wurden 25-mal unter den in Beispiel 1 angegebenen Be¬ dingungen mit den Mitteln M1 beziehungsweise V1 gewaschen, anschließend getrock¬ net, eingewogen und verascht. Nach dem Erkalten wurde der Glührückstand zurückgewogen. In der nachfolgenden Tabelle 2 sind die so erhaltenen Aschewerte, ausgedückt in Prozent der Einwage, angegeben. Zum Vergleich ist der Anfangswert (nicht gewaschenes Gewebe) mit angegeben.Clean tissue samples were washed 25 times under the conditions given in Example 1 with agents M1 and V1, then dried, weighed and ashed. After cooling, the residue on ignition was weighed out. Table 2 below shows the ash values obtained in this way, expressed as a percentage of the weight. For comparison, the initial value (unwashed fabric) is also given.
Tabelle 2: Aschewerte [%]Table 2: Ash values [%]
Gewebe A: WFK-Testgewebe B: Bleichnessel C: FrotteeFabric A: WFK test fabric B: bleaching nettle C: terry cloth
Zur Bestimmung der Inkrustation wurden wie oben beschrieben gewaschene Gewebe¬ proben ausgewogen und dann in einer 5 %igen EDTA-Lösung mit einem Flotten¬ verhältnis von 1 : 20 ( Textileinwaage zu EDTA-Lösung) ausgekocht und anschließend mit destilliertem Wasser mehrmals gründlich gespült. Die Gewebe wurden getrocknet und wieder gewogen. Die Gewichtsdifferenz der Proben vor und nach der Behandlung, ausgedückt in Prozent der Einwage, ergibt die lösliche Inkrustation.To determine the incrustation, washed tissue samples were weighed out as described above and then boiled out in a 5% EDTA solution with a liquor ratio of 1:20 (textile weight to EDTA solution) and then rinsed thoroughly several times with distilled water. The tissues were dried and weighed again. The difference in weight of the samples before and after treatment, expressed as a percentage of the weight, gives the soluble incrustation.
Die exkrustierten Gewebeabschnitte wurden anschließend wie oben beschrieben ver¬ ascht. Die ermittelten Werte stellen die Restasche (unlösliche Anteile) dar. Die Versuchsergebnisse sind in der nachfolgenden Tabelle 3 dargestellt.The excreted tissue sections were then ashed as described above. The values determined represent the residual ash (insoluble components). The test results are shown in Table 3 below.
Tabelle 3: Inkrustation und RestascheTable 3: Incrustation and residual ash
Gewebe A: WFK-Testgewebe B: BieichnesselTissue A: WFK test fabric B: stinging nettle
Wie in Beispiel 1 angegeben, wurde die Remission der 25 mal mit dem jeweiligen Mitel gewaschenen Testgewebe bestimmt, um die durch die Waschvorgänge hervorgerufene Vergrauung der Gewebe festzustellen. In der nachfolgenden Tabelle 4 sind die gemes¬ senen Remissionswerte (niedrige Werte bedeuten hohe Vergrauung) als Mittelwerte von Doppelbestimmungen aufgeführt.As indicated in Example 1, the reflectance of the test fabric washed 25 times with the respective agent was determined in order to determine the graying of the fabric caused by the washing processes. Table 4 below shows the measured reflectance values (low values mean high graying) as mean values of duplicate determinations.
Tabelle 4: Vergrauung [% Remission]Table 4: Graying [% remission]
Gewebe A: WFK-Testgewebe B: Bleichnessel C: Frottee Fabric A: WFK test fabric B: bleaching nettle C: terry cloth

Claims

Patentansprüche claims
1. Wasch- oder Reinigungsmittel, enthaltend Tensid, anorganischen Builder, Bleichmittel auf Sauerstoffbasis, Bleichaktivator und/oder Enzym, dadurch gekennzeichnet, daß es als Builder- beziehungsweise Cobuilderkomponente ein Oli¬ gosaccharid enthält, welches an seinem ursprünglich reduzierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH aufweist.1. washing or cleaning agent containing surfactant, inorganic builder, bleaching agent based on oxygen, bleach activator and / or enzyme, characterized in that it contains, as a builder or cobuilder component, an oligosaccharide which at its originally reducing end instead of the group -CH (OH) -CHO has a group -COOH.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, daß der mittlere Oligomeri¬ sierungsgrad des modifizierten Oligosaccharids im Bereich von 2 bis 20, insbesondere 2 bis 10 liegt.2. Composition according to claim 1, characterized in that the average degree of oligomerization of the modified oligosaccharide is in the range from 2 to 20, in particular 2 to 10.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß am ursprünglich redu¬ zierenden Ende des Oligosaccharids eine Arabinonsäure-Einheit vorliegt.3. Composition according to claim 1 or 2, characterized in that an arabinonic acid unit is present at the originally reducing end of the oligosaccharide.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es 0,5 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew -% bis 7 Gew.-% des oxidativ modifizierten Oligosaccharids enthält.4. Composition according to one of claims 1 to 3, characterized in that it contains 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight, of the oxidatively modified oligosaccharide.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-% Builder, 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-% Tensid, 10 Gew.-% bis 30 Gew.-%, insbesondere von 15 Gew.-% bis 25 Gew.-% Bleichmittel auf Sauerstoffbasis, bis zu 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 2 Gew.-% Enzym und/oder nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-% wassermischbares Lösungsmittel enthält.5. Composition according to one of claims 1 to 4, characterized in that it is up to 60 wt .-%, in particular from 5 wt .-% to 40 wt .-% builder, 5 wt .-% to 50 wt .-% , in particular from 8% by weight to 30% by weight of surfactant, 10% by weight to 30% by weight, in particular from 15% by weight to 25% by weight of oxygen-based bleach, up to 5% by weight. %, in particular from 0.2% by weight to 2% by weight of enzyme and / or not more than 30% by weight, in particular from 6% by weight to 20% by weight, of water-miscible solvent.
6. Mittel für die Reinigung von Geschirr nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 0,1 Gew.-% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 5 Gew.-% Tensid enthält.6. Agent for cleaning dishes according to one of claims 1 to 4, characterized in that it is 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactant contains.
7. Verwendung von Oligosacchariden, die an ihrem ursprünglich reduzierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH aufweisen, als Vergrauungsin- hibitoren in Waschmitteln für die Textilwäsche. Verwendung von Oligosacchaπden, die an ihrem ursprunglich reduzierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH aufweisen, als Vergrauungsm- hibitoren in wäßrigen Waschflotten für die Textilwasche7. Use of oligosaccharides which have a group -COOH instead of the group -CH (OH) -CHO at their originally reducing end as graying inhibitors in detergents for textile washing. Use of oligosacchaπden which have a group -COOH instead of the group -CH (OH) -CHO at their originally reducing end as graying inhibitors in aqueous washing liquors for washing textiles
Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die Konzentration an oxidativ modifiziertem Oligosacchaπd in der Waschflotte von 0,001 Gew -% bis 0,05 Gew -% beträgtUse according to claim 8, characterized in that the concentration of oxidatively modified oligosacchaπd in the wash liquor is from 0.001% by weight to 0.05% by weight
Waschverfahren für Textilien in wäßπger, insbesondere tensidhaltiger Flotte, dadurch gekennzeichnet, daß man Oligosacchaπde, die an ihrem ursprunglich reduzierenden Ende statt der Gruppe -CH(OH)-CHO eine Gruppe -COOH aufweisen, als Vergrauungsinhibitoren einsetztWashing process for textiles in an aqueous, in particular surfactant-containing liquor, characterized in that oligosaccharides which have a -COOH group instead of the -CH (OH) -CHO group at their originally reducing end are used as graying inhibitors
Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die Konzentration an oxidativ modifiziertem Oligosacchaπd in der Waschflotte von 0,001 Gew -% bis 0,05 Gew -% beträgt. Method according to claim 10, characterized in that the concentration of oxidatively modified oligosacchaπd in the wash liquor is from 0.001% by weight to 0.05% by weight.
EP96944014A 1996-01-03 1996-12-19 Washing agents with specific oxidized oligosaccharides Expired - Lifetime EP0874890B1 (en)

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DE19600018 1996-01-03
DE19600018A DE19600018A1 (en) 1996-01-03 1996-01-03 Detergent with certain oxidized oligosaccharides
PCT/EP1996/005713 WO1997025399A1 (en) 1996-01-03 1996-12-19 Washing agents with specific oxidized oligosaccharides

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DE (2) DE19600018A1 (en)
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EP0874890B1 (en) 2000-02-16
US6187055B1 (en) 2001-02-13
ATE189829T1 (en) 2000-03-15
WO1997025399A1 (en) 1997-07-17
ES2143800T3 (en) 2000-05-16
JP2000502742A (en) 2000-03-07
DE19600018A1 (en) 1997-07-10
DE59604471D1 (en) 2000-03-23

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