EP0874889A1 - Agent de lavage comprenant un systeme adjuvant contenant du carbonate et/ou un agent de blanchiment contenant du percarbonate - Google Patents

Agent de lavage comprenant un systeme adjuvant contenant du carbonate et/ou un agent de blanchiment contenant du percarbonate

Info

Publication number
EP0874889A1
EP0874889A1 EP96941609A EP96941609A EP0874889A1 EP 0874889 A1 EP0874889 A1 EP 0874889A1 EP 96941609 A EP96941609 A EP 96941609A EP 96941609 A EP96941609 A EP 96941609A EP 0874889 A1 EP0874889 A1 EP 0874889A1
Authority
EP
European Patent Office
Prior art keywords
weight
builder
water
alkali
dextrin
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.)
Ceased
Application number
EP96941609A
Other languages
German (de)
English (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
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
Priority claimed from DE1995145727 external-priority patent/DE19545727A1/de
Priority claimed from DE1996113880 external-priority patent/DE19613880A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0874889A1 publication Critical patent/EP0874889A1/fr
Ceased legal-status Critical Current

Links

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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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 a specific builder combination in the form of inorganic water-insoluble builder material, inorganic water-soluble builder material which consists at least partly of alkali carbonate, and optionally oxidized dextrin.
  • the carbonate portion of the builder system can be replaced at least in part by alkali percarbonate.
  • detergents and cleaning agents In addition to the surfactants which 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 be eliminated from the wash liquor so that they do not interact negatively 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 be eliminated from the wash liquor so that they do not interact negatively with the surfactants.
  • a known example of such builders that improve pruri-washing power is zeolite Na-A, which is known to be able to form complexes with calcium ions in particular that are so insoluble that their reaction with water-hardness-forming anions, especially carbonate Connections is suppressed.
  • the builders in particular in textile detergents, are intended to reload the dirt detached from the fiber or generally from the surface to be cleaned, and also from the reaction of water-hardness-forming cations with water-harding anions to form insoluble compounds on the cleaned textile or prevent the surface.
  • co-builders usually polymeric polycarboxylates, are used, which, in addition to their contribution to the secondary washing ability, also have a complexing action against the water-hardening cations. From German patent application DE 40 11 487 it is known that certain polyglucose can enhance the washing and cleaning action of surfactants.
  • the invention therefore relates to a washing or cleaning agent which contains a combination of inorganic water-insoluble builder material, inorganic water-soluble builder material which consists at least in part of alkali carbonate, and dextrin which has optionally been oxidized.
  • Another object of the invention is the use of optionally oxidized dextrin as a builder or co-builder in detergents and cleaning agents which contain a combination of inorganic water-insoluble builder material and inorganic contain water-soluble builder material, which consists at least partially of alkali carbonate.
  • the invention relates to a washing or cleaning agent which contains a combination of optionally oxidized dextrin and bleaching agent containing alkalipercarbonate.
  • Another object of the invention is the use of dextrin as a builder or co-builder in detergents and cleaning agents containing alkipercarbonate.
  • this relates to agents which contain at least an amount of other builder described below as the main builder corresponding to the amount of dextrin.
  • dextrins are understood to mean oligomers or polymers of carbohydrates which are accessible by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary methods, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 440 to 500,000.
  • the dextrin used in compositions according to the invention is preferably a polysaccharide with a dextrose equivalent (DE) in the range from 0. 5 to 40. in particular from 2 to 30, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100.
  • DE dextrose equivalent
  • dextrins Both maltodextrins (DE 3 - 20) and dry glucose syrups (DE 20 - 37) as well as so-called yellow dextrins and white dextrins with higher average molecular weights in the range from approximately 2,000 to 30,000 can be used.
  • a preferred dextrin is in European patent application EP 0 703,292.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 427 349, EP 472 042 and EP 542 496 and the international patent applications WO 93/08251, WO 93/161 10, WO 95/07303 and WO 95/12619.
  • a product oxidized at C 6 of the saccharide ring is preferably used, as can be obtained according to the method of international patent applications WO 93/161 10, WO 94/28030, WO 95/20608 and WO 96/03439. It is also possible to use dextrins which have been oxidatively modified at their 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: (glucose) - ⁇ (glucose) nI- arabinonic acid.
  • the average degree of oligomerization n which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20. in particular 2 to 10.
  • This latter 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, using Pd, Pt, Rh or Os catalysts, as described in European patent EP 0 232 202, or using a quinone / Hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide.
  • oxidized dextrin is contained in agents according to the invention preferably in amounts of 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight.
  • crystalline or amorphous, water-dispersible alkali alumosilicates are used as water-insoluble inorganic builder materials, in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of 5% by weight to 15% by weight. % used.
  • the detergent-grade crystalline sodium aluminosilicates in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Amounts 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.
  • Your calcium binding capacity which according to the information in German patent DE 24 12 837 no PCT / EP96 / 05263 97/20905
  • alkali carbonate is preferably contained in the compositions according to the invention in amounts of 5% by weight to 20% by weight, in particular from 6% by weight to 18% by weight. It can be replaced at least in part by alkali percarbonate or the agent can additionally contain alkali percarbonate, alkali percarbonate being in the agents according to the invention preferably in amounts of 10% by weight to 30% by weight. in particular from 15% by weight to 25% by weight is contained and sodium percarbonate is particularly preferred.
  • 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.
  • water-soluble inorganic builder materials can be included.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali silicate builders.
  • Such water-soluble inorganic builder materials are preferably contained in agents according to the invention in amounts of 1% by weight to 20% by weight, in particular 5% by weight to 15% by weight.
  • the alkali silicates which can be used as builder materials 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 molar ratio Na 2 OtSiO 2 from 1: 2 to 1: 2.8. Those with a Na 2 O: SiO 2 molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. In the course of the preparation of agents according to the invention, they are preferably added as a solid and not in the form of a solution.
  • Crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 y H 2 O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
  • Crystalline layered silicates that 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.
  • both ⁇ - and ⁇ -sodium disilicate are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced in accordance with Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • 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 .
  • a granular compound of alkali silicate and alkali carbonate is used, as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of optionally oxidized dextrin to water-insoluble inorganic builder in the washing or cleaning agent is 1: 1 to 1: 6, in particular 2: 3 to 1: 3.
  • the weight ratio of optionally oxidized dextrin to alkali percarbonate is preferably 1: 1 to 1: 8, in particular 1: 2 to 1: 5. In a further preferred embodiment of agents according to the invention, the weight ratio of optionally oxidized dextrin to alkali carbonate is 3: 1 to 1: 5, in particular 2: 1 to 1: 4. If alkali carbonate and alkali percarbonate are contained together in the agent according to the invention, the weight ratio of optionally oxidized dextrin to the sum of alkali carbonate and alkali percarbonate is preferably 1: 1 to 1:10, in particular 1: 2 to 1: 7. Preferred weight ratios of water-insoluble inorganic builder to water-soluble inorganic builder, in particular the sum of alkali silicate and alkali carbonate, are in the range from 2: 1 to 1: 2, in particular 3: 2 to 2: 3.
  • 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 addition to the active ingredient combination of inorganic builders and optionally oxidized dextrin used according to the invention, in principle all known and conventional agents Contain ingredients.
  • the washing and cleaning agents according to the invention can in particular include 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, graying inhibitors, color transfer inhibitors, foam regulators, and abrasives Dyes and fragrances.
  • 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.
  • 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 surfactants of the sulfate type which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 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 include linear alkyl benzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon 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 proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight.
  • the surfactant content in such agents is preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight.
  • organic bleaches, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the conditions of use are suitable as bleaching agents, in particular based on peroxygen, if desired.
  • peroxygen compounds are to be used, they can be in the form of powders or granules can be used, which can also be coated in a manner known in principle.
  • alkali perborate monohydrate is preferably used.
  • a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight.
  • the bleach activators optionally contained in the agents according to the invention include in particular compounds, compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular
  • Tetraacetylethylenediamine TAED
  • acylated triazine derivatives especially 1, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT)
  • acylated glycolurils especially tetraacetylglycoluril (TAGU)
  • N-acylimides especially N-nonanoyosuccinimide
  • acylated phenol sulfonates especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
  • carboxylic acid anhydrides especially phthalic anhydride
  • acylated polyhydric alcohols especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acet
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferred used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446 982 and EP 0 453 003 can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron and cobalt compounds known from German patent application DE 195 29 905.
  • German patent application DE 196 20 267 the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from German patent application DE 195 36 082, which in the German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt known from German patent application DE 196 20 41 1 , Iron, copper and ruthenium-amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030, which are derived from the European patent ⁇ Message EP 0 693 550 manganese complexes known, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 5
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.
  • an agent according to the invention can optionally contain further water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include aminopolycarboxylic acids, in particular nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and l -hydroxyethane-l, l-diphosphonic acid, in particular, citric acid, polyrononic acid, polyrononic acid, polycarboxylic acid, Poly-) carboxylic acids such as polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain a small amount of polymerizable substances without carboxylic acid functionalized in copolymerized form.
  • 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 ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Te ⁇ olymers 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 monoethylenically 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.
  • Vinyl alcohol derivatives are preferred in which short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, are esterified with vinyl alcohol.
  • Preferred polymers 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 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • 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 r C 4 alkyl radical. or an aromatic radical, which is preferably derived from benzene or benzene derivatives.
  • Preferred polymers 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% by weight to 25% by weight, of methallylsulfonic acid or methyl allyl sulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight, of a carbohydrate .
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Among these, sucrose is particularly preferred.
  • the use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These polymers can be produced in particular by processes which are described in German patent DE 42 21 381 and German patent application DE 43 00 772, and generally have a relative molecular weight 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 in particular for the production of liquid agents, can be in the form of aqueous solvents. 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 metal salts.
  • the use of optionally oxidized dextrin makes it possible to completely dispense with such conventional organic co-builders without suffering a loss in the performance of the washing or cleaning agent.
  • detergents with the builder system according to the invention perform better in the secondary washing performance than detergents which contain conventional organic co-builders instead of the possibly oxidized dextrin.
  • 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 upper limit mentioned are preferably used in pasty or liquid agents according to the invention.
  • Enzymes which can be used in the agents are those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases, 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 Pseudo ⁇ monas cepacia, are particularly suitable.
  • the enzymes which may be used, as described for example in international patent applications WO 92/1 1347 or WO 94/23005, can be adsorbed on carriers and / or embedded in enveloping 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 up to 2% by weight, in particular from 0.2% by weight to 1.5% by weight.
  • the organic solvents which can be used in the agents according to the invention include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert.
  • Such was- Mixable solvents are preferably not present in the washing, cleaning and disinfecting agents according to the invention in excess of 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 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.
  • Color transfer inhibitors that are suitable for use in compositions according to the invention, in particular those for washing textiles, include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly- (vinylipyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular of the textile fiber suspended in the liquor and thus to support the co-builder.
  • water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch products other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which replace the Mo ⁇ holino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- ( 4- chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C Ig -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes. Microcrystalline waxes and their mixtures with silanized silica or bis fatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • 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 dextrin, peroxygen compounds and, if appropriate, other thermally sensitive ingredients being added separately later.
  • dextrins in particular maltodextrins
  • dextrins are usually polysaccharides, in particular starches, broken down by enzymatic means
  • their processing in aqueous-alkaline washing Medium ingredient slurries via a spray tower often discolor the spray product, which may be due to typical sugar reactions, such as occur during caramelization. It is therefore preferred to spray-dry a dextrin which is present in a relatively neutral aqueous environment after separation of the enzymatic active ingredients, using the lowest possible temperatures, and to mix the powder obtained in this way with the other detergent ingredients using conventional mixing units.
  • Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • a basic detergent BW1 containing 15% by weight of a 2: 1 mixture of sodium alkylbenzenesulfonate and sodium fatty alkyl sulfate, 1% by weight of soap, 4% by weight of 5-fold ethoxylated C 12 / ⁇ g alcohol, 25% by weight .-% zeolite Na-A, 6 wt .-% TAED and 100 wt .-% enzyme granules, foam inhibitor granules, water and salts, based on the basic detergent, 5.5 wt .-% dextrinic co-builder (DE approx. 12) and 19 wt .-% sodium percarbonate (Ml) or 16 wt .-% sodium perborate monohydrate (VI).
  • the amounts of percarbonate and perborate used result in equal amounts of active oxygen.
  • Clean tissue samples were 25 times under the specified conditions of Example 1 with the means Ml, VI or a further comparative composition C2, which was composed as Ml, but instead of the dextrinischen Co-Builders the same amount of polymer of a polycarboxylate (Sokalan ® CP 5) contained, an agent M2 according to the invention, which instead of C 6 oxidized starch according to WO 93/161 10 or an agent M3 according to the invention, which instead contained oxidized starch according to EP 472 042, 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.
  • Fabric A WFK test fabric B: bleaching nettle C: terry cloth
  • 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.
  • 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 shows the measured reflectance values (low values mean high graying) as mean values of duplicate determinations.
  • Table 4 Graying [% remission]
  • Example 2 To determine the secondary washing capacity, as in Example 2, clean tissue samples from the materials specified there were washed 25 times at 90 ° C. (detergent dosage in each case 80 g; water hardness 23 ° d) in a household washing machine (Miele® W701), dried and incinerated. The ash values obtained in this way, expressed as a percentage of the weight, are given in Table 5 below. For comparison, the initial value AW (unwashed fabric) is also given. Table 5: Ash values [%]
  • agents according to the invention have a better secondary washing ability than agents with conventional organic co-builders.

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  • Wood Science & Technology (AREA)
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Abstract

La fonction des agents appelés co-adjuvants est d'empêcher que la saleté libérée des fibres ou d'une surface à nettoyer se redépose et d'empêcher également la formation de composés non solubles produits par la réaction entre les cations et les anions qui sont à l'origine de la dureté de l'eau, sur le textile ou sur la surface nettoyé(e). Des dextrines oxydées peuvent éventuellement très bien convenir pour assurer cette fonction, en particulier en présence de carbonate alcalin et/ou de percarbonate alcalin.
EP96941609A 1995-12-07 1996-11-28 Agent de lavage comprenant un systeme adjuvant contenant du carbonate et/ou un agent de blanchiment contenant du percarbonate Ceased EP0874889A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1995145727 DE19545727A1 (de) 1995-12-07 1995-12-07 Alkalipercarbonathaltiges Waschmittel
DE19545727 1995-12-07
DE1996113880 DE19613880A1 (de) 1996-04-06 1996-04-06 Waschmittel mit speziellem Buildersystem
DE19613880 1996-04-06
PCT/EP1996/005263 WO1997020905A1 (fr) 1995-12-07 1996-11-28 Agent de lavage comprenant un systeme adjuvant contenant du carbonate et/ou un agent de blanchiment contenant du percarbonate

Publications (1)

Publication Number Publication Date
EP0874889A1 true EP0874889A1 (fr) 1998-11-04

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Application Number Title Priority Date Filing Date
EP96941609A Ceased EP0874889A1 (fr) 1995-12-07 1996-11-28 Agent de lavage comprenant un systeme adjuvant contenant du carbonate et/ou un agent de blanchiment contenant du percarbonate

Country Status (2)

Country Link
EP (1) EP0874889A1 (fr)
WO (1) WO1997020905A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19936612A1 (de) * 1999-08-04 2001-02-08 Henkel Kgaa Niederdosierter, löslicher Builder
DE19936726A1 (de) * 1999-08-06 2001-02-08 Henkel Kgaa Verfahren zur Herstellung cobuilder-haltiger Zubereitungen
US7727945B2 (en) 2005-07-15 2010-06-01 Akzo Nobel N.V. Modified polysaccharides

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Publication number Priority date Publication date Assignee Title
DE2233977A1 (de) * 1971-07-14 1973-02-01 Unilever Nv Verfahren zur herstellung oxydierter kohlenhydrate
ATE124960T1 (de) * 1989-11-10 1995-07-15 Tno Verfahren zur herstellung von polydicarboxysacchariden.
DE4011487A1 (de) * 1990-04-09 1991-10-10 Henkel Kgaa Tensidmischung fuer die verwendung in wasch- und reinigungsmitteln
IT1249883B (it) * 1990-08-13 1995-03-30 Ferruzzi Ricerca & Tec Agenti sequestranti del calcio a base di carboidrati ossidati e loro impiego come builder per detergenti
IT1245063B (it) * 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec Procedimento per l'ossidazione di carboidrati
EP0542496B1 (fr) * 1991-11-14 1998-05-20 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
ATE143378T1 (de) * 1991-12-23 1996-10-15 Cerestar Holding Bv Verfahren zur herstellung von sauerstoffsäuren aus kohlenhydraten
GB9419091D0 (en) * 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process

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Title
See references of WO9720905A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Also Published As

Publication number Publication date
WO1997020905A1 (fr) 1997-06-12

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