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WO2004005444A1 - Detergent contenant une composante d'entretien des textiles a base de cellulose - Google Patents

Detergent contenant une composante d'entretien des textiles a base de cellulose Download PDF

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Publication number
WO2004005444A1
WO2004005444A1 PCT/EP2003/006842 EP0306842W WO2004005444A1 WO 2004005444 A1 WO2004005444 A1 WO 2004005444A1 EP 0306842 W EP0306842 W EP 0306842W WO 2004005444 A1 WO2004005444 A1 WO 2004005444A1
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WO
WIPO (PCT)
Prior art keywords
detergent
detergent according
acid
cellulose
weight
Prior art date
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PCT/EP2003/006842
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German (de)
English (en)
Inventor
Christian Block
Josef Penninger
Konstanze Mayer
Berthold Schreck
Evelyn Langen
Maren Jekel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU2003246621A priority Critical patent/AU2003246621A1/en
Publication of WO2004005444A1 publication Critical patent/WO2004005444A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/16—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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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

Definitions

  • the present invention relates to a solid detergent with a textile care component and a washing method for washing textiles using portioned detergents in a household washing machine.
  • the invention further relates to the use of the solid detergent to reduce the formation of creases, improve the ironing properties and reduce the formation of pills.
  • WO 99/16956 A1 describes the removal of fluff or pills by using cellulases.
  • the cellulases digest microfibers protruding from the textile fabrics and thus ensure a smooth and therefore pill-free textile surface.
  • celluloses and cellulose derivatives as disintegrants for detergent tablets is known from the prior art.
  • detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the present invention had for its object to provide a solid detergent which causes both a reduction in wrinkling and a reduction in pill formation on the washed textiles. Another task was to make ironing easier on washed textile fabrics.
  • the invention relates to a solid detergent containing a textile care component selected from the group consisting of finely divided cellulose and / or cellulose derivatives, the particles of the textile care component having an average particle size of less than 100 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 20 ⁇ m ,
  • the detergents according to the invention contain, as an essential component, a care component which is selected from the group consisting of finely divided cellulose and / or cellulose derivatives. Without being bound by theory, it is assumed that the finely divided cellulose or cellulose derivatives have a particular substantivity to textile fabrics which impart the desired properties to the treated textiles.
  • Particularly preferred care components come from the group of finely divided celluloses.
  • Pure cellulose has the formal gross composition (C6H 10 O 5 ) n and, viewed formally, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • those celluloses are preferred in which at least 60%, preferably at least 80% and in particular at least 90% of the molecular weight is of biological or biotechnological origin.
  • Microcrystalline cellulose of natural origin for example Arbocel ® BE 600-10, Arbocel ® BE 600-20 and Arbocel ® BE 600-30 ex Rettenmaier or biotechnological origin, for example Cellulon ® ex Kelco, are extremely preferred.
  • Microbiologically fermented celluloses such as are described, for example, in US Pat. No. 6,329,192 B1, are also suitable for use as a textile care component.
  • Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions are also preferably used as a cellulose-based care component in the context of the present invention.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, cellulose esters and ethers and aminocelluloses.
  • cellulose derivatives which can be used as textile care components are the alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, for example hydroxypropylmethyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), propyl cellulose ( PC), Carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropylcellulose (HPC), Hydroxycylmethyl (HPC), Hydroxypropylcellox (HPC), Hydroxypropylcellym Methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC) and mixtures thereof, methylcellulose, methylhydroxyprop
  • the particles of the textile care component have an average particle size of less than 100 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 20 ⁇ m.
  • the particle sizes can be determined according to the relevant measuring methods. In the context of the present invention, the particle sizes were determined using a Coulter counter (volume distribution).
  • the detergents according to the invention preferably contain the care component in an amount of 0.1 to 10% by weight, particularly preferably 1 to 5% by weight, in each case based on the total detergent.
  • the detergents according to the invention can contain further ingredients, the amounts of which depend on the intended use of the detergent. So are in particular substances from the groups of surfactants, builders, Electrolytes that are not builders and the polymers are suitable for use in the detergent formulations according to the invention.
  • All of the builders commonly used in detergents and cleaning agents can be present in the detergents according to the invention, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ H 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1, 9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium phosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 exists as a dihydrate (density 1.91, preferably “3 , melting point 60 °) and as a monohydrate (density 2.04, preferably " 3 ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O g ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) x ] and is easily soluble in water.
  • Dinate hydrogen phosphate (secondary sodium phosphate), Na 2 HP0, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1, 52 like “3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 0 5 ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P 2 0 5 ), a density of 2.536 3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or three-base potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 0 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 0 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water, the pH value being 1 % solution at 25 ° is 10.4.
  • Condensation of NaH 2 P0 or KH 2 P0 4 produces higher molecular weight sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates.
  • melt or glow phosphates Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 0 5 , 25% K 2 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolysing sodium tri-metaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Organic cobuilders which can be used in the detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such carboxylic acids being used under polycarboxylic acids. standing that have more than one acid function.
  • These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses stated in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or salts of acrylic acid and 2-alkylallylsulfonic acid as monomers.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 can be used and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
  • 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.
  • oxidizing agents 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-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycine trisuccinates are also preferred in this connection.
  • Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt alkaline (pH 9).
  • Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • EDTMP hexasodium salt of EDTMP or as the hepta and octa-sodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the amount of builder is usually up to 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • water-soluble builders By using predominantly water-soluble builders or co-builders, builder residues are avoided, which are particularly visible on colored textiles and also negatively affect the textile surfaces.
  • the detergents according to the invention therefore have less than 20% by weight, preferably less than 10% by weight, in each case based on the total composition, and in a particularly preferred embodiment are essentially free of water-insoluble builders, in particular free of zeolites.
  • the detergents according to the invention contain water-soluble builders in amounts of up to 50% by weight, preferably from 15 to 40% by weight and in particular from 20 to 35% by weight, in each case based on the total composition
  • the detergents according to the invention can contain one or more surfactants.
  • Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergents according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view.
  • the total surfactant content of the detergents is 5 to 60% by weight, based on the total detergent, with surfactant contents above 10% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9- thereby ⁇ 3 -Alkylbenzolsulfo- nate, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfo naten, as obtained, for example, from C 12-i 8 monoolefins with terminal or internal Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkanesulfonates obtained from C 12-18 alkanes are also suitable. They are also the same Esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 2 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 1 - C 15 alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-alkyl sulfates which are produced for example according to U.S. Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide 21 alcohols, such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 - fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • Sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) yl-succinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or its salts.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or tri-ethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the detergents according to the invention contain anionic surfactants selected from the group of alkylbenzenesulfonates and / or soaps.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 ⁇ alcohols with 3 EO or 4 EO, C 9 n alcohol with 7 EO, C 13 i 5 alcohols
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-linked compound, can also be used as further nonionic surfactants.
  • R is a primary straight-chain or methyl-linked compound
  • R is a primary straight-chain or methyl-linked compound
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants.
  • branched in particular in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R-CO-N- [Z] (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 up to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical , whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic and nonionic surfactants can be used advantageously in the detergents according to the invention.
  • detergents are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 6: 1 and 1: 2 is.
  • detergents which are preferably anionic and / or nonionic surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight, particularly preferred from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the total composition.
  • electrolytes which are not builders results in improved color fixation and a reduction in dye transfer from one item of laundry to the other.
  • a wide number of different salts can be used as suitable electrolytes, which have no builder properties, from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals
  • preferred anions are the halides and sulfates. From a production point of view, the use of alkali metal and / or alkaline earth metal sulfates in the agents according to the invention is preferred.
  • the content of electrolytes which are not builders is advantageously up to 35% by weight, preferably 11 to 30% by weight and in particular 17 to 28% by weight, in each case based on the total composition.
  • Enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, isoamylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • the detergents according to the invention contain enzymes selected from the group of cellulases because of their color-preserving and pill-reducing action.
  • the detergents according to the invention can contain further ingredients from the group of dyes, fragrances, optical brighteners, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, color transfer inhibitors, incrustation inhibitors, bleaching agents, bleach activators, perfumes, which are customary in detergents. Contain fluorescent agents, anti-redeposition agents, odor absorbers and complexing agents.
  • Preferred detergents additionally contain one or more substances selected from the group of bleaching agents, bleach activators, perfumes, fluorescent agents, dyes, foam inhibitors, anti-redeposition agents, optical brighteners, color transfer inhibitors, odor absorbers and complexing agents.
  • the detergents according to the invention can additionally contain bleaching agents.
  • bleaching agents Of the compounds used as bleaching agents and providing H 2 0 2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further usable bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 H 2 0 2 , can also be used.
  • the agents for cleaning hard surfaces for example in automatic dishwashing
  • they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is also possible in principle for agents for textile washing.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperimoxycapidoxyhex (phyto), o-carboxybenzamidoperoxycaproic acid, N-nonenylamide operadipic acid and N-none-nylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydalsyl acid, 4-diperoxydiacid, 2-diperoxybasic acid, 2-diperoxybrasyl, 2-diperoxyacid, diacid
  • the bleach activator (s) in the detergent according to the invention can contain, which is preferred in the context of the present invention.
  • Bleach activators are incorporated into detergents and cleaning agents in order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or given if substituted perbenzoic acid result, are used. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylene diamine
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • the detergents according to the invention usually contain, based on the total detergent, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more bleach activators or bleach catalysts.
  • bleach activators used are N, N, N ' , N ' tetraacetylethylene diamine (TAED), which is widely used in detergents and cleaning agents, and n-nonanoyloxybenzenesulfonate (NOBS). Accordingly, preferred detergents contain as a bleach activator tetraacetylethylene diamine, which is used in the amounts mentioned above.
  • TAED N, N, N ' , N ' tetraacetylethylene diamine
  • NOBS n-nonanoyloxybenzenesulfonate
  • Dyes and fragrances are added to the detergents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propylate propionate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal, the ketones include, for example, the jonones, cc-isomethylionone and methyl cedryl ketone, the alcohols ethanol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol are the main ones Terpenes like limes and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content in the detergent according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 5% by weight of the entire formulation.
  • the fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.
  • Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or carry 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).
  • Suitable compounds originate for example from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic), 4,4'-biphenylene -Distyryl, rone Methylumbellife-, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides , Benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • the optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based in each case on the total composition.
  • foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. Mixtures of these active ingredients are also possible.
  • Additives which are solid at room temperature in particular in the case of the foam-inhibiting active substances mentioned, paraffin waxes, silicas, which can also be hydrophobicized in a known manner, and of C 2 .
  • Foam-inhibiting paraffin oils that can be used which may be present in a mixture with paraffin waxes, are generally complex substance mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst” 87 (1962), 420, and / or the freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • Paraffins with less than 17 carbon atoms cannot be used according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit which is significantly measurable with customary analytical methods, for example gas chromatography. Paraffins which solidify in the range from 20 ° C. to 70 ° C. are preferably used.
  • paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin oils.
  • the liquid content is as high as possible at 40 ° C. without being 100% at this temperature.
  • Preferred paraffin wax mixtures have a liquid fraction of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid fraction of at least 90% by weight at 60 ° C. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. In addition, Make sure that the paraffins contain no volatile components if possible.
  • Paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the paraffin oils can contain bisamides which are solid at room temperature and which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18, C atoms and from alkylenediamines with 2 to 7 C atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.
  • An agent according to the invention can additionally preferably contain 0.1% by weight to 2% by weight, in particular 0.2% by weight to 1% by weight, of a color transfer inhibitor which, in a preferred embodiment of the invention, is a polymer of vinylpyrrolidone, vinylimidazole , Vinylpyridine-N-oxide or a copolymer of these.
  • Both the polyvinylpyrrolidones known from European patent application EP 0 262 897 with molecular weights of 15,000 to 50,000 and the polyvinylpyrrolidones known from international patent application WO 95/06098 with molecular weights over 1,000,000, in particular from 1,500,000 to 4, can be used 000 000, the N-vinylimidazole / N-vinylpyrrolidone copolymers known from German patent applications DE 28 14 287 or DE 38 03 630 or international patent applications WO 94/10281, WO 94/26796, WO 95/03388 and WO 95/03382 , the polyvinyl oxazolidones known from German patent application DE 28 14 329, the copolymers based on vinyl monomers and carboxamides known from European patent application EP 610 846, the polyesters and polyamides containing pyrrolidone groups known from international patent application WO 95/09194 international patent application WO 94/29422 known grafted poly
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which is hydrogen peroxide-free in water, as are known, for example, from international patent applications WO 92/18687 and WO 91/05839.
  • a mediator compound for peroxidase for example an acetosyringone known from international patent application WO 96/10079, a phenol derivative known from international patent application WO 96/12845 or a phenotiazine or phenoxazine known from international patent application WO 96/12846 is shown in preferred in this case, it also being possible to use the above-mentioned polymeric color transfer inhibitor active ingredients.
  • polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 to 60,000, in particular in the range from 25,000 to 50,000.
  • copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molar mass in the range from 5,000 to 50,000, in particular 10,000 to 20,000, are preferred.
  • odor absorbers has proven to be very helpful for the deodorization of malodorous recipe components, such as amine-containing components, but also for the sustainable deodorization of the washed textiles.
  • the detergents according to the invention contain odor absorbers.
  • Deodorant substances in the sense of the invention are one or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or polydroxy hydroxyl fatty acid with at least 16 carbon atoms and / or a resin acid with the exception of the alkali metal salts and any mixtures thereof.
  • a particularly preferred unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 16 carbon atoms is ricinoleic acid.
  • a particularly preferred resin acid is abietic acid.
  • Preferred metals are the transition metals and the lanthanoids, in particular the transition metals of the groups Villa, Ib and llb of the periodic table, and lanthanum, cerium and neodymium, particularly preferably cobalt, nickel, copper and zinc, extremely preferably zinc.
  • the cobalt, nickel and copper salts and the zinc salts have a similar effect, but the zinc salts are preferred for toxicological reasons.
  • One or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate, are to be used as advantageous and therefore particularly preferred as deodorant substances.
  • Cyclodextrins as well as any mixtures of the aforementioned metal salts with cyclodextries, preferably in a weight ratio of 1:10 to 10: 1, particularly preferably 1: 5 to 5: 1 and in particular, have proven to be further suitable deodorant substances in the sense of the invention from 1: 3 to 3: 1.
  • the term "cyclodextrin” includes all known cyclodextrins, i.e. both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alpha, beta and gamma cyclodextrins and their mixtures and / or their derivatives and / or their mixtures.
  • the detergents according to the invention are in the form of powder, granules or extrudate.
  • the agent is in the form of portioned tablets, preferably compressed tablets, in particular as tablets.
  • the detergents according to the invention can also be present as granules or extrudates.
  • the term “granulation” denotes any shaping process that leads to particles of predeterminable size.
  • press agglomeration processes can also be used, for example.
  • the granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 5 minutes.
  • Conventional mixers and mixing granulators are also suitable for granulation. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower circulation speeds and in particular combinations of the two can be used as mixers.
  • Suitable mixers are, for example, Eirich ® mixers of the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Schugi ® Flexomix, the Fukae ® FS-G mixers (trademark of Fukae Powtech, Kogyo Co., Japan) Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais-Werke GmbH, Mannheim).
  • the residence times of the granules in the mixer combination are in the range of less than 60 seconds high-speed mixer and less than 7 minutes in the low-speed mixer, the residence time also depends on the speed of the mixer. The dwell times are reduced accordingly the faster the mixer runs.
  • the washing composition in the plastic solidification area of the casing is compressed under pressure and under the action of shear forces and homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes used for producing the detergent compositions are extrusion, roller compaction and pelleting.
  • the detergent composition is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head to the predetermined extrusion temperature can be heated.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head, and finally, under pressure, which is preferably at least 10 bar, but can also be lower at extremely high throughputs depending on the machine used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size.
  • granules of an essentially uniformly predeterminable particle size can be produced, and in particular the absolute particle sizes can be adapted to the intended use.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 0.7: 1 to about 3: 1.
  • edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press, in the extruder, or in the plastic agglomerator (Pallmann company).
  • the manufacturing process for the detergent composition is carried out by means of roller compaction.
  • the detergent composition is metered into the plastic solidification area of the casing between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a leaf-shaped compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs or individual pellets can be produced, in which, for example, certain shapes of the later granules or shaped bodies can be specified.
  • the sliver belt is subsequently broken into smaller pieces by a knocking-off and comminution process and can be processed into granules in this way, which can be further tempered by further surface treatment methods known per se, in particular in an approximately spherical shape.
  • the preparation of the detergent composition is carried out by means of pelleting.
  • the detergent and cleaning agent composition is applied to a perforated surface in the plastic solidification area of the casing and pressed through the holes by means of a pressure-generating body.
  • the detergent composition is compressed under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which results in a reduced shear stress and thus a lower temperature increase in the premix. is lisizable.
  • Another pressing agglomeration process that can be used to produce the detergent composition is tableting.
  • the detergent composition is pressed in a mold to form a mold, and coated solid particles can be produced in a wide variety of forms by designing the upper and lower punches of the tablet press.
  • Preferred portioned detergent compositions are produced by a granulation or press agglomeration process, in particular by extrusion.
  • the production of tablets by press agglomeration is extremely preferred.
  • the non-aqueous liquid detergents according to the invention are present as a portion in a completely or partially water-soluble envelope, preferably in a water-soluble bag or a dimensionally stable, water-soluble packaging.
  • the detergent portions packed with water-soluble wrappings make it easier for the consumer to dose them.
  • the coating provides protection for the agent according to the invention, which entails additional physical and chemical stabilization.
  • the detergents are preferably packed in foil bags.
  • Foil bags made of water-soluble foil make it unnecessary for the consumer to tear open the packaging. In this way, it is convenient to dose a single portion measured for one wash cycle by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand wash basin or sink. possible.
  • the foil pouch surrounding the washing portion dissolves without residue when a certain temperature is reached.
  • Detergents packaged in bags made of water-soluble film are also described in large numbers in the prior art.
  • the older patent application DE 198 31 703 discloses a portioned washing or cleaning agent preparation in a bag made of water-soluble film, in particular in a bag made of (optionally acetalized) polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or cleaning agent -Preparation have particle sizes> 800 ⁇ m.
  • PVAL polyvinyl alcohol
  • thermoforming process as described, for example, in WO-A1 00/55068, is also suitable for the production of plastic bags or dimensionally stable detergent portions.
  • the water-soluble envelopes do not necessarily have to consist of a film material, but can also represent dimensionally stable packaging that can be obtained, for example, by means of an injection molding process.
  • Sealing takes place at the positions where the polymer tape of one drum meets the polymer tape of the opposite drum.
  • the filling material is fed into the capsule that is being formed, the polymer tapes being pressed into the spherical half-shell cavities, advantageously by applying a vacuum through openings in the cavities.
  • a process for the production of water-soluble capsules, in which the filling and then the sealing takes place, is disclosed in WO 01/64421.
  • the manufacturing process is based on the so-called Bottle- Pack® method, as described, for example, in German published application DE 14 114 69.
  • a tube-like preform is guided into a two-part cavity. The cavity is closed, the lower tube section being sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymer thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their Derivatives, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethyl cellulose and / or polyvinyl alcohol blends.
  • the polyvinyl alcohols described above are commercially available, for example under the trade name Mowiol ® (Clariant).
  • polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5- 88, Mowiol ® 8-88 and Clariant L648.
  • ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH-22, C- 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP- 06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK) ,
  • the water-soluble thermoplastic used to produce the portion according to the invention can additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol "1 lies.
  • thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the water-soluble polymer thermoplastic.
  • the polymeric thermoplastics can be used to improve their machinability plasticizing aids, i.e. Plasticizers. This can be particularly advantageous if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proven particularly useful as plasticizers.
  • the polymer thermoplastics in amounts of at least> 0% by weight, preferably of> 10% by weight, particularly preferably of> 20% by weight and in particular of> 30% by weight, in each case based on the weight of the wrapping material.
  • pre-portioned detergents according to the invention whether as a portioned shaped body or shaped body with a water-soluble coating or as a detergent powder, granules or extrudate according to the invention with a water-soluble coating, has enormous advantages, in particular with regard to meterability.
  • the portions can be applied directly into the washing drum of a standard washing machine without the need for a dosing aid. In addition, problems resulting from a lack of wash-in can be avoided.
  • Another object of the invention is therefore a washing method for washing textiles using a pre-portioned according to the invention in a commercially available washing machine, wherein the detergent can be added to the laundry without a dosing aid to the laundry.
  • detergent portions are both detergent tablets, molded articles packaged with a water-soluble coating and detergent powders, granules, extrudates or other solid formulations packed with a water-soluble coating, which can be packaged with water-soluble coatings to give portions which are sufficient for one wash cycle.
  • the washing method according to the invention comprises textile washing in a household washing machine using a detergent portion which is added to the washing drum without a metering aid.
  • the placement of the detergent portion (or the detergent portions if several portions are to be used) in the drum is freely selectable by the consumer. So first the laundry can be put into the machine and then the detergent portion can be added, which is placed on the laundry or in the middle of it Laundry is placed.
  • a washing method in which the detergent portion is added to or into the laundry in the drum before the washing cycle is a preferred embodiment of the present invention.
  • the detergent portions can be dispensed without residue even when dosed via the dispensing chamber and the detergent is thus available to the washing process.
  • a washing method according to the invention in which the detergent portion can also be dosed without residue via the induction chamber, is therefore preferred according to the invention.
  • “residue-free” means that, after the washing-in process, a maximum of 5% by weight of the originally metered amount of detergent is in the washing-up chamber, the amount remaining in the chamber being weighed out after drying.
  • Another object of the invention is the use of a detergent according to the invention to reduce the formation of creases in textile fabrics.
  • Another object of the invention is the use of a detergent according to the invention to improve the ironing properties of textile fabrics.
  • Another object of the invention is the use of a detergent according to the invention to reduce the pill formation of textile fabrics.
  • Table 1 shows the recipe E1 according to the invention and the comparison recipe V1. All information is given in percent by weight, based in each case on the total agent.
  • a commercially available iron from the Rowenta P2 Professional company was pulled by a Zwick universal testing machine (type 2.5 / TN1P) over a pulley in the longitudinal direction at a speed of 800 mm per minute over the fabric.
  • the temperature of the iron was set to level III.
  • the weight of the 1680 g iron was increased to 2940 g by additional weights.
  • the force required to move the iron was measured in [N].
  • test fabrics (textile: bleaching nettle; 100%) cotton; 1, 2 * 0.2 m) were treated with the formulations E1 and the comparison formulation without textile care component V1 as follows: 6 fabric strips were washed with 109 g of the respective formulation [water hardness: 16 ° dH] (Miele Novotronik W918; washing program: Standard Cotton / Color 60 ° C / Spinning: 900 rpm) and then dried (2 days hanging on a line in a climate room at 20 ° C and 65% humidity). The washing and drying cycles were repeated 3 times each.
  • Table 2 shows the measured sliding friction forces depending on the test fabric treated with the formulations:
  • the determination of the creasing is based on the AATCC Test 124 (American Association of Textile and Color Chemistry). The creasing is assessed after the washing and subsequent drying process, with a panel of five people assessing the creasing of the test fabric against crumpled standard fabric (AATCC124). The grade 5 is given for crease-free fabrics and the grade 1 for heavily crumpled fabrics. The overall grade represents the arithmetic mean of the ratings.
  • test fabrics (textile: bleaching nettle; 100% cotton; 1.0 m * 0.9 m) were treated with the formulations E1 and the comparison formulation without textile care component V1 as follows: 3 pieces of fabric were washed with 109 g of the respective formulation [water hardness: 16 ° dH] (Miele Novotronik W918; washing program: Standard Cotton / Color 60 ° C / Spinning: 900 rpm) and then dried (2 days hanging on a line in a climate room at 20 ° C and 65% humidity).
  • Table 3 shows the evaluation of the creases of the test fabrics depending on the:
  • the formulation E1 according to the invention shows a significantly reduced wrinkling compared to V1.

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

Abstract

L'invention concerne un détergent solide contenant une composante d'entretien des textiles sélectionnée dans le groupe de la cellulose ou des dérivés de cellulose à fines particules. L'invention concerne également un procédé de lavage pour le lavage de textiles, utilisant des détergents en portions dans un lave-linge domestique. L'invention concerne en outre l'utilisation du détergent solide selon l'invention pour diminuer le froissement, améliorer les propriétés de repassage et réduire le boulochage.
PCT/EP2003/006842 2002-07-06 2003-06-27 Detergent contenant une composante d'entretien des textiles a base de cellulose Ceased WO2004005444A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003246621A AU2003246621A1 (en) 2002-07-06 2003-06-27 Detergent containing a textile care constituent based on cellulose

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002130416 DE10230416A1 (de) 2002-07-06 2002-07-06 Waschmittel mit Textilpflegekomponente auf Cellulosebasis
DE10230416.5 2002-07-06

Publications (1)

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WO2004005444A1 true WO2004005444A1 (fr) 2004-01-15

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AU (1) AU2003246621A1 (fr)
DE (1) DE10230416A1 (fr)
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Cited By (1)

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WO2008135334A1 (fr) * 2007-05-07 2008-11-13 Henkel Ag & Co. Kgaa Agent lavant ou détergent contenant un polysaccharide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005062648A1 (de) * 2005-12-23 2007-06-28 Henkel Kgaa Duftstofffixierung aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen

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DE19723028A1 (de) * 1997-06-03 1998-12-10 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
EP0926232A2 (fr) * 1997-12-22 1999-06-30 Henkel KGaA Composition détergente sous forme de particules
WO2000042144A1 (fr) * 1999-01-13 2000-07-20 The Procter & Gamble Company Compositions detergentes contenant un polymere de cellulose
WO2000058431A1 (fr) * 1999-03-29 2000-10-05 Ciba Specialty Chemicals Holding Inc. Utilisation d'un pigment eclaircissant dans des nettoyants ou des detergents
WO2000065014A1 (fr) * 1999-04-27 2000-11-02 The Procter & Gamble Company Compositions de traitement a base de polysaccharides
GB2357294A (en) * 1999-12-15 2001-06-20 Unilever Plc Fabric treatment composition
DE10002008A1 (de) * 2000-01-19 2001-07-26 Cognis Deutschland Gmbh Verfahren zur Herstellung von Tablettensprengmitteln

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US5336433A (en) * 1992-06-08 1994-08-09 Eka Nobel Ab Bleaching agent
CN1192086C (zh) * 1997-09-15 2005-03-09 普罗格特-甘布尔公司 含有基于阴离子改性的环胺的聚合物的洗衣洗涤剂组合物
DE19754838A1 (de) * 1997-12-10 1999-06-17 Henkel Kgaa Cellulasehaltiges Enzymgranulat
DE19853173A1 (de) * 1998-11-19 2000-05-25 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19855677A1 (de) * 1998-12-02 2000-06-08 Henkel Kgaa Herstellung Aufheller-haltiger Waschmittel-Granulate
DE19949981A1 (de) * 1999-10-16 2001-04-19 Henkel Kgaa Wasch- oder Reinigungsmittel-Portion mit einem Sprengmittel

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Publication number Priority date Publication date Assignee Title
WO1998029528A2 (fr) * 1996-12-26 1998-07-09 The Procter & Gamble Company Compositions detergentes pour lessives, renfermant des polymeres cellulosiques destines a ameliorer l'aspect et l'integrite des tissus laves avec ces compositions
DE19723028A1 (de) * 1997-06-03 1998-12-10 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
EP0926232A2 (fr) * 1997-12-22 1999-06-30 Henkel KGaA Composition détergente sous forme de particules
WO2000042144A1 (fr) * 1999-01-13 2000-07-20 The Procter & Gamble Company Compositions detergentes contenant un polymere de cellulose
WO2000058431A1 (fr) * 1999-03-29 2000-10-05 Ciba Specialty Chemicals Holding Inc. Utilisation d'un pigment eclaircissant dans des nettoyants ou des detergents
WO2000065014A1 (fr) * 1999-04-27 2000-11-02 The Procter & Gamble Company Compositions de traitement a base de polysaccharides
GB2357294A (en) * 1999-12-15 2001-06-20 Unilever Plc Fabric treatment composition
DE10002008A1 (de) * 2000-01-19 2001-07-26 Cognis Deutschland Gmbh Verfahren zur Herstellung von Tablettensprengmitteln

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008135334A1 (fr) * 2007-05-07 2008-11-13 Henkel Ag & Co. Kgaa Agent lavant ou détergent contenant un polysaccharide
US7842658B2 (en) 2007-05-07 2010-11-30 Henkel Ag & Co. Kgaa Detergent or cleaning agent comprising polysaccharide

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AU2003246621A1 (en) 2004-01-23
DE10230416A1 (de) 2004-02-12

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